Polymerizable monomer, polymer compound, resist composition, and pattern forming method

Abstract

To provide a polymerizable monomer having sensitivity and resolution higher than those of the previously-known positive resist materials, and exhibiting small edge roughness and size variations, and a desirable pattern shape after exposure, as well as a polymer compound, a resist composition, and a patterning process each using the polymerizable monomer.SOLUTION: The present invention provides a polymerizable monomer represented by the general formula (1). (RA represents H, F, a methyl group or a trifluoromethyl group; ZL represents a single bond or (backbone)-C(=O)-O-; RALU represents an acid-labile group formed with adjacent O; XL represents O or S; Raa represents H or F; R1a independently represents a C1-20 hydrocarbyl group; n1 represents an integer of 0-2; n2 represents an integer of 1 or 2; n3 represents an integer of 1 or 2; n4 represents an integer of 0-4).SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a polymerizable monomer, a polymer compound, a resist composition, and a pattern forming method. [Background technology]

[0002] As LSIs become more highly integrated and faster, pattern rules are becoming increasingly miniaturized. This is due to the increasing popularity of 5G high-speed communications and artificial intelligence (AI), which require high-performance devices to process these. The most advanced miniaturization technology is extreme ultraviolet (EUV) lithography with a wavelength of 13.5 nm, which is currently used to mass-produce 5 nm node devices. Furthermore, the use of EUV lithography is being considered for next-generation 3 nm node devices and the next-generation 2 nm node devices.

[0003] As miniaturization progresses, image blurring due to acid diffusion has become a problem. To ensure resolution in fine patterns with dimensions of 45 nm and smaller, it has been suggested that controlling acid diffusion is important, in addition to improving dissolution contrast, as has been proposed previously (Non-Patent Document 1). However, because chemically amplified resist materials increase sensitivity and contrast through acid diffusion, attempts to minimize acid diffusion by lowering the post-exposure bake (PEB) temperature or shortening the time result in significant decreases in sensitivity and contrast.

[0004] The triangle trade-off relationship between sensitivity, resolution, and edge roughness (LER, LWR) is shown. To improve resolution, it is necessary to suppress acid diffusion, but as the acid diffusion distance becomes shorter, sensitivity decreases.

[0005] It is effective to suppress acid diffusion by adding an acid generator that generates bulky acid. Therefore, it has been proposed to incorporate repeating units derived from onium salts having polymerizable unsaturated bonds into a polymer. In this case, the polymer also functions as an acid generator (polymer-bound acid generator). Patent Document 1 proposes sulfonium salts and iodonium salts having polymerizable unsaturated bonds that generate specific sulfonic acids. Patent Document 2 proposes sulfonium salts in which sulfonic acids are directly linked to the main chain.

[0006] The structure of the acid labile group of the base polymer is important as a component that contributes to the performance of a positive resist material. Tertiary ester-type acid labile groups bonded to aromatic groups substituted with fluorine atoms have been proposed (Patent Documents 3 and 4). Tertiary ester-type acid labile groups bonded to aromatic groups have a very high elimination reactivity with acid, making it difficult to control acid diffusion. However, by introducing fluorine atoms into the aromatic groups, the elimination reactivity is moderately suppressed.

[0007] Fluorine atoms are the second smallest element after hydrogen atoms in terms of steric size, and are also highly hydrophobic and lipophilic. Among these, trifluoromethoxy groups are known as substituents with significantly superior hydrophobicity compared to the corresponding methoxy groups (Non-Patent Document 2). Tertiary ester-type acid labile groups in which these groups are substituted with aromatic groups have also been proposed (Patent Document 5).

[0008] On the other hand, the olefin-containing tertiary ester-type acid labile group exemplified in paragraph

[0036] of Patent Document 6 has very high elimination reactivity with acid, making it difficult to control acid diffusion.Furthermore, the olefin-containing secondary ester-type acid labile group exemplified in paragraph

[0188] of Patent Document 7 has low elimination reactivity with acid, making it difficult to obtain a high dissolution contrast.

[0009] These tertiary ester-type acid-labile groups generate carboxylic acids after deprotection with acid. Carboxylic acids swell in alkaline developers, which can lead to pattern collapse during fine pattern formation. To meet the demand for further miniaturization, there is a need to develop acid-labile monomers that have good acid-elimination reactivity and suppress swelling in alkaline developers even after the elimination reaction. [Prior art documents] [Patent documents]

[0010] [Patent Document 1] Japanese Patent Application Laid-Open No. 2006-045311 [Patent Document 2] Japanese Patent Application Laid-Open No. 2006-178317 [Patent Document 3] Patent No. 3832564 [Patent Document 4] Patent No. 5655754 [Patent Document 5] Japanese Patent Application Publication No. 2019-214554 [Patent Document 6] Japanese Patent Application Laid-Open No. 2001-302728 [Patent Document 7] Japanese Patent Publication No. 2022-025610 [Non-patent literature]

[0011] [Non-Patent Document 1] SPIE Vol. 6520 65203L-1 (2007) [Non-patent document 2] "Introduction to Fluorine Chemistry 2010 - The Frontiers of Fundamentals and Applications," edited by the 155th Committee on Fluorine Chemistry of the Japan Society for the Promotion of Science, Sankyo Publishing, 2010 Summary of the Invention [Problem to be solved by the invention]

[0012] The present invention has been made in view of the above circumstances, and an object of the present invention is to provide a polymerizable monomer that has sensitivity and resolution that exceed those of conventional positive resist materials, has small edge roughness and dimensional variation, and produces a good pattern shape after exposure, as well as a polymer compound and a resist composition that use the same, and a pattern formation method.

[0013] The present invention aims to provide a polymerizable monomer used in a chemically amplified resist composition that has excellent solvent solubility, high sensitivity, high contrast, and excellent lithography performance such as exposure latitude (EL) and LWR, as well as pattern shape, particularly in photolithography using high-energy rays such as KrF excimer laser light, ArF excimer laser light, electron beam (EB), and EUV; a polymer compound using the same; a chemically amplified resist composition; and a pattern formation method using the chemically amplified resist composition. [Means for solving the problem]

[0014] In order to solve the above problems, the present invention provides: The present invention provides a polymerizable monomer represented by the following general formula (1): [ka] (In the formula, R A is a hydrogen atom, a fluorine atom, a methyl group, or a trifluoromethyl group. L is a single bond or (main chain) -C(=O)-O-. ALU is an acid labile group formed with the adjacent oxygen atom. L represents an oxygen atom or a sulfur atom. aa represents a hydrogen atom or a fluorine atom. 1a are each independently a linear, branched or cyclic hydrocarbyl group having 1 to 20 carbon atoms which may contain a heteroatom. n1 is an integer of 0 to 2. n2 is an integer of 1 or 2. n3 is an integer of 1 or 2. n4 is an integer of 0 to 4. When n2=1, -OR ALU and -X L -CF2(R aa) are bonded to adjacent carbon atoms on the aromatic ring. Furthermore, when n2=2, two -OR ALU One of them is -X L -CF2(R aa ) is bonded to the carbon atom adjacent to the carbon atom on the aromatic ring to which it is bonded.

[0015] Such a polymerizable monomer can be used as a raw material for a resist material that has sensitivity and resolution superior to conventional positive resist materials, has small edge roughness and dimensional variation, and produces a good pattern shape after exposure.

[0016] The general formula (1) is preferably represented by the following formula (1-A). [ka] (In the formula, R A , Z L , X L , R 1a , R ALU , n1, n2, n3, and n4 are the same as above.)

[0017] Such a compound is more suitable as the polymerizable monomer.

[0018] R ALU is preferably represented by the following formula (AL-1) or (AL-2) together with the adjacent oxygen atom. [ka] (In formula (AL-1), R 21 , R 22 , and R 23 are each independently a hydrocarbyl group having 1 to 12 carbon atoms which may contain a heteroatom. 21 , R 22 , and R 23 Any two of these may be bonded to each other to form a ring. t is an integer of 0 or 1. In formula (AL-2), R 24 , and R 25are each independently a hydrogen atom or a hydrocarbyl group having 1 to 10 carbon atoms. 26 is a hydrocarbyl group having 1 to 20 carbon atoms, or R 24 , or R 25 and bond to each other, and the carbon atoms to which they are bonded and X a may form a heterocyclic group having 3 to 20 carbon atoms together with X. Furthermore, -CH2- contained in the above hydrocarbyl group and heterocyclic group may be replaced with -O- or -S-. a represents an oxygen atom or a sulfur atom. u is an integer of 0 or 1. * represents a bond to the adjacent oxygen atom.

[0019] Such a group will function better as an acid labile group.

[0020] The present invention also provides a polymer compound containing a repeating unit obtained from the above polymerizable monomer, wherein the repeating unit is represented by the following general formula (1a): [ka] (In the formula, R A , Z L , X L , R 1a , R ALU , R aa , n1, n2, n3, and n4 are the same as above.)

[0021] Resist materials containing such polymer compounds can be produced that have sensitivity and resolution superior to conventional positive resist materials, have small edge roughness and dimensional variation, and produce good pattern shapes after exposure.

[0022] In addition, it is preferable that the polymer compound contains a repeating unit obtained from the above polymerizable monomer, and the repeating unit is represented by the following general formula (1-Aa). [ka] (In the formula, R A , ZL , X L , R 1a , R ALU , n1, n2, n3, and n4 are the same as above.)

[0023] Such a compound is more suitable as the polymer compound.

[0024] R ALU is represented by the following formula (AL-1) or (AL-2) together with the adjacent oxygen atom is preferred . [ka] (In the formula, R 21 , R 22 , R 23 ,t,R 24 , R 25 , R 26 , X a , u is the same as above.)

[0025] Such a group will function better as an acid labile group.

[0026] Furthermore, the polymer compound preferably contains at least one repeating unit selected from the repeating units represented by the following general formula (a1) or (a2). [ka] (In the formula, R A are each independently a hydrogen atom, a fluorine atom, a methyl group, or a trifluoromethyl group. A represents a single bond, an alkoxy group which may be substituted with a halogen atom, a phenylene group which may be substituted with a halogen atom, a naphthylene group, or (main chain) -C(=O)-OZ A1 - and Z A1Z is a straight-chain, branched or cyclic alkanediyl group having 1 to 20 carbon atoms which may contain a heteroatom, an alkoxy group having 1 to 10 carbon atoms which may contain a fluorine atom, a hydroxy group, an ether bond, an ester bond, a lactone ring, a thioether bond, a sulfonyl group or a sulfonamide structure, or a phenylene group or a naphthylene group. B is a single bond or (main chain)-C(=O)-OZ B1 -It is. Z B1 X is a single bond or an alkanediyl group having 1 to 10 carbon atoms which may have an ester bond and / or an ether bond. A and X B are each independently an acid labile group. b is a linear, branched or cyclic monovalent hydrocarbon group having 1 to 20 carbon atoms which may contain a halogen atom, a nitro group or a heteroatom, and n is an integer of 0 to 4.

[0027] Such a polymer compound exhibits better functions.

[0028] Furthermore, it is preferable that the repeating unit contains at least one selected from the repeating units represented by the following general formula (b1) or (b2). [ka] (In the formula, R A are each independently a hydrogen atom, a fluorine atom, a methyl group, or a trifluoromethyl group. A is a hydrogen atom or a polar group containing at least one structure selected from a hydroxy group, a cyano group, a carbonyl group, a carboxy group, an ether bond, an ester bond, a sulfonate ester bond, a sulfonamide bond, a carbonate bond, a lactone ring, a sultone ring, a sulfur atom, and a carboxylic acid anhydride. B is a single bond or (main chain)-C(=O)-OZ B1 -It is. Z B1 R is a single bond or an alkanediyl group having 1 to 10 carbon atoms which may have an ester bond and / or an ether bond. brepresents a linear, branched or cyclic monovalent hydrocarbon group having 1 to 20 carbon atoms which may contain a halogen atom, a nitro group or a heteroatom; m represents an integer of 1 to 4; and m' represents an integer of 0 to 4.

[0029] Such a polymer compound exhibits better functions.

[0030] Furthermore, it is preferable that the repeating unit contains at least one selected from the repeating units represented by the following general formulae (C1) to (C4). [ka] (In the formula, R A are each independently a hydrogen atom, a fluorine atom, a methyl group, or a trifluoromethyl group. 1 is a single bond or a phenylene group. 2 is a single bond, *-C(=O)-OZ 21 -, *-C(=O)-NH-Z 21 -or*-OZ 21 -It is. Z 21 Z is an aliphatic hydrocarbylene group having 1 to 12 carbon atoms, a phenylene group, or a divalent group obtained by combining these, and may contain a carbonyl group, an ester bond, an ether bond, or a hydroxy group. 3 is a single bond, a phenylene group, a naphthylene group, or *-C(=O)-OZ 31 -It is. Z 31 Z is an aliphatic hydrocarbylene group having 1 to 14 carbon atoms which may contain a single bond, a hydroxy group, an ether bond, an ester bond or a lactone ring, or a phenylene group or a naphthylene group. 4 is a single bond, a methylene group or *-Z 41 -C(=O)-O-. Z 41 Z is a hydrocarbylene group having 1 to 20 carbon atoms which may contain an ether bond, an ester bond, or a heteroatom. 5 represents 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)-OZ 51-, *-C(=O)-N(H)-Z 51 -or*-OZ 51 -It is. Z 51 is an aliphatic hydrocarbylene 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 contain a carbonyl group, an ester bond, an ether bond, or a hydroxy group. * represents a bond to a carbon atom in the main chain. R 21 ' and R 22 Each of R' is independently a hydrocarbyl group having 1 to 20 carbon atoms which may contain a heteroatom. 21 ' and R 22 and may be bonded to each other to form a ring together with the sulfur atom to which they are attached. 1 is a single bond, an ether bond, an ester bond, a carbonyl group, a sulfonate ester bond, a carbonate bond or a carbamate bond. 1 and Rf 2 Rf are each independently a fluorine atom or a fluorinated alkyl group having 1 to 6 carbon atoms. 3 and Rf 4 Rf are each independently a hydrogen atom, a fluorine atom, or a fluorinated alkyl group having 1 to 6 carbon atoms. 5 and Rf 6 are each independently a hydrogen atom, a fluorine atom, or a fluorinated alkyl group having 1 to 6 carbon atoms, provided that all Rf 5 and Rf 6 and cannot simultaneously become hydrogen atoms. - is a non-nucleophilic counterion. + is an onium cation, and c is an integer of 0 to 3.

[0031] Such a polymer compound exhibits even better functions.

[0032] The present invention also provides a resist composition containing a base resin made of the above polymer compound and an organic solvent.

[0033] Any composition containing the above polymer compound and an organic solvent will be suitable as a resist composition.

[0034] Furthermore, it is preferable that the compound contains at least one selected from the group consisting of a quencher and an acid generator.

[0035] Such a composition will exhibit better functionality as a resist composition.

[0036] Furthermore, the resist composition preferably contains a surfactant that is insoluble or slightly soluble in water but soluble in an alkaline developer, and / or a surfactant that is insoluble or slightly soluble in both water and an alkaline developer.

[0037] Such a composition will exhibit even better functionality as a resist composition.

[0038] The present invention also provides a pattern forming method, comprising the steps of: forming a resist film on a substrate using the resist composition; exposing the resist film to high-energy rays; and developing the exposed resist film using a developer.

[0039] Such a pattern forming method makes it possible to form a good pattern.

[0040] The high-energy beam is preferably KrF excimer laser light, ArF excimer laser light, an electron beam, or extreme ultraviolet light having a wavelength of 3 to 15 nm.

[0041] Using such high energy rays, better patterns can be obtained. [Effects of the Invention]

[0042] When a pattern is formed using a chemically amplified resist composition containing, as a base polymer, a polymer compound obtained using the polymerizable monomer of the present invention, it is possible to form a resist pattern that has high contrast and good sensitivity, and is excellent in lithography performance such as DOF (depth of focus) and LWR, and in which pattern collapse is suppressed. DETAILED DESCRIPTION OF THE INVENTION

[0043] There has been a demand for polymerizable monomers that have sensitivity and resolution superior to conventional positive resist materials, have small edge roughness and dimensional variations, and produce good pattern shapes after exposure.

[0044] As a result of extensive research to achieve the above object, the present inventors have discovered that polymerizable monomers having specific structures have excellent solvent solubility, and that chemically amplified resist compositions using polymeric compounds containing such monomers as base polymers have high sensitivity and high contrast, and are excellent in lithography performance such as EL (exposure latitude) and LWR, and are extremely effective in suppressing pattern collapse during fine pattern formation, which has led to the completion of the present invention.

