Onium salt, resist composition, and pattern forming process

Abstract

Onion salt, inhibitor composition, and patterning method are provided. [Problem] To provide an LWR in far-ultraviolet lithography and EUV lithography, a chemical amplification inhibitor composition with excellent resolution and capable of suppressing inhibitor pattern collapse, an onion salt used therein, and a patterning method using the inhibitor composition. [Solution] An onion salt represented by the following formula (1).

Description

Onium Salt, Resist Composition, and Pattern Forming Method The present invention relates to an onium salt, a resist composition, and a pattern forming method. With the high integration and high speed of LSIs, the miniaturization of pattern rules is rapidly progressing. This is because the high-speed communication of 5G and artificial intelligence (AI) are gradually becoming popular, and high-performance devices for processing them are required. As the most advanced miniaturization technology, mass production of devices with a 5 nm node is carried out using extreme ultraviolet (EUV) lithography with a wavelength of 13.5 nm. Furthermore, research using EUV lithography is underway for next-generation 3 nm node devices and the next-next-generation 2 nm node devices. At the same time as miniaturization, image blur caused by acid diffusion has become a problem. In order to ensure the resolution in fine patterns with a size of 45 nm or less, it has been proposed that not only improving the dissolution contrast proposed in the past is important, but also controlling acid diffusion is important. However, since the chemically amplified resist composition improves sensitivity and contrast through acid diffusion, if the post-exposure bake (PEB) temperature is lowered or the time is shortened to suppress acid diffusion to the limit, the sensitivity and contrast are significantly reduced. Sensitivity, resolution, and line edge roughness (LER, LWR) show a triangular trade-off relationship. In order to improve the resolution, it is necessary to suppress acid diffusion, but when the acid diffusion distance becomes short, the sensitivity decreases. Adding an acid generator that generates a large-volume acid to suppress acid diffusion is effective. Thus, it has been proposed to make the polymer contain a repeating unit derived from an onium salt having a polymerizable unsaturated bond. At this time, the polymer also functions as an acid generator (polymer-bonded acid generator). Patent Document 1 proposes sulfonium salts and iodonium salts having a polymerizable unsaturated bond that generate specific sulfonic acids. Patent Document 2 proposes sulfonium salts in which sulfonic acid is directly connected to the main chain. Sensitivity, resolution, and line edge roughness show a triangular trade-off relationship. In order to improve the resolution, it is necessary to suppress acid diffusion, but when the acid diffusion distance becomes short, the sensitivity decreases. In addition, various studies have been conducted on quenching agents (acid diffusion control agents). As quenching agents, various amines are mainly used, but there are many issues to be improved in terms of line width roughness (LWR), which is an index of pattern roughness, pattern shape, etc. In addition, studies using weak acid onium salts as quenching agents have also been reported. For example, Patent Document 1 describes that a pattern with small roughness can be formed by using a compound that generates a carboxylic acid having a boiling point of 150°C or higher. Patent Document 2 describes that the sensitivity, resolution, and exposure margin are improved by adding ammonium sulfonate or ammonium carboxylate. Patent Document 3 describes that a resist composition for KrF or electron beam (EB) lithography containing a combination of a photoacid generator that generates a fluorine atom-containing carboxylic acid has excellent resolution, and the process acceptability such as exposure margin and depth of focus is improved. Patent Document 4 describes a positive photosensitive composition for ArF excimer laser exposure containing a carboxylic acid onium salt. Patent Document 5 describes an onium salt of fluoroalkane sulfonamide that becomes a weak acid onium salt, but when it is used, in the generation of ultrafine processing that seeks the use of ArF lithography and ArF immersion lithography, the LWR, which represents its pattern roughness, and the resolution are also insufficient, and further development of a weak acid onium salt with excellent function as a quenching agent is expected. In addition, in Patent Document 6, an onium salt of α,α-difluorocarboxylic acid is described as a carboxylic acid onium salt. When it is used, the acidity of the carboxylic acid after proton exchange with a strong acid is not sufficiently low, and therefore, depending on the situation, it may also function as an acid generator. Therefore, the quenching ability is low, and the LWR and resolution are not satisfactory. In addition, in EUV lithography, which has been significantly developed in recent years, examples of using aromatic carboxylic acid onium salts that have not been actively applied in ArF lithography have also been reported. Furthermore, onium salts of carboxylic acids containing a nitrogen-containing structure within the same molecule have also been reported. Patent Documents 7 to 9 describe onium salts of indole, indoline, and piperidinecarboxylic acid structures as nitrogen-containing heterocyclic compounds, Patent Document 10 describes an onium salt of aminobenzoic acid structure, and Patent Document 11 describes an onium salt having an amide bond. They also function as quenching agents, but the basicity of aromatic amines and amide bonds is not high, so the acid diffusion control ability is insufficient, and the water solubility of piperidinecarboxylic acid is extremely high, and there are many issues in industrial manufacturing. Regarding the onium salts of this series of weak acids, a strong acid (sulfonic acid) generated by other photoacid generators through exposure exchanges with the weak acid onium salt to form a weak acid and a strong acid onium salt. Thus, it is replaced from a strong acid with high acidity (α,α-difluorosulfonic acid) to a weak acid (alkylsulfonic acid, carboxylic acid, etc.), thereby suppressing the acid dissociation reaction of acid-labile groups and reducing (controlling) the acid diffusion distance, and functioning as a quencher macroscopically. However, in recent years with further miniaturization, especially in EUV lithography, even for the resist compositions obtained using these weak acid onium salts, products that can meet requirements such as resolution, roughness, and depth of focus cannot be obtained. In the case of using alkylsulfonate, the acidity is not sufficiently low, so the quencher ability is low. For carboxylate, not only are the aforementioned properties insufficient, but also due to high hydrophilicity, the affinity for the alkaline developer is high, and the developer is introduced into the exposed area, thereby causing swelling. Especially in the formation of fine line patterns, the collapse of the resist pattern due to this swelling becomes a problem. In order to further meet the requirements of miniaturization, there is also a need to develop a quencher with good sensitivity, excellent acid diffusion control ability, and capable of suppressing the collapse of the resist pattern caused by swelling from the alkaline developer. [Prior Art Documents] [Patent Documents] Patent Document 1: Japanese Patent Application Laid-Open No. 11-125907 Patent Document 2: Japanese Patent Application Laid-Open No. 11-327143 Patent Document 3: Japanese Patent Application Laid-Open No. 2001-281849 Patent Document 4: Japanese Patent No. 4226803 Patent Document 5: Japanese Patent Application Laid-Open No. 2012-108447 Patent Document 6: Japanese Patent Application Laid-Open No. 2015-54833 Patent Document 7: Japanese Patent No. 6217561 Patent Document 8: Japanese Patent No. 6874738 Patent Document 9: Japanese Patent No. 6512049 Patent Document 10: Japanese Patent No. 6323302 Patent Document 11: International Publication No. 2019 / 087626 [Problems to be Solved by the Invention] In view of the foregoing circumstances, the present invention is made. Its purpose is to provide a chemically amplified resist composition excellent in LWR and resolution in far-ultraviolet lithography and EUV lithography and capable of suppressing the collapse of the resist pattern, an onium salt used therein, and a pattern forming method using the resist composition. [Means for Solving the Problems] The inventors of the present invention repeatedly conducted in-depth research to achieve the aforementioned purpose, and as a result, found that: the resist film of the resist composition containing an onium salt as a quencher has excellent resolution, small LWR, and further suppresses swelling during development, which is extremely effective for precise microfabrication. The onium salt contains an anion having an aliphatic heterocycle containing a nitrogen atom and a fluorocarboxylic acid structure, thereby completing the present invention. That is, the present invention provides the following onium salts, resist compositions, and pattern forming methods. 1. An onium salt represented by the following formula (1). (In the formula, n1 is an integer from 0 to 6. n2 is an integer from 0 to 3. n3 is an integer from 1 to 4. W is an aliphatic heterocycle containing a nitrogen atom and having 2 to 20 carbon atoms, which may also contain a heteroatom. L A and L B are each independently a single bond, an ether bond, an ester bond, an amide bond, a sulfonate bond, a carbonate bond, or a carbamate bond. X L is a single bond or an alkylene group having 1 to 40 carbon atoms, which may also contain a heteroatom. R 1 is a hydrocarbon group having 1 to 20 carbon atoms, which may also contain a heteroatom. When n1 ≥ 2, multiple Rs 1 may be bonded to each other and together with the carbon atoms on W to which they are bonded form a ring. Q 1 ~Q 4 are each independently a hydrogen atom, a fluorine atom, a hydrocarbon group having 1 to 6 carbon atoms, or a fluorinated hydrocarbon group having 1 to 6 carbon atoms. Among them, at least one of Q 1 ~Q 4 is a fluorine atom or a fluorinated hydrocarbon group having 1 to 6 carbon atoms. In addition, Q 3 and Q 4 may be bonded to each other and together with the carbon atoms to which they are bonded form a ring. R AL is an acid-labile group. Z + is an onium cation.) 2. The onium salt according to 1, wherein R AL is a group represented by the following formula (AL-1) or (AL-2). (In the formula, L C is -O- or -S-. R 2 、R 3 and R 4 are each independently a hydrocarbon group having 1 to 10 carbon atoms. In addition, R 2 、R 3 and R 4 Any two of them can also be bonded to each other and together with the carbon atom to which they are bonded form a ring. R 5 and R 6 are each independently a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms. R 7 is a hydrocarbon group having 1 to 20 carbon atoms, and the —CH 2 — of this hydrocarbon group can also be replaced by —O— or —S—. In addition, R 6 and R 7 can also be bonded to each other and together with the carbon atom and L to which they are bonded C form a heterocyclic group having 3 to 20 carbon atoms, and the —CH 2 — of this heterocyclic group can also be replaced by —O— or —S—. m1 and m2 are each independently 0 or 1. * represents a bond connected to the adjacent —O—.) 3. The onium salt according to 1 or 2, wherein Z + is a sulfonium cation represented by the following formula (cation-1), an iodonium cation represented by the following formula (cation-2), or an ammonium cation represented by the following formula (cation-3). (In the formula, R 11 ~R 19 are each independently a hydrocarbon group having 1 to 30 carbon atoms which may also contain a heteroatom. In addition, R 11 and R 12 can also be bonded to each other and together with the sulfur atom to which they are bonded form a ring.) 4. The onium salt according to any one of 1 to 3, which is represented by the following formula (1A). (In the formula, n1~n3, W, L A , X L , R 1 , Q 1 ~Q 4 , R AL and Z + The same as described above.) 5. The onium salt according to 4 is represented by the following formula (1B). (In the formula, n1, W, L A , X L , R 1 , Q 1 ~Q 3 , R AL and Z + The same as described above.) 6. A quencher composed of the onium salt according to any one of 1 to 5. 7. A resist composition containing the quencher according to 6. 8. The resist composition according to 7, further containing an organic solvent. 9. The resist composition according to 7 or 8, containing a base polymer having a repeating unit represented by the following formula (a1). (In the formula, R A is a hydrogen atom, a fluorine atom, a methyl group or a trifluoromethyl group. X 1 is a single bond, a phenylene group, a naphthylene group or *-C(=O)-O-X 11 -, and the phenylene group or naphthylene group may also be substituted by an alkoxy group having 1 to 10 carbon atoms or a halogen atom which may contain a fluorine atom. X 11 is a saturated hydrocarbon group having 1 to 10 carbon atoms, a phenylene group or a naphthylene group, and the saturated hydrocarbon group may also contain a hydroxyl group, an ether bond, an ester bond or a lactone ring. * represents a bond connected to a carbon atom of the main chain. AL 1 is an acid-labile group.) 10. The resist composition according to 9, wherein the base polymer further contains a repeating unit represented by the following formula (a2). (In the formula, R A is a hydrogen atom, a fluorine atom, a methyl group or a trifluoromethyl group. X 2 is a single bond or *-C(=O)-O-. * represents a bond connected to a carbon atom of the main chain. R 21is a halogen atom, a cyano group, a hydrocarbon group having 1 to 20 carbon atoms which may contain a hetero atom, a hydrocarbon oxy group having 1 to 20 carbon atoms which may contain a hetero atom, a hydrocarbon group carbonyl having 2 to 20 carbon atoms which may contain a hetero atom, a hydrocarbon group carbonyloxy group having 2 to 20 carbon atoms which may contain a hetero atom, or a hydrocarbon oxy group carbonyl having 2 to 20 carbon atoms which may contain a hetero atom. AL 2 is an acid-labile group. a is an integer of 0 to 4.) 11. The resist composition according to 9 or 10, wherein the base polymer further contains a repeating unit represented by the following formula (b1) or (b2). (In the formula, R A are each independently a hydrogen atom, a fluorine atom, a methyl group, or a trifluoromethyl group. Y 1 is a single bond or *-C(=O)-O-. * represents a bond connected to a carbon atom of the main chain. R 22 is a hydrogen atom, or a group having 1 to 20 carbon atoms containing at least one or more structures selected from hydroxyl groups, cyano groups, carbonyl groups, carboxyl groups, ether bonds, ester bonds, sulfonate ester bonds, carbonate ester bonds, lactone rings, sultone rings, and carboxylic anhydrides (-C(=O)-O-C(=O)-) other than phenolic hydroxyl groups. R 23 is a halogen atom, a nitro group, a hydrocarbon group having 1 to 20 carbon atoms which may contain a hetero atom, a hydrocarbon oxy group having 1 to 20 carbon atoms which may contain a hetero atom, a hydrocarbon group carbonyl having 2 to 20 carbon atoms which may contain a hetero atom, a hydrocarbon group carbonyloxy group having 2 to 20 carbon atoms which may contain a hetero atom, or a hydrocarbon oxy group carbonyl having 2 to 20 carbon atoms which may contain a hetero atom. b is an integer of 1 to 4. c is an integer of 0 to 4. Among them, 1 ≤ b + c ≤ 5.) 12. The resist composition according to any one of 9 to 11, wherein the base polymer further contains a repeating unit represented by any one of the following formulas (c1) to (c4). (In the formula, R A are each independently a hydrogen atom, a fluorine atom, a methyl group, or a trifluoromethyl group. Z 1 is a single bond or a phenylene group. Z 2 is *-C(=O)-O-Z 21 -, *-C(=O)-NH-Z 21 - or *-O-Z 21 -. Z 21is an aliphatic hydrocarbon group having 1 to 6 carbon atoms, a phenylene group, or a divalent group obtained by combining them, and may also contain a carbonyl group, an ester bond, an ether bond or a hydroxyl group. Z 3 are each independently a single bond, a phenylene group, a naphthylene group or *-C(=O)-O-Z 31 -.Z 31 is an aliphatic hydrocarbon group having 1 to 10 carbon atoms, a phenylene group or a naphthylene group, and the aliphatic hydrocarbon group may also contain a hydroxyl group, an ether bond, an ester bond or a lactone ring. Z 4 are each independently a single bond, *-Z 41 -C(=O)-O-, *-C(=O)-NH-Z 41 - or *-O-Z 41 -.Z 41 is a hydrocarbon group having 1 to 20 carbon atoms which may also contain a heteroatom. Z 5 are each independently a single bond, *-Z 51 -C(=O)-O-, *-C(=O)-NH-Z 51 - or *-O-Z 51 -.Z 51 is a hydrocarbon group having 1 to 20 carbon atoms which may also contain a heteroatom. Z 6 is a single bond, a methylene group, an ethylene group, a phenylene group, a fluorinated phenylene group, a phenylene group substituted with a trifluoromethyl group, *-C(=O)-O-Z 61 -, *-C(=O)-N(H)-Z 61 - or *-O-Z 61 -.Z 61 is an aliphatic hydrocarbon group having 1 to 6 carbon atoms, a phenylene group, a fluorinated phenylene group or a phenylene group substituted with a trifluoromethyl group, and may also contain a carbonyl group, an ester bond, an ether bond or a hydroxyl group. * represents a bond connected to a carbon atom of the main chain. R 31 and R 32Each independently is a hydrocarbon group having 1 to 20 carbon atoms which may also contain heteroatoms. In addition, R 31 and R 32 may also be bonded to each other and together with the sulfur atom to which they are bonded form a ring. L 1 is a single bond, an ether bond, an ester bond, a carbonyl group, a sulfonate bond, a carbonate bond or a carbamate bond. Rf 1 and Rf 2 Each independently is a fluorine atom or a fluorinated saturated hydrocarbon group having 1 to 6 carbon atoms. Rf 3 and Rf 4 Each independently is a hydrogen atom, a fluorine atom or a fluorinated saturated hydrocarbon group having 1 to 6 carbon atoms. Rf 5 and Rf 6 Each independently is a hydrogen atom, a fluorine atom or a fluorinated saturated hydrocarbon group having 1 to 6 carbon atoms. Among them, all Rf 5 and Rf 6 are not simultaneously hydrogen atoms. M - is a non-nucleophilic counterion. A + is an onium cation. d is an integer from 0 to 3.) 