Actinic ray-sensitive or radiation-sensitive resin composition, pattern forming method, resist film, and method for manufacturing electronic device

Abstract

To provide an actinic ray-sensitive or radiation-sensitive resin composition that is capable of giving a pattern having excellent LWR performance even if the composition has been stored for a long period of time, and to provide a resist film, a pattern forming method, and a method for manufacturing an electronic device, each employing the actinic ray-sensitive or radiation-sensitive resin composition.SOLUTION: An actinic ray-sensitive or radiation-sensitive resin composition includes one or more specific compounds selected from the group consisting of a compound represented by general formula (1), a compound represented by general formula (2), and a compound represented by general formula (3), and an acid-decomposable resin.SELECTED DRAWING: None

Description

[Technical field]

[0001] The present invention relates to an actinic ray-sensitive or radiation-sensitive resin composition, a pattern forming method, a resist film, and a method for producing an electronic device. [Background technology]

[0002] 2. Description of the Related Art In the manufacturing process of semiconductor devices such as ICs (Integrated Circuits) and LSIs (Large Scale Integrated circuits), fine processing is carried out by lithography using a photosensitive composition. Lithography methods include a method in which a resist film is formed from a photosensitive composition, the resulting film is exposed to light, and then developed. For example, Patent Document 1 discloses a resist composition containing the following compound.

[0003] [ka] [Prior art documents] [Patent documents]

[0004] [Patent Document 1] JP 2014-235248 A Summary of the Invention [Problem to be solved by the invention]

[0005] The present inventors have specifically studied the technology disclosed in Patent Document 1 and have found that when the composition of Patent Document 1 is applied to pattern formation after being stored for a long period of time (e.g., three months) after production, there is room for improvement in the LWR (line width roughness) performance of the resulting pattern.

[0006] Therefore, an object of the present invention is to provide an actinic ray-sensitive or radiation-sensitive resin composition which can give a pattern having excellent LWR performance even after long-term storage. Another object of the present invention is to provide a resist film, a pattern forming method, and a method for producing an electronic device, which relate to the actinic ray-sensitive or radiation-sensitive resin composition. [Means for solving the problem]

[0007] The present inventors have found that the above problems can be solved by the following configuration.

[0008] [1] One or more specific compounds selected from the group consisting of a compound represented by general formula (1), a compound represented by general formula (2), and a compound represented by general formula (3), and an acid-decomposable resin. [ka] In general formula (1), X - represents an organic anion. Ar 1 and Ar 2 each independently represents an aromatic hydrocarbon ring group having at least one substituent. Ar 3 represents an aromatic hydrocarbon ring group represented by general formula (1R). In formula (1R), * represents a bonding position. R 1 ~R 5 each independently represents a hydrogen atom, a fluorine atom, or an alkyl group which may have a substituent. However, R 1 and R 5 At least one of these represents a fluorine-containing group selected from the group consisting of a fluorine atom and a fluoroalkyl group. In general formula (1), Ar 1 , Ar 2 , and Ar 3 At least two of these represent groups having different structures. [ka] In general formula (2), X - represents an organic anion. Ar 4 and Ar 5 each independently represents an aromatic hydrocarbon ring group having at least one substituent. Ar 6 represents an aromatic hydrocarbon ring group represented by general formula (2R). In formula (2R), * represents the bonding position. R 6 , R 7 , R 9 , and R 10 each independently represents a hydrogen atom, a fluorine atom, or an alkyl group which may have a substituent. R 8 represents a fluorine-containing group selected from the group consisting of a fluorine atom and a fluoroalkyl group. In the general formula (2), Ar 4 , Ar 5 , and Ar 6 At least two of these represent groups having different structures. In addition, in the general formula (2), Ar 4 , Ar 5 , and Ar 6 The aromatic hydrocarbon ring group represented by the following formula (I) has a total of two or more fluorine-containing groups. [ka] In general formula (3), X - represents an organic anion. Ar 7 and Ar 8 each independently represents an aromatic hydrocarbon ring group which may have an organic group other than an electron-withdrawing group. However, Ar 7 and Ar 8 The aromatic hydrocarbon ring group represented by the following formula (I) has a total of one or more organic groups other than the electron-withdrawing group. Ar 9represents an aromatic hydrocarbon ring group represented by general formula (3R). In formula (3R), * represents the bonding position. R 11 , R 13 , and R 15 each independently represents a hydrogen atom, a fluorine atom, or an alkyl group which may have a substituent. R 12 and R 14 each independently represents a fluorine-containing group selected from the group consisting of a fluorine atom and a fluoroalkyl group. [2] The actinic ray-sensitive or radiation-sensitive resin composition according to [1], wherein the fluorine-containing group in the general formulae (1) to (3) is a fluoroalkyl group. [3] In the above general formula (1), Ar 1 , Ar 2 , and Ar 3 the aromatic hydrocarbon ring group represented by the formula (I) has a total of three or more fluoroalkyl groups, or a total of one or more organic groups other than electron-withdrawing groups, and the total number of carbon atoms contained in the total of one or more organic groups other than electron-withdrawing groups is 3 or more; In the above general formula (2), Ar 4 , Ar 5 , and Ar 6 The aromatic hydrocarbon ring group represented by the formula (I) has a total of three or more fluorine-containing groups as described above, or Ar 4 , Ar 5 , and Ar 6 the aromatic hydrocarbon ring group represented by the formula (I) has a total of one or more linear or branched organic groups other than electron-withdrawing groups, and the total number of carbon atoms contained in the total of one or more linear or branched organic groups other than electron-withdrawing groups is 3 or more; In the above general formula (3), Ar 7 , Ar 8 , and Ar 9 The actinic ray-sensitive or radiation-sensitive resin composition according to [1] or [2], wherein the total number of carbon atoms contained in the organic groups other than the electron-withdrawing group, which are contained in the aromatic hydrocarbon ring group represented by the formula: [4] Ar 6 represents a group represented by general formula (2S): [ka] In formula (2S), * represents a bonding position. R 8F represents a fluoroalkyl group. [5] Ar 5 and Ar 6 represents a group represented by general formula (2S). [6] A resist film formed using the actinic ray-sensitive or radiation-sensitive resin composition according to any one of [1] to [5]. [7] A step of forming a resist film on a substrate using the actinic ray-sensitive or radiation-sensitive resin composition according to any one of [1] to [5]; exposing the resist film to light; and developing the exposed resist film with a developer to form a pattern. [8] A method for manufacturing an electronic device, comprising the pattern forming method according to [7]. Effect of the Invention

[0009] According to the present invention, there is provided an actinic ray-sensitive or radiation-sensitive resin composition which can give a pattern having excellent LWR performance even after long-term storage. The present invention also provides a resist film, a pattern forming method, and a method for producing an electronic device, which relate to the actinic ray-sensitive or radiation-sensitive resin composition. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0010] An example of an embodiment of the present invention will be described below. In this specification, a numerical range expressed using "to" means a range that includes the numerical values ​​before and after "to" as the lower and upper limits. In the description of groups (atomic groups) in this specification, the notation without indicating whether substituted or unsubstituted includes both unsubstituted and substituted groups. For example, "alkyl group" includes not only alkyl groups without a substituent (unsubstituted alkyl groups) but also alkyl groups with a substituent (substituted alkyl groups). Unless otherwise specified, the substituent is preferably a monovalent substituent. As used herein, an "organic group" refers to a group containing at least one carbon atom.

[0011] In this specification, examples of