[0045] That is, the present invention is The polymerizable monomer is characterized by being represented by the following general formula (1): [ka] (In the formula, R A is a hydrogen atom, a fluorine atom, a methyl group, or a trifluoromethyl group. L is a single bond or (main chain) -C(=O)-O-. ALU is an acid labile group formed with the adjacent oxygen atom. L represents an oxygen atom or a sulfur atom. aa represents a hydrogen atom or a fluorine atom. 1aare each independently a linear, branched or cyclic hydrocarbyl group having 1 to 20 carbon atoms which may contain a heteroatom. n1 is an integer of 0 to 2. n2 is an integer of 1 or 2. n3 is an integer of 1 or 2. n4 is an integer of 0 to 4. When n2=1, -OR ALU and -X L -CF2(R aa ) are bonded to adjacent carbon atoms on the aromatic ring. Furthermore, when n2=2, two -OR ALU One of them is -X L -CF2(R aa ) is bonded to the carbon atom adjacent to the carbon atom on the aromatic ring to which it is bonded.

[0046] The present invention also provides a polymeric compound containing a repeating unit obtained from the above polymerizable monomer, a resist composition containing a base resin consisting of the polymeric compound and an organic solvent, and a pattern formation method using this resist composition.

[0047] The present invention will be described in detail below, but the present invention is not limited thereto.

[0048] [Polymerizable monomer] The polymerizable monomer of the present invention is represented by the following formula (1). [ka] (In the formula, R A is a hydrogen atom, a fluorine atom, a methyl group, or a trifluoromethyl group. L is a single bond or (main chain) -C(=O)-O-. ALU is an acid labile group formed with the adjacent oxygen atom. L represents an oxygen atom or a sulfur atom. aa represents a hydrogen atom or a fluorine atom. 1aare each independently a linear, branched or cyclic hydrocarbyl group having 1 to 20 carbon atoms which may contain a heteroatom. n1 is an integer of 0 to 2. n2 is an integer of 1 or 2. n3 is an integer of 1 or 2. n4 is an integer of 0 to 4. When n2=1, -OR ALU and -X L -CF2(R aa ) are bonded to adjacent carbon atoms on the aromatic ring. Furthermore, when n2=2, two -OR ALU One of them is -X L -CF2(R aa ) is bonded to the carbon atom adjacent to the carbon atom on the aromatic ring to which it is bonded.

[0049] In formula (1), R A is a hydrogen atom, a fluorine atom, a methyl group, or a trifluoromethyl group, and among these, a hydrogen atom or a methyl group is preferred.

[0050] Z L is a single bond or (main chain)-C(=O)-O-. Among these, a single bond is preferred.

[0051] In formula (1), R 1a are each independently a linear, branched, or cyclic hydrocarbyl group having 1 to 20 carbon atoms, which may contain a heteroatom. The hydrocarbyl group may be saturated or unsaturated, and may be linear, branched, or cyclic. Specific examples include alkyl groups having 1 to 20 carbon atoms, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, and tert-butyl; cyclic saturated hydrocarbyl groups having 3 to 20 carbon atoms, such as cyclopropyl, cyclopentyl, cyclohexyl, cyclopropylmethyl, 4-methylcyclohexyl, cyclohexylmethyl, norbornyl, and adamantyl; alkenyl groups having 2 to 20 carbon atoms, such as vinyl, allyl, propenyl, butenyl, and hexenyl; cyclic unsaturated hydrocarbyl groups having 3 to 20 carbon atoms, such as cyclohexenyl; and unsaturated hydrocarbyl groups having 3 to 20 carbon atoms, such as phenyl and naphthyl. 6Examples of the hydrocarbyl group include aryl groups having 7 to 20 carbon atoms; aralkyl groups having 7 to 20 carbon atoms, such as benzyl, 1-phenylethyl, and 2-phenylethyl; and groups obtained by combining these. Of these, aryl groups are preferred. Furthermore, some or all of the hydrogen atoms in the hydrocarbyl group may be substituted with a group containing a heteroatom, such as an oxygen atom, sulfur atom, nitrogen atom, or halogen atom, and some of the -CH2- groups constituting the hydrocarbyl group may be substituted with a group containing a heteroatom, such as an oxygen atom, sulfur atom, or nitrogen atom, resulting in the hydrocarbyl group containing a hydroxy group, cyano group, fluorine atom, chlorine atom, bromine atom, iodine atom, carbonyl group, ether bond, ester bond, sulfonate ester bond, carbonate bond, lactone ring, sultone ring, carboxylic acid anhydride, haloalkyl group, etc.

[0052] In formula (1), X L represents an oxygen atom or a sulfur atom, but is preferably an oxygen atom in view of ease of raw material procurement.

[0053] In formula (1), R aa represents a hydrogen atom or a fluorine atom, but is preferably a hydrogen atom in view of ease of raw material procurement.

[0054] In formula (1), R ALU represents an acid labile group formed together with the adjacent oxygen atom, and specifically, a structure represented by the following formula (AL-1) or (AL-2) is preferred. [ka] (In formula (AL-1), R 21 , R 22 , and R 23 are each independently a hydrocarbyl group having 1 to 12 carbon atoms which may contain a heteroatom. 21 , R 22 , and R 23 Any two of these may be bonded to each other to form a ring. t is an integer of 0 or 1. In formula (AL-2), R 24 , and R 25are each independently a hydrogen atom or a hydrocarbyl group having 1 to 10 carbon atoms. 26 is a hydrocarbyl group having 1 to 20 carbon atoms, or R 24 , or R 25 and bond to each other, and the carbon atoms to which they are bonded and X a may form a heterocyclic group having 3 to 20 carbon atoms together with X. Furthermore, -CH2- contained in the above hydrocarbyl group and heterocyclic group may be replaced with -O- or -S-. a represents an oxygen atom or a sulfur atom. u is an integer of 0 or 1. * represents a bond to the adjacent oxygen atom.

[0055] In formula (AL-1), R 21 , R 22 , and R 23 are each preferably independently a hydrocarbyl group having 1 to 10 carbon atoms. 21 , R 22 , and R 23 Any two of these may be bonded to each other to form a ring. t is an integer of 0 or 1. In formula (AL-2), R 24 , and R 25 are each independently a hydrogen atom or a hydrocarbyl group having 1 to 10 carbon atoms. 26 is a hydrocarbyl group having 1 to 20 carbon atoms, or R 24 , or R 25 and bond to each other, and the carbon atoms to which they are bonded and X a may form a heterocyclic group having 3 to 20 carbon atoms together with X. Furthermore, -CH2- contained in the above hydrocarbyl group and heterocyclic group may be replaced with -O- or -S-. a represents an oxygen atom or a sulfur atom, and u is an integer of 0 or 1. * represents a bond to the adjacent oxygen atom.

[0056] Examples of the structure of the acid labile group represented by formula (AL-1) include, but are not limited to, those shown below: * represents a bond to the adjacent oxygen atom. [ka]

[0057] [ka]

[0058] [ka]

[0059] Examples of the structure of the acid labile group represented by formula (AL-2) include, but are not limited to, those shown below: * represents a bond to the adjacent oxygen atom. [ka]

[0060] In formula (1), -OR ALU and -X L -CF2(R aa ) must be bonded to adjacent carbon atoms on the aromatic ring. ALU The acidity of the aromatic alcohol produced after deprotection of the aryl group is increased.

[0061] In formula (1), n1 is an integer of 0 to 2. When n1 is 0, it is a benzene ring, when n1 is 1 it is a naphthalene ring, and when n1 is 2 it is an anthracene ring, but from the viewpoint of solvent solubility, it is preferable that n1 is 0 and is a benzene ring.

[0062] In formula (1), n2 is an integer of 1 or 2, but n2 is preferably 1 from the viewpoint of ease of procurement of raw materials.

[0063] In formula (1), n3 is an integer of 1 or 2, but n3 is preferably 1 from the viewpoint of ease of procurement of raw materials.

[0064] In formula (1), n4 is an integer of 0 to 4, but n4 is preferably an integer of 0 to 2 from the viewpoint of ease of procurement of raw materials.

[0065] The polymerizable monomer represented by formula (1) is further preferably one represented by the following formula (1-A). [ka] (In the formula, R A , Z L , X L , R 1a , R ALU , n1, n2, n3, and n4 are the same as above.)

[0066] Examples of the polymerizable monomers represented by formula (1) and formula (1-A) include, but are not limited to, the following: In addition, the substitution positions of the substituents on the aromatic ring are not limited to the above as long as the groups bounded by n2 and n3 are adjacent to each other. [ka]

[0067] [ka]

[0068] [ka]

[0069] [ka]

[0070] [ka]

[0071] [ka]

[0072] [ka]

[0073]

change

[0074]

change

[0075]

change

[0076]

change

[0077]

change

[0078]

change

[0079]

change

[0080]

change

[0081]

change

[0082]

change

[0083]

change

[0084] [ka]

[0085] [ka]

[0086] The polymerizable monomer (1) of the present invention can be synthesized by a known method. For example, in the above formula (1), Z L is a single bond, X L The polymerizable monomer (1') in which is an oxygen atom will be described. [ka] (In the formula, R A , R 1a , R ALU , n1, n2, n3, and n4 are the same as above. X hal is a chlorine atom, a bromine atom, or an iodine atom. AL -H is an alkali metal or alkaline earth metal hydride. Metal cat. is a transition metal complex catalyst.

[0087] The first reaction is HO-R ALU This reaction involves preparing a metal alkoxide from the alcohol, and then subjecting the raw material (SM-1') to an aromatic nucleophilic substitution reaction to obtain the target precursor (Pre-1').

[0088] Raw materials (SM-1') and HO-R ALU M can be synthesized according to known methods or can be obtained commercially. AL Alkali metal or alkaline earth metal hydride represented by -H is suspended in a solvent such as THF, and HO-R ALUThe metal alkoxide is prepared by adding the above solution dropwise. To efficiently prepare the metal alkoxide, it is preferable to heat the internal temperature of the solvent from 50°C to the boiling point of the solvent. After preparing the metal alkoxide, the raw material (SM-1') is added and the reaction can be carried out by heating as necessary. From the viewpoint of yield, it is desirable to monitor the reaction by gas chromatography (GC) or silica gel thin layer chromatography (TLC) and complete the reaction, but the reaction time is usually about 12 to 24 hours. The target precursor (Pre-1') can be obtained from the reaction mixture by conventional aqueous work-up, and if necessary, it can be purified by conventional methods such as distillation, chromatography, and recrystallization.

[0089] In the second reaction, a Grignard reagent is prepared from the target precursor (Pre-1'), and the target compound (1') is obtained by a cross-coupling reaction with a vinyl halide compound in the presence of a transition metal complex catalyst.

[0090] The Grignard reagent can be prepared from the target precursor (Pre-1') using a known method. After preparing the Grignard reagent, the reaction mixture is cooled and a transition metal complex catalyst is added. The transition metal complex catalyst preferably contains a central metal such as palladium, nickel, platinum, cobalt, rhodium, iridium, iron, ruthenium, or copper, and is composed of various amine, phosphine, or N-heterocyclic carbene ligands. A vinyl halide compound diluted with a reaction solvent is then added dropwise. To improve the reaction conversion, the reaction can be heated as needed. The reaction time is typically 0.5 to 3 hours, although it is desirable to monitor the reaction by gas chromatography (GC) or silica gel thin-layer chromatography (TLC) to ensure complete reaction. The target product (1') can be obtained from the reaction mixture by conventional aqueous workup, and if necessary, can be purified by conventional methods such as distillation, chromatography, or recrystallization.

[0091] The above-mentioned production method is merely an example, and the method for producing the polymerizable monomer of the present invention is not limited to this.

[0092] A structural feature of the polymerizable monomer of the present invention is that it has an acid labile group bonded to a hydroxyl group on an aromatic ring and a fluorine-containing alkoxy group, which are bonded to adjacent carbon atoms. The acid labile group in the exposed region undergoes a deprotection reaction with the generated acid, generating an aromatic hydroxyl group. This improves the contrast between the exposed and unexposed regions. The adjacent fluorine-containing alkoxy group not only improves the solubility of the base polymer obtained by copolymerization in a resist solvent, but also increases the acidity of the aromatic hydroxyl group generated in the exposed region due to its electron-withdrawing property. When the resist film is developed with an alkaline developer after exposure, the affinity between the generated aromatic hydroxyl group and the alkaline developer is improved, allowing the exposed region to be effectively removed by the developer. Furthermore, the aromatic hydroxyl group adjacent to the fluorine-containing alkoxy group is thought to have the effect of attracting less alkaline developer to the unexposed region than a simple carboxyl group due to the water-repellent effect of multiple fluorine atoms, thereby reducing swelling caused by the alkaline developer. This prevents the resist pattern from collapsing in the unexposed region. Due to these synergistic effects, when the polymerizable monomer of the present invention is used, it is possible to form a pattern that has high dissolution contrast, excellent LWR of a line pattern and CDU of a hole pattern, and is resistant to pattern collapse, and therefore it is suitable as a positive resist material.

[0093] [Resist composition] The resist composition of the present invention, particularly the chemically amplified resist composition, comprises: (A) a base resin comprising a polymeric compound, particularly a copolymerized polymeric compound, containing a repeating unit obtained from a polymerizable monomer represented by formula (1); and (B) Contains an organic solvent.

[0094] The resist composition of the present invention may further comprise, if necessary: (C) quencher, (D) Acid generators such as photoacid generators and optionally further comprising (E) A surfactant that is insoluble or slightly soluble in water but soluble in an alkaline developer, and / or a surfactant that is insoluble or slightly soluble in water and an alkaline developer. and optionally further comprising (F) Other ingredients may include:

[0095] [High molecular compound] The polymerizable monomer can be suitably used as a constituent unit of a base polymer in a resist composition. The polymer compound of the present invention is a polymer compound containing a repeating unit obtained from the polymerizable monomer of the present invention, and the repeating unit contains a repeating unit represented by the following general formula (1a) (hereinafter also referred to as repeating unit A). [ka] (In the formula, R A , Z L , X L , R 1a , R ALU , R aa , n1, n2, n3, and n4 are the same as above.)

[0096] Furthermore, the polymer compound of the present invention preferably contains a repeating unit characterized by being represented by the following general formula (1-Aa): [ka] (In the formula, R A , Z L , X L , R 1a , R ALU , n1, n2, n3, and n4 are the same as above.)

[0097] Furthermore, the above R ALU together with the adjacent oxygen atom preferably represents the following formula (AL-1) or (AL-2). [ka] (In the formula, R 21 , R 22 , R 23 ,t,R 24 , R 25 , R 26 , X a , u is the same as above.)

[0098] With regard to the repeating unit A, two or more different types of repeating units may be copolymerized as the constituent units of the base polymer.

[0099] The polymer compound of the present invention preferably contains a repeating unit represented by the following general formula (a1) (hereinafter also referred to as repeating unit a1) or a repeating unit represented by the following general formula (a2) (hereinafter also referred to as repeating unit a2): [ka] (In the formula, R A are each independently a hydrogen atom, a fluorine atom, a methyl group, or a trifluoromethyl group. A represents a single bond, an alkoxy group which may be substituted with a halogen atom, a phenylene group which may be substituted with a halogen atom, a naphthylene group, or (main chain) -C(=O)-OZ A1 - and Z A1 Z is a straight-chain, branched or cyclic alkanediyl group having 1 to 20 carbon atoms which may contain a heteroatom, an alkoxy group having 1 to 10 carbon atoms which may contain a fluorine atom, a hydroxy group, an ether bond, an ester bond, a lactone ring, a thioether bond, a sulfonyl group or a sulfonamide structure, or a phenylene group or a naphthylene group. B is a single bond or (main chain)-C(=O)-OZ B1 -It is. Z B1 X is a single bond or an alkanediyl group having 1 to 10 carbon atoms which may have an ester bond and / or an ether bond. A and X B are each independently an acid labile group. bis a linear, branched or cyclic monovalent hydrocarbon group having 1 to 20 carbon atoms which may contain a halogen atom, a nitro group or a heteroatom, and n is an integer of 0 to 4.

[0100] In formulas (a1) and (a2), R A are each independently a hydrogen atom, a fluorine atom, a methyl group, or a trifluoromethyl group. A is a single bond, (main chain)-C(=O)-OZ A1 Z is preferably an alkoxy group having 1 to 10 carbon atoms which may contain a fluorine atom, or a phenylene group or naphthylene group which may contain a halogen atom. A1 is preferably a linear, branched or cyclic alkanediyl group (aliphatic hydrocarbylene group) having 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms, which may contain a heteroatom, a fluorine atom, an alkoxy group having 1 to 10 carbon atoms, which may contain a hydroxy group, an ether bond, an ester bond, a lactone ring, a thioether bond, a sulfonyl group or a sulfonamide structure, a phenylene group or a naphthylene group. B is preferably a single bond or (main chain) -C(=O)-O-. A and X B are each independently an acid labile group.

[0101] In formula (a2), R b is a hydrocarbyl group having 1 to 20 carbon atoms which may contain a halogen atom, a nitro group, or a heteroatom. The hydrocarbyl group may be saturated or unsaturated, and may be linear, branched, or cyclic. Specific examples thereof include R in (1a). 1a Examples include the same ones as those exemplified in the explanation of 1. n is an integer of 0 to 4, and preferably 0 or 1.