13. The resist composition according to any one of 7 to 12, further comprising a photoacid generator. 14. The resist composition according to any one of 7 to 13, further comprising a quencher other than the quencher of 6. 15. The resist composition according to any one of 7 to 14, further comprising a surfactant. 16. A pattern forming method, comprising the steps of: forming a resist film on a substrate using the resist composition according to any one of 7 to 15; exposing the resist film with high energy rays; and developing the exposed resist film with a developer. 17. The pattern forming method according to 16, wherein the high energy rays are KrF excimer laser, ArF excimer laser, EB or EUV having a wavelength of 3 to 15 nm. [Effects of the Invention] The onium salt of the present invention functions well as a quencher in a resist composition. The resist film obtained from the resist composition containing the onium salt of the present invention has good sensitivity and excellent dissolution contrast. As a result, the size uniformity (CDU) of the hole pattern and the LWR of the line pattern are improved, and a high-resolution pattern profile with excellent rectangularity can be constructed. [onium salt] The onium salt of the present invention is represented by the following formula (1). In formula (1), n1 is an integer from 0 to 6. n2 is an integer from 0 to 3, preferably 0 or 1. n3 is an integer from 1 to 4, preferably 1 or 2, more preferably 1. In formula (1), W is an aliphatic heterocycle containing a nitrogen atom and having 2 to 20 carbon atoms, which may also contain a heteroatom. Specific examples of the structure of W include the examples shown below, but are not limited to them. It should be noted that in the following formulas, * represents the bond connected to L A and ** represents the bond connected to R AL -O-C(=O)-bond. In formula (1), L A and L B are each independently a single bond, an ether bond, an ester bond, an amide bond, a sulfonate bond, a carbonate bond or a carbamate bond. Among these, a single bond, an ether bond, an ester bond or an amide bond is preferred, and a single bond, an ester bond or an amide bond is more preferred. In formula (1), X L is a single bond or an alkylene group having 1 to 40 carbon atoms, which may also contain a heteroatom. The aforementioned alkylene group can be linear, branched or cyclic. Specific examples thereof include alkanediyl, cyclic saturated alkylene groups, etc. Specific examples of the aforementioned heteroatom include an oxygen atom, a nitrogen atom, a sulfur atom, etc. As specific examples of the alkylene group having 1 to 40 carbon atoms, which may also contain a heteroatom, represented by X L include the examples shown below, but are not limited to them. It should be noted that in the following formulas, * respectively represents the bond connected to L A and L B connected bond. Among these, X L -0 to X L -22 and X L -47 to X L -49 are preferred, and X L -0 to X L -17 is more preferred. In formula (1), R 1 is a hydrocarbon group having 1 to 20 carbon atoms which may also contain heteroatoms. The aforementioned hydrocarbon group may be saturated or unsaturated, and may be any of linear, branched, and cyclic. Specific examples thereof include alkyl groups having 1 to 20 carbon atoms such as methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, n-pentyl, tert-pentyl, n-hexyl, n-octyl, 2-ethylhexyl, n-nonyl, n-decyl; cyclopentyl, cyclohexyl, cyclopentylmethyl, cyclopentylethyl, cyclopentylbutyl, cyclohexylmethyl, cyclohexylethyl, cyclohexylbutyl, norbornyl, tricyclo[5.2.1.0 2,6 decyl, adamantyl, adamantylmethyl and other cyclic saturated hydrocarbon groups having 3 to 20 carbon atoms; aryl groups having 6 to 20 carbon atoms such as phenyl, naphthyl, anthryl; groups obtained by combining them, etc. In addition, part or all of the hydrogen atoms of the aforementioned hydrocarbon group may also be substituted by groups containing heteroatoms such as oxygen atoms, sulfur atoms, nitrogen atoms, and halogen atoms, and part of -CH 2 - of the aforementioned hydrocarbon group may also be substituted by groups containing heteroatoms such as oxygen atoms, sulfur atoms, and nitrogen atoms. As a result, it may also contain hydroxyl groups, fluorine atoms, chlorine atoms, bromine atoms, iodine atoms, cyano groups, carbonyl groups, ether bonds, ester bonds, sulfonate bonds, carbonate bonds, carbamate bonds, amide bonds, imide bonds, lactone rings, sultone rings, thiolactone rings, lactam rings, sultam rings, carboxylic anhydrides (-C(=O)-O-C(=O)-), haloalkyl groups, etc. In addition, when n1≥2, multiple Rs 1 may also be bonded to each other and together with the carbon atoms on W to which they are bonded form a ring. Specific examples of the ring formed at this time include cyclopropane rings, cyclobutane rings, cyclopentane rings, cyclohexane rings, norbornane rings, adamantane rings, etc. In addition, part or all of the hydrogen atoms in the aforementioned ring may also be substituted by groups containing heteroatoms such as oxygen atoms, sulfur atoms, nitrogen atoms, and halogen atoms, and part of -CH 2 - in the aforementioned ring may also be substituted by groups containing heteroatoms such as oxygen atoms, sulfur atoms, and nitrogen atoms. As a result, it may also contain hydroxyl groups, fluorine atoms, chlorine atoms, bromine atoms, iodine atoms, cyano groups, carbonyl groups, ether bonds, ester bonds, sulfonate bonds, carbonate bonds, lactone rings, sultone rings, carboxylic anhydrides (-C(=O)-O-C(=O)-), haloalkyl groups, etc. In addition, two Rs 1 bonded to the same atom forming W are bonded to each other to form a ring, and a spiro ring may also be formed. In formula (1), Q 1 ~Q 4 Each independently represents a hydrogen atom, a fluorine atom, a hydrocarbon group having 1 to 6 carbon atoms, or a fluorinated hydrocarbon group having 1 to 6 carbon atoms. Among them, Q 1 ~Q 4 At least one of them is a fluorine atom or a fluorinated hydrocarbon group having 1 to 6 carbon atoms. The aforementioned hydrocarbon group may be saturated or unsaturated and may be any of linear, branched, and cyclic. As specific examples thereof, hydrocarbon groups having 1 to 6 carbon atoms among the hydrocarbon groups exemplified as the hydrocarbon group having 1 to 20 carbon atoms represented by R 1 can be cited. As the fluorinated hydrocarbon group having 1 to 6 carbon atoms, trifluoromethyl is preferred. In addition, Q 3 and Q 4 may also be bonded to each other and form a ring together with the carbon atom to which they are bonded. As specific examples of the ring formed at this time, a cyclopropane ring, a cyclobutane ring, a cyclopentane ring, a cyclohexane ring, a norbornane ring, an adamantane ring, etc. can be cited. In formula (1), R AL is an acid-labile group. Specifically, R AL is preferably a group represented by the following formula (AL-1) or (AL-2). (In the formula, * represents a bond connected to the adjacent -O-.) In formula (AL-2), L C is -O- or -S-. In formula (AL-1), R 2 、R 3 and R 4 Each independently represents a hydrocarbon group having 1 to 10 carbon atoms. In addition, any two of R 2 、R 3 and R 4 may also be bonded to each other and form a ring together with the carbon atom to which they are bonded. m1 is 0 or 1. In formula (AL-2), R 5 and R 6 Each independently represents a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms. R 7 is a hydrocarbon group having 1 to 20 carbon atoms, and the -CH 2 - of this hydrocarbon group may also be replaced by -O- or -S-. Additionally, R 6 and R 7 may also be bonded to each other and, together with the carbon atoms to which they are bonded and L C form a heterocyclic group having 3 to 20 carbon atoms, and the -CH 2 - of this heterocyclic group may also be replaced by -O- or -S-. m2 is 0 or 1. As specific examples of the acid-labile group represented by formula (AL-1), the following examples can be cited, but are not limited to them. It should be noted that in the following formulas, * represents a bond connected to the adjacent -O-. As specific examples of the acid-labile group represented by formula (AL-2), the following examples can be cited, but are not limited to them. It should be noted that in the following formulas, * represents a bond connected to the adjacent -O-. As the onium salt represented by formula (1), the onium salt represented by the following formula (1A) is preferred. (In the formula, n1 to n3, W, L A , X L , R 1 , Q 1 ~Q 4 , R AL and Z + are the same as those described above.) As the onium salt represented by formula (1A), the onium salt represented by the following formula (1B) can be cited. (In the formula, n1, W, L A , X L , R 1 , Q 1 ~Q 3 , R AL and Z + are the same as those described above.) Specific examples of the anion of the onium salt represented by formula (1) include, but are not limited to, the examples shown below. In formula (1), Z + is an onium cation. As the aforementioned onium cation, a sulfonium cation represented by the following formula (cation-1), an iodonium cation represented by the following formula (cation-2), or an ammonium cation represented by the following formula (cation-3) is preferred. In formulas (cation-1) to (cation-3), R 11 ~R 19 are each independently a hydrocarbon group having 1 to 30 carbon atoms which may also contain a heteroatom. The aforementioned hydrocarbon group may be saturated or unsaturated and may be any of linear, branched, or cyclic. Specific examples thereof include alkyl groups having 1 to 30 carbon atoms such as methyl, ethyl, n-propyl, isopropyl, n-butyl, and tert-butyl; cycloalkyl saturated hydrocarbon groups having 3 to 30 carbon atoms such as cyclopropyl, cyclopentyl, cyclohexyl, cyclopropylmethyl, 4-methylcyclohexyl, cyclohexylmethyl, norbornyl, and adamantyl; alkenyl groups having 2 to 30 carbon atoms such as vinyl, allyl, propenyl, butenyl, and hexenyl; cyclic unsaturated hydrocarbon groups having 3 to 30 carbon atoms such as cyclohexenyl; aryl groups having 6 to 30 carbon atoms such as phenyl, naphthyl, and thienyl; aralkyl groups having 7 to 30 carbon atoms such as benzyl, 1-phenylethyl, and 2-phenylethyl; and groups obtained by combining them, with aryl groups being preferred. In addition, some or all of the hydrogen atoms of the aforementioned hydrocarbon group may be substituted with a group containing a heteroatom such as an oxygen atom, a sulfur atom, a nitrogen atom, or a halogen atom, and a part of -CH 2 - may also be substituted with a group containing a heteroatom such as an oxygen atom, a sulfur atom, or a nitrogen atom, and as a result, it may contain a hydroxyl group, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a cyano group, a carbonyl group, an ether bond, an ester bond, a sulfonate bond, a carbonate bond, a lactone ring, a sultone ring, a carboxylic anhydride (-C(=O)-O-C(=O)-), a haloalkyl group, etc. In addition, R 11 and R 12 may also be bonded to each other and together with the sulfur atom to which they are bonded form a ring. In this case, specific examples of the sulfonium cation represented by formula (cation-1) include examples shown by the following formula, etc. (In the formula, the dashed line is a bond connecting to R 13 .) As specific examples of the cation of the sulfonium salt represented by formula (cation-1), the examples shown below can be cited, but they are not limited thereto. As specific examples of the oxonium cation represented by formula (cation-2), the examples shown below can be cited, but they are not limited thereto. As specific examples of the ammonium cation represented by formula (cation-3), the examples shown below can be cited, but they are not limited thereto. As specific examples of the onium salt of the present invention, any combination of the aforementioned anions and cations can be cited. The onium salt of the present invention can be synthesized by a known method. As an example, the manufacturing method of the onium salt represented by the following formula (NSQ-1-ex) will be described. (In the formula, n1 to n3, W, L A , X L , R 1 , Q 1 to Q 4 , R AL and Z + are the same as those described above. R X is a group that forms a primary ester or a secondary ester together with the adjacent -CO 2 -. M + is a counter cation. X - is a counter anion.) The first step is a step of obtaining intermediate In-1-ex by reacting starting material SM-1, which is a commercially available product or can be synthesized by a known synthesis method, with starting material SM-2. When directly forming an ester bond from the carboxyl group of starting material SM-1 and the hydroxyl group of starting material SM-2, various condensing agents can be used. Examples of the condensing agent used include N,N'-dicyclohexylcarbodiimide, N,N'-diisopropylcarbodiimide, 1-[3-(dimethylamino)propyl]-3-ethylcarbodiimide, 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide hydrochloride, etc. From the viewpoint of the ease of removing the urea compound generated as a by-product after the reaction, 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide hydrochloride is preferably used. The reaction is carried out by dissolving starting material SM-1 and starting material SM-2 in a halogen-based solvent such as dichloromethane and adding a condensing agent. If 4-dimethylaminopyridine is added as a catalyst, the reaction rate can be increased. From the viewpoint of the yield, it is ideal to terminate the reaction by tracking the reaction using silica gel thin layer chromatography (TLC). The reaction time is usually about 12 to 24 hours. After stopping the reaction, if necessary, the by-produced urea compound is removed by filtration or washing with water, and then the reaction solution is subjected to a usual aqueous work-up, whereby intermediate In-1-ex can be obtained. If necessary, the obtained intermediate In-1-ex can be purified by conventional methods such as distillation, chromatography, and recrystallization. The second step is a step of obtaining intermediate In-2-ex by subjecting intermediate In-1-ex to base hydrolysis. Specifically, it is a step of subjecting the carboxylic acid ester in intermediate In-1-ex to base hydrolysis using an alkali metal hydroxide salt or a hydroxide salt of an organic cation to obtain intermediate In-2-ex as a carboxylate salt. Examples of the alkali metal hydroxide salt used include lithium hydroxide, sodium hydroxide, potassium hydroxide, etc. Examples of the hydroxide salt of an organic cation include tetramethylammonium hydroxide, benzyltrimethylammonium hydroxide, etc. The reaction is carried out by dissolving intermediate In-1-ex in an ether-based solvent such as tetrahydrofuran or 1,4-dioxane and adding an aqueous solution of various hydroxide salts. From the viewpoint of the yield, it is ideal to terminate the reaction by tracking the reaction using silica gel thin layer chromatography (TLC). The reaction time is usually about 12 to 24 hours. By subjecting the reaction mixture to a usual aqueous work-up, intermediate In-2-ex can be obtained. If necessary, the obtained intermediate In-2-ex can be purified by conventional methods such as chromatography and recrystallization. The third step is to react the obtained intermediate In-2-ex with Z + X -Salt exchange occurs at the shown gallium salts to give the step of gallium salts NSQ-1-ex. It should be noted that as X - , starting from the aspect that can easily and quantitatively carry out the exchange reaction, preferably chloride ion, bromide ion, iodide ion or methyl sulfate anion. From the point of view of yield, it is ideal to utilize silicone thin-layer chromatography (TLC) to confirm the progression of the reaction. The gillium salt NSQ-1-ex was obtained by the usual aqueous work-up from the reaction mixture. If necessary, purification can be performed according to conventional methods such as chromatography and recrystallization. In the aforementioned route, the third step of ion exchange can be easily carried out using well-known methods, which can be referred to, for example, the Gazette of Japan Special Kai No. 2007-145797. It should be noted that the foregoing method of manufacture is nothing more than an example, and the method of manufacture of gallium salts of the present invention is not limited to this. [Quenchant] The gillium salt of the present invention is useful as a quenching agent. It should be stated that in the present invention, a quencher refers to a material used to capture the acid produced by the photoacid generating agent in the retardant composition and prevent its diffusion into the unexposed portion, forming the desired pattern. If the gallium salts of the present invention are allowed to coexist with gallium salts producing strong acids such as sulfonic acids, amidosines, or methylated acids fluorinated at the α position, the corresponding carboxylic acids and strong acids are produced by light irradiation. On the other hand, large amounts of undecomposed gallium salts are present in the less exposed parts. Strong acids function as catalysts used to initiate deprotection reactions of acid labile groups of the base polymer, but the inventive gallium salts almost do not undergo deprotection reactions. The strong acid undergoes ion exchange with the residual carboxylate stannous salt to form the strong acid strontium salt, which instead releases the carboxylic acid. In other words, by ion exchange, the strong acid is neutralized by the salt of gallium carboxylate. That is, the gillium salt of the invention functions as a quenching agent. This gallium salt type quencher usually has a tendency to have a smaller LWR of the blocker pattern compared to quenchers using amine compounds. Salt exchange of strong acids with gallium carboxylate salts is repeated countless times. The site where the strong acid was produced at the end of the exposure was different from the site where the strong acid-producing type of gallium salt was initially present. It can be speculated that the acid production points are averaged by repeatedly performing multiple cycles of light-based acid production and salt exchange, whereby the LWR of the developed resistor pattern becomes smaller. As materials having a quencher effect through the same mechanism, for example, carboxonium salts, alkanesulfonium salts, arenesulfonium salts, α,α-difluorocarboxonium salts, etc. are described in Patent Documents 1 to 6. As the types of sulfonium salts, sulfonium salts, iodonium salts, or ammonium salts can be cited. In the case of using alkanesulfonium salts or arenesulfonium salts, the acid strength of the generated acid is large to a certain extent. Therefore, a part of them is not a quencher but acts as an acid generator to trigger a deprotection reaction, resulting in a decrease in resolution performance, an increase in acid diffusion, and deterioration of resist performance such as exposure latitude (EL) and mask error factor (MEF). In addition, although the α,α-difluorocarboxonium salt of Patent Document 6 is a carboxonium salt, since it has a fluorine atom at the α-position of the carboxylate anion, the acidity of the generated acid is large to a certain extent, similar to the aforementioned sulfonium salt, and it may trigger a deprotection reaction by selecting an acid-labile group of the base polymer. Similarly, the fluorocarboxonium salt with a simply extended straight chain also has a large acid diffusion, undergoes salt exchange with the strong acid in the unexposed part, and as a result, it can be considered that the resolution, EL, and MEF will decrease. In the case of alkane carboxylic acids, the hydrophilicity of the substance that functions as a quencher is very high. The fluoroalkane carboxonium salt described in Patent Document 3 can control the hydrophilicity to a certain extent compared with the non-fluorinated type, but when the number of carbon atoms is small, the control of hydrophilicity is not sufficient. There are also examples of perfluoroalkane carboxonium salts with a large number of carbon atoms, but in this case, it can be considered that the carboxylic acid exhibits physical properties similar to those of a surfactant and has poor compatibility with the resist composition. If the compatibility with the resist composition is poor, it may cause defects. Furthermore, from the viewpoint of organisms / environment, perfluoroalkane carboxylic acids are not preferred. In addition, Patent Documents 7 to 9 describe indole, indoline, and carboxonium salts having a piperidinecarboxylic acid structure as nitrogen-containing heterocyclic compounds, Patent Document 10 describes carboxonium salts having an aminobenzoic acid structure, and Patent Document 11 describes carboxonium salts having an amide bond. They also function as quenchers, but the basicity of aromatic amines and amide bonds is not high, so the ability to control acid diffusion is insufficient. The water solubility of piperidinecarboxylic acid is extremely high, so there is a concern that it will promote the penetration of the alkali developer into the unexposed part, cause the collapse of the resist pattern, and peeling from the substrate. The onium salts of the present invention can solve the aforementioned problems. An onium salt having an aliphatic heterocycle containing a nitrogen atom and a fluorocarboxylic acid structure in the anion functions as a quencher, effectively capturing the strong acid generated by the acid generator in the exposed portion at the fluorocarboxylic acid anion site, and the acid-labile group protecting the aliphatic heterocycle portion containing a nitrogen atom undergoes a deprotection reaction due to the strong acid, generating an aliphatic heterocyclic compound with a high basicity containing a nitrogen atom. Due to the deprotection reaction by the acid, an aliphatic heterocyclic structure with a high basicity containing a nitrogen atom is generated. Therefore, fluorocarboxylic acid is generated in the exposed portion, but the deprotection reaction of the base polymer does not occur. In addition, the aliphatic heterocyclic portion with a high basicity containing a nitrogen atom inhibits the excessive diffusion of the acid to the unexposed portion, and the carboxylic acid anion site continues to repeatedly perform proton exchange with the strong acid. It is considered that the dissolution contrast between the exposed portion and the unexposed portion is improved by their synergistic effect, and the acid diffusion of the strong acid is appropriately controlled. Thus, good lithography performance can also be achieved in the formation of fine patterns. In addition, by making the fluorocarboxylic acid structure and the acid-labile group protecting the aliphatic heterocycle portion containing a nitrogen atom have a more appropriate number of carbon atoms, the solubility in an organic solvent is improved. Therefore, the penetration of the alkali developer into the unexposed portion, the accompanying collapse and peeling of the resist pattern can be effectively inhibited. [Resist composition] The resist composition of the present invention contains (A) a quencher as an essential component, and the quencher is composed of an onium salt represented by the formula (1). In the resist composition of the present invention, the content of (A) the quencher is preferably 0.1 to 40 parts by mass, more preferably 1 to 20 parts by mass, relative to 80 parts by mass of the following (C) base polymer. If the content of (A) the quencher is within the aforementioned range, it functions sufficiently as a quencher, and there is no need to worry about performance deterioration such as a decrease in sensitivity or the generation of foreign substances due to insufficient solubility. [(B) Organic solvent] The resist composition of the present invention may contain an organic solvent as the (B) component. As the (B) organic solvent, there is no particular limitation as long as it can dissolve the (A) component and the following respective components. Specific examples of such organic solvents include ketones such as cyclopentanone, cyclohexanone, and methyl-2-n-pentyl ketone; alcohols such as 3-methoxybutanol, 3-methyl-3-methoxybutanol, 1-methoxy-2-propanol, and 1-ethoxy-2-propanol; ketols such as diacetone alcohol (DAA); ethers such as propylene glycol monomethyl ether (PGME), ethylene glycol monomethyl ether, propylene glycol monoethyl ether, ethylene glycol monoethyl ether, propylene glycol dimethyl ether, and diethylene glycol dimethyl ether; esters such as propylene glycol monomethyl ether acetate (PGMEA), propylene glycol monoethyl ether acetate, ethyl lactate, ethyl pyruvate, butyl acetate, methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, tert-butyl acetate, tert-butyl propionate, and propylene glycol monoter-butyl ether acetate; lactones such as γ-butyrolactone (GBL); and their mixed solvents. Among these organic solvents, PGME, PGMEA, cyclohexanone, GBL, DAA, ethyl lactate, and their mixed solvents, which are particularly excellent in solubility of the base polymer as the component (C), are preferred. In the resist composition of the present invention, the content of the (B) organic solvent is preferably 200 to 5000 parts by mass, more preferably 400 to 3500 parts by mass, relative to 80 parts by mass of the following (C) base polymer. The (B) organic solvent can be used alone or in combination of two or more. [(C) Base polymer] The resist composition of the present invention may contain a base polymer as the component (C). The (C) base polymer contains a repeating unit represented by the following formula (a1) (hereinafter also referred to as repeating unit a1). In the formula (a1), R A is a hydrogen atom, a fluorine atom, a methyl group, or a trifluoromethyl group. X 1 is a single bond, a phenylene group, a naphthylene group, or *-C(=O)-O-X 11 -, and the phenylene group or naphthylene group may also be substituted with an alkoxy group having 1 to 10 carbon atoms or a halogen atom which may contain a fluorine atom. X 11 is a saturated hydrocarbon group having 1 to 10 carbon atoms, a phenylene group, or a naphthylene group, and the saturated hydrocarbon group may also contain a hydroxyl group, an ether bond, an ester bond, or a lactone ring. * represents a bond connected to a carbon atom of the main chain. In the formula (a1), AL 1 is an acid-labile group. As the aforementioned acid-labile group, for example, the groups described in JP-A-2013-80033 and JP-A-2013-83821 can be cited. Typically, as the aforementioned acid-labile group, the groups represented by the following formulas (AL-3) to (AL-5) can be cited. (In the formula, the dashed line is a connecting bond.) In the formulas (AL-3) and (AL-4), R L1 and R L2 are each independently a saturated hydrocarbon group having 1 to 40 carbon atoms, and may also contain heteroatoms such as an oxygen atom, a sulfur atom, a nitrogen atom, and a fluorine atom. The aforementioned saturated hydrocarbon group may be linear, branched, or cyclic. As the aforementioned saturated hydrocarbon group, a group having 1 to 20 carbon atoms is preferred. In the formula (AL-3), k is an integer of 0 to 10, preferably an integer of 1 to 5. In the formula (AL-4), R L3 and R L4 are each independently a hydrogen atom or a saturated hydrocarbon group having 1 to 20 carbon atoms, and may also contain heteroatoms such as an oxygen atom, a sulfur atom, a nitrogen atom, and a fluorine atom. The aforementioned hydrocarbon group may be any of linear, branched, and cyclic. In addition, R L2 、R L3 and R L4 Any two of them may also be bonded to each other and form a ring having 3 to 20 carbon atoms together with the carbon atoms to which they are bonded or the carbon atoms and oxygen atoms. As the aforementioned ring, a ring having 4 to 16 carbon atoms is preferred, and an alicyclic ring is particularly preferred. In formula (AL-5), R L5 、R L6 and R L7 are each independently a saturated hydrocarbon group having 1 to 20 carbon atoms, and may also contain heteroatoms such as an oxygen atom, a sulfur atom, a nitrogen atom, and a fluorine atom. The aforementioned hydrocarbon group may be any of linear, branched, and cyclic. In addition, R L5 、R L6 and R L7 Any two of them may also be bonded to each other and form a ring having 3 to 20 carbon atoms together with the carbon atoms to which they are bonded. As the aforementioned ring, a ring having 4 to 16 carbon atoms is preferred, and an alicyclic ring is particularly preferred. As specific examples of the repeating unit a1, the following examples can be cited, but are not limited to them. It should be noted that in the following formulas, R A and AL 1 are the same as those described above. The aforementioned base polymer may further contain a repeating unit represented by the following formula (a2) (hereinafter also referred to as repeating unit a2). In formula (a2), R A is a hydrogen atom, a fluorine atom, a methyl group, or a trifluoromethyl group. X 2 is a single bond or *-C(=O)-O-. * represents a bond connected to a carbon atom of the main chain. R 21is a halogen atom, a cyano group, a hydrocarbon group having 1 to 20 carbon atoms which may contain a hetero atom, a hydrocarbon oxy group having 1 to 20 carbon atoms which may contain a hetero atom, a hydrocarbon carbonyl group having 2 to 20 carbon atoms which may contain a hetero atom, a hydrocarbon carbonyloxy group having 2 to 20 carbon atoms which may contain a hetero atom, or a hydrocarbon oxycarbonyl group having 2 to 20 carbon atoms which may contain a hetero atom. AL 2 is an acid-labile group. As the aforementioned acid-labile group, groups the same as those exemplified as the acid-labile group shown as AL 1 can be cited. a is an integer of 0 to 4, preferably 0 or 1. As specific examples of the repeating unit a2, the following examples can be cited, but are not limited to them. It should be noted that in the following formulas, R A and AL 2 are the same as those described above. The aforementioned base polymer preferably further contains a repeating unit represented by the following formula (b1) (hereinafter also referred to as repeating unit b1) or a repeating unit represented by the following formula (b2) (hereinafter also referred to as repeating unit b2). In formulas (b1) and (b2), R A are each independently a hydrogen atom, a fluorine atom, a methyl group, or a trifluoromethyl group. Y 1 is a single bond or *-C(=O)-O-. * represents a bond connected to the carbon atom of the main chain. R 22 is a hydrogen atom, or a group having 1 to 20 carbon atoms containing at least one or more structures selected from hydroxyl groups other than phenolic hydroxyl groups, cyano groups, carbonyl groups, carboxyl groups, ether bonds, ester bonds, sulfonate ester bonds, carbonate ester bonds, lactone rings, sultone rings, and carboxylic anhydrides (-C(=O)-O-C(=O)-). R 23 is a halogen atom, a nitro group, a hydrocarbon group having 1 to 20 carbon atoms which may contain a hetero atom, a hydrocarbon oxy group having 1 to 20 carbon atoms which may contain a hetero atom, a hydrocarbon carbonyl group having 2 to 20 carbon atoms which may contain a hetero atom, a hydrocarbon carbonyloxy group having 2 to 20 carbon atoms which may contain a hetero atom, or a hydrocarbon oxycarbonyl group having 2 to 20 carbon atoms which may contain a hetero atom. b is an integer of 1 to 4. c is an integer of 0 to 4. Among them, 1≤b + c≤5. As specific examples of the repeating unit b1, the following examples can be cited, but are not limited to them. It should be noted that in the following formulas, R A is the same as those described above. As a specific example of the repeating unit b2, the examples shown below can be cited, but they are not limited thereto. It should be noted that in the following formulas, R A is the same as described above. As the repeating unit b1 or b2, in ArF lithography, it is particularly preferable to have a lactone ring as a polar group, and in KrF lithography, EB lithography, and EUV lithography, it is preferable to have a phenol moiety. The aforementioned base polymer may further contain a repeating unit represented by any one of the following formulas (c1) to (c4) (hereinafter also referred to as repeating units c1 to c4, respectively). In the formulas (c1) to (c4), R A are each independently a hydrogen atom, a fluorine atom, a methyl group, or a trifluoromethyl group. Z 1 is a single bond or a phenylene group. Z 2 is *-C(=O)-O-Z 21 -, *-C(=O)-NH-Z 21 - or *-O-Z 21 -. Z 21 is an aliphatic hydrocarbon group having 1 to 6 carbon atoms, a phenylene group, or a divalent group obtained by combining them, and may also contain a carbonyl group, an ester bond, an ether bond, or a hydroxyl group. Z 3 are each independently a single bond, a phenylene group, a naphthylene group, or *-C(=O)-O-Z 31 -. Z 31 is an aliphatic hydrocarbon group having 1 to 10 carbon atoms, a phenylene group, or a naphthylene group, and the aliphatic hydrocarbon group may also contain a hydroxyl group, an ether bond, an ester bond, or a lactone ring. Z 4 are each independently a single bond, *-Z 41 -C(=O)-O-, *-C(=O)-NH-Z 