[0102] In formulas (a1) and (a2), X A and X B Examples of the acid labile group represented by the formula (I) include those described in JP-A Nos. 2013-80033 and 2013-83821.

[0103] Typically, the acid labile group includes those represented by the following formulae (AL-1)' to (AL-3)'. [ka] (In the formula, the dashed lines represent bonds.)

[0104] In formulas (AL-1)′ and (AL-2)′, R L1 and R L2 are each independently a saturated hydrocarbyl group having 1 to 40 carbon atoms, which may contain a heteroatom such as an oxygen atom, a sulfur atom, a nitrogen atom, or a fluorine atom. The saturated hydrocarbyl group may be linear, branched, or cyclic. The saturated hydrocarbyl group preferably has 1 to 20 carbon atoms.

[0105] In formula (AL-1)′, a represents an integer of 0 to 10, and an integer of 1 to 5 is preferred.

[0106] In formula (AL-2)', R L3 and R L4 are each independently a hydrogen atom or a saturated hydrocarbyl group having 1 to 20 carbon atoms, and may contain a heteroatom such as an oxygen atom, a sulfur atom, a nitrogen atom, or a fluorine atom. The hydrocarbyl group may be linear, branched, or cyclic. L2 , R L3 and R L4 Any two of these may be bonded to each other to form a ring having 3 to 20 carbon atoms together with the carbon atom or the carbon atom and oxygen atom to which they are bonded. As the ring, a ring having 4 to 16 carbon atoms is preferred, and an alicyclic ring is particularly preferred.

[0107] In formula (AL-3)', R L5 , R L6 and R L7 are each independently a saturated hydrocarbyl group having 1 to 20 carbon atoms, which may contain a heteroatom such as an oxygen atom, a sulfur atom, a nitrogen atom, or a fluorine atom. The hydrocarbyl group may be linear, branched, or cyclic. L5 , R L6 and RL7 Any two of these may be bonded to each other together with the carbon atoms to which they are bonded to form a ring having 3 to 20 carbon atoms. As the ring, a ring having 4 to 16 carbon atoms is preferred, and an alicyclic ring is particularly preferred.

[0108] Examples of the repeating unit a1 include, but are not limited to, those shown below. A and X A is the same as above. [ka]

[0109] [ka]

[0110] Examples of the repeating unit a2 include, but are not limited to, those shown below. A and X B is the same as above.

[0111] [ka]

[0112] The polymer compound 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): [ka] (In the formula, R A are each independently a hydrogen atom, a fluorine atom, a methyl group, or a trifluoromethyl group. Ais a hydrogen atom or a polar group containing at least one structure selected from a hydroxy group, a cyano group, a carbonyl group, a carboxy group, an ether bond, an ester bond, a sulfonate ester bond, a sulfonamide bond, a carbonate bond, a lactone ring, a sultone ring, a sulfur atom, and a carboxylic acid anhydride. B is a single bond or (main chain)-C(=O)-OZ B1 -It is. Z B1 R is a single bond or an alkanediyl group having 1 to 10 carbon atoms which may have an ester bond and / or an ether bond. b represents a linear, branched or cyclic monovalent hydrocarbon group having 1 to 20 carbon atoms which may contain a halogen atom, a nitro group or a heteroatom; m represents an integer of 1 to 4; and m' represents an integer of 0 to 4.

[0113] In formulas (b1) and (b2), R A , R b , Z B is the same as above. Y A is preferably a hydrogen atom or a polar group containing at least one structure selected from a hydroxy group, a cyano group, a carbonyl group, a carboxy group, an ether bond, an ester bond, a sulfonate ester bond, a sulfonamide bond, a carbonate bond, a lactone ring, a sultone ring, a sulfur atom, and a carboxylic acid anhydride. m is an integer of 1 to 4. m' is an integer of 0 to 4.

[0114] Above Y A may be a hydrogen atom, or a polar group containing at least one structure selected from a hydroxy group other than a phenolic hydroxy group, a cyano group, a carbonyl group, a carboxy group, an ether bond, an ester bond, a sulfonate ester bond, a carbonate bond, a lactone ring, a sultone ring, and a carboxylic acid anhydride.

[0115] Examples of the repeating unit b1 include, but are not limited to, those shown below. A is the same as above.

[0116] [ka]

[0117] [ka]

[0118] [ka]

[0119] [ka]

[0120] [ka]

[0121] [ka]

[0122] [ka]

[0123] [ka]

[0124] Examples of the repeating unit b2 include, but are not limited to, those shown below. A is the same as above. [ka]

[0125] [ka]

[0126] [ka]

[0127] As the repeating unit b1 or b2, those having a lactone ring as a polar group are particularly preferred for ArF lithography, and those having a phenol moiety are preferred for KrF lithography, EB lithography and EUV lithography.

[0128] The polymer compound 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). [ka] (In the formula, R A are each independently a hydrogen atom, a fluorine atom, a methyl group, or a trifluoromethyl group. 1 is a single bond or a phenylene group. 2 is a single bond, *-C(=O)-OZ 21 -, *-C(=O)-NH-Z 21 -or*-OZ 21 -It is. Z 21 Z is an aliphatic hydrocarbylene group having 1 to 12 carbon atoms, a phenylene group, or a divalent group obtained by combining these, and may contain a carbonyl group, an ester bond, an ether bond, or a hydroxy group. 3 is a single bond, a phenylene group, a naphthylene group, or *-C(=O)-OZ 31 -It is. Z 31 Z is an aliphatic hydrocarbylene group having 1 to 14 carbon atoms which may contain a single bond, a hydroxy group, an ether bond, an ester bond or a lactone ring, or a phenylene group or a naphthylene group. 4 is a single bond, a methylene group or *-Z 41 -C(=O)-O-. Z 41 Z is a hydrocarbylene group having 1 to 20 carbon atoms which may contain an ether bond, an ester bond, or a heteroatom. 5represents 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)-OZ 51 -, *-C(=O)-N(H)-Z 51 -or*-OZ 51 -It is. Z 51 is an aliphatic hydrocarbylene 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 contain a carbonyl group, an ester bond, an ether bond, or a hydroxy group. * represents a bond to a carbon atom in the main chain. R 21 ' and R 22 Each of R' is independently a hydrocarbyl group having 1 to 20 carbon atoms which may contain a heteroatom. 21 ' and R 22 and may be bonded to each other to form a ring together with the sulfur atom to which they are attached. 1 is a single bond, an ether bond, an ester bond, a carbonyl group, a sulfonate ester bond, a carbonate bond or a carbamate bond. 1 and Rf 2 Rf are each independently a fluorine atom or a fluorinated alkyl group having 1 to 6 carbon atoms. 3 and Rf 4 Rf are each independently a hydrogen atom, a fluorine atom, or a fluorinated alkyl group having 1 to 6 carbon atoms. 5 and Rf 6 are each independently a hydrogen atom, a fluorine atom, or a fluorinated alkyl group having 1 to 6 carbon atoms, provided that all Rf 5 and Rf 6 and cannot simultaneously become hydrogen atoms. - is a non-nucleophilic counterion. + is an onium cation, and c is an integer of 0 to 3.

[0129] In formulas (C1) to (C4), R A is the same as above. Z 1 is a single bond or a phenylene group. 2 is a single bond, -C(=O)-OZ 21 -, -C(=O)-NH-Z21 -or- OZ 21 -It is. Z 21 Z is an aliphatic hydrocarbylene group having 1 to 12 carbon atoms, preferably 1 to 6 carbon atoms, a phenylene group, or a divalent group obtained by combining these, and may contain a carbonyl group, an ester bond, an ether bond, or a hydroxy group. 3 represents a single bond, a phenylene group, a naphthylene group, or (main chain) -C(=O)-OZ 31 -It is. Z 31 Z is an aliphatic hydrocarbylene group having 1 to 14 carbon atoms which may contain a hydroxy group, an ether bond, an ester bond or a lactone ring, or a phenylene group or a naphthylene group. 4 is a single bond, a methylene group, or -Z 41 -C(=O)-O-. Z 41 is a hydrocarbylene group having 1 to 20 carbon atoms which may contain a heteroatom, an ether bond, or an ester bond. 5 represents a single bond, a methylene group, an ethylene group, a phenylene group substituted with a trifluoromethyl group, a phenylene group, a fluorinated phenylene group, -C(=O)-OZ 51 -, -C(=O)-N(H)-Z 51 -or- OZ 51 -It is. Z 51 represents an aliphatic hydrocarbylene 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 contain a carbonyl group, an ester bond, an ether bond, or a hydroxy group.

[0130] Z 21 , Z 31 and Z 51 Specific examples of the structure represented by the formula (a1) may be linear, branched, or cyclic. A Examples of the above-mentioned examples are the same as those given in the explanation of the above.

[0131] Z 41The hydrocarbylene group represented by the formula (I) may be saturated or unsaturated, and may be linear, branched, or cyclic. Specific examples thereof include, but are not limited to, those shown below. [ka] (In the formula, the dashed lines represent bonds.)

[0132] In formula (C1), R 21 ' and R 22 R' are each independently a hydrocarbyl group having 1 to 20 carbon atoms which may contain a heteroatom. 21 ' and R 22 The hydrocarbyl group represented by "'" may be saturated or unsaturated, and may be linear, branched, or cyclic. Specific examples include alkyl groups such as methyl, ethyl, n-propyl, isopropyl, n-butyl, and tert-butyl; cyclic saturated hydrocarbyl groups such as cyclopropyl, cyclopentyl, cyclohexyl, cyclopropylmethyl, 4-methylcyclohexyl, cyclohexylmethyl, norbornyl, and adamantyl; alkenyl groups such as vinyl, allyl, propenyl, butenyl, and hexenyl; cyclic unsaturated hydrocarbyl groups such as cyclohexenyl; aryl groups such as phenyl, naphthyl, and thienyl; aralkyl groups such as benzyl, 1-phenylethyl, and 2-phenylethyl; and groups obtained by combining these groups, with aryl groups being preferred. In addition, some of the hydrogen atoms of the hydrocarbyl group may be substituted with a heteroatom-containing group such as an oxygen atom, a sulfur atom, a nitrogen atom or a halogen atom, and a heteroatom-containing group such as an oxygen atom, a sulfur atom or a nitrogen atom may be present between the carbon atoms of these groups, and as a result, the group may contain a hydroxy group, a cyano group, a carbonyl group, an ether bond, an ester bond, a sulfonate ester bond, a carbonate bond, a lactone ring, a sultone ring, a carboxylic acid anhydride, a haloalkyl group, or the like.

[0133] Also, R 21 ' and R 22' may be bonded to each other to form a ring together with the sulfur atom to which they are bonded. Specific examples include those represented by the following formulas. [ka]

[0134] Examples of the cation of the repeating unit c1 include, but are not limited to, the following: A is the same as above. [ka]

[0135] [ka]

[0136] [ka]

[0137] [ka]

[0138] In formula (C1), M - is a non-nucleophilic counter ion. Examples of the non-nucleophilic counter ion include those described in paragraphs

[0236] to

[0290] below.

[0139] In formula (C2), L 1 is a single bond, an ether bond, an ester bond, a carbonyl group, a sulfonate ester 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.

[0140] In formula (C2), Rf 1 and Rf 2are each independently a fluorine atom or a fluorinated alkyl group having 1 to 6 carbon atoms. 1 and Rf 2 In order to increase the acid strength of the generated acid, it is preferable that Rf be a fluorine atom. 3 and Rf 4 are each independently a hydrogen atom, a fluorine atom, or a fluorinated alkyl group having 1 to 6 carbon atoms. Of these, Rf 3 and Rf 4 At least one of these is preferably a trifluoromethyl group.

[0141] In formula (C2), c is an integer of 0 to 3, with 1 being preferred.

[0142] Specific examples of the anion of the repeating unit represented by formula (C2) include, but are not limited to, those shown below. A is the same as above.

[0143] [ka]

[0144] [ka]

[0145] [ka]

[0146] [ka]

[0147] [ka]

[0148] [ka]

[0149] In formula (c3), L 1 is a single bond, an ether bond, an ester bond, a carbonyl group, a sulfonate ester 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.

[0150] In formula (c3), Rf 5 and Rf 6 are each independently a hydrogen atom, a fluorine atom, or a fluorinated alkyl group having 1 to 6 carbon atoms. Of these, Rf 5 and Rf 6 At least one of these is preferably a trifluoromethyl group.

[0151] In formula (c3), c is an integer of 0 to 3, with 1 being preferred.

[0152] Specific examples of the anion of the repeating unit represented by formula (c3) include, but are not limited to, those shown below. A is the same as above

[0153] [ka]

[0154] [ka]

[0155] [ka]

[0156] Specific examples of the anion of the repeating unit represented by formula (C4) include, but are not limited to, those shown below. A is the same as above.

[0157] [ka]

[0158] In formulas (C2) to (C4), A + is an onium cation. Examples of the onium cation include an ammonium cation, a sulfonium cation, and an iodonium cation, and the sulfonium cation and the iodonium cation are preferred, and the sulfonium cation represented by the following general formula (cation-1) and the iodonium cation represented by the following formula (cation-2) are more preferred. [ka]

[0159] In formulas (cation-1) and (cation-2), R 11 ~R 15are each preferably independently a hydrocarbyl group having 1 to 30 carbon atoms which may contain a heteroatom. The hydrocarbyl group may be saturated or unsaturated, and may be linear, branched, or cyclic. Specific examples thereof include alkyl groups such as methyl, ethyl, n-propyl, isopropyl, n-butyl, and tert-butyl; cyclic saturated hydrocarbyl groups such as cyclopropyl, cyclopentyl, cyclohexyl, cyclopropylmethyl, 4-methylcyclohexyl, cyclohexylmethyl, norbornyl, and adamantyl; alkenyl groups such as vinyl, allyl, propenyl, butenyl, and hexenyl; cyclic unsaturated hydrocarbyl groups such as cyclohexenyl; aryl groups such as phenyl, naphthyl, and thienyl; aralkyl groups such as benzyl, 1-phenylethyl, and 2-phenylethyl; and groups obtained by combining these groups, with aryl groups being preferred. In addition, some of the hydrogen atoms of the hydrocarbyl group may be substituted with a heteroatom-containing group such as an oxygen atom, a sulfur atom, a nitrogen atom or a halogen atom, and a heteroatom-containing group such as an oxygen atom, a sulfur atom or a nitrogen atom may be present between the carbon atoms of these groups, and as a result, the group may contain a hydroxy group, a cyano group, a carbonyl group, an ether bond, an ester bond, a sulfonate ester bond, a carbonate bond, a lactone ring, a sultone ring, a carboxylic acid anhydride, a haloalkyl group, or the like.

[0160] Also, R 11 and R 12 However, they may be bonded to each other to form a ring together with the sulfur atom to which they are bonded. In this case, examples of the sulfonium cation represented by formula (cation-1) include those represented by the following formula: [ka] (In the formula, the dashed line indicates R 13 )

[0161] Examples of the sulfonium cation represented by formula (cation-1) include, but are not limited to, those shown below.

[0162]

change

[0163]

change

[0164]

change

[0165]

change

[0166]

change

[0167]

change

[0168]

change

[0169]

change

[0170]

change

[0171]

change

[0172]

change

[0173] [ka]

[0174] [ka]

[0175] [ka]

[0176] [ka]

[0177] [ka]

[0178] [ka]

[0179] [ka]

[0180] [ka]

[0181] Examples of the iodonium cation represented by formula (cation-2) include, but are not limited to, those shown below. [ka]

[0182] Specific structures of the repeating units represented by formulae (C1) to (C4) include any combination of the above-mentioned anions and cations.

[0183] As the repeating unit C, repeating units c2, c3 and c4 are preferred from the viewpoint of controlling acid diffusion, repeating units c2 and c4 are more preferred from the viewpoint of the acid strength of the generated acid, and repeating unit c2 is more preferred from the viewpoint of solvent solubility.

[0184] The polymer compound may further contain a repeating unit having a structure in which a hydroxy group is protected by an acid labile group (hereinafter also referred to as repeating unit d). The repeating unit d is not particularly limited as long as it has one or more structures in which a hydroxy group is protected and the protecting group is decomposed by the action of an acid to generate a hydroxy group, but is preferably one represented by the following formula (d1): [ka]

[0185] In formula (d1), R A is the same as above. R 41 R is a (d+1)-valent hydrocarbon group having 1 to 30 carbon atoms which may contain a heteroatom. 42 is an acid labile group. d is an integer of 1 to 4.

[0186] In formula (d1), R 42 The acid labile group represented by R may be any group that can be deprotected by the action of an acid to generate a hydroxy group. 42 Although the structure is not particularly limited, an acetal structure, a ketal structure, an alkoxycarbonyl group, an alkoxymethyl group represented by the following formula (d2), and the like are preferred, and an alkoxymethyl group represented by the following formula (d2) is particularly preferred. [ka] (In the formula, the dashed lines represent bonds. R 43 is a hydrocarbyl group having 1 to 15 carbon atoms.