41 - or *-O-Z 41 -. Z 41 is a hydrocarbon group having 1 to 20 carbon atoms that may also contain a heteroatom. Z 5 are each independently a single bond, *-Z 51 -C(=O)-O-, *-C(=O)-NH-Z 51 - or *-O-Z 51 -.Z 51 is a hydrocarbon group with 1 to 20 carbon atoms that may also contain heteroatoms. Z 6 is a single bond, methylene, ethylene, phenylene, fluorinated phenylene, phenylene substituted with trifluoromethyl, *-C(=O)-O-Z 61 -, *-C(=O)-N(H)-Z 61 - or *-O-Z 61 -.Z 61 is an aliphatic hydrocarbon group with 1 to 6 carbon atoms, phenylene, fluorinated phenylene or phenylene substituted with trifluoromethyl, and may also contain a carbonyl group, an ester bond, an ether bond or a hydroxyl group. * represents a bond connected to the carbon atom of the main chain. Z 21 , Z 31 and Z 61 The aliphatic hydrocarbon group shown by Z can be any of linear, branched and cyclic. As specific examples thereof, methylenediyl, ethane-1,1-diyl, ethane-1,2-diyl, propane-1,1-diyl, propane-1,2-diyl, propane-1,3-diyl, propane-2,2-diyl, butane-1,1-diyl, butane-1,2-diyl, butane-1,3-diyl, butane-2,3-diyl, butane-1,4-diyl, 1,1-dimethylethane-1,2-diyl, pentane-1,5-diyl, 2-methylbutane-1,2-diyl, hexane-1,6-diyl alkane diyls; cyclopropane diyl, cyclobutane diyl, cyclopentane diyl, cyclohexane diyl and other cycloalkane diyls; groups obtained by combining them, etc. can be cited. Z 41 and Z 51 The hydrocarbon group shown by Z can be saturated or unsaturated and can be any of linear, branched and cyclic. As specific examples thereof, the examples shown below can be cited, but are not limited thereto. (In the formula, the dotted line is a connecting bond.) In formula (c1), R 31 and R 32 Each independently is a hydrocarbon group having 1 to 20 carbon atoms which may also contain heteroatoms. The aforementioned hydrocarbon group may be saturated or unsaturated, and may be any of linear, branched, or cyclic. Specific examples thereof include alkyl groups having 1 to 20 carbon atoms such as methyl, ethyl, n-propyl, isopropyl, n-butyl, tert-butyl; cyclic saturated hydrocarbon groups having 3 to 20 carbon atoms such as cyclopropyl, cyclopentyl, cyclohexyl, cyclopropylmethyl, 4-methylcyclohexyl, cyclohexylmethyl, norbornyl, adamantyl; alkenyl groups having 2 to 20 carbon atoms such as vinyl, allyl, propenyl, butenyl, hexenyl; cyclic unsaturated hydrocarbon groups having 3 to 20 carbon atoms such as cyclohexenyl; aryl groups having 6 to 20 carbon atoms such as phenyl, naphthyl, thienyl; aralkyl groups such as benzyl, 1-phenylethyl, 2-phenylethyl; groups obtained by combining them, etc., and aryl groups are preferred. In addition, some or all of the hydrogen atoms of the aforementioned hydrocarbon group may be substituted with groups containing heteroatoms such as oxygen atoms, sulfur atoms, nitrogen atoms, halogen atoms, and a part of -CH 2 - of the aforementioned hydrocarbon group may also be substituted with groups containing heteroatoms such as oxygen atoms, sulfur atoms, nitrogen atoms, etc., and as a result, it may contain hydroxyl groups, fluorine atoms, chlorine atoms, bromine atoms, iodine atoms, cyano groups, carbonyl groups, ether bonds, ester bonds, sulfonate bonds, carbonate bonds, lactone rings, sultone rings, carboxylic anhydrides (-C(=O)-O-C(=O)-), haloalkyl groups, etc. In addition, R 31 and R 32 may also be bonded to each other and form a ring together with the sulfur atom to which they are bonded. At this time, examples of the aforementioned ring include the same rings as those exemplified for the ring formed by bonding R 11 and R 12 and forming a ring together with the sulfur atom to which they are bonded in the description of formula (cation-1). Specific examples of the cation of repeating unit c1 include the examples shown below, but are not limited thereto. It should be noted that in the following formulas, R A is the same as the aforementioned. In formula (c1), M -is a non-nucleophilic counter ion. Specific examples of the non-nucleophilic counter ion include halide ions such as chloride ion and bromide ion; fluoroalkylsulfonate ions such as trifluoromethanesulfonate ion, 1,1,1-trifluoroethanesulfonate ion, and nonafluorobutanesulfonate ion; arylsulfonate ions such as toluenesulfonate ion, benzenesulfonate ion, 4-fluorobenzenesulfonate ion, and 1,2,3,4,5-pentafluorobenzenesulfonate ion; alkylsulfonate ions such as methanesulfonate ion and butanesulfonate ion; imide ions such as bis(trifluoromethylsulfonyl)imide ion, bis(perfluoroethylsulfonyl)imide ion, and bis(perfluorobutylsulfonyl)imide ion; methylide ions such as tris(trifluoromethylsulfonyl)methylide ion and tris(perfluoroethylsulfonyl)methylide ion, etc. Furthermore, specific examples of the non-nucleophilic counter ion include sulfonate anions in which the α-position is substituted with a fluorine atom represented by the following formula (c1-1) and sulfonate anions in which the α-position is substituted with a fluorine atom and the β-position is substituted with a trifluoromethyl group represented by the following formula (c1-2). In formula (c1-1), R 33 is a hydrogen atom, a hydrocarbon group having 1 to 30 carbon atoms, a hydrocarbon oxycarbonyl group having 2 to 30 carbon atoms, or a hydrocarbon oxycarbonyl group having 2 to 30 carbon atoms. The hydrocarbon group may also contain a halogen atom, an ether bond, an ester bond, a carbonyl group, or a lactone ring. The hydrocarbon group and the hydrocarbon moieties of the hydrocarbon oxycarbonyl group and the hydrocarbon oxycarbonyl group may be saturated or unsaturated and may be linear, branched, or cyclic. Specific examples thereof include the same groups as those exemplified for the hydrocarbon group represented by R fa1 shown in the following formula (2A'). In formula (c1-2), R 34 is a hydrogen atom, a hydrocarbon group having 1 to 30 carbon atoms, or a hydrocarbon carbonyl group having 2 to 30 carbon atoms. The hydrocarbon group and the hydrocarbon carbonyl group may also contain a halogen atom, an ether bond, an ester bond, a carbonyl group, or a lactone ring. R 35 is a hydrogen atom, a fluorine atom, or a fluorinated alkyl group having 1 to 6 carbon atoms. The hydrocarbon group and the hydrocarbon moieties of the hydrocarbon carbonyl group may be saturated or unsaturated and may be linear, branched, or cyclic. Specific examples thereof include the same groups as those exemplified for the hydrocarbon group represented by R fa1 shown in the following formula (2A'). As R 35 , trifluoromethyl is preferred. Specific examples of the sulfonate anion represented by formula (c1-1) or (c1-2) include the following examples, but are not limited thereto. It should be noted that in the following formula, R 35 Similarly to the above, Ac is an acetyl group. In formulas (C2) and (C3), L 1 is a single bond, an ether bond, an ester bond, a carbonyl group, a sulfonate bond, a carbonate bond or a carbamate bond. Among these, from the viewpoint of synthesis, an ether bond, an ester bond or a carbonyl group is preferred, and an ester bond or a carbonyl group is more preferred. In formula (C2), Rf 1 and Rf 2 are each independently a fluorine atom or a fluorinated saturated hydrocarbon group having 1 to 6 carbon atoms. Among these, as Rf 1 and Rf 2 , in order to increase the acid strength of the generated acid, both are preferably fluorine atoms. Rf 3 and Rf 4 are each independently a hydrogen atom, a fluorine atom or a fluorinated saturated hydrocarbon group having 1 to 6 carbon atoms. Among these, in order to improve the solvent solubility, it is preferred that at least one of Rf 3 and Rf 4 is a trifluoromethyl group. In formula (C3), Rf 5 and Rf 6 are each independently a hydrogen atom, a fluorine atom or a fluorinated saturated hydrocarbon group having 1 to 6 carbon atoms. Among them, all Rf 5 and Rf 6 are not simultaneously hydrogen atoms. Among these, in order to improve the solvent solubility, it is preferred that at least one of Rf 5 and Rf 6 is a trifluoromethyl group. In formulas (C2) and (C3), d is an integer of 0 to 3, preferably 1. As specific examples of the anion of the repeating unit c2, the following examples can be cited, but are not limited to them. It should be noted that in the following formulas, R A is the same as described above. As specific examples of the anion of the repeating unit c3, the examples shown below can be cited, but are not limited to them. It should be noted that in the following formulas, R A is the same as described above. As specific examples of the anion of the repeating unit c4, the examples shown below can be cited, but are not limited to them. It should be noted that in the following formulas, R A is the same as described above. In formulas (C2) to (C4), A + is an onium cation. As the aforementioned onium cation, sulfonium cations, iodonium cations, ammonium cations, etc. can be cited, and sulfonium cations and iodonium cations are preferred. As their specific structures, cations the same as the cations exemplified as the cations shown in formulas (cation-1) to (cation-3) can be cited. The repeating units c1 to c4 function as a photoacid generator. When using a base polymer containing the repeating units c1 to c4 (i.e., a polymer-bonded acid generator), the resist composition of the present invention may or may not contain the aforementioned (D) photoacid generator described later. The aforementioned base polymer may further contain a repeating unit having a structure in which a hydroxyl group is protected by an acid-labile group (hereinafter also referred to as a repeating unit d). As the repeating unit d, there is no particular limitation as long as it has a structure protecting one or two or more hydroxyl groups and the protecting group is decomposed by the action of an acid to generate a hydroxyl group, and a repeating unit represented by the following formula (d1) is preferred. In formula (d1), R A is the same as described above. R 41 is a (e + 1)-valent hydrocarbon group having 1 to 30 carbon atoms which may also contain a heteroatom. R 42 is an acid-labile group. e is an integer from 1 to 4. In formula (d1), the acid-labile group represented by R 42 only needs to be deprotected by the action of an acid to generate a hydroxyl group. The structure of R 42 is not particularly limited, and an acetal structure, a ketal structure, an alkoxycarbonyl group, an alkoxymethyl group represented by the following formula (d2), etc. are preferred, and an alkoxymethyl group represented by the following formula (d2) is particularly preferred. (In the formula, * represents a linking bond. R 43 is a hydrocarbon group having 1 to 15 carbon atoms.) As R 42 Specific examples of the acid-labile group, alkoxymethyl group represented by formula (d2), and repeating unit d include the same examples as those exemplified in the description of repeating unit d described in Japanese Patent Application Laid-Open No. 2020-111564. The foregoing base polymer may further contain a repeating unit e derived from indene, benzofuran, benzothiophene, vinylnaphthalene, chromone, coumarin, norbornadiene, or a derivative thereof. Specific examples of the monomer that provides the repeating unit e include the examples shown below, but are not limited thereto. The foregoing base polymer may further contain a repeating unit f derived from indane, vinylpyridine, or vinylcarbazole. In the polymer of the present invention, the content ratios of the repeating units a1, a2, b1, b2, c1 to c4, d, e, and f are preferably 0 < a1 ≤ 0.8, 0 ≤ a2 ≤ 0.8, 0 < а1 + a2 ≤ 0.8, 0 ≤ b1 ≤ 0.6, 0 ≤ b2 ≤ 0.6, 0 ≤ b1 + b2 ≤ 0.6, 0 ≤ c1 ≤ 0.4, 0 ≤ c2 ≤ 0.4, 0 ≤ c3 ≤ 0.4, 0 ≤ c4 ≤ 0.4, 0 ≤ c1 + c2 + c3 + c4 ≤ 0.4, 0 ≤ d ≤ 0.5, 0 ≤ e ≤ 0.3, and 0 ≤ f ≤ 0.3, and more preferably 0 < a1 ≤ 0.7, 0 ≤ a2 ≤ 0.7, 0 < а1 + a2 ≤ 0.7, 0 ≤ b1 ≤ 0.5, 0 ≤ b2 ≤ 0.5, 0 ≤ b1 + b2 ≤ 0.5, 0 ≤ c1 ≤ 0.3, 0 ≤ c2 ≤ 0.3, 0 ≤ c3 ≤ 0.3, 0 ≤ c4 ≤ 0.3, 0 ≤ c1 + c2 + c3 + c4 ≤ 0.3, 0 ≤ d ≤ 0.3, 0 ≤ e ≤ 0.3, and 0 ≤ f ≤ 0.3. Among them, a1 + a2 + b1 + b2 + c1 + c2 + c3 + c4 + d + e + f = 1.0. The weight average molecular weight (Mw) of the foregoing polymer is preferably 1000 to 500000, and more preferably 3000 to 100000. If Mw is within this range, sufficient etching resistance can be obtained, and there is no need to worry about a decrease in resolution due to the inability to ensure a difference in dissolution rate before and after exposure. It should be noted that in the present invention, Mw is a polystyrene conversion measurement value obtained by gel permeation chromatography (GPC) using tetrahydrofuran (THF) or N,N-dimethylformamide (DMF) as a solvent. Furthermore, regarding the molecular weight distribution (Mw / Mn) of the foregoing polymer, the influence of Mw / Mn tends to increase as the pattern rule becomes finer. Therefore, in order to obtain a resist composition suitable for a fine pattern size, Mw / Mn is preferably narrowly dispersed to 1.0 to 2.0. If it is within the foregoing range, there are few low molecular weight and high molecular weight polymers, and there is no need to worry about observing foreign substances on the pattern or deterioration of the pattern shape after exposure. To synthesize the aforementioned polymer, for example, it is only necessary to add a radical polymerization initiator to the monomers providing the aforementioned repeating units in an organic solvent and heat to perform polymerization. Examples of the organic solvent used in the polymerization include toluene, benzene, THF, diethyl ether, dioxane, cyclohexane, cyclopentane, methyl ethyl ketone (MEK), PGMEA, GBL, etc. Examples of the aforementioned polymerization initiator include 2,2'-azobisisobutyronitrile (AIBN), 2,2'-azobis(2,4-dimethylvaleronitrile), dimethyl-2,2-azobis(2-methylpropionate), 1,1'-azobis(1-acetoxy-1-phenylethane), benzoyl peroxide, lauroyl peroxide, etc. The addition amount of these initiators is preferably 0.01 to 25 mol% relative to the total of the monomers to be polymerized. The reaction temperature is preferably 50 to 150 °C, more preferably 60 to 100 °C. The reaction time is preferably 2 to 24 hours, and from the viewpoint of production efficiency, more preferably 2 to 12 hours. The aforementioned polymerization initiator can be added to the aforementioned monomer solution and supplied to the reaction kettle, or an initiator solution can be separately prepared from the aforementioned monomer solution and independently supplied to the reaction kettle. During the waiting time, there may be a polymerization reaction due to the free radicals generated by the initiator to form ultra-high molecular substances. Therefore, from the viewpoint of quality control, it is preferably to separately and independently prepare the monomer solution and the initiator solution and add them dropwise. The acid-labile group can directly use the group introduced into the monomer, or can be protected or partially protected after polymerization. In addition, in order to adjust the molecular weight, known chain transfer agents such as dodecyl mercaptan and 2-mercaptoethanol can also be used in combination. In this case, the addition amount of these chain transfer agents is preferably 0.01 to 20 mol% relative to the total of the monomers to be polymerized. In the case of monomers containing hydroxyl groups, the hydroxyl groups can be pre-replaced with acetal groups such as ethoxyethoxy that are easily deprotected by acid during polymerization, and deprotected with weak acid and water after polymerization, or can be pre-replaced with acetyl, formyl, pivaloyl, etc., and subjected to base hydrolysis after polymerization. In the case of copolymerizing hydroxystyrene or hydroxyvinylnaphthalene, hydroxystyrene or hydroxyvinylnaphthalene and other monomers can be added with a radical polymerization initiator in an organic solvent and heated for polymerization, or acetoxystyrene or acetoxyvinylnaphthalene can be used, and the acetoxy group can be deprotected by base hydrolysis after polymerization to form polyhydroxystyrene or hydroxyvinylnaphthalene. As the base for base hydrolysis, ammonia water, triethylamine, etc. can be used. In addition, the reaction temperature is preferably -20 to 100 °C, more preferably 0 to 60 °C. The reaction time is preferably 0.2 to 100 hours, more preferably 0.5 to 20 hours. It should be noted that the amounts of the respective monomers in the aforementioned monomer solution may be appropriately set as long as, for example, they are in the preferred content ratios of the aforementioned repeating units. Regarding the polymer obtained by the aforementioned production method, the reaction solution obtained by the polymerization reaction may be used as the final product, or the powder obtained through purification steps such as a reprecipitation method in which the polymerization solution is added to a poor solvent may be regarded as the final product. From the viewpoints of operation efficiency and quality stabilization, it is preferred to regard the polymer solution obtained by dissolving the powder obtained through the purification steps in a solvent as the final product. Specific examples of the solvent used at this time include ketones such as cyclohexanone and methyl-2-n-amyl ketone described in paragraphs

[0144] to

[0145] of JP-A-2008-111103; alcohols such as 3-methoxybutanol, 3-methyl-3-methoxybutanol, 1-methoxy-2-propanol, and 1-ethoxy-2-propanol; ethers such as PGME, ethylene glycol monomethyl ether, propylene glycol monoethyl ether, ethylene glycol monoethyl ether, propylene glycol dimethyl ether, and diethylene glycol dimethyl ether; esters such as PGMEA, propylene glycol monoethyl ether acetate, ethyl lactate, ethyl pyruvate, butyl acetate, methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, tert-butyl acetate, tert-butyl propionate, and propylene glycol mono-tert-butyl ether acetate; lactones such as GBL; alcohols such as DAA; high-boiling alcohol solvents such as diethylene glycol, propylene glycol, glycerin, 1,4-butanediol, and 1,3-butanediol; and mixed solvents thereof. In the aforementioned polymer solution, the concentration of the polymer is preferably 0.01 to 30% by mass, more preferably 0.1 to 20% by mass. The aforementioned reaction solution and polymer solution are preferably filtered through a filter. By performing filtration through a filter, foreign matters and gels that may cause defects can be removed, which is effective in terms of quality stabilization. Examples of the material of the filter used in the aforementioned filter filtration include fluorocarbon-based, cellulose-based, nylon-based, polyester-based, hydrocarbon-based materials, etc. In the filtration step of the resist composition, a filter made of a fluorocarbon-based material such as the so-called Teflon (registered trademark), a hydrocarbon-based material such as polyethylene or polypropylene, or nylon is preferred. The pore size of the filter can be appropriately selected according to the target cleanliness, preferably 100 nm or less, more preferably 20 nm or less. In addition, these filters can be used alone or in combination of multiple filters. The filtration method can be such that the solution is passed through only once, and more preferably, the solution is circulated for multiple filtrations. The filtration step can be carried out in any order and number in the polymer production step, and it is preferred to filter the reaction solution after the polymerization reaction, the polymer solution, or both. (C) The base polymer may be used alone or in combination of two or more having different composition ratios, Mw, and / or Mw / Mn. In addition to the aforementioned polymer, (C) the base polymer may contain a hydride of a ring-opening metathesis polymer, and substances described in JP-A-2003-66612 may be used. [(D) Photoacid generator] The resist composition of the present invention may contain a photoacid generator as the component (D). The photoacid generator of the component (D) is not particularly limited as long as it is a compound that generates a strong acid upon irradiation with high-energy rays. Specific examples of suitable photoacid generators include the photoacid generators represented by the following formula (2-1) or (2-2). In formulae (2-1) and (2-2), R 101 ~R 105 are each independently a hydrocarbon group having 1 to 30 carbon atoms which may also contain a heteroatom. In addition, any two of R 101 , R 102 and R 103 may also be bonded to each other and form a ring together with the sulfur atom to which they are bonded. Specific examples of the sulfonium cation represented by formula (2-1) include the same sulfonium cations as those exemplified as the sulfonium cation represented by the aforementioned formula (cation-1), but are not limited thereto. In addition, specific examples of the iodonium cation represented by formula (2-2) include the same iodonium cations as those exemplified as the iodonium cation represented by the aforementioned formula (cation-2), but are not limited thereto. In formulae (2-1) and (2-2), Xa - is an anion selected from the following formulae (2A) to (2D). In formula (2A), R fa is a fluorine atom or a hydrocarbon group having 1 to 40 carbon atoms which may also contain a heteroatom. The aforementioned hydrocarbon group may be saturated or unsaturated and may be linear, branched, or cyclic. Specific examples thereof include the same hydrocarbon groups as those exemplified as the R fa1 shown in the following formula (2A'). As the anion represented by formula (2A), the anion represented by the following formula (2A') is preferred. In formula (2A'), R HFrepresents a hydrogen atom or a trifluoromethyl group, which is a hydrogen atom or a trifluoromethyl group, preferably a trifluoromethyl group. R fa1 is a hydrocarbon group having 1 to 38 carbon atoms which may also contain a heteroatom. As the aforementioned heteroatom, an oxygen atom, a nitrogen atom, a sulfur atom, a halogen atom, etc. are preferable, and an oxygen atom is more preferable. From the viewpoint of obtaining high resolution in fine pattern formation, the aforementioned hydrocarbon group is particularly preferably a group having 6 to 30 carbon atoms. R fa1 The hydrocarbon group having 1 to 38 carbon atoms shown may be saturated or unsaturated, and may be any of linear, branched, and cyclic. As specific examples thereof, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, pentyl, neopentyl, hexyl, heptyl, octyl, 2-ethylhexyl, nonyl, decyl, undecyl, dodecyl, tridecyl, pentadecyl, heptadecyl, icosyl, etc. alkyl groups having 1 to 38 carbon atoms; cyclopentyl, cyclohexyl, 1-adamantyl, 2-adamantyl, 1-adamantylmethyl, norbornyl, norbornylmethyl, tricyclodecyl, tetracyclododecyl, tetracyclododecylmethyl, dicyclohexylmethyl, etc. cyclic saturated hydrocarbon groups having 3 to 38 carbon atoms; allyl, 3-cyclohexenyl, etc. unsaturated aliphatic hydrocarbon groups having 2 to 38 carbon atoms; phenyl, 1-naphthyl, 2-naphthyl, etc. aryl groups having 6 to 38 carbon atoms; benzyl, diphenylmethyl, etc. aralkyl groups having 7 to 38 carbon atoms; groups obtained by combining them, etc. In addition, part or all of the hydrogen atoms of the aforementioned hydrocarbon group may also be substituted with a group containing a heteroatom such as an oxygen atom, a sulfur atom, a nitrogen atom, or a halogen atom, and part of the aforementioned hydrocarbon group -CH 2 - may also be substituted with a group containing a heteroatom such as an oxygen atom, a sulfur atom, or a nitrogen atom, and as a result, it may contain a hydroxyl group, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a cyano group, a carbonyl group, an ether bond, an ester bond, a sulfonate bond, a carbonate bond, a lactone ring, a sultone ring, a carboxylic anhydride (-C(=O)-O-C(=O)-), a haloalkyl group, etc. As specific examples of the hydrocarbon group containing a heteroatom, tetrahydrofuranyl, methoxymethyl, ethoxymethyl, methylthiomethyl, acetamidomethyl, trifluoroethyl, (2-methoxyethoxy)methyl, acetoxymethyl, 2-carboxy-1-cyclohexyl, 2-oxopropyl, 4-oxo-1-adamantyl, 5-hydroxy-1-adamantyl, 5-tert-butylcarbonyloxy-1-adamantyl, 4-oxatricyclo[4.2.1.0 3,7 nonane-5-one-2-yl, 3-oxocyclohexyl, etc. For the synthesis of sulfonium salts having anions represented by formula (2A'), details can be found in Japanese Patent Application Laid-Open Nos. 2007-145797, 2008-106045, 2009-7327, 2009-258695, etc. Additionally, sulfonium salts described in Japanese Patent Application Laid-Open Nos. 2010-215608, 2012-41320, 2012-106986, 2012-153644, etc. can also be appropriately used. As specific examples of the anion represented by formula (2A), anions the same as those exemplified as the anions represented by formula (c1-1) and (c1-2) can be cited. In formula (2B), R fb1 and R fb2 are each independently a fluorine atom or a hydrocarbon group having 1 to 40 carbon atoms which may contain heteroatoms. The aforementioned hydrocarbon group may be saturated or unsaturated and may be any of linear, branched, or cyclic. As specific examples thereof, hydrocarbon groups the same as those exemplified as the hydrocarbon groups represented by R fa1 in formula (2A') can be cited. As R fb1 and R fb2 , a fluorine atom or a linear fluorinated alkyl group having 1 to 4 carbon atoms is preferred. Additionally, R fb1 and R fb2 may also be bonded to each other and together with the group (-CF 2 -SO 2 -N - -SO 2 -CF 2 -) form a ring. In this case, as the group obtained by bonding R fb1 and R fb2 to each other, a fluorinated ethylene group or a fluorinated propylene group is preferred. In formula (2C), R fc1 , R fc2 and R fc3 Each independently represents a fluorine atom or a hydrocarbon group having 1 to 40 carbon atoms which may also contain a heteroatom. The aforementioned hydrocarbon group may be saturated or unsaturated and may be any of linear, branched, or cyclic. Specific examples thereof include hydrocarbon groups the same as those exemplified for the hydrocarbon group represented by R in formula (2A'). fa1 As the hydrocarbon group represented by R fc1 , R fc2 and R fc3 , a fluorine atom or a linear fluorinated alkyl group having 1 to 4 carbon atoms is preferred. Further, R fc1 and R fc2 may also be bonded to each other and together with the group (-CF 2 -SO 2 -C - -SO 2 -CF 2 -) form a ring. In this case, as the group formed by bonding R fc1 and R fc2 to each other, a fluorinated ethylene group or a fluorinated propylene group is preferred. In formula (2D), R fd is a hydrocarbon group having 1 to 40 carbon atoms which may also contain a heteroatom. The aforementioned hydrocarbon group may be saturated or unsaturated and may be any of linear, branched, or cyclic. Specific examples thereof include hydrocarbon groups the same as those exemplified for the hydrocarbon group represented by R in formula (2A'). fa1 For the synthesis of the sulfonium salt having the anion represented by formula (2D), see Japanese Unexamined Patent Application Publication No. 2010-215608 and Japanese Unexamined Patent Application Publication No. 2014-133723 for details. As specific examples of the anion represented by formula (2D), the following examples are listed, but are not limited thereto. As examples of the aforementioned non-nucleophilic counterion, anions having an aromatic ring substituted with an iodine atom or a bromine atom can be further listed. Specific examples of such anions include the anions represented by the following formula (2E). In formula (2E), x is an integer satisfying 1 ≤ x ≤ 3. y and z are integers satisfying 1 ≤ y ≤ 5, 0 ≤ z ≤ 3, and 1 ≤ y + z ≤ 5. y is preferably an integer satisfying 1 ≤ y ≤ 3, and more preferably 2 or 3. z is preferably an integer satisfying 0 ≤ z ≤ 2. In formula (2E), X BI is an iodine atom or a bromine atom, and when x and / or y is 2 or more, they may be the same as or different from each other. In formula (2E), L 11 is a single bond, an ether bond, an ester bond, or a saturated hydrocarbon group having 1 to 6 carbon atoms which may contain an ether bond or an ester bond. The aforementioned saturated hydrocarbon group may be linear, branched, or cyclic. In formula (2E), L 12 is a single bond or a divalent linking group having 1 to 20 carbon atoms when x is 1, and is an (x + 1)-valent linking group having 1 to 20 carbon atoms when x is 2 or 3. The linking group may also contain an oxygen atom, a sulfur atom, or a nitrogen atom. In formula (2E), R fe is a hydroxyl group, a carboxyl group, a fluorine atom, a chlorine atom, a bromine atom, or an amino group; or a hydrocarbon group having 1 to 20 carbon atoms, a hydrocarbon oxy group having 1 to 20 carbon atoms, a hydrocarbon carbonyl group having 2 to 20 carbon atoms, a hydrocarbon oxycarbonyl group having 2 to 10 carbon atoms, a hydrocarbon carbonyloxy group having 2 to 20 carbon atoms, or a hydrocarbon sulfonyloxy group having 1 to 20 carbon atoms which may contain a fluorine atom, a chlorine atom, a bromine atom, a hydroxyl group, an amino group, or an ether bond; or -N(R feA )(R feB ), -N(R feC )-C(=O)-R feD or -N(R feC )-C(=O)-O-R feD . R feA and R feB are each independently a hydrogen atom or a saturated hydrocarbon group having 1 to 6 carbon atoms. R feC is a hydrogen atom or a saturated hydrocarbon group having 1 to 6 carbon atoms, and may also contain a halogen atom, a hydroxyl group, a saturated hydrocarbon oxy group having 1 to 6 carbon atoms, a saturated hydrocarbon carbonyl group having 2 to 6 carbon atoms, or a saturated hydrocarbon carbonyloxy group having 2 to 6 carbon atoms. R feD is an aliphatic hydrocarbon group having 1 to 16 carbon atoms, an aryl group having 6 to 12 carbon atoms, or an aralkyl group having 7 to 15 carbon atoms, and may also contain a halogen atom, a hydroxyl group, a saturated hydrocarbon oxy group having 1 to 6 carbon atoms, a saturated hydrocarbon group carbonyl group having 2 to 6 carbon atoms, or a saturated hydrocarbon group carbonyloxy group having 2 to 6 carbon atoms. The aforementioned aliphatic hydrocarbon group may be saturated or unsaturated, and may be any of linear, branched, and cyclic. The aforementioned hydrocarbon group, hydrocarbon oxy group, hydrocarbon group carbonyl group, hydrocarbon oxy carbonyl group, hydrocarbon group carbonyloxy group, and hydrocarbon group sulfonyloxy group may be any of linear, branched, and cyclic. When x and / or z is 2 or more, each R 8 may also be the same as or different from each other. Among these, as R fe , preferably a hydroxyl group, -N(R feC )-C(=O)-R feD , -N(R feC )-C(=O)-O-R feD , a fluorine atom, a chlorine atom, a bromine atom, a methyl group, a methoxy group, etc. In formula (2E), Rf 11 ~Rf 14 are each independently a hydrogen atom, a fluorine atom, or a trifluoromethyl group, and at least one of these is a fluorine atom or a trifluoromethyl group. In addition, Rf 11 and Rf 12 may also together form a carbonyl group. Particularly preferably, Rf 13 and Rf 14 are both fluorine atoms. As specific examples of the anion of the onium salt represented by formula (2E), the examples shown below can be cited, but are not limited to them. It should be noted that in the following formulas, X BI is the same as the aforementioned. As the aforementioned non-nucleophilic counterion, it is also possible to use the fluorobenzenesulfonic acid anion bonded to an aromatic group containing an iodine atom as described in Japanese Patent No. 6648726, the anion having a mechanism of decomposing due to an acid as described in International Publication No. 2021 / 200056 and Japanese Unexamined Patent Application Publication No. 2021-070692, the anion having a cyclic ether group as described in Japanese Unexamined Patent Application Publication No. 2018-180525 and Japanese Unexamined Patent Application Publication No. 2021-35935, and the anion as described in Japanese Unexamined Patent Application Publication No. 2018-092159. As the aforementioned non-nucleophilic counterion, furthermore, it is also possible to use the anion of a bulky benzenesulfonic acid derivative containing no fluorine atom as described in Japanese Unexamined Patent Application Publication No. 2006-276759, Japanese Unexamined Patent Application Publication No. 2015-117200, Japanese Unexamined Patent Application Publication No. 2016-65016, and Japanese Unexamined Patent Application Publication No. 2019-202974; the benzenesulfonic acid anion and the alkylsulfonic acid anion bonded to an aromatic group containing an iodine atom and containing no fluorine atom as described in Japanese Patent No. 6645464. As the aforementioned non-nucleophilic counterion, furthermore, it is also possible to use the anion of a disulfonic acid as described in Japanese Unexamined Patent Application Publication No. 2015-206932; the anion of a sulfonamide or sulfonimide having a sulfonic acid on one side and different from it on the other side as described in International Publication No. 2020 / 158366; and the anion of a compound having a sulfonic acid on one side and a carboxylic acid on the other side as described in Japanese Unexamined Patent Application Publication No. 2015-024989. In addition, as the photoacid generator of component (D), a photoacid generator represented by the following formula (3) is also preferably used. In formula (3), R 201 and R 202 are each independently a hydrocarbon group having 1 to 30 carbon atoms which may also contain a heteroatom. R 203 is an alkylene group having 1 to 30 carbon atoms which may also contain a heteroatom. In addition, any two of R 201 , R 202 and R 203 may also be bonded to each other and form a ring together with the sulfur atom to which they are bonded. R 201 and R 202The hydrocarbon group having 1 to 30 carbon atoms shown may be saturated or unsaturated, and may be any of linear, branched, or cyclic. As specific examples thereof, there may be mentioned alkyl groups having 1 to 30 carbon atoms such as methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, tert-pentyl, n-pentyl, n-hexyl, n-octyl, 2-ethylhexyl, n-nonyl, n-decyl; cycloalkyl saturated hydrocarbon groups having 3 to 30 carbon atoms such as cyclopentyl, cyclohexyl, cyclopentylmethyl, cyclopentylethyl, cyclopentylbutyl, cyclohexylmethyl, cyclohexylethyl, cyclohexylbutyl, norbornyl, oxanorbornyl, tricyclo[5.2.1.0 2,6 decyl, adamantyl; aryl groups having 6 to 30 carbon atoms such as phenyl, methylphenyl, ethylphenyl, n-propylphenyl, isopropylphenyl, n-butylphenyl, isobutylphenyl, sec-butylphenyl, tert-butylphenyl, naphthyl, methylnaphthyl, ethylnaphthyl, n-propylnaphthyl, isopropylnaphthyl, n-butylnaphthyl, isobutylnaphthyl, sec-butylnaphthyl, tert-butylnaphthyl, anthryl; groups obtained by combining them, etc. In addition, part or all of the hydrogen atoms of the aforementioned hydrocarbon group may be substituted with a group containing a heteroatom such as an oxygen atom, a sulfur atom, a nitrogen atom, or a halogen atom, and part of the aforementioned hydrocarbon group -CH 2 - may also be substituted with a group containing a heteroatom such as an oxygen atom, a sulfur atom, or a nitrogen atom. As a result, it may contain a hydroxyl group, a cyano group, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a carbonyl group, an ether bond, an ester bond, a sulfonate bond, a carbonate bond, a lactone ring, a sultone ring, a carboxylic anhydride (-C(=O)-O-C(=O)-), a haloalkyl group, etc. R 203The hydrocarbyl group having 1 to 30 carbon atoms shown may be saturated or unsaturated and may be any of linear, branched, or cyclic. Specific examples thereof include methanediyl, ethane-1,1-diyl, ethane-1,2-diyl, propane-1,3-diyl, butane-1,4-diyl, pentane-1,5-diyl, hexane-1,6-diyl, heptane-1,7-diyl, octane-1,8-diyl, nonane-1,9-diyl, decane-1,10-diyl, undecane-1,11-diyl, dodecane-1,12-diyl, tridecane-1,13-diyl, tetradecane-1,14-diyl, pentadecane-1,15-diyl, hexadecane-1,16-diyl, heptadecane-1,17-diyl, etc., which are alkanediyl groups having 1 to 30 carbon atoms; cyclopentanediyl, cyclohexanediyl, norbornanediyl, adamantanediyl, etc., which are cyclic saturated hydrocarbyl groups having 3 to 30 carbon atoms; phenylene, methylphenylene, ethylphenylene, n-propylphenylene, isopropylphenylene, n-butylphenylene, isobutylphenylene, sec-butylphenylene, tert-butylphenylene, naphthylene, methylnaphthylene, ethylnaphthylene, n-propylnaphthylene, isopropylnaphthylene, n-butylnaphthylene, isobutylnaphthylene, sec-butylnaphthylene, tert-butylnaphthylene, etc., which are arylene groups having 6 to 30 carbon atoms. In addition, part or all of the hydrogen atoms of the aforementioned hydrocarbyl group may be substituted with a group containing a heteroatom such as an oxygen atom, a sulfur atom, a nitrogen atom, or a halogen atom, and part of the aforementioned hydrocarbyl group -CH 2 - may also be substituted with a group containing a heteroatom such as an oxygen atom, a sulfur atom, or a nitrogen atom, and as a result, it may contain a hydroxyl group, a cyano group, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a carbonyl group, an ether bond, an ester bond, a sulfonate bond, a carbonate bond, a lactone ring, a sultone ring, a carboxylic anhydride (-C(=O)-O-C(=O)-), a haloalkyl group, etc. As the aforementioned heteroatom, an oxygen atom is preferred. In formula (3), L A is a single bond, an ether bond, or a hydrocarbyl group having 1 to 20 carbon atoms that may also contain a heteroatom. The aforementioned hydrocarbyl group may be saturated or unsaturated and may be any of linear, branched, or cyclic. Specific examples thereof include the same hydrocarbyl groups as those exemplified as the hydrocarbyl group shown as R 203 . In formula (3), X a , X b , X c and X d are each independently a hydrogen atom, a fluorine atom, or a trifluoromethyl group. Among them, X a , X b , X c and X d At least one of them is a fluorine atom or a trifluoromethyl group. As the photoacid generator represented by formula (3), the photoacid generator represented by the following formula (3') is preferably used. In formula (3'), L A is the same as described above. X e is a hydrogen atom or a trifluoromethyl group, preferably a trifluoromethyl group. R 301 , R 302 and R 303 are each independently a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms which may contain a hetero atom. The aforementioned hydrocarbon group may be saturated or unsaturated, and may be any of linear, branched, and cyclic. As specific examples thereof, the hydrocarbon groups the same as the hydrocarbon groups exemplified as the R fa1 shown in formula (2A') can be cited. p1 and p2 are each independently an integer of 0 to 5, and p3 is an integer of 0 to 4. As the photoacid generator represented by formula (3), the photoacid generators the same as the photoacid generators exemplified as the photoacid generator represented by formula (2) of Japanese Patent Application Laid-Open No. 2017-026980 can be cited. Among the aforementioned other photoacid generators, the photoacid generators containing anions represented by formula (2A') or (2D) have small acid diffusion and excellent solubility in solvents, and thus are particularly preferred. In addition, the photoacid generator represented by formula (3') has extremely small acid diffusion, and thus is particularly preferred. When the resist composition of the present invention contains a (D) photoacid generator, its content is preferably 0.1 to 40 parts by mass, more preferably 0.5 to 20 parts by mass, relative to 80 parts by mass of the (C) base polymer. If the addition amount of the photoacid generator of the (D) component is within the aforementioned range, the resolution is good, and there is no need to worry about the problem of foreign matters generated during development or peeling of the resist film, and thus it is preferred. The photoacid generator of the (D) component can be used alone or in combination of two or more. By making the aforementioned base polymer contain any one of the repeating units c1 to c4 and / or contain the (D) photoacid generator, the resist composition of the present invention can function as a chemically amplified resist composition. [(E) Nitrogen-containing compound] In the resist composition of the present invention, the quencher of component (A) is an essential component, and on this basis, a nitrogen-containing compound may be included as another quencher. Examples of such nitrogen-containing compounds include primary amine compounds, secondary amine compounds, or tertiary amine compounds described in paragraphs