[0187] R 42 Examples of the acid-labile group represented by the formula, the alkoxymethyl group represented by the formula (d2), and the repeating unit d are the same as those exemplified in the description of the repeating unit d described in JP-A-2020-111564.

[0188] The polymer compound may further contain a repeating unit e derived from indene, benzofuran, benzothiophene, acenaphthylene, chromone, coumarin, norbornadiene or a derivative thereof. Examples of the monomer that provides the repeating unit e include, but are not limited to, those shown below.

Chemical formula

[0189] The polymer compound may further contain a repeating unit f derived from indane, vinyl pyridine or vinyl carbazole.

[0190] In the polymer of the present invention, the content ratios of the repeating units A, a1, a2, b1, b2, c1 to c4, d, e, and f are preferably 0 < A ≤ 0.8, 0 ≤ a1 ≤ 0.8, 0 ≤ a = 2 ≤ 0.8, 0 ≤ b1 ≤ 0.6, 0 ≤ b2 ≤ 0.6, 0 ≤ c1 ≤ 0.4, 0 ≤ c2 ≤ 0.4, 0 ≤ c3 ≤ 0.4, 0 ≤ c4 ≤ 0.4, 0 ≤ d ≤ 0.5, 0 ≤ e ≤ 0.3 and 0 ≤ f ≤ 0.3, and more preferably 0 < A ≤ 0.7, 0 ≤ a1 ≤ 0.7, 0 ≤ a2 ≤ 0.7, 0 ≤ b1 ≤ 0.5, 0 ≤ b2 ≤ 0.5, 0 ≤ c1 ≤ 0.3, 0 ≤ c2 ≤ 0.3, 0 ≤ c3 ≤ 0.3, 0 ≤ c4 ≤ 0.3, 0 ≤ d ≤ 0.3, 0 ≤ e ≤ 0.3 and 0 ≤ f ≤ 0.3.

[0191] [[ID=2']] The weight-average molecular weight (Mw) of the polymer is preferably 1,000 to 500,000, more preferably 3,000 to 100,000. When Mw is within this range, sufficient etching resistance is obtained, and the difference in dissolution rate before and after exposure is ensured, so there is no risk of a decrease in resolution. In the present invention, Mw is a value measured in terms of polystyrene by gel permeation chromatography (GPC) using tetrahydrofuran (THF) or N,N-dimethylformamide (DMF) as a solvent.

[0192] Furthermore, since the influence of Mw / Mn on the molecular weight distribution of the polymer tends to become greater as the pattern rule becomes finer, in order to obtain a resist composition that is suitable for use with fine pattern dimensions, it is preferable that Mw / Mn be a narrow dispersity of 1.0 to 2.0. If it is within this range, there will be little low-molecular-weight or high-molecular-weight polymer, and there will be no risk of foreign matter being observed on the pattern or deterioration of the pattern shape after exposure.

[0193] To synthesize the polymer, for example, a monomer that provides the repeating unit described above can be polymerized by adding a radical polymerization initiator to the monomer in an organic solvent and heating the mixture.

[0194] Examples of organic solvents used during polymerization include toluene, benzene, THF, diethyl ether, dioxane, cyclohexane, cyclopentane, methyl ethyl ketone (MEK), propylene glycol monomethyl ether acetate (PGMEA), and γ-butyrolactone (GBL). Examples of the 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, and lauroyl peroxide. The amount of these initiators added is preferably 0.01 to 25 mol% based on the total amount of 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 more preferably 2 to 12 hours from the viewpoint of production efficiency.

[0195] The polymerization initiator may be added to the monomer solution and then fed to the reaction vessel. Alternatively, an initiator solution may be prepared separately from the monomer solution and then fed to the reaction vessel independently. Because radicals generated from the initiator during the waiting time may cause the polymerization reaction to proceed, resulting in the formation of ultra-high molecular weight polymers, it is preferable to prepare the monomer solution and the initiator solution independently and add them dropwise from the perspective of quality control. The acid labile group introduced into the monomer may be used as is, or may be protected or partially protected after polymerization. Furthermore, known chain transfer agents such as dodecyl mercaptan and 2-mercaptoethanol may be used in combination to adjust the molecular weight. In this case, the amount of these chain transfer agents added is preferably 0.01 to 20 mol % of the total amount of monomers to be polymerized.

[0196] In the case of a monomer containing a hydroxy group, the hydroxy group may be substituted with an acetal group, such as an ethoxyethoxy group, which is easily deprotected by an acid, during polymerization, and then deprotected with a weak acid and water after polymerization. Alternatively, the hydroxy group may be substituted with an acetyl group, a formyl group, a pivaloyl group, or the like, and then subjected to alkaline hydrolysis after polymerization.

[0197] When copolymerizing hydroxystyrene or hydroxyvinylnaphthalene, hydroxystyrene or hydroxyvinylnaphthalene and other monomers may be polymerized by heating in an organic solvent with the addition of a radical polymerization initiator. Alternatively, acetoxystyrene or acetoxyvinylnaphthalene may be used, and after polymerization, the acetoxy group may be deprotected by alkaline hydrolysis to form polyhydroxystyrene or hydroxypolyvinylnaphthalene.

[0198] The base that can be used in alkaline hydrolysis includes aqueous ammonia, triethylamine, etc. 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.

[0199] The amount of each monomer in the monomer solution may be appropriately set so as to achieve the preferred content ratio of the repeating units described above.

[0200] The polymer obtained by the above-mentioned production method may be a reaction solution obtained by a polymerization reaction as a final product, or a powder obtained through a purification step such as a reprecipitation method in which a polymerization solution is added to a poor solvent to obtain a powder, and the resulting powder may be handled as a final product. However, from the viewpoint of work efficiency and quality stability, it is preferable to handle a polymer solution obtained by dissolving the powder obtained by the purification step in a solvent as a final product.

[0201] Specific examples of the solvent used in this case include ketones such as cyclohexanone and methyl-2-n-pentyl ketone, as described in paragraphs

[0144] to

[0145] of JP-A No. 2008-111103; alcohols such as 3-methoxybutanol, 3-methyl-3-methoxybutanol, 1-methoxy-2-propanol, and 1-ethoxy-2-propanol; 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 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 diacetone alcohol (DAA); high-boiling alcohol solvents such as diethylene glycol, propylene glycol, glycerin, 1,4-butanediol, and 1,3-butanediol; and mixed solvents thereof.

[0202] The concentration of the polymer in the polymer solution is preferably 0.01 to 30% by mass, more preferably 0.1 to 20% by mass.

[0203] The reaction solution and polymer solution are preferably filtered through a filter, which is effective in stabilizing quality by removing foreign matter and gels that may cause defects.

[0204] Examples of filter materials used in the above-mentioned filter filtration include fluorocarbon, cellulose, nylon, polyester, and hydrocarbon-based materials. However, in the filtration process of the resist composition, filters made of fluorocarbons, such as Teflon (registered trademark), hydrocarbons such as polyethylene and polypropylene, or nylon are preferred. The pore size of the filter can be selected appropriately depending on the target cleanliness, but is preferably 100 nm or less, more preferably 20 nm or less. These filters may be used alone or in combination. The filtration method may involve passing the solution through the filter only once, but it is more preferable to circulate the solution and filter it multiple times. The filtration process can be performed in any order and any number of times in the polymer production process. However, it is preferable to filter the reaction solution after the polymerization reaction, the polymer solution, or both.

[0205] The polymers may be used singly or in combination of two or more different in composition ratio, Mw, and / or Mw / Mn. The polymer compound of the present invention may contain, in addition to the polymers, a hydrogenated ring-opening metathesis polymer, and the one described in JP-A-2003-66612 can be used.

[0206] [(B) Organic solvent] The organic solvent for component (B) is not particularly limited as long as it can dissolve the components described above and below. 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; ketoalcohols such as DAA; 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 monotert-butyl ether acetate; lactones such as GBL, and mixtures thereof.

[0207] Of these organic solvents, 1-ethoxy-2-propanol, PGMEA, cyclohexanone, GBL, DAA, and mixed solvents thereof are preferred, as they have particularly excellent solubility for the polymer compound of component (A).

[0208] The amount of the organic solvent used is preferably 200 to 5,000 parts by mass, more preferably 400 to 3,500 parts by mass, relative to 80 parts by mass of the (A) polymer compound. The (B) organic solvent may be used alone or in combination of two or more.

[0209] [(C) Quencher] The quencher (C) may be an onium salt represented by the following general formula (1)' or (2)'. [ka]

[0210] In the above general formula (1′), R q1is a hydrogen atom or a hydrocarbyl group having 1 to 40 carbon atoms which may contain a heteroatom, but excludes those in which the hydrogen atom bonded to the carbon atom at the α-position of the sulfo group is substituted with a fluorine atom or a fluoroalkyl group. q2 is a hydrogen atom or a hydrocarbyl group having 1 to 40 carbon atoms which may contain a heteroatom.

[0211] R q1 Specific examples of the hydrocarbyl group represented by the formula (I) include alkyl groups such as a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, a tert-butyl group, an n-pentyl group, a tert-pentyl group, an n-hexyl group, an n-octyl group, a 2-ethylhexyl group, an n-nonyl group, and an n-decyl group; a cyclopentyl group, a cyclohexyl group, a cyclopentylmethyl group, a cyclopentylethyl group, a cyclopentylbutyl group, a cyclohexylmethyl group, a cyclohexylethyl group, a cyclohexylbutyl group, a norbornyl group, and a tricyclo[5.2.1.0] group. 2,6 cyclic saturated hydrocarbyl groups such as a ]decanyl group and an adamantyl group; and aryl groups such as a phenyl group, a naphthyl group and an anthracenyl group. In addition, some or all of the hydrogen atoms of these groups may be substituted with heteroatom-containing groups such as oxygen atoms, sulfur atoms, nitrogen atoms and halogen atoms, or some of the carbon atoms of these groups may be substituted with heteroatom-containing groups such as oxygen atoms, sulfur atoms and nitrogen atoms, and as a result, they may contain hydroxy groups, cyano groups, carbonyl groups, ether bonds, ester bonds, sulfonate ester bonds, carbonate bonds, lactone rings, sultone rings, carboxylic acid anhydrides, haloalkyl groups, etc.

[0212] R q2 Specific examples of the hydrocarbyl group represented by R q1 In addition to the specific examples of the substituents, examples include fluorinated alkyl groups such as a trifluoromethyl group and a trifluoroethyl group, and fluorinated aryl groups such as a pentafluorophenyl group and a 4-trifluoromethylphenyl group.

[0213] Examples of the anion of the onium salt represented by the above general formula (1)' include, but are not limited to, those shown below.

[0214] [ka]

[0215] [ka]

[0216] Examples of the anion of the onium salt represented by the above general formula (2)' include, but are not limited to, those shown below.

[0217] [ka]

[0218] [ka]

[0219] In the above general formulas (1)' and (2'), Mq + is an onium cation. The onium cation is preferably one represented by the following formula (cation-1), (cation-2) or (cation-3). [ka]

[0220] Regarding formulas (cation-1) and (cation-2), A in formulas (C2) to (C4) + (cation-3) In R 16 ~R 19 are each independently a hydrocarbyl group having 1 to 40 carbon atoms which may contain a heteroatom. 16 and R 17and may be bonded to each other to form a ring together with the nitrogen atom to which they are bonded. The hydrocarbyl group includes R 11 ~R 15 Examples of the above-mentioned examples are the same as those given in the explanation of the above.

[0221] MQ + In the onium cation represented by the formula (1), examples of the ammonium cation represented by (cation-3) include, but are not limited to, those shown below. [ka]

[0222] Specific examples of the onium salts represented by the general formula (1)' or (2)' include any combination of the anions and cations described above. These onium salts can be easily prepared by ion exchange reactions using known organic chemistry methods. For details on ion exchange reactions, see, for example, JP-A-2007-145797.

[0223] The onium salts represented by the general formula (1)' or (2)' function as quenchers in the chemically amplified resist composition of the present invention. This is because the counter anions of the onium salts are the conjugate bases of weak acids. The term "weak acid" used here refers to an acidity that is insufficient to deprotect the acid labile groups in the acid labile group-containing units used in the base polymer.

[0224] The onium salts represented by the general formula (1)' or (2)' function as quenchers when used in combination with an onium salt-type photoacid generator having a counter anion that is a conjugate base of a strong acid, such as a sulfonic acid fluorinated at the α-position. Specifically, when an onium salt that generates a strong acid, such as a sulfonic acid fluorinated at the α-position, is mixed with an onium salt that generates a weak acid, such as a non-fluorinated sulfonic acid or carboxylic acid, the strong acid generated from the photoacid generator upon irradiation with high-energy radiation collides with an onium salt having an unreacted weak acid anion, releasing the weak acid through salt exchange and generating an onium salt having a strong acid anion. In this process, the strong acid is exchanged for a weak acid with lower catalytic activity, apparently deactivating the acid and enabling control of acid diffusion.

[0225] Furthermore, as the (C) quencher, onium salts having a sulfonium cation and a phenoxide anion moiety in the same molecule as described in Japanese Patent No. 6,848,776, onium salts having a sulfonium cation and a carboxylate anion moiety in the same molecule as described in Japanese Patent No. 6,583,136 and JP-A No. 2020-200311, and onium salts having an iodonium cation and a carboxylate anion moiety in the same molecule as described in Japanese Patent No. 6,274,755 can also be used.

[0226] Here, when the photoacid generator that generates a strong acid is an onium salt, the strong acid generated by irradiation with high-energy rays can be exchanged for a weak acid as described above, but on the other hand, it is thought that the weak acid generated by irradiation with high-energy rays collides with the unreacted onium salt that generates the strong acid, making it difficult to carry out salt exchange. This is due to the phenomenon that the onium cation is more likely to form an ion pair with the anion of the strong acid.

[0227] When the onium salt-type quencher (C) contains an onium salt represented by the above general formula (1)' or (2)', the content thereof is preferably 0.1 to 20 parts by mass, more preferably 0.1 to 10 parts by mass, relative to 80 parts by mass of the polymer compound (A). It is preferable that the onium salt-type quencher of component (C) is in the above range, since the resolution is good and there is no significant decrease in sensitivity. The onium salt represented by formula (1)' or (2)' can be used alone or in combination of two or more.

[0228] The chemically amplified resist composition of the present invention may further contain a nitrogen-containing quencher. In the present invention, the nitrogen-containing quencher is a material that traps the acid generated by the photoacid generator in the chemically amplified resist composition, thereby preventing the acid from diffusing to unexposed areas and forming a desired pattern.

[0229] Examples of the nitrogen-containing quencher of component (C) include primary, secondary, or tertiary amine compounds described in paragraphs

[0146] to

[0164] of JP 2008-111103 A, particularly amine compounds having a hydroxy group, an ether bond, an ester bond, a lactone ring, a cyano group, or a sulfonate ester bond. Also included are compounds in which a primary or secondary amine is protected with a carbamate group, such as the compounds described in JP 3790649 A.

[0230] Alternatively, a sulfonate sulfonium salt having a nitrogen-containing substituent may be used as a nitrogen-containing quencher. Such a compound functions as a quencher in unexposed areas and loses its quenching ability in exposed areas by neutralizing with the acid generated by the compound itself, functioning as a so-called photodegradable base. The use of a photodegradable base can further enhance the contrast between exposed and unexposed areas. For example, JP-A Nos. 2009-109595 and 2012-46501 can be used as references for the photodegradable base.

[0231] When a nitrogen-containing quencher (C) is contained, 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 polymer compound (A). The nitrogen-containing compounds can be used singly or in combination of two or more.

[0232] [(D) Acid generator (photoacid generator)] The chemically amplified resist composition of the present invention may contain, as component (D), an acid generator (photoacid generator) other than the repeating units c1 to c4 of component (A). There are no particular limitations on the photoacid generator, so long as it is a compound that generates an acid upon exposure to high-energy rays. Suitable other photoacid generators include those represented by the following general formula (3) or (4): [ka]

[0233] In the above general formula (3), R 101 ~R 105 are each independently a hydrocarbyl group having 1 to 20 carbon atoms which may contain a heteroatom. 101 , R 102 and R 103 Any two of these may be bonded to each other to form a ring together with the sulfur atom to which they are bonded. The hydrocarbyl group includes R 11 ~R 15 Examples of the above-mentioned examples are the same as those given in the explanation of the above.

[0234] In the above general formula (3), examples of the sulfonium cation include the same as those exemplified as the sulfonium cation represented by formula (cation-1).

[0235] In the above general formula (4), examples of the iodonium cation include the same as those exemplified as the iodonium cation represented by formula (cation-2).