[0146] to

[0164] of Japanese Patent Application Laid-Open No. 2008-111103, especially amine compounds having a hydroxyl group, an ether bond, an ester bond, a lactone ring, a cyano group, or a sulfonate bond. In addition, compounds in which a primary amine or a secondary amine is protected with a carbamate group, such as those described in Japanese Patent No. 3790649, may also be mentioned. In addition, as the aforementioned nitrogen-containing compound, a sulfonium salt having a nitrogen-containing substituent can be used. Such a compound functions as a quencher in the unexposed portion and functions as a so-called photo-destructible base that loses its quencher ability by neutralizing the acid generated by itself in the exposed portion. By using a photo-destructible base, the contrast between the exposed portion and the unexposed portion can be further enhanced. As the photo-destructible base, reference can be made to, for example, Japanese Patent Application Laid-Open No. 2009-109595, Japanese Patent Application Laid-Open No. 2012-46501, etc. When the resist composition of the present invention contains (E) a nitrogen-containing compound, its content is preferably 0.001 to 12 parts by mass, more preferably 0.01 to 8 parts by mass, relative to 80 parts by mass of the (C) base polymer. The (E) nitrogen-containing compound can be used alone or in combination of two or more. [(F) Surfactant] The resist composition of the present invention may further contain (F) a surfactant. As the surfactant of component (F), a surfactant that is insoluble or hardly soluble in water and soluble in an alkaline developer, or a surfactant that is insoluble or hardly soluble in water and an alkaline developer is preferred. As such a surfactant, reference can be made to the substances described in Japanese Patent Application Laid-Open No. 2010-215608 and Japanese Patent Application Laid-Open No. 2011-16746. Among the surfactants described in the aforementioned publications, as the surfactant that is insoluble or hardly soluble in water and an alkaline developer, FC-4430 (manufactured by 3M), Surflon (registered trademark) S-381 (manufactured by AGC SEIMI CHEMICAL), OLFINE (registered trademark) E1004 (manufactured by Nissin Chemical Industry), KH-20, KH-30 (manufactured by AGC SEIMI CHEMICAL), and oxetane ring-opening polymers represented by the following formula (surf-1) are preferred. Here, R, Rf, A, B, C, m, and n are independent of the foregoing description and are only applicable to formula (surf-1). R is an aliphatic group having 2 to 5 carbon atoms with a valence of 2 to 4. Regarding the foregoing aliphatic group, as a divalent group, examples include ethylene, 1,4-butylene, 1,2-propylene, 2,2-dimethyl-1,3-propylene, 1,5-pentylene, etc. As a trivalent or tetravalent group, the following groups can be cited. (In the formula, the dotted lines are linking bonds and are substructures derived from glycerol, trimethylolethane, trimethylolpropane, and pentaerythritol, respectively.) Among these, 1,4-butylene, 2,2-dimethyl-1,3-propylene, etc. are preferred. Rf is trifluoromethyl or pentafluoroethyl, preferably trifluoromethyl. m is an integer from 0 to 3, n is an integer from 1 to 4, and the sum of n and m is the valence of R, which is an integer from 2 to 4. A is 1. B is an integer from 2 to 25, preferably an integer from 4 to 20. C is an integer from 0 to 10, preferably 0 or 1. In addition, the arrangement of each structural unit in formula (surf-1) is not limited, and it can be block-bonded or randomly bonded. For the manufacture of the surfactant of the partially fluorinated oxetane ring-opening polymer system, details can be found in the specification of U.S. Patent No. 5650483, etc. When no resist protective film is used in ArF immersion lithography, a surfactant that is insoluble or hardly soluble in water and soluble in an alkali developer has the function of reducing the penetration and leaching of water by orienting on the surface of the resist film. Therefore, it is useful for suppressing the dissolution of water-soluble components from the resist film and reducing the damage to the exposure apparatus. In addition, it can be solubilized during alkali aqueous solution development after exposure and after PEB, and it is also difficult to form foreign substances that cause defects, so it is useful. Such a surfactant exhibits the property of being insoluble or hardly soluble in water and soluble in an alkali developer. It is a polymer-type surfactant and is also called a hydrophobic resin, and a substance with particularly high water repellency and improved water lubricity is particularly preferred. As a specific example of such a polymer-type surfactant, a substance containing at least one kind selected from the repeating units shown in the following formulas (4A) to (4E) can be cited. In formulas (4A) to (4E), R B is a hydrogen atom, a fluorine atom, a methyl group, or a trifluoromethyl group. W 1 is -CH 2 -, -CH 2 CH 2 -, -O-, or two -H separated from each other. R s1Each independently represents a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms. R s2 is a single bond or a straight-chain or branched-chain hydrocarbon group having 1 to 5 carbon atoms. R s3 Each independently represents a hydrogen atom, a hydrocarbon group or a fluorinated hydrocarbon group having 1 to 15 carbon atoms, or an acid-labile group. When R s3 is a hydrocarbon group or a fluorinated hydrocarbon group, an ether bond or a carbonyl group may be interposed between carbon-carbon bonds. R s4 is a (u + 1)-valent hydrocarbon group or fluorinated hydrocarbon group having 1 to 20 carbon atoms. u is an integer from 1 to 3. R s5 Each independently represents a hydrogen atom or a group represented by the formula -C(=O)-O-R sa shown, R sa is a fluorinated hydrocarbon group having 1 to 20 carbon atoms. R s6 is a hydrocarbon group or a fluorinated hydrocarbon group having 1 to 15 carbon atoms, and an ether bond or a carbonyl group may be interposed between its carbon-carbon bonds. R s1 The hydrocarbon group shown is preferably a saturated hydrocarbon group and can be any of straight-chain, branched-chain, and cyclic. Specific examples thereof include alkyl groups such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, and n-decyl; and cyclic saturated hydrocarbon groups such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, adamantyl, and norbornyl. Among these, a hydrocarbon group having 1 to 6 carbon atoms is preferred. R s2 The hydrocarbon group shown is preferably a saturated hydrocarbon group and can be any of straight-chain, branched-chain, and cyclic. Specific examples thereof include methylene, ethylene, propylene, butylene, pentylene, etc. R s3 or R s6 The hydrocarbon group shown can be saturated or unsaturated and can be any of straight-chain, branched-chain, and cyclic. Specific examples thereof include saturated hydrocarbon groups, aliphatic unsaturated hydrocarbon groups such as alkenyl and alkynyl groups, etc., and a saturated hydrocarbon group is preferred. As the aforementioned saturated hydrocarbon group, in addition to the hydrocarbon groups exemplified as the hydrocarbon group shown by R s1 shown, n-undecyl, n-dodecyl, tridecyl, tetradecyl, pentadecyl, etc. can be cited. As R s3 or R s6 The fluorinated hydrocarbon group shown may include a group in which part or all of the hydrogen atoms bonded to the carbon atoms of the aforementioned hydrocarbon group are replaced by fluorine atoms. As described above, an ether bond or a carbonyl group may also be interposed between these carbon-carbon bonds. As R s3 Specific examples of the acid-labile group shown may include the groups shown in the aforementioned formulas (AL-3) to (AL-5), a trialkylsilyl group in which each alkyl group is an alkyl group having 1 to 6 carbon atoms, an alkyl group having an oxo group and 4 to 20 carbon atoms, and the like. R s4 The (u + 1)-valent hydrocarbon group or fluorinated hydrocarbon group shown by R may be linear, branched, or cyclic. Specific examples thereof may include a group obtained by further removing u hydrogen atoms from the aforementioned hydrocarbon group or fluorinated hydrocarbon group. R sa The fluorinated hydrocarbon group shown by R is preferably a saturated group and may be linear, branched, or cyclic. Specific examples thereof may include a group in which part or all of the hydrogen atoms of the aforementioned hydrocarbon group are replaced by fluorine atoms, and examples thereof may include trifluoromethyl, 2,2,2-trifluoroethyl, 3,3,3-trifluoro-1-propyl, 3,3,3-trifluoro-2-propyl, 2,2,3,3-tetrafluoropropyl, 1,1,1,3,3,3-hexafluoroisopropyl, 2,2,3,3,4,4,4-heptafluorobutyl, 2,2,3,3,4,4,5,5-octafluoropentyl, 2,2,3,3,4,4,5,5,6,6,7,7-dodecafluoroheptyl, 2-(perfluorobutyl)ethyl, 2-(perfluorohexyl)ethyl, 2-(perfluorooctyl)ethyl, 2-(perfluorodecyl)ethyl, and the like. Specific examples of the repeating units shown by formulas (4A) to (4E) may include the examples shown below, but are not limited thereto. It should be noted that in the following formulas, R B is the same as the aforementioned. The aforementioned polymeric surfactant may further include other repeating units in addition to the repeating units shown by formulas (4A) to (4E). Examples of other repeating units may include repeating units obtained from methacrylic acid, α-trifluoromethyl methacrylic acid derivatives, and the like. In the polymeric surfactant, the content of the repeating units shown by formulas (4A) to (4E) is preferably 20 mol% or more, more preferably 60 mol% or more, and further preferably 100 mol% in all the repeating units. The Mw of the aforementioned polymeric surfactant is preferably from 1,000 to 500,000, more preferably from 3,000 to 100,000. The Mw / Mn is preferably from 1.0 to 2.0, more preferably from 1.0 to 1.6. As a method for synthesizing the aforementioned polymeric surfactant, the following methods can be mentioned: For monomers containing unsaturated bonds of the repeating units represented by formulas (4A) to (4E) and other repeating units as required, a radical initiator is added in an organic solvent and heated to polymerize it. Examples of the organic solvent used during polymerization include toluene, benzene, THF, diethyl ether, dioxane, etc. Examples of the polymerization initiator include AIBN, 2,2'-azobis(2,4-dimethylvaleronitrile), dimethyl-2,2-azobis(2-methylpropionate), benzoyl peroxide, lauroyl peroxide, etc. The reaction temperature is preferably from 50 to 100 °C. The reaction time is preferably from 4 to 24 hours. The acid-labile group can be directly the group introduced into the monomer, or can be protected or partially protected after polymerization. When synthesizing the aforementioned polymeric surfactant, in order to adjust the molecular weight, known chain transfer agents such as dodecyl mercaptan and 2-mercaptoethanol can be used. In this case, the addition amount of these chain transfer agents is preferably from 0.01 to 10 mol% relative to the total molar amount of the monomers to be polymerized. When the resist composition of the present invention contains (F) surfactant, its content is preferably from 0.1 to 50 parts by mass, more preferably from 0.5 to 10 parts by mass, relative to 80 parts by mass of the (C) base polymer. If the content of the (F) surfactant is 0.1 part by mass or more, the receding contact angle of the resist film surface with water is sufficiently increased. If it is 50 parts by mass or less, the dissolution rate of the resist film surface with respect to the developer is small, and the height of the formed fine pattern is sufficiently maintained. The (F) surfactant can be used alone or in combination of two or more. [(G) Other Components] The resist composition of the present invention may contain a compound that generates an acid upon decomposition by an acid (acid-proliferating compound), an organic acid derivative, a fluorine-substituted alcohol, a compound having a molecular weight (Mw) of 3000 or less whose solubility in a developer changes due to the action of an acid (anti-solvent), etc. as (G) other components. As the aforementioned acid-proliferating compound, reference can be made to the compounds described in Japanese Patent Application Laid-Open No. 2009-269953 or Japanese Patent Application Laid-Open No. 2010-215608. When the aforementioned acid-proliferating compound is included, its content is preferably 0 to 5 parts by mass, more preferably 0 to 3 parts by mass, relative to 80 parts by mass of the (C) base polymer. If the content is too large, it is difficult to control acid diffusion, and sometimes deterioration of resolution and pattern shape may occur. As the aforementioned organic acid derivative, fluorine-substituted alcohol, and anti-solvent, reference can be made to the compounds described in Japanese Patent Application Laid-Open No. 2009-269953 or Japanese Patent Application Laid-Open No. 2010-215608. [Pattern Formation Method] The pattern formation method of the present invention includes the following steps: a step of forming a resist film on a substrate using the aforementioned resist composition; a step of exposing the aforementioned resist film with high-energy rays; and a step of developing the exposed resist film using a developer. As the aforementioned substrate, for example, a substrate for manufacturing an integrated circuit (Si, SiO 2 , SiN, SiON, TiN, WSi, BPSG, SOG, organic anti-reflective film, etc.), or a substrate for manufacturing a mask circuit (Cr, CrO, CrON, MoSi 2 , SiO 2 , etc.) can be used. The resist film can be formed by, for example, coating the aforementioned resist composition by a method such as spin coating so that the film thickness is preferably 0.05 to 2 μm, and pre-baking it on a hot plate preferably at 60 to 150 °C for 1 to 10 minutes, more preferably at 80 to 140 °C for 1 to 5 minutes. Examples of the high-energy rays used in the exposure of the resist film include i-rays, KrF excimer laser, ArF excimer laser, EB, EUV, etc. When KrF excimer laser, ArF excimer laser, or EUV is used for exposure, by using a mask for forming a target pattern, the exposure dose is preferably 1 to 200 mJ / cm 2 , more preferably 10 to 100 mJ / cm 2Irradiation is performed by the following method. When using EB, a mask for forming a target pattern is used, or the exposure dose is preferably 1 to 300 μC / cm 2 , more preferably 10 to 200 μC / cm 2 and irradiation is performed in this way. It should be noted that in addition to the usual exposure method, the immersion method in which a liquid with a refractive index of 1.0 or more is sandwiched between the resist film and the projection lens can also be used for exposure. In this case, a water-insoluble protective film can also be used. The aforementioned water-insoluble protective film is used to prevent the eluate from the resist film and improve the hydrophilicity of the film surface, and it is roughly divided into two types. One is an organic solvent peelable type that needs to be peeled off with an organic solvent that does not dissolve the resist film before development in an alkaline aqueous solution, and the other is an alkaline aqueous solution soluble type that is soluble in the alkaline developer and removes the protective film while removing the soluble part of the resist film. The latter is particularly preferably a material based on a polymer having 1,1,1,3,3,3-hexafluoro-2-propanol residues that is insoluble in water and soluble in an alkaline developer, and is soluble in an alcohol-based solvent having 4 or more carbon atoms, an ether-based solvent having 8 to 12 carbon atoms, and a mixed solvent thereof. It is also possible to prepare a material obtained by dissolving the aforementioned surfactant that is insoluble in water and soluble in an alkaline developer in an alcohol-based solvent having 4 or more carbon atoms, an ether-based solvent having 8 to 12 carbon atoms, or a mixed solvent thereof. After exposure, PEB can be performed. PEB can be performed, for example, by heating on a hot plate preferably at 60 to 150 °C for 1 to 5 minutes, more preferably at 80 to 140 °C for 1 to 3 minutes. Development is carried out by using a developer such as an alkaline aqueous solution of preferably 0.1 to 5% by mass, more preferably 2 to 3% by mass of tetramethylammonium hydroxide (TMAH), and preferably developing for 0.1 to 3 minutes, more preferably 0.5 to 2 minutes by conventional methods such as the dip method, the puddle method, and the spray method, so as to dissolve the exposed part and form a target pattern on the substrate. In addition, after forming the resist film, extraction of an acid generator or the like from the film surface or rinsing of particles can be carried out by performing pure water rinsing, and rinsing for removing the water remaining on the film can also be carried out after exposure. Furthermore, pattern formation can be carried out by a double patterning method. As the double patterning method, there can be mentioned: a trench method of processing a base of a 1:3 trench pattern by first exposure and etching, staggering positions and forming a 1:1 pattern by second exposure to form a 1:3 trench pattern; a line method of processing a first base of a 1:3 isolated residue pattern by first exposure and etching, staggering positions and processing a second base having a 1:3 isolated residue pattern formed thereunder by second exposure to form a 1:1 pattern with a halved pitch. In the pattern formation method of the present invention, the following method can be used: as the developer, an organic solvent is used instead of the aforementioned aqueous alkali solution, and a negative tone development method in which an unexposed portion is dissolved. In the aforementioned organic solvent development, as the developer, 2-octanone, 2-nonanone, 2-heptanone, 3-heptanone, 4-heptanone, 2-hexanone, 3-hexanone, diisobutyl ketone, methylcyclohexanone, acetophenone, methylacetophenone, propyl acetate, butyl acetate, isobutyl acetate, pentyl acetate, butenyl acetate, isopentyl acetate, propyl formate, butyl formate, isobutyl formate, pentyl formate, isopentyl formate, methyl valerate, methyl pentenoate, methyl crotonate, ethyl crotonate, methyl propionate, ethyl propionate, ethyl 3-ethoxypropionate, methyl lactate, ethyl lactate, propyl lactate, butyl lactate, isobutyl lactate, pentyl lactate, isopentyl lactate, methyl 2-hydroxyisobutyrate, ethyl 2-hydroxyisobutyrate, methyl benzoate, ethyl benzoate, phenyl acetate, benzyl acetate, methyl phenylacetate, ethyl phenylacetate, benzyl formate, phenyl ethyl formate, methyl 3-phenylpropionate, benzyl propionate, 2-phenylethyl acetate, etc. can be used. These organic solvents can be used alone or in combination of two or more. [Examples] Hereinafter, synthesis examples, examples and comparative examples are shown to specifically illustrate the present invention, but the present invention is not limited to the following examples. It should be noted that the devices used are as follows. ・IR: NICOLET 6700 manufactured by Thermo Fisher Scientific ・ 1 1H-NMR: ECA-500 manufactured by JEOL Ltd. ・MALDI TOF-MS: S3000 manufactured by JEOL Ltd. [1] Synthesis of onium salt [Example 1-1] Synthesis of onium salt NSQ-1 (1) Synthesis of Intermediate In-1 Under a nitrogen atmosphere, compound SM-1 (10.2 g), compound SM-2 (7.9 g), 4-dimethylaminopyridine (DMAP) (0.5 g), and dichloromethane (50 g) were charged into a reaction vessel and cooled with an ice bath. While maintaining the temperature inside the reaction vessel below 20 °C, 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide hydrochloride (9.2 g) was added in a powder state. After the addition, the temperature was raised to room temperature and aged for 12 hours. After aging, water was added to stop the reaction, and normal aqueous work-up was carried out, and the solvent was distilled off, whereby Intermediate In-1 was obtained in the form of an oil (yield: 16.4 g, yield rate: 95%). (2) Synthesis of Intermediate In-2 Under a nitrogen atmosphere, Intermediate In-1 (16.2 g) was dissolved in THF (40 g). Thereafter, a 25 mass% aqueous solution of benzyltrimethylammonium hydroxide (23.9 g) was added dropwise thereto. After the addition, the reaction solution was heated to 40 °C and aged for 4 hours. After aging, the reaction system was cooled to room temperature, the solvent was distilled off, and diisopropyl ether was added for washing, whereby Intermediate In-2 was obtained in the form of an oil (yield: 19.9 g, yield rate: 90%). (3) Synthesis of Onium Salt NSQ-1 Under a nitrogen atmosphere, Intermediate In-2 (19.9 g) and compound SM-3 (13.4 g) were mixed with dichloromethane (100 g) and water (80 g), and stirred at room temperature for 2 hours. After stirring, normal aqueous work-up was carried out, the solvent was distilled off, and diisopropyl ether was added for washing, whereby onium salt NSQ-1 was obtained in the form of an oil (yield: 20.6 g, yield rate: 86%). The following shows the IR spectral data and TOF-MS results of onium salt NSQ-1. In addition, the nuclear magnetic resonance spectrum ( 1 1H-NMR / DMSO-d 6 ) results are shown in Figure 1. In addition, in the nuclear magnetic resonance spectrum ( 1 1H-NMR / DMSO-d 6In the results of , dichloromethane used in the solvent and diisopropyl ether used for cleaning were detected. IR (D-ATR): ν = 3409, 3086, 3059, 2985, 2873, 1736, 1687, 1652, 1469, 1448, 1427, 1374, 1313, 1292, 1274, 1175, 1126, 1090, 1037, 1000, 933, 866, 800, 764, 735, 707, 681, 613, 526, 490, 424 cm -1 . MALDI TOF-MS: POSITIVE M + 261 (corresponding to C 18 H 13 S + equivalent) NEGATIVE M - 404 (corresponding to C 19 H 28 F 2 NO 6 - equivalent) [Examples 1-2 to 1-6] Synthesis of Onium Salts NSQ-2 to NSQ-7 Using the corresponding raw materials and known organic chemical reactions, onium salts NSQ-2 to NSQ-7 represented by the following formula were synthesized. [Synthesis Example] Synthesis of Basic Polymers (Polymers P-1 to P-5) Combining each monomer, copolymerization reaction was carried out in MEK as a solvent, and it was poured into hexane. The precipitated solid was washed with hexane, separated, and dried to obtain basic polymers (polymers P-1 to P-5) having the following composition. The composition of the obtained basic polymer was confirmed by 1 1H-NMR, and Mw and Mw / Mn were confirmed by GPC (solvent: DMF, standard: polystyrene). [3] Preparation of Resist Composition [Examples 2-1 to 2-20, Comparative Examples 1-1 to 1-12] According to the compositions shown in Tables 1 and 2 below, the onium salts (NSQ-1 to NSQ-6) of the present invention, quenching agents for comparison (SQ-A to SQ-D, AQ-A), base polymers (P-1 to P-5), and photoacid generators (PAG-1, PAG-2) were dissolved in a solvent in which FC-4430 manufactured by 3M Co., Ltd. as a surfactant at 100 ppm was dissolved to prepare a solution, and the solution was filtered through a 0.2-μm Teflon (registered trademark) filter to prepare a resist composition. In Tables 1 and 2, each component is as follows. ・ Organic solvent: PGMEA (propylene glycol monomethyl ether acetate), DAA (diacetone alcohol) ・ Photoacid generator: PAG-1, PAG-2 ・ Quenching agent for comparison: SQ-A to SQ-D, AQ-A [Table 1] [Table 2] [4] EUV Lithography Evaluation (1) [Examples 3-1 to 3-20, Comparative Examples 2-1 to 2-12] Each chemically amplified resist composition (R-1 to R-20, CR-1 to CR-12) was spin-coated on a Si substrate on which a spin-on hard mask SHB-A940 (silicon content: 43 mass%) manufactured by Shin-Etsu Chemical Co., Ltd. was formed with a film thickness of 20 nm, and pre-baked at 100 °C for 60 seconds using a hot plate to produce a resist film with a film thickness of 50 nm. For the aforementioned resist film, using an EUV scanner NXE3300 manufactured by ASML (NA: 0.33, σ: 0.9 / 0.6, dipole illumination), while changing the exposure dose and focus (exposure dose pitch: 1 mJ / cm 2 , focus pitch: 0.020 μm), an LS pattern with a line width of 18 nm and a pitch of 36 nm was exposed on the wafer. After exposure, PEB was performed for 60 seconds at the temperatures shown in Tables 3 and 4. Thereafter, immersion development was performed for 30 seconds using a 2.38 mass% TMAH aqueous solution, rinsing was performed using a rinsing material containing a surfactant, and spin drying was performed to obtain a positive pattern. The developed LS pattern was observed using a length-measuring SEM (CG6300) manufactured by Hitachi High-Technologies Corporation, and sensitivity, EL, LWR, DOF, and collapse limit were evaluated according to the following methods. The results are shown in Tables 5 and 6. [Sensitivity Evaluation] The optimal exposure dose E op (mJ / cm 2 ) at which an LS pattern with a line width of 18 nm and a pitch of 36 nm can be obtained was determined, and this was taken as the sensitivity. [EL Evaluation] Based on the exposure dose formed within the range of ±10% (16.2 - 19.8 nm) of the 18 nm space width in the aforementioned LS pattern, EL (unit: %) is calculated using the following formula. The larger this value, the better the performance. EL(%) = (|E 1 - E 2 | / E op ) × 100 E 1 : The optimal exposure dose E for an LS pattern with a line width of 16.2 nm and a pitch of 36 nm 2 : The optimal exposure dose E for an LS pattern with a line width of 19.8 nm and a pitch of 36 nm op : The optimal exposure dose for an LS pattern with a line width of 18 nm and a pitch of 36 nm [LWR Evaluation] For the LS pattern obtained by irradiation with E op , measure the dimensions of 10 parts along the length direction of the line. Based on the results, calculate three times the standard deviation (3σ) as LWR. The smaller this value, the smaller the roughness and the more uniform the line width of the pattern that can be obtained. [DOF Evaluation] As the focus depth evaluation, calculate the focus range formed within the range of ±10% (16.2 - 19.8 nm) of the 18 nm dimension in the aforementioned LS pattern. The larger this value, the wider the focus depth. [Collapse Limit Evaluation of Line Pattern] For the line dimensions of each exposure dose at the optimal focus of the aforementioned LS pattern, measure 10 parts along the length direction. Take the thinnest line dimension obtained without collapsing as the collapse limit dimension. The smaller this value, the better the collapse limit. [Table 3] [Table 4] Based on the results shown in Table 3 and Table 4, it can be confirmed that: the resist composition of the present invention has good sensitivity, excellent various lithography performances, and exhibits the performance of resisting pattern collapse. [5] EUV Lithography Evaluation (2) [Examples 4-1 to 4-20, Comparative Examples 3-1 to 3-12] Each chemically amplified resist composition (R-1 to R-20, CR-1 to CR-12) was spin-coated on a Si substrate on which a silicon spin-on hard mask SHB-A940 (silicon content: 43 mass%) manufactured by Shin-Etsu Chemical Co., Ltd. was formed with a film thickness of 20 nm, and pre-baked at 100 °C for 60 seconds using a hot plate to produce a resist film with a film thickness of 60 nm. Next, the aforementioned resist film was exposed using an EUV scanner NXE3400 (NA: 0.33, σ: 0.9 / 0.6, quadrupole illumination, mask of a hole pattern with a pitch of 44 nm and a +20% deviation in size on the wafer) manufactured by ASML Corporation, and PEB was performed at the temperatures described in Tables 5 and 6 for 60 seconds on a hot plate, developed with a 2.38 mass% TMAH aqueous solution for 30 seconds, and a hole pattern with a size of 22 nm was obtained in Examples 4-1 to 4-18 and Comparative Examples 3-1 to 3-10, and a dot pattern with a size of 22 nm was obtained in Examples 4-19, 4-20 and Comparative Examples 3-11, 3-12. Using a length-measuring SEM (CG6300) manufactured by Hitachi High-Technologies Corporation, the exposure dose when holes or dots were formed with a size of 22 nm was measured and used as the sensitivity. In addition, the sizes of 50 holes or dots at this time were measured, and three times the standard deviation (σ) calculated from the results (3σ) was used as the CDU. The results are shown in Tables 5 and 6. [Table 5] [Table 6] From the results shown in Tables 5 and 6, it was confirmed that the chemically amplified resist composition containing a quencher composed of the onium salt of the present invention has good sensitivity and excellent CDU. Figure 1 shows the 1 1H-NMR spectrum of the onium salt NSQ-1 obtained in Example 1-1.

Claims

1. A onium salt, represented by the following formula (1), wherein in formula (1), n1 is an integer from 0 to 6; n2 is an integer from 0 to 3; n3 is an integer from 1 to 4; W is a group represented by the following formula (6); LA and LB are each independently a single bond, ether bond, ester bond, amide bond, sulfonate bond, carbonate bond or carbamate bond; XL is a single bond or a hydrocarbon group with 1 to 40 carbon atoms that may also contain heteroatoms; R1 is a hydrocarbon group with 1 to 20 carbon atoms that may also contain heteroatoms, and when n1≥2, multiple R1s may also bond to each other and form a ring together with the carbon atoms on the W to which they are bonded; Q1 to Q4 are each independently a hydrogen atom, a fluorine atom, a hydrocarbon group with 1 to 6 carbon atoms or a fluorinated hydrocarbon group with 1 to 6 carbon atoms, wherein, At least one of Q1 to Q4 is a fluorine atom or a fluorinated hydrocarbon group with 1 to 6 carbon atoms. In addition, Q3 and Q4 can also bond to each other and form a ring together with the carbon atoms they are bonded to; RAL is an acid-unstable group; Z+ is an onium cation; In formula (6), * represents the bond linked to LA, and ** represents the bond linked to RAL-OC(=O)-.

2. As in request item 1, the onium salt, where, RAL is a group represented by formula (AL-1) or (AL-2) below, where LC is -O- or -S-; R2, R3, and R4 are each independently a hydrocarbon group with 1 to 10 carbon atoms. In addition, any two of R2, R3, and R4 can be bonded to each other and form a ring together with the carbon atoms they are bonded to; R5 and R6 are each independently a hydrogen atom or a hydrocarbon group with 1 to 10 carbon atoms, and R7 is a hydrocarbon group with 1 to 20 carbon atoms. The -CH2- of this hydrocarbon group can also be replaced by -O- or -S-. In addition, R6 and R7 can be bonded to each other and form a heterocyclic group with 3 to 20 carbon atoms together with the carbon atoms they are bonded to and LC. The -CH2- of this heterocyclic group can also be replaced by -O- or -S-; m1 and m2 are each independently 0 or 1; * indicates a bond with an adjacent -O-.

3. As in request item 1, the onium salt, where, Z+ is a strontium cation as shown in formula (cation-1), a monium cation as shown in formula (cation-2), or an ammonium cation as shown in formula (cation-3), wherein R11 to R19 are each independently a hydrocarbon group with 1 to 30 carbon atoms, which may also contain heteroatoms. In addition, R11 and R12 may also be bonded to each other and form a ring together with the sulfur atoms they are bonded to.

4. The onium salt of request item 1 is represented by the following formula (1A), in which n1~n3, W, LA, XL, R1, Q1~Q4, RAL and Z+ are the same as those described above.

5. The onium salt of claim 4 is represented by the following formula (1B), in which n1, W, LA, XL, R1, Q1~Q3, RAL and Z+ are the same as those described above.

6. A quenching agent comprising any one of the onium salts of claims 1 to 5.

7. An inhibitor composition comprising a quencher as claimed in claim 6.

8. The inhibitor composition of claim 7 further comprises an organic solvent.

9. The inhibitor composition of claim 7, comprising a base polymer containing a repeating unit as shown in formula (a1), wherein in formula (a1), RA is a hydrogen atom, a fluorine atom, a methyl or trifluoromethyl atom; X1 is a single bond, a phenyl group, a naphthyl group, or *-C(=O)-O-X11-, which may also be substituted by an alkoxy or halogen atom with 1 to 10 carbon atoms, which may also contain a fluorine atom; X11 is a saturated alkyl group, a phenyl group, or a naphthyl group with 1 to 10 carbon atoms, which may also contain a hydroxyl group, an ether bond, an ester bond, or a lactone ring; * indicates a bond linked to a carbon atom of the main chain; AL1 is an acid-labile group.

10. The inhibitor composition as claimed in claim 9, wherein, The basic polymer also contains repeating units as shown in formula (a2), where RA is a hydrogen atom, a fluorine atom, a methyl group, or a trifluoromethyl group; X2 is a single bond or *-C(=O)-O-; * indicates a bond linked to a carbon atom of the main chain; R21 is a halogen atom, a cyano group, or a hydrocarbon group containing 1 to 20 carbon atoms with heteroatoms, or a hydrocarbon carbonyl group containing 2 to 20 carbon atoms with heteroatoms, or a hydrocarbon carbonyl group containing 2 to 20 carbon atoms with heteroatoms, or a hydrocarbon carbonyl group containing 2 to 20 carbon atoms with heteroatoms; AL2 is an acid-labile group; and a is an integer from 0 to 4.

11. The inhibitor composition as claimed in claim 9, wherein, The basic polymer also contains repeating units as shown in formula (b1) or (b2) below, where RA is independently a hydrogen atom, a fluorine atom, a methyl group, or a trifluoromethyl group; Y1 is a single bond or *-C(=O)-O-; * indicates a bond linked to a carbon atom of the main chain; R22 is a hydrogen atom, or a group containing at least one structure with 1 to 20 carbon atoms selected from hydroxyl groups other than phenolic hydroxyl groups, cyano groups, carbonyl groups, carboxyl groups, ether bonds, ester bonds, sulfonate bonds, carbonate bonds, lactone rings, sulcinolone rings, and carboxylic anhydrides (-C(=O)-OC(=O)-). R23 is a halogen atom, a nitro group, or a hydrocarbon group with 1 to 20 carbon atoms that may contain heteroatoms, or a hydrocarbon oxygen group with 1 to 20 carbon atoms that may contain heteroatoms, or a hydrocarbon carbonyl group with 2 to 20 carbon atoms that may contain heteroatoms, or a hydrocarbon carbonyl group with 2 to 20 carbon atoms that may contain heteroatoms; b is an integer from 1 to 4; c is an integer from 0 to 4; where 1 ≤ b + c ≤ 5.

12. The inhibitor composition as claimed in claim 9, wherein, The basic polymer also contains repeating units represented by any of the following formulas (c1) to (c4), wherein RA is independently a hydrogen atom, a fluorine atom, a methyl group, or a trifluoromethyl group; Z1 is a single bond or an phenyl group; Z2 is *-C(=O)-O-Z21-, *-C(=O)-NH-Z21-, or *-O-Z21-; Z21 is an aliphatic alkyl group, an phenyl group, or a divalent group obtained by combining them with 1 to 6 carbon atoms, and may also contain a carbonyl group, an ester bond, an ether bond, or a hydroxyl group; Z3 is independently a single bond, an phenyl group, an naphthyl group, or *-C(=O)-O-Z31-; Z31 is an aliphatic alkyl group, an phenyl group, or an naphthyl group with 1 to 10 carbon atoms, and the aliphatic alkyl group may also contain a hydroxyl group, an ether bond, an ester bond, or a lactone ring; Z4 can be a single bond, *-Z41-C(=O)-O-, *-C(=O)-NH-Z41-, or *-O-Z41-, where Z41 is an elongated hydrocarbon group with 1 to 20 carbon atoms that may also contain heteroatoms; Z5 can be a single bond, *-Z51-C(=O)-O-, *-C(=O)-NH-Z51-, or *-O-Z51-, where Z51 is an elongated hydrocarbon group with 1 to 20 carbon atoms that may also contain heteroatoms; Z6 is a single bond, methylene, ethyl, phenyl, fluorinated phenyl, trifluoromethyl-substituted phenyl, *-C(=O)-O-Z61-, *-C(=O)-N(H)-Z61-, or *-O-Z61-; Z61 is an aliphatic alkyl group with 1 to 6 carbon atoms, phenyl, fluorinated phenyl, or trifluoromethyl-substituted phenyl, and may also contain carbonyl, ester, ether, or hydroxyl groups; * indicates a bond linked to a carbon atom in the main chain; R31 and R32 are each independently a hydrocarbon group with 1 to 20 carbon atoms, and may also contain heteroatoms. In addition, R31 and R32 may also bond to each other and form a ring with the sulfur atoms to which they are bonded; L1 is a single bond, ether, ester, carbonyl, sulfonate, carbonate, or carbamate bond; Rf1 and Rf2 are each independently a fluorine atom or a fluorinated saturated hydrocarbon group with 1 to 6 carbon atoms; Rf3 and Rf4 are each independently a hydrogen atom, a fluorine atom, or a fluorinated saturated hydrocarbon group with 1 to 6 carbon atoms; Rf5 and Rf6 are each independently a hydrogen atom, a fluorine atom, or a fluorinated saturated hydrocarbon group with 1 to 6 carbon atoms, wherein not all Rf5 and Rf6 are hydrogen atoms simultaneously; M- is a non-nucleophilic counterion; A+ is an onium cation; d is an integer from 0 to 3.

13. The inhibitor composition of claim 7 further comprises a photoacid generator.

14. The inhibitor composition of claim 7 further includes a quencher other than the quencher of claim 6.

15. The inhibitor composition of claim 7 further comprises a surfactant.

16. A pattern forming method comprising the steps of: forming a resist film on a substrate using a resist composition as claimed in claim 7; exposing the resist film to high-energy rays; and developing the exposed resist film using a developing solution.

17. The pattern forming method as described in claim 16, wherein, The high-energy rays are KrF excimer lasers, ArF excimer lasers, electron beams, or extreme ultraviolet rays with wavelengths of 3-15 nm.

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