[0236] In the above general formulas (3) and (4), Xa- is a non-nucleophilic counter ion. Examples of the non-nucleophilic counter ion include halide ions such as chloride ion and bromide ion; fluoroalkylsulfonate ions such as triflate ion, 1,1,1-trifluoroethanesulfonate ion and nonafluorobutanesulfonate ion; arylsulfonate ions such as tosylate ion, benzenesulfonate ion, 4-fluorobenzenesulfonate ion and 1,2,3,4,5-pentafluorobenzenesulfonate ion; alkylsulfonate ions such as mesylate ion and butanesulfonate ion; imide ions such as bis(trifluoromethylsulfonyl)imide ion, bis(perfluoroethylsulfonyl)imide ion and bis(perfluorobutylsulfonyl)imide ion; and methide ions such as tris(trifluoromethylsulfonyl)methide ion and tris(perfluoroethylsulfonyl)methide ion.

[0237] Other examples of the non-nucleophilic counter ion include anions selected from the following general formulae (1A) to (1D). [ka]

[0238] In the above general formula (1A), R fa is a hydrocarbyl group having 1 to 40 carbon atoms which may contain a fluorine atom or a heteroatom. The hydrocarbyl group may be saturated or unsaturated, and may be linear, branched, or cyclic. Specific examples thereof include R in the general formula (1A') described below. fa1 Examples of the hydrocarbyl group represented by the formula (I) include the same as those exemplified above.

[0239] The anion represented by the above general formula (1A) is preferably one represented by the following formula (1A'). [ka]

[0240] In formula (1A'), Q1 and Q 2 are each independently a hydrogen atom, a fluorine atom, or a fluorinated alkyl group having 1 to 6 carbon atoms, but in order to improve solvent solubility, it is preferable that at least one of them is a trifluoromethyl group. k is an integer of 0 to 4, and is particularly preferably 1. R fa1 is a hydrocarbyl group having 1 to 50 carbon atoms which may contain a heteroatom. The heteroatom is preferably an oxygen atom, a nitrogen atom, a sulfur atom, a halogen atom, or the like, and more preferably an oxygen atom. In order to obtain high resolution in the formation of a fine pattern, the hydrocarbyl group is particularly preferably one having 6 to 30 carbon atoms.

[0241] In formula (1A'), R fa1 The hydrocarbyl group represented by the formula (I) may be saturated or unsaturated, and may be linear, branched, or cyclic. Specific examples thereof include alkyl groups having 1 to 38 carbon atoms, such as methyl, ethyl, n-propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, pentyl, neopentyl, hexyl, heptyl, 2-ethylhexyl, nonyl, undecyl, tridecyl, pentadecyl, heptadecyl, and icosanyl groups; cyclopentyl, cyclohexyl, 1-adamantyl, 2-adamantyl, 1-adamantylmethyl, norbornyl, and norbornyl groups. Examples of such groups include saturated cyclic hydrocarbyl groups having 3 to 38 carbon atoms, such as an allyl group, a tricyclodecanyl group, a tetracyclododecanyl group, a tetracyclododecanylmethyl group, and a dicyclohexylmethyl group; unsaturated aliphatic hydrocarbyl groups having 2 to 38 carbon atoms, such as an allyl group and a 3-cyclohexenyl group; aryl groups having 6 to 38 carbon atoms, such as a phenyl group, a 1-naphthyl group, a 2-naphthyl group, and a 9-fluorenyl group; aralkyl groups having 7 to 38 carbon atoms, such as a benzyl group and a diphenylmethyl group; and groups obtained by combining these groups.

[0242] Furthermore, some or all of the hydrogen atoms of the 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 some of the -CH- groups of the hydrocarbyl group may be substituted with a group containing a heteroatom such as an oxygen atom, a sulfur atom or a nitrogen atom, and as a result, the hydrocarbyl group may contain a hydroxy group, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a cyano group, a nitro group, a carbonyl group, an ether bond, an ester bond, a sulfonate ester bond, a carbonate bond, a lactone ring, a sultone ring, a carboxylic anhydride (-C(=O)-OC(=O)-), a haloalkyl group, etc. Examples of hydrocarbyl groups containing hetero atoms include tetrahydrofuryl, methoxymethyl, ethoxymethyl, methylthiomethyl, acetamidomethyl, trifluoroethyl, (2-methoxyethoxy)methyl, acetoxymethyl, 2-carboxy-1-cyclohexyl, 2-oxopropyl, 4-oxo-1-adamantyl, and 3-oxocyclohexyl groups.

[0243] In formula (1A'), L a1 is a single bond, an ether bond, an ester bond, a sulfonate ester bond, a carbonate bond or a carbamate bond, but from the viewpoint of synthesis, an ether bond or an ester bond is preferred, and an ester bond is more preferred.

[0244] Examples of the anion represented by formula (1A) include, but are not limited to, the following: 1 is the same as above, and Ac is an acetyl group. [ka]

[0245] [ka]

[0246] [ka]

[0247] [ka]

[0248] [ka]

[0249] [ka]

[0250] [ka]

[0251] [ka]

[0252] In formula (1B), R fb1 and R fb2 are each independently a hydrocarbyl group having 1 to 40 carbon atoms which may contain a fluorine atom or a heteroatom. The hydrocarbyl group may be saturated or unsaturated, and may be linear, branched, or cyclic. Specific examples thereof include R in formula (1A'). fa1 Examples of the hydrocarbyl group represented by R include the same as those exemplified above. fb1 and R fb2 is preferably a fluorine atom or a linear fluorinated alkyl group having 1 to 4 carbon atoms. fb1 and R fb2 means that the groups to which they are bonded (-CF2-SO2-N - -SO2-CF2-) together to form a ring, in which case, R fb1 and R fb2 The group obtained by bonding together is preferably a fluorinated ethylene group or a fluorinated propylene group.

[0253] In formula (1C), R fc1 , R fc2 and R fc3 are each independently a hydrocarbyl group having 1 to 40 carbon atoms which may contain a fluorine atom or a heteroatom. The hydrocarbyl group may be saturated or unsaturated, and may be linear, branched, or cyclic. Specific examples thereof include R in formula (1A'). fa1 Examples of the hydrocarbyl group represented by R include the same as those exemplified above. fc1 , R fc2 and R fc3 is preferably a fluorine atom or a linear fluorinated alkyl group having 1 to 4 carbon atoms. fc1 and R fc2 are groups that are bonded together and bonded to each other (-CF2-SO2-C - -SO2-CF2-) together to form a ring, in which case, R fc1 and R fc2 The group obtained by bonding together is preferably a fluorinated ethylene group or a fluorinated propylene group.

[0254] In formula (1D), R fd is a hydrocarbyl group having 1 to 40 carbon atoms which may contain a heteroatom. The hydrocarbyl group may be saturated or unsaturated, and may be linear, branched, or cyclic. Specific examples thereof include R in formula (1A'). fa1 Examples of the hydrocarbyl group represented by the formula (I) include the same as those exemplified above.

[0255] Examples of the anion represented by formula (1D) include, but are not limited to, those shown below. [ka]

[0256] [ka]

[0257] Further examples of the non-nucleophilic counter ion include anions having an aromatic ring substituted with an iodine atom or a bromine atom, such as those represented by the following formula (1E): [ka]

[0258] In formula (1E), x is an integer that satisfies 1≦x≦3. y and z are integers that satisfy 1≦y≦5, 0≦z≦3, and 1≦y+z≦5. y is preferably an integer that satisfies 1≦y≦3, more preferably 2 or 3. z is preferably an integer that satisfies 0≦z≦2.

[0259] In formula (1E), X BI is an iodine atom or a bromine atom, and when x and / or y are 2 or more, they may be the same or different.

[0260] In formula (1E), L 1 ' is a single bond, an ether bond or an ester bond, or a saturated hydrocarbylene group having 1 to 6 carbon atoms which may contain an ether bond or an ester bond. The saturated hydrocarbylene group may be linear, branched or cyclic.

[0261] In formula (1E), L 2 When x is 1, ' represents a single bond or a divalent linking group having 1 to 20 carbon atoms, and when x is 2 or 3, represents an (x+1)-valent linking group having 1 to 20 carbon atoms, and the linking group may contain an oxygen atom, a sulfur atom, or a nitrogen atom.

[0262] In formula (1E), R 8is a hydroxy group, a carboxy group, a fluorine atom, a chlorine atom, a bromine atom, or an amino group, or a hydrocarbyl group having 1 to 20 carbon atoms, a hydrocarbyloxy group having 1 to 20 carbon atoms, a hydrocarbylcarbonyl group having 2 to 20 carbon atoms, a hydrocarbyloxycarbonyl group having 2 to 10 carbon atoms, a hydrocarbylcarbonyloxy group having 2 to 20 carbon atoms, or a hydrocarbylsulfonyloxy group having 1 to 20 carbon atoms, which may contain a fluorine atom, a chlorine atom, a bromine atom, a hydroxy group, an amino group, an ether bond, an ester bond, or an amide bond, or —N(R 8A )(R 8B ), -N(R 8C )-C(=O)-R 8D or -N(R 8C )-C(=O)-OR 8D R 8A and R 8B are each independently a hydrogen atom or a saturated hydrocarbyl group having 1 to 6 carbon atoms. 8C is a hydrogen atom or a saturated hydrocarbyl group having 1 to 6 carbon atoms, and may contain a halogen atom, a hydroxy group, a saturated hydrocarbyloxy group having 1 to 6 carbon atoms, a saturated hydrocarbylcarbonyl group having 2 to 6 carbon atoms, or a saturated hydrocarbylcarbonyloxy group having 2 to 6 carbon atoms. 8D is an aliphatic hydrocarbyl 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 contain a halogen atom, a hydroxy group, a saturated hydrocarbyloxy group having 1 to 6 carbon atoms, a saturated hydrocarbylcarbonyl group having 2 to 6 carbon atoms, or a saturated hydrocarbylcarbonyloxy group having 2 to 6 carbon atoms. The aliphatic hydrocarbyl group may be saturated or unsaturated and may be linear, branched, or cyclic. The hydrocarbyl group, hydrocarbyloxy group, hydrocarbylcarbonyl group, hydrocarbyloxycarbonyl group, hydrocarbylcarbonyloxy group, and hydrocarbylsulfonyloxy group may be linear, branched, or cyclic. When x and / or z is 2 or more, each R 8 may be the same or different from each other.

[0263] Of these, R 8Examples of the hydroxyl group include -N(R 8C )-C(=O)-R 8D , -N(R 8C )-C(=O)-OR 8D fluorine atom, chlorine atom, bromine atom, methyl group, methoxy group, etc. are preferred.

[0264] In formula (1E), Rf 1 '~Rf 4 Rf ' are each independently a hydrogen atom, a fluorine atom, or a trifluoromethyl group, and at least one of them is a fluorine atom or a trifluoromethyl group. 1 ' and Rf 2 ' may combine to form a carbonyl group. In particular, Rf 3 ' and Rf 4 It is preferable that both of the groups ' are fluorine atoms.

[0265] Examples of the anion of the onium salt represented by formula (1E) include, but are not limited to, those shown below. BI is the same as above. [ka]

[0266] [ka]

[0267] [ka]

[0268] [ka]

[0269] [ka]

[0270]

change

[0271]

change

[0272]

change

[0273]

change

[0274]

change

[0275]

change

[0276]

change

[0277]

change

[0278]

change

[0279]

change

[0280]

change

[0281] [ka]

[0282] [ka]

[0283] [ka]

[0284] [ka]

[0285] [ka]

[0286] [ka]

[0287] [ka]

[0288] Examples of the non-nucleophilic counter ion include a fluorobenzenesulfonate anion bonded to an aromatic group containing an iodine atom as described in Japanese Patent No. 6648726, an anion having a mechanism for decomposing with an acid as described in International Publication No. 2021 / 200056 and Japanese Patent Application Publication No. 2021-070692, an anion having a cyclic ether group as described in Japanese Patent Application Publication No. 2018-180525 and Japanese Patent Application Publication No. 2021-35935, and an anion as described in Japanese Patent Application Publication No. 2018-092159.

[0289] Further examples of the non-nucleophilic counter ion include anions of bulky benzenesulfonic acid derivatives that do not contain fluorine atoms, as described in JP 2006-276759 A, JP 2015-117200 A, JP 2016-65016 A, and JP 2019-202974 A, and benzenesulfonic acid anions and alkylsulfonic acid anions that do not contain fluorine atoms bonded to aromatic groups containing iodine atoms, as described in Japanese Patent No. 6645464 A.

[0290] Further examples of the non-nucleophilic counter ion include the anion of a bissulfonic acid described in JP 2015-206932 A, the anion of a sulfonamide or sulfonimide having a sulfonic acid on one side and a different sulfonic acid on the other side described in WO 2020 / 158366 A, and the anion of a sulfonic acid on one side and a carboxylic acid on the other described in JP 2015-024989 A.

[0291] Furthermore, as the other photoacid generator of component (D), compounds represented by the following formula (5) are also preferred. [ka]

[0292] In formula (5), R 201 and R 202 R are each independently a hydrocarbyl group having 1 to 30 carbon atoms which may contain a heteroatom. 203 is a hydrocarbylene group having 1 to 30 carbon atoms which may contain a heteroatom. 201 , R 202 and R 203 Any two of may be bonded to each other to form a ring together with the sulfur atom to which they are attached.

[0293] R 201 and R 202The hydrocarbyl group represented by the formula (I) may be saturated or unsaturated, and may be linear, branched, or cyclic. Specific examples thereof include alkyl groups having 1 to 30 carbon atoms, such as methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, tert-pentyl, n-pentyl, n-hexyl, n-octyl, 2-ethylhexyl, n-nonyl, and n-decyl; cyclopentyl, cyclohexyl, cyclopentylmethyl, cyclopentylethyl, cyclopentylbutyl, cyclohexylmethyl, cyclohexylethyl, cyclohexylbutyl, norbornyl, oxanorbornyl, and tricyclo[5.2.1.0]. 2,6 cyclic saturated hydrocarbyl groups having 3 to 30 carbon atoms such as a phenyl group, a methylphenyl group, an ethylphenyl group, an n-propylphenyl group, an isopropylphenyl group, an n-butylphenyl group, an isobutylphenyl group, a sec-butylphenyl group, a tert-butylphenyl group, a naphthyl group, a methylnaphthyl group, an ethylnaphthyl group, an n-propylnaphthyl group, an isopropylnaphthyl group, an n-butylnaphthyl group, an isobutylnaphthyl group, a sec-butylnaphthyl group, a tert-butylnaphthyl group, an anthracenyl group, and the like; and groups obtained by combining these. Furthermore, some or all of the hydrogen atoms of the 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, or some of the -CH- constituting the hydrocarbyl group may be substituted with a group containing a heteroatom such as an oxygen atom, a sulfur atom or a nitrogen atom, and as a result, the hydrocarbyl group may contain a hydroxy 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 ester bond, a carbonate bond, a lactone ring, a sultone ring, a carboxylic acid anhydride, a haloalkyl group, or the like.

[0294] R 203The hydrocarbylene group represented by the formula (I) may be saturated or unsaturated, and may be linear, branched, or cyclic. Specific examples thereof include alkanediyl groups having 1 to 30 carbon atoms, such as 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, and heptadecane-1,17-diyl; cyclopentanediyl; and cyclic saturated hydrocarbylene groups having 3 to 30 carbon atoms, such as a cyclohexanediyl group, a cyclohexanediyl group, a norbornanediyl group, or an adamantanediyl group; and cyclic unsaturated hydrocarbylene groups, such as a phenylene group, a methylphenylene group, an ethylphenylene group, an n-propylphenylene group, an isopropylphenylene group, an n-butylphenylene group, an isobutylphenylene group, a sec-butylphenylene group, a tert-butylphenylene group, a naphthylene group, a methylnaphthylene group, an ethylnaphthylene group, an n-propylnaphthylene group, an isopropylnaphthylene group, an n-butylnaphthylene group, an isobutylnaphthylene group, a sec-butylnaphthylene group, or a tert-butylnaphthylene group. In addition, some or all of the hydrogen atoms of the hydrocarbylene 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, or some of the -CH- constituting the hydrocarbylene group may be substituted with a group containing a heteroatom such as an oxygen atom, a sulfur atom or a nitrogen atom, resulting in the hydrocarbylene group containing a hydroxy 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 ester bond, a carbonate bond, a lactone ring, a sultone ring, a carboxylic acid anhydride or a haloalkyl group. The heteroatom is preferably an oxygen atom.

[0295] In formula (5), L Ais a single bond, an ether bond, or a hydrocarbylene group having 1 to 20 carbon atoms which may contain a heteroatom. The hydrocarbylene group may be saturated or unsaturated, and may be linear, branched, or cyclic. Specific examples thereof include R 203 Examples of the hydrocarbylene group represented by the formula (I) include the same as those exemplified above.

[0296] In formula (5), X a , X b , X c and X d are each independently a hydrogen atom, a fluorine atom, or a trifluoromethyl group, provided that X a , X b , X c and X d At least one of the groups is a fluorine atom or a trifluoromethyl group.

[0297] The photoacid generator represented by formula (5) is preferably one represented by the following formula (5'). [ka]

[0298] In formula (5'), L A is the same as above. X e is a hydrogen atom or a trifluoromethyl group, preferably a trifluoromethyl group. 301 , R 302 and R 303 are each independently a hydrogen atom or a hydrocarbyl group having 1 to 20 carbon atoms which may contain a heteroatom. The hydrocarbyl group may be saturated or unsaturated, and may be linear, branched, or cyclic. Specific examples thereof include R in formula (3): 101 Examples of the hydrocarbyl group represented by m include the same as those exemplified above. 1 and m 2 are each independently an integer of 0 to 5, and m 3 is an integer from 0 to 4.

[0299] Examples of the photoacid generator represented by formula (5) include the same compounds as those exemplified as the photoacid generator represented by formula (2) in JP-A-2017-026980.

[0300] Among the other photoacid generators, those containing an anion represented by formula (1A') or (1D) are particularly preferred because of their small acid diffusion and excellent solubility in solvents. Also, those represented by formula (5') are particularly preferred because of their extremely small acid diffusion.

[0301] When an acid generator (D), particularly a photoacid generator, is included, its content is preferably 0.1 to 40 parts by mass, and more preferably 0.5 to 20 parts by mass, relative to 80 parts by mass of the polymer compound (A). When the amount of the acid generator (D) added is within the above range, the resolution is good and there is no risk of problems with foreign matter occurring after development of the resist film or during stripping, which is preferable. The acid generator (D) may be used alone or in combination of two or more.

[0302] [(E) A surfactant that is insoluble or slightly soluble in water but soluble in an alkaline developer, and / or a surfactant that is insoluble or slightly soluble in water and an alkaline developer] The resist composition of the present invention, particularly the chemically amplified resist composition, may further comprise (E) a surfactant that is insoluble or slightly soluble in water but soluble in an alkaline developer, and / or a surfactant that is insoluble or slightly soluble in water and an alkaline developer. Examples of such surfactants include those described in JP-A-2010-215608 and JP-A-2011-16746.

[0303] Among the surfactants described in the above publications, preferred surfactants that are insoluble or slightly soluble in water and alkaline developers include FC-4430 (manufactured by 3M), Surflon (registered trademark) S-381 (manufactured by AGC Seimi Chemical Co., Ltd.), Olfine (registered trademark) E1004 (manufactured by Nissin Chemical Industry Co., Ltd.), KH-20, KH-30 (manufactured by AGC Seimi Chemical Co., Ltd.), and oxetane ring-opening polymers represented by the following formula (surf-1): [ka]

[0304] Here, R, Rf, A, B, C, m, and n apply only to formula (surf-1), regardless of the above descriptions. R is a divalent to tetravalent aliphatic group having 2 to 5 carbon atoms. Examples of the divalent aliphatic group include an ethylene group, a 1,4-butylene group, a 1,2-propylene group, a 2,2-dimethyl-1,3-propylene group, and a 1,5-pentylene group, and examples of the trivalent or tetravalent aliphatic group include the following: [ka] (In the formula, the dashed lines represent bonds and are partial structures derived from glycerol, trimethylolethane, trimethylolpropane, and pentaerythritol, respectively.)

[0305] Among these, a 1,4-butylene group, a 2,2-dimethyl-1,3-propylene group, and the like are preferred.

[0306] Rf is a trifluoromethyl group or a pentafluoroethyl group, preferably a trifluoromethyl group. m is an integer of 0 to 3, n is an integer of 1 to 4, and the sum of n and m is the valence of R, which is an integer of 2 to 4. A is 1. B is an integer of 2 to 25, preferably an integer of 4 to 20. C is an integer of 0 to 10, preferably 0 or 1. The order of the structural units in formula (surf-1) is not specified, and they may be bonded in blocks or randomly. The production of surfactants based on partially fluorinated oxetane ring-opening polymers is described in detail in the specification of U.S. Pat. No. 5,650,483, etc.

[0307] Surfactants that are insoluble or slightly soluble in water but soluble in alkaline developers have the function of reducing water penetration and leaching by orienting themselves on the surface of the resist film when a resist protective film is not used in ArF immersion lithography. Therefore, they are useful for suppressing the elution of water-soluble components from the resist film and reducing damage to the exposure equipment. Furthermore, they are useful because they become soluble during alkaline aqueous development after exposure (post-exposure bake) and are less likely to become contaminants that cause defects. Such surfactants are insoluble or slightly soluble in water but soluble in alkaline developers. They are also called hydrophobic resins, and are particularly preferred because they have high water repellency and improve water slippage.

[0308] Such polymer surfactants include those containing at least one repeating unit selected from those represented by any of the following formulae (8A) to (8E). [ka]

[0309] In formulas (8A) to (8E), R B is a hydrogen atom, a fluorine atom, a methyl group, or a trifluoromethyl group. 1 is -CH2-, -CH2CH2-, -O- or two -H groups separated from each other. s1 are each independently a hydrogen atom or a hydrocarbyl group having 1 to 10 carbon atoms. s2 R is a single bond or a linear or branched hydrocarbylene group having 1 to 5 carbon atoms. s3 R are each independently a hydrogen atom, a hydrocarbyl group or a fluorinated hydrocarbyl group having 1 to 15 carbon atoms, or an acid labile group. s3 When R is a hydrocarbyl group or a fluorinated hydrocarbyl group, an ether bond or a carbonyl group may be present between the carbon-carbon bonds. s4 is a hydrocarbon group or a fluorinated hydrocarbon group having 1 to 20 carbon atoms and a valence of (u'+1). u' is an integer of 1 to 3. R s5 are each independently a hydrogen atom or -C(=O)-ORs7 R is a group represented by s7 is a fluorinated hydrocarbyl group having 1 to 20 carbon atoms. s6 is a hydrocarbyl group or a fluorinated hydrocarbyl group having 1 to 15 carbon atoms, and an ether bond or a carbonyl group may be present between the carbon-carbon bonds.

[0310] R s1 The hydrocarbyl group represented by the formula (I) may be linear, branched, or cyclic, and specific examples thereof include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, a cyclopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, a cyclobutyl group, an n-pentyl group, a cyclopentyl group, an n-hexyl group, a cyclohexyl group, an n-heptyl group, an n-octyl group, an n-nonyl group, an n-decyl group, an adamantyl group, a norbornyl group, etc. Among these, those having 1 to 6 carbon atoms are preferred.

[0311] R s2 The hydrocarbylene group represented by the formula (I) may be linear, branched or cyclic, and specific examples thereof include a methylene group, an ethylene group, a propylene group, a butylene group, and a pentylene group.

[0312] R s3 or R s6 The hydrocarbyl group represented by the formula (I) may be linear, branched, or cyclic, and specific examples thereof include alkyl groups, alkenyl groups, and alkynyl groups, with alkyl groups being preferred. s1 In addition to the examples of the hydrocarbyl group represented by the formula (R), examples include an n-undecyl group, an n-dodecyl group, a tridecyl group, a tetradecyl group, and a pentadecyl group. s3 or R s6 Examples of the fluorinated hydrocarbyl group represented by the formula (I) include groups in which some or all of the hydrogen atoms bonded to the carbon atoms of the aforementioned hydrocarbyl group have been substituted with fluorine atoms. As mentioned above, an ether bond or a carbonyl group may be present between these carbon-carbon bonds.

[0313] R s3 Examples of the acid labile group represented by the formula (L1) to (L4) include the groups represented by the formulas (L1) to (L4) above, tertiary hydrocarbyl groups having 4 to 20 carbon atoms, preferably 4 to 15 carbon atoms, trialkylsilyl groups in which each alkyl group has 1 to 6 carbon atoms, and oxoalkyl groups having 4 to 20 carbon atoms.

[0314] R s4 The (u'+1)-valent hydrocarbon group or fluorinated hydrocarbon group represented by the formula (I) may be linear, branched, or cyclic, and specific examples thereof include groups obtained by further eliminating u hydrogen atoms from the aforementioned hydrocarbyl group or fluorinated hydrocarbyl group.

[0315] R s7 The fluorinated hydrocarbyl group represented by the formula (I) may be linear, branched or cyclic, and specific examples thereof include those in which some or all of the hydrogen atoms of the hydrocarbyl group have been substituted with fluorine atoms. Specific examples thereof include a trifluoromethyl group, a 2,2,2-trifluoroethyl group, a 3,3,3-trifluoro-1-propyl group, a 3,3,3-trifluoro-2-propyl group, a 2,2,3,3-tetrafluoropropyl group, a 1,1,1 , 3,3,3-hexafluoroisopropyl group, 2,2,3,3,4,4,4-heptafluorobutyl group, 2,2,3,3,4,4,5,5-octafluoropentyl group, 2,2,3,3,4,4,5,5,6,6,7,7-dodecafluoroheptyl group, 2-(perfluorobutyl)ethyl group, 2-(perfluorohexyl)ethyl group, 2-(perfluorooctyl)ethyl group, 2-(perfluorodecyl)ethyl group, and the like.

[0316] Examples of the repeating unit represented by any one of formulas (8A) to (8E) include, but are not limited to, the following: B is the same as above. [ka]

[0317] [ka]

[0318] [ka]

[0319] [ka]

[0320] [ka]

[0321] The polymer surfactant may further contain other repeating units in addition to the repeating units represented by formulae (8A) to (8E). Examples of such other repeating units include repeating units obtained from methacrylic acid and α-trifluoromethylacrylic acid derivatives. In the polymer surfactant, the content of the repeating units represented by formulae (8A) to (8E) is preferably 20 mol % or more, more preferably 60 mol % or more, and even more preferably 100 mol %, of all repeating units.

[0322] The Mw of the polymer surfactant is preferably from 1,000 to 500,000, and more preferably from 3,000 to 100,000. The Mw / Mn is preferably from 1.0 to 2.0, and more preferably from 1.0 to 1.6.

[0323] The polymer surfactant can be synthesized by heating a monomer containing an unsaturated bond that provides the repeating units represented by formulas (8A) to (8E) and, if necessary, other repeating units, in an organic solvent with the addition of a radical initiator to polymerize the monomer. Examples of organic solvents used in polymerization include toluene, benzene, THF, diethyl ether, and dioxane. Examples of polymerization initiators include AIBN, 2,2'-azobis(2,4-dimethylvaleronitrile), dimethyl 2,2-azobis(2-methylpropionate), benzoyl peroxide, and lauroyl peroxide. The reaction temperature is preferably 50 to 100°C. The reaction time is preferably 4 to 24 hours. The acid labile group introduced into the monomer may be used as is, or may be protected or partially protected after polymerization.

[0324] When synthesizing the polymer surfactant, known chain transfer agents such as dodecyl mercaptan and 2-mercaptoethanol may be used to adjust the molecular weight. In this case, the amount of the chain transfer agent added is preferably 0.01 to 10 mol % based on the total number of moles of the monomers to be polymerized.

[0325] When a surfactant (E) is included, its content is preferably 0.1 to 50 parts by mass, and more preferably 0.5 to 10 parts by mass, relative to 80 parts by mass of the polymer compound (A). If the added amount is 0.1 part by mass or more, the receding contact angle between the resist film surface and water is sufficiently improved, and if it is 50 parts by mass or less, the dissolution rate of the resist film surface in the developer is low, and the height of the formed fine pattern is sufficiently maintained.

[0326] [(F) Other ingredients] The chemically amplified resist composition of the present invention may contain, as other components (F), a compound that decomposes in the presence of acid to generate acid (acid amplifying compound), an organic acid derivative, a fluorine-substituted alcohol, or a compound with a Mw of 3,000 or less whose solubility in a developer changes upon the action of acid (dissolution inhibitor). Examples of the acid amplifying compound include the compounds described in JP-A-2009-269953 and JP-A-2010-215608. When the acid amplifying compound is contained, its content is preferably 0 to 5 parts by weight, more preferably 0 to 3 parts by weight, relative to 80 parts by weight of the polymeric compound (A). A content of 5 parts by weight or less facilitates control of acid diffusion, preventing degradation of resolution and pattern shape. Examples of the organic acid derivative, fluorine-substituted alcohol, and dissolution inhibitor include the compounds described in JP-A-2009-269953 and JP-A-2010-215608.

[0327] [Pattern formation method] The present invention provides a pattern forming method comprising the steps of: forming a resist film on a substrate using the resist composition of the present invention; exposing the resist film to high-energy rays; and developing the exposed resist film using a developer.

[0328] The pattern forming method of the present invention includes the steps of forming a resist film on a substrate using the above-mentioned resist composition, particularly the chemically amplified resist composition; exposing the resist film to KrF excimer laser light, ArF excimer laser light, EB, or EUV; and developing the exposed resist film using a developer.

[0329] The substrate may be, for example, a substrate for integrated circuit manufacturing (Si, SiO2, SiN, SiON, TiN, WSi, BPSG, SOG, organic anti-reflective coating, etc.) or a substrate for mask circuit manufacturing (Cr, CrO, CrON, MoSi2, SiO2, etc.).

[0330] The resist film can be formed, for example, by applying the chemically amplified resist composition by a method such as spin coating to a film thickness of 0.05 to 2 μm, and then pre-baking the applied composition 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.

[0331] The high-energy radiation is preferably KrF excimer laser light, ArF excimer laser light, electron beam, or extreme ultraviolet light with a wavelength of 3 to 15 nm.

[0332] When KrF excimer laser light, ArF excimer laser light, or EUV is used to expose the resist film, a mask for forming a desired pattern is used, and the exposure dose is preferably 1 to 200 mJ / cm . 2 , more preferably 10 to 100 mJ / cm 2 When EB is used, the exposure dose is preferably 1 to 300 μC / cm 2 , either directly or through a mask for forming a desired pattern. 2 , more preferably 10 to 200 μC / cm 2 Irradiate so that

[0333] In addition to the usual exposure method, the immersion method can also be used, in which a liquid with a refractive index of 1.0 or higher is placed between the resist film and the projection lens. In this case, a water-insoluble protective film can also be used.

[0334] The water-insoluble protective film is used to prevent elution from the resist film and increase the water sliding property of the film surface. It can be broadly divided into two types. One is an organic solvent-removable type that requires stripping before alkaline aqueous development using an organic solvent that does not dissolve the resist film. The other is an alkaline aqueous solution-soluble type that is soluble in alkaline developer and removes the protective film along with removing the soluble portion of the resist film. The latter is particularly based on a polymer containing 1,1,1,3,3,3-hexafluoro-2-propanol residues that is insoluble in water but soluble in alkaline developer, and is preferably dissolved in an alcohol solvent with 4 or more carbon atoms, an ether solvent with 8 to 12 carbon atoms, or a mixed solvent thereof. Materials can also be prepared by dissolving the water-insoluble, alkaline developer-soluble surfactant described above in an alcohol solvent with 4 or more carbon atoms, an ether solvent with 8 to 12 carbon atoms, or a mixed solvent thereof.

[0335] After the exposure, PEB may be performed by heating on a hot plate, for example, preferably at 60 to 150° C. for 1 to 5 minutes, more preferably at 80 to 140° C. for 1 to 3 minutes.

[0336] The development is carried out using a developer, for example, an alkaline aqueous solution of tetramethylammonium hydroxide (TMAH) or the like, preferably at 0.1 to 5 mass %, more preferably 2 to 3 mass %, for preferably 0.1 to 3 minutes, more preferably 0.5 to 2 minutes, by a conventional method such as dipping, puddling, or spraying, whereby the exposed areas are dissolved and the desired pattern is formed on the substrate.

[0337] As a means for forming a pattern, after forming a resist film, a pure water rinse (post-soak) may be performed to extract an acid generator or the like from the film surface or to wash away particles, or a rinse (post-soak) may be performed to remove water remaining on the film after exposure.

[0338] Furthermore, the pattern may be formed by a double patterning method, such as a trench method in which a first exposure and etching process is performed to process an underlayer with a 1:3 trench pattern, and then a second exposure process is performed with a shifted position to form a 1:3 trench pattern, thereby forming a 1:1 pattern, or a line method in which a first underlayer with a 1:3 isolated leave pattern is processed by a first exposure and etching process, and then a second exposure process is performed with a shifted position to process a second underlayer with a 1:3 isolated leave pattern formed below the first underlayer, thereby forming a 1:1 pattern with half the pitch.

[0339] In the pattern forming method of the present invention, a negative tone development method in which an organic solvent is used as the developer instead of the aqueous alkaline solution may be used to dissolve the unexposed areas.

[0340] The organic solvent development may be performed using the following developers: 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, propyl methyl methyl valerate, methyl pentenoate, methyl crotonate, ethyl methyl crotonate, propyl methyl methyl valerate, propyl methyl methyl pentenoate, propyl methyl methyl crotonate, propyl methyl methyl methyl crotonate, propyl methyl methyl methyl valerate, propyl methyl methyl pentenoate, propyl methyl methyl methyl crotonate, propyl methyl methyl methyl hexano ... Examples of organic solvents that can be used include 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, benzyl formate, phenylethyl formate, methyl 3-phenylpropionate, benzyl propionate, ethyl phenylacetate, and 2-phenylethyl acetate. These organic solvents may be used alone or in combination of two or more. [Example]

[0341] The present invention will be specifically explained below by showing synthesis examples, examples, and comparative examples, but the present invention is not limited to the following examples. The apparatuses used are as follows. IR: Thermo Fisher Scientific NICOLET 6700 · 1 H-NMR: ECA-500 manufactured by JEOL Ltd. MALDI TOF-MS: JEOL S3000

[0342] [1] Synthesis of polymerizable monomers [Example 1-1] Synthesis of Monomer A1 (1) Synthesis of intermediate Pre-A1 [ka] Under a nitrogen atmosphere, sodium hydride (purity 55% by mass, 30.6 g) was suspended in THF (170 ml), and a solution consisting of 1-methylcyclopentanol (80.0 g) and THF (80 ml) was added dropwise. After the dropwise addition, the mixture was heated under reflux for 4 hours to prepare a metal alkoxide. Then, raw material M-1 (181.3 g) was added dropwise, and the mixture was heated under reflux and aged for 18 hours. The reaction solution was cooled in an ice bath, and the reaction was quenched with water (300 ml). The target product was extracted twice with a solvent consisting of toluene (200 ml) and hexane (200 ml), followed by standard aqueous work-up. The solvent was distilled off, and the resulting mixture was purified by distillation to obtain 154.0 g of intermediate Pre-A1 as a colorless oil (62% yield).

[0343] (2) Synthesis of Monomer A1 [ka] A Grignard reagent was prepared from magnesium (9.4 g), THF (110 g), and intermediate Pre-A1 (104.7 g) under a nitrogen atmosphere. The reaction mixture was diluted with toluene (55 g) and cooled to below 10°C. Subsequently, [1,3-bis(diphenylphosphino)propane]nickel(II) dichloride (1.0 g) was added and stirred at an internal temperature of below 10°C for 30 minutes. After stirring, a solution consisting of vinyl bromide (50.9 g), THF (55 g), and toluene (55 g) was added dropwise while maintaining the internal temperature below 20°C. After the addition, the mixture was aged for 1 hour at an internal temperature below 20°C. After aging, the reaction mixture was cooled, and an aqueous solution consisting of ammonium chloride (40 g), 20% by weight hydrochloric acid (40 g), and water (200 g) was added dropwise to quench the reaction. Thereafter, the target substance was extracted with hexane (100 g), subjected to a conventional aqueous work-up, and after the solvent was distilled off, the residue was purified by distillation to obtain 63.3 g of Monomer A1 as a colorless oil (yield 74%).

[0344] IR spectrum data and nuclear magnetic resonance spectrum ( 1 The results of H-NMR / DMSO-d6) are shown below. IR(D-ATR): ν= 2971, 2876, 1599, 1583, 1504, 1450, 1417, 1393, 1379, 1252, 1225, 1202, 1168, 1121, 1031, 986, 967, 913, 870, 832, 801, 754, 697, 628cm -1 . 1 H-NMR (600MHz in DMSO-d6): δ= 7.28(1H, d), 7.18(1H, d), 7.17(1H, d), 6.74(1H, dd), 5.82(1H, d), 5.30(1H, d), 2.01(2H, m), 1.67(6H, m), 1.45(3H, s) ppm.

[0345] [Example 1-2] Synthesis of Monomer A2 [ka]

[0346] Monomer A2 was synthesized in the same manner as in Example 1-1, except that 1-methylcyclopentanol was changed to 1-isopropylcyclopentanol (yield: 81.3 g, two-step yield: 68%).

[0347] IR spectrum data and nuclear magnetic resonance spectrum ( 1 The results of H-NMR / DMSO-d6) are shown below. IR(D-ATR): ν= 2966, 2877, 1597, 1584, 1504, 1470, 1454, 1417, 1391, 1369, 1352, 1253, 1225, 1201, 1167, 1122, 1033, 984, 911, 868, 831, 800, 752, 699, 627cm -1 . 1 H-NMR (600MHz in DMSO-d6): δ= 7.27(1H, d), 7.18(1H, d), 7.13(1H, d), 6.74(1H, dd), 5.80(1H, d), 5.29(1H, d), 2.47(2H, m), 1.87(4H, m), 1.54(4H, m), 0.90(6H, d) ppm.

[0348] [Example 1-3] Synthesis of Monomer A3 [ka]

[0349] Monomer A3 was synthesized in the same manner as in Example 1-1, except that the metal alkoxide prepared from 1-methylcyclopentanol and sodium hydride was changed to potassium t-butoxide (yield 92.3 g, two-step yield 66%).

[0350] IR spectrum data and nuclear magnetic resonance spectrum ( 1 The results of H-NMR / DMSO-d6) are shown below. IR(D-ATR): ν= 3092, 2982, 1601, 1581, 1503, 1414, 1393, 1369, 1250, 1224, 1203, 1166, 1121, 1031, 987, 967, 912, 895, 838, 802, 766, 723, 667, 600cm -1 . 1 H-NMR (600MHz in DMSO-d6): δ= 7.28(3H, m), 6.73(1H, dd), 5.84(1H, d), 5.30(1H, d), 1.32(9H, s) ppm.

[0351] [Examples 1-4 to 1-11] Synthesis of Monomers A4 to A11 Various polymerizable monomers were synthesized using the corresponding raw materials and various organic synthesis reactions. The structures of the polymerizable monomers used in the chemically amplified resist compositions are shown below. [ka]

[0352] [2] Synthesis of base polymer Of the monomers used in the synthesis of the base polymer, those other than Monomers A1 to A11 are as follows. [ka]

[0353] [ka]

[0354] [ka]

[0355] [ka]

[0356] [ka]

[0357] [Example 2-1] Synthesis of Polymer P-1 Under a nitrogen atmosphere, a flask was charged with 50.1 g of Monomer A1, 50.1 g of Monomer a1-1, 24.8 g of Monomer b2-1, 38.0 g of Monomer c-1, 3.96 g of V-601 (Wako Pure Chemical Industries, Ltd.), and 127 g of MEK to prepare a monomer-polymerization initiator solution. 46 g of MEK was charged to a separate flask under a nitrogen atmosphere and heated to 80°C with stirring, followed by dropwise addition of the monomer-polymerization initiator solution over 4 hours. After completion of the dropwise addition, stirring was continued for 2 hours while maintaining the temperature of the polymerization solution at 80°C, and then the mixture was cooled to room temperature. The resulting polymerization solution was added dropwise to 2,000 g of vigorously stirred hexane, and the precipitated polymer was filtered off. The resulting polymer was then washed twice with 600 g of hexane and vacuum-dried at 50°C for 20 hours to obtain Polymer P-1 as a white powder (yield: 98.1 g, 98%). Polymer P-1 had an Mw of 9,600 and an Mw / Mn of 1.81. Note that Mw was measured in terms of polystyrene by GPC using DMF as a solvent. [ka]

[0358] [Examples 2-2 to 2-3 - 30, Comparative Examples 1-1 to 1-15] Synthesis of Polymers P-2 to P-30, CP-1 to CP-15 The base polymers shown in Tables 1 and 2 were synthesized in the same manner as in Example 2-1, except that the types and compounding ratios of the respective monomers were changed.

[0359] [Table 1]

[0360] [Table 2]

[0361] [3] Preparation of chemically amplified resist composition [Examples 3-1 to 2-30, Comparative Examples 2-1 to 2-15] The base polymers of the present invention (P-1 to P-30), comparative base polymers (CP-1 to CP-15), photoacid generators (PAG-X to PAG-Y), and quenchers (SQ-1 to SQ-3, AQ-1) were dissolved in a solvent containing 0.01% by mass of surfactant A (Omnova) in the compositions shown in Tables 3 and 4 below to prepare solutions. The solutions were then filtered through a 0.2 μm Teflon (registered trademark) filter to prepare chemically amplified resist compositions (R-1 to R-30, CR-1 to CR-15).

[0362] [Table 3]

[0363] [Table 4]

[0364] In Tables 3 and 4, the components are as follows. Organic solvent: PGMEA (propylene glycol monomethyl ether acetate) DAA (diacetone alcohol)

[0365] Photoacid generator: PAG-X, PAG-Y [ka]

[0366] Quencher: SQ-1 to SQ-3, AQ-1 [ka]

[0367] [4] EUV Lithography Evaluation (1) [Examples 4-1 to 4-30, Comparative Examples 3-1 to 3-15] Each chemically amplified resist composition (R-1 to R-30, CR-1 to CR-15) shown in Tables 3 and 4 was spin-coated onto a Si substrate on which a 20-nm-thick silicon-containing spin-on hard mask SHB-A940 (silicon content: 43% by mass) manufactured by Shin-Etsu Chemical Co., Ltd. had been formed, and the resulting resist film was pre-baked at 100°C for 60 seconds using a hot plate to produce a 50-nm-thick resist film. This was then exposed to an LS pattern with an on-wafer dimension of 18 nm and a pitch of 36 nm using an ASML EUV scanner NXE3300 (NA 0.33, σ 0.9 / 0.6, dipole illumination) while varying the exposure dose and focus (exposure dose pitch: 1 mJ / cm). 2 After exposure, PEB was performed for 60 seconds at the temperatures shown in Tables 5 and 6. Thereafter, puddle development was performed with a 2.38 mass % TMAH aqueous solution for 30 seconds, followed by rinsing with a surfactant-containing rinse material and spin drying to obtain a positive pattern.

[0368] The obtained LS patterns were observed with a critical dimension SEM (CG6300) manufactured by Hitachi High-Technologies Corporation, and the sensitivity, exposure latitude (EL), LWR, depth of focus (DOF), and tilt limit were evaluated according to the following methods. The results are shown in Tables 5 and 6.

[0369] [Sensitivity evaluation] The optimum exposure dose E for obtaining an LS pattern with a line width of 18 nm and a pitch of 36 nm op (mJ / cm 2 The smaller this value, the higher the sensitivity.

[0370] [EL Rating] EL (unit: %) was calculated from the exposure amount formed within a range of ±10% (16.2 to 19.8 nm) of the 18 nm space width in the LS pattern using the following formula: The larger this value, the better the performance. EL(%)=(|E1-E2| / E op ) x 100 E1: Optimal exposure dose for LS pattern with line width of 16.2 nm and pitch of 36 nm E2: Optimal exposure dose for LS pattern with line width of 19.8 nm and pitch of 36 nm E op : Optimal exposure dose to produce LS pattern with line width of 18nm and pitch of 36nm

[0371] [LWR rating] E op The dimensions of the LS pattern obtained by irradiation at 10 points in the longitudinal direction of the line were measured, and the LWR was calculated as three times the standard deviation (σ) (3σ). The smaller this value, the less roughness and the more uniform the line width pattern obtained.

[0372] [DOF evaluation] For the evaluation of the depth of focus, the focus range formed within a range of ±10% (16.2 to 19.8 nm) of the 18 nm dimension of the LS pattern was determined. The larger this value, the wider the depth of focus.

[0373] [Line pattern collapse limit evaluation] The line dimension of the LS pattern at each exposure dose at the optimum focus was measured at 10 points in the longitudinal direction. The thinnest line dimension obtained without collapse was defined as the collapse limit dimension. The smaller this value, the better the collapse limit.

[0374] [Table 5]

[0375] [Table 6]

[0376] The results shown in Tables 5 and 6 demonstrate that the chemically amplified resist composition containing the photoacid generator of the present invention has good sensitivity and excellent EL, LWR, and DOF. It was also confirmed that the collapse limit value was small and that the composition is resistant to pattern collapse even in the formation of fine patterns. This demonstrates that the chemically amplified resist composition of the present invention is suitable as a material for EUV lithography.

[0377] [5] EUV Lithography Evaluation (2) [Examples 5-1 to 5-30, Comparative Examples 4-1 to 4-15] Each chemically amplified resist composition (R-1 to R-30, CR-1 to CR-15) shown in Tables 3 and 4 was spin-coated onto a Si substrate on which a 20 nm thick silicon-containing spin-on hard mask SHB-A940 (silicon content 43% by mass) manufactured by Shin-Etsu Chemical Co., Ltd. had been formed, and the resulting resist film was pre-baked at 105°C for 60 seconds using a hot plate to produce a 50 nm thick resist film. This was then exposed using an ASML EUV scanner NXE3400 (NA 0.33, σ 0.9 / 0.6, quadrupole illumination, a mask with a hole pattern with a 46 nm pitch on the wafer and a +20% bias), and then exposed using a hot plate. Tables 7 and 8 PEB was performed at the temperature described above for 60 seconds, and development was performed in a 2.38% by mass aqueous solution of TMAH for 30 seconds to form a hole pattern with a dimension of 23 nm.

[0378] Using a critical dimension SEM (CG6300) manufactured by Hitachi High-Technologies Corporation, the exposure dose when a hole dimension of 23 nm was formed was measured and used as the sensitivity. The dimensions of 50 holes were also measured, and the standard deviation (σ) calculated from the results was tripled (3σ) to give the dimensional variation (CDU). The results are shown in Tables 7 and 8.

[0379] [Table 7]

[0380] [Table 8]

[0381] The results shown in Tables 7 and 8 confirm that the chemically amplified resist composition of the present invention has good sensitivity and excellent CDU.

[0382] The present invention includes the following aspects. [1]: A polymerizable monomer characterized by being represented by the following general formula (1): [ka] (In the formula, R A is a hydrogen atom, a fluorine atom, a methyl group, or a trifluoromethyl group. L is a single bond or (main chain) -C(=O)-O-. ALU is an acid labile group formed with the adjacent oxygen atom. L represents an oxygen atom or a sulfur atom. aa represents a hydrogen atom or a fluorine atom. 1a are each independently a linear, branched or cyclic hydrocarbyl group having 1 to 20 carbon atoms which may contain a heteroatom. n1 is an integer of 0 to 2. n2 is an integer of 1 or 2. n3 is an integer of 1 or 2. n4 is an integer of 0 to 4. When n2=1, -OR ALU and -X L -CF2(R aa ) are bonded to adjacent carbon atoms on the aromatic ring. Furthermore, when n2=2, two -OR ALU One of them is -X L -CF2(R aa ) is bonded to the carbon atom adjacent to the carbon atom on the aromatic ring to which it is bonded. [2]: In the general formula (1), R ALU The polymerizable monomer according to the above item [1], characterized in that: is represented by the following formula (AL-1) or (AL-2) together with the adjacent oxygen atom: [ka] (In the formula, R A , Z L , X L , R 1a , R ALU , n1, n2, n3, and n4 are the same as above.) [3]: R ALUThe polymerizable monomer according to the above [1] or [2], characterized in that, together with the adjacent oxygen atom, it is represented by the following formula (AL-1) or (AL-2): [ka] (In formula (AL-1), R 21 , R 22 , and R 23 are each independently a hydrocarbyl group having 1 to 12 carbon atoms which may contain a heteroatom. 21 , R 22 , and R 23 Any two of these may be bonded to each other to form a ring. t is an integer of 0 or 1. In formula (AL-2), R 24 , and R 25 are each independently a hydrogen atom or a hydrocarbyl group having 1 to 10 carbon atoms. 26 is a hydrocarbyl group having 1 to 20 carbon atoms, or R 24 , or R 25 and bond to each other, and the carbon atoms to which they are bonded and X a may form a heterocyclic group having 3 to 20 carbon atoms together with X. Furthermore, -CH2- contained in the above hydrocarbyl group and heterocyclic group may be replaced with -O- or -S-. a represents an oxygen atom or a sulfur atom. u is an integer of 0 or 1. * represents a bond to the adjacent oxygen atom. [4]: A polymer compound containing a repeating unit obtained from the polymerizable monomer according to any one of the above [1] to [3], wherein the repeating unit is represented by the following general formula (1a): [ka] (In the formula, R A , Z L , X L , R 1a , R ALU , R aa , n1, n2, n3, and n4 are the same as above.) [5]: A polymer compound containing a repeating unit obtained from the polymerizable monomer according to any one of [1] to [3] above, wherein the repeating unit is represented by the following general formula (1-Aa): [ka] [6]: R ALU is represented by the following formula (AL-1) or (AL-2) together with the adjacent oxygen atom: [ka] (In the formula, R 21 , R 22 , R 23 ,t,R 24 , R 25 , R 26 , X a , u is the same as above.) [7]: The polymer compound according to any one of the above [4] to [6], further comprising at least one repeating unit selected from the repeating units represented by the following general formula (a1) or (a2): [ka] (In the formula, R A are each independently a hydrogen atom, a fluorine atom, a methyl group, or a trifluoromethyl group. A represents a single bond, an alkoxy group which may be substituted with a halogen atom, a phenylene group which may be substituted with a halogen atom, a naphthylene group, or (main chain) -C(=O)-OZ A1 - and Z A1 Z is a straight-chain, branched or cyclic alkanediyl group having 1 to 20 carbon atoms which may contain a heteroatom, an alkoxy group having 1 to 10 carbon atoms which may contain a fluorine atom, a hydroxy group, an ether bond, an ester bond, a lactone ring, a thioether bond, a sulfonyl group or a sulfonamide structure, or a phenylene group or a naphthylene group. Bis a single bond or (main chain)-C(=O)-OZ B1 -It is. Z B1 X is a single bond or an alkanediyl group having 1 to 10 carbon atoms which may have an ester bond and / or an ether bond. A and X B are each independently an acid labile group. b is a linear, branched or cyclic monovalent hydrocarbon group having 1 to 20 carbon atoms which may contain a halogen atom, a nitro group or a heteroatom, and n is an integer of 0 to 4. [8]: The polymer compound according to any one of the above [4] to [7], further comprising at least one repeating unit selected from the repeating units represented by the following general formula (b1) or (b2): [ka] (In the formula, R A are each independently a hydrogen atom, a fluorine atom, a methyl group, or a trifluoromethyl group. A is a hydrogen atom or a polar group containing at least one structure selected from a hydroxy group, a cyano group, a carbonyl group, a carboxy group, an ether bond, an ester bond, a sulfonate ester bond, a sulfonamide bond, a carbonate bond, a lactone ring, a sultone ring, a sulfur atom, and a carboxylic acid anhydride. B is a single bond or (main chain)-C(=O)-OZ B1 -It is. Z B1 R is a single bond or an alkanediyl group having 1 to 10 carbon atoms which may have an ester bond and / or an ether bond. b represents a linear, branched or cyclic monovalent hydrocarbon group having 1 to 20 carbon atoms which may contain a halogen atom, a nitro group or a heteroatom; m represents an integer of 1 to 4; and m' represents an integer of 0 to 4. [9]: The polymer compound according to any one of the above [4] to [8], further comprising at least one repeating unit selected from the repeating units represented by the following general formulae (C1) to (C4): [ka] (In the formula, R A are each independently a hydrogen atom, a fluorine atom, a methyl group, or a trifluoromethyl group. 1 is a single bond or a phenylene group. 2 is a single bond, *-C(=O)-OZ 21 -, *-C(=O)-NH-Z 21 -or*-OZ 21 -It is. Z 21 Z is an aliphatic hydrocarbylene group having 1 to 12 carbon atoms, a phenylene group, or a divalent group obtained by combining these, and may contain a carbonyl group, an ester bond, an ether bond, or a hydroxy group. 3 is a single bond, a phenylene group, a naphthylene group, or *-C(=O)-OZ 31 -It is. Z 31 Z is an aliphatic hydrocarbylene group having 1 to 14 carbon atoms which may contain a single bond, a hydroxy group, an ether bond, an ester bond or a lactone ring, or a phenylene group or a naphthylene group. 4 is a single bond, a methylene group or *-Z 41 -C(=O)-O-. Z 41 Z is a hydrocarbylene group having 1 to 20 carbon atoms which may contain an ether bond, an ester bond, or a heteroatom. 5 represents 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)-OZ 51 -, *-C(=O)-N(H)-Z 51 -or*-OZ 51 -It is. Z 51 is an aliphatic hydrocarbylene 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 contain a carbonyl group, an ester bond, an ether bond, or a hydroxy group. * represents a bond to a carbon atom in the main chain. R 21 ' and R 22 Each of R' is independently a hydrocarbyl group having 1 to 20 carbon atoms which may contain a heteroatom. 21' and R 22 and may be bonded to each other to form a ring together with the sulfur atom to which they are attached. 1 is a single bond, an ether bond, an ester bond, a carbonyl group, a sulfonate ester bond, a carbonate bond or a carbamate bond. 1 and Rf 2 Rf are each independently a fluorine atom or a fluorinated alkyl group having 1 to 6 carbon atoms. 3 and Rf 4 Rf are each independently a hydrogen atom, a fluorine atom, or a fluorinated alkyl group having 1 to 6 carbon atoms. 5 and Rf 6 are each independently a hydrogen atom, a fluorine atom, or a fluorinated alkyl group having 1 to 6 carbon atoms, provided that all Rf 5 and Rf 6 and cannot simultaneously become hydrogen atoms. - is a non-nucleophilic counterion. + is an onium cation, and c is an integer of 0 to 3.

[10] : A resist composition comprising a base resin made of the polymer compound according to any one of [4] to [9] above and an organic solvent.

[11] : The resist composition according to any one of the above [4] to

[10] , further comprising at least one selected from the group consisting of a quencher and an acid generator.

[12] : The resist composition according to any one of items [4] to

[11] above, further comprising a surfactant that is insoluble or poorly soluble in water but soluble in an alkaline developer, and / or a surfactant that is insoluble or poorly soluble in both water and an alkaline developer.

[13] : A pattern formation method comprising the steps of: forming a resist film on a substrate using the resist composition according to any one of items [4] to

[12] above; exposing the resist film to high-energy rays; and developing the exposed resist film using a developer.

[14] : The pattern forming method according to the above

[13] , wherein the high-energy beam is KrF excimer laser light, ArF excimer laser light, an electron beam, or extreme ultraviolet light having a wavelength of 3 to 15 nm.

[0383] The present invention is not limited to the above-described embodiments. The above-described embodiments are merely examples, and anything that has substantially the same configuration as the technical idea described in the claims of the present invention and that exhibits similar effects is included within the technical scope of the present invention.

Claims

1. A polymerizable monomer characterized by being represented by the following general formula (1): 【Chemical 1】 (In the formula, R Ａ is a hydrogen atom, a fluorine atom, a methyl group, or a trifluoromethyl group. Ｌ is a single bond or (main chain) -C(=O)-O-. ＡＬＵ is an acid labile group formed together with the adjacent oxygen atom. Ｌ represents an oxygen atom or a sulfur atom. ａａ represents a hydrogen atom or a fluorine atom. １ａ are each independently a linear, branched or cyclic hydrocarbyl group having 1 to 20 carbon atoms which may contain a heteroatom. n1 is an integer of 0 to 2. n2 is an integer of 1 or 2. n3 is an integer of 1 or 2. n4 is an integer of 0 to 4. When n2=1, -O-R ＡＬＵ and -X Ｌ -CF ２ (R ａａ ) are bonded to adjacent carbon atoms on the aromatic ring. ＡＬＵ One of them is -X Ｌ -CF ２ (R ａａ ) is bonded to the carbon atom adjacent to the carbon atom on the aromatic ring to which

2. 2. The polymerizable monomer according to claim 1, wherein the general formula (1) is represented by the following formula (1-A): 【Chemistry 2】 (In the formula, R Ａ , Z Ｌ , X Ｌ , R １ａ , R ＡＬＵ , n1, n2, n3, and n4 are the same as above.)

3. In the general formula (1), R ＡＬＵ is, together with the adjacent oxygen atom, represented by the following formula (AL-1) or (AL-2): 【Chemistry 3】 (In formula (AL-1), R ２１ , R ２２ , and R ２３ are each independently a hydrocarbyl group having 1 to 12 carbon atoms which may contain a heteroatom. ２１ , R ２２ , and R ２３ Any two of these may be bonded to each other to form a ring. t is an integer of 0 or 1. In formula (AL-2), R ２４ , and R ２５ are each independently a hydrogen atom or a hydrocarbyl group having 1 to 10 carbon atoms. ２６ is a hydrocarbyl group having 1 to 20 carbon atoms, or R ２４ , or R ２５ and the carbon atoms to which they are bonded and X ａ may form a heterocyclic group having 3 to 20 carbon atoms together with the —CH ２ - may be replaced by -O- or -S-. ａ represents an oxygen atom or a sulfur atom; u is an integer of 0 or 1; * represents a bond to the adjacent oxygen atom.

4. In the general formula (1-A), R ＡＬＵ The polymerizable monomer according to claim 2, wherein, together with an adjacent oxygen atom, the polymerizable monomer is represented by the following formula (AL-1) or (AL-2): 【Chemistry 4】 (In formula (AL-1), R ２１ , R ２２ , and R ２３ are each independently a hydrocarbyl group having 1 to 12 carbon atoms which may contain a heteroatom. ２１ , R ２２ , and R ２３ Any two of these may be bonded to each other to form a ring. t is an integer of 0 or 1. In formula (AL-2), R ２４ , and R ２５ are each independently a hydrogen atom or a hydrocarbyl group having 1 to 10 carbon atoms. ２６ is a hydrocarbyl group having 1 to 20 carbon atoms, or R ２４ , or R ２５ and the carbon atoms to which they are bonded and X ａ may form a heterocyclic group having 3 to 20 carbon atoms together with the —CH ２ - may be replaced by -O- or -S-. ａ represents an oxygen atom or a sulfur atom; u is an integer of 0 or 1; * represents a bond to the adjacent oxygen atom.

5. A polymer compound containing a repeating unit obtained from the polymerizable monomer according to claim 1, wherein the repeating unit is represented by the following general formula (1a): 【Chemistry 5】 (In the formula, R Ａ , Z Ｌ , X Ｌ , R １ａ , R ＡＬＵ , R ａａ , n1, n2, n3, and n4 are the same as above.)

6. A polymer compound containing a repeating unit obtained from the polymerizable monomer according to claim 2, wherein the repeating unit is represented by the following general formula (1-Aa): 【Chemistry 6】 (In the formula, R Ａ , Z Ｌ , X Ｌ , R １ａ , R ＡＬＵ , n1, n2, n3, and n4 are the same as above.)

7. In the general formula (1a), R ＡＬＵ is represented by the following formula (AL-1) or (AL-2) together with an adjacent oxygen atom: 【Chemistry 7】 In formula (AL-1), R 21 , R 22 , and R 23 each independently represent a hydrocarbyl group having 1 to 12 carbon atoms which may contain a heteroatom. Any two of R 21 , R 22 , and R 23 may be bonded to each other to form a ring. t is an integer of 0 or 1. In formula (AL-2), R 24 and R 25 each independently represent a hydrogen atom or a hydrocarbyl group having 1 to 10 carbon atoms. R 26 may be a hydrocarbyl group having 1 to 20 carbon atoms, or may be bonded to R 24 or R 25 to form a heterocyclic group having 3 to 20 carbon atoms together with the carbon atom to which they are bonded and X a . In addition, —CH 2 — contained in the hydrocarbyl group and heterocyclic group may be replaced by —O— or —S—. X a represents an oxygen atom or a sulfur atom; u is an integer of 0 or 1; * represents a bond to the adjacent oxygen atom.

8. In the general formula (1-Aa), R ＡＬＵ is represented by the following formula (AL-1) or (AL-2) together with an adjacent oxygen atom: 【Chemistry 8】 In formula (AL-1), R 21 , R 22 , and R 23 each independently represent a hydrocarbyl group having 1 to 12 carbon atoms which may contain a heteroatom. Any two of R 21 , R 22 , and R 23 may be bonded to each other to form a ring. t is an integer of 0 or 1. In formula (AL-2), R 24 and R 25 each independently represent a hydrogen atom or a hydrocarbyl group having 1 to 10 carbon atoms. R 26 may be a hydrocarbyl group having 1 to 20 carbon atoms, or may be bonded to R 24 or R 25 to form a heterocyclic group having 3 to 20 carbon atoms together with the carbon atom to which they are bonded and X a . In addition, —CH 2 — contained in the hydrocarbyl group and heterocyclic group may be replaced by —O— or —S—. X a represents an oxygen atom or a sulfur atom; u is an integer of 0 or 1; * represents a bond to the adjacent oxygen atom.

9. 6. The polymer compound according to claim 5, further comprising at least one repeating unit selected from the repeating units represented by the following general formula (a1) or (a2): 【Chemistry 9】 (In the formula, R Ａ are each independently a hydrogen atom, a fluorine atom, a methyl group, or a trifluoromethyl group. Ａ represents a single bond, an alkoxy group which may be substituted with a halogen atom, a phenylene group which may be substituted with a halogen atom, a naphthylene group, or (main chain) -C(=O)-O-Z Ａ１ - and Z Ａ１ is a straight-chain, branched or cyclic alkanediyl group having 1 to 20 carbon atoms which may contain a heteroatom, an alkoxy group having 1 to 10 carbon atoms which may contain a fluorine atom, a hydroxy group, an ether bond, an ester bond, a lactone ring, a thioether bond, a sulfonyl group or a sulfonamide structure, or a phenylene group or a naphthylene group. Ｂ represents a single bond or (main chain) -C(=O)-O-Z Ｂ１ - is. Z Ｂ１ X is a single bond or an alkanediyl group having 1 to 10 carbon atoms which may have an ester bond and / or an ether bond. Ａ and X Ｂ are each independently an acid labile group. ｂ is a linear, branched, or cyclic monovalent hydrocarbon group having 1 to 20 carbon atoms, which may contain a halogen atom, a nitro group, or a heteroatom; and n is an integer of 0 to 4.

10. 6. The polymer compound according to claim 5, further comprising at least one repeating unit selected from the repeating units represented by the following general formula (b1) or (b2): 【Chemistry 10】 (In the formula, R Ａ are each independently a hydrogen atom, a fluorine atom, a methyl group, or a trifluoromethyl group. Ａ is a hydrogen atom or a polar group containing at least one structure selected from a hydroxy group, a cyano group, a carbonyl group, a carboxy group, an ether bond, an ester bond, a sulfonate ester bond, a sulfonamide bond, a carbonate bond, a lactone ring, a sultone ring, a sulfur atom, and a carboxylic acid anhydride. Ｂ represents a single bond or (main chain) -C(=O)-O-Z Ｂ１ - is. Z Ｂ１ R is a single bond or an alkanediyl group having 1 to 10 carbon atoms which may have an ester bond and / or an ether bond. ｂ represents a linear, branched, or cyclic monovalent hydrocarbon group having 1 to 20 carbon atoms which may contain a halogen atom, a nitro group, or a heteroatom; m represents an integer of 1 to 4; and m' represents an integer of 0 to 4.

11. 6. The polymer compound according to claim 5, further comprising at least one repeating unit selected from the repeating units represented by the following general formulae (C1) to (C4): 【Chemistry 11】 (In the formula, R Ａ are each independently a hydrogen atom, a fluorine atom, a methyl group, or a trifluoromethyl group. １ is a single bond or a phenylene group. ２ is a single bond, *-C(=O)-O-Z ２１ -, *-C(=O)-NH-Z ２１ - or *-O-Z ２１ - is. Z ２１ represents an aliphatic hydrocarbylene group having 1 to 12 carbon atoms, a phenylene group, or a divalent group obtained by combining these, and may contain a carbonyl group, an ester bond, an ether bond, or a hydroxy group. ３ represents a single bond, a phenylene group, a naphthylene group, or *-C(=O)-O-Z ３１ - is. Z ３１ Z is an aliphatic hydrocarbylene group having 1 to 14 carbon atoms which may contain a single bond, a hydroxy group, an ether bond, an ester bond or a lactone ring, or a phenylene group or a naphthylene group. ４ is a single bond, a methylene group or *-Z ４１ -C(=O)-O-. Z ４１ is a hydrocarbylene group having 1 to 20 carbon atoms which may contain an ether bond, an ester bond, or a heteroatom. ５ represents 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 ５１ -, *-C(=O)-N(H)-Z ５１ - or *-O-Z ５１ - is. Z ５１ represents an aliphatic hydrocarbylene 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 contain a carbonyl group, an ester bond, an ether bond, or a hydroxy group. * represents a bond to a carbon atom in the main chain. R ２１ ' and R ２２ Each of R ′ is independently a hydrocarbyl group having 1 to 20 carbon atoms which may contain a heteroatom. ２１ ' and R ２２ and may be bonded to each other to form a ring together with the sulfur atom to which they are attached. １ is a single bond, an ether bond, an ester bond, a carbonyl group, a sulfonate ester bond, a carbonate bond or a carbamate bond. １ and Rf ２ are each independently a fluorine atom or a fluorinated alkyl group having 1 to 6 carbon atoms. ３ and Rf ４ are each independently a hydrogen atom, a fluorine atom, or a fluorinated alkyl group having 1 to 6 carbon atoms. ５ and Rf ６ are each independently a hydrogen atom, a fluorine atom, or a fluorinated alkyl group having 1 to 6 carbon atoms. ５ and Rf ６ and cannot simultaneously become hydrogen atoms. － is a non-nucleophilic counterion. ＋ is an onium cation. c is an integer of 0 to 3.

12. A resist composition comprising a base resin made of the polymer compound according to any one of claims 5 to 11 and an organic solvent.

13. 13. The resist composition according to claim 12, further comprising at least one selected from the group consisting of a quencher and an acid generator.

14. 13. The resist composition according to claim 12, further comprising a surfactant that is insoluble or slightly soluble in water but soluble in an alkaline developer, and / or a surfactant that is insoluble or slightly soluble in water and an alkaline developer.

15. 13. A pattern forming method comprising the steps of: forming a resist film on a substrate using the resist composition according to claim 12; exposing the resist film to high-energy rays; and developing the exposed resist film using a developer.

16. 16. The pattern formation method according to claim 15, wherein the high-energy beam is a KrF excimer laser beam, an ArF excimer laser beam, an electron beam, or extreme ultraviolet light having a wavelength of 3 to 15 nm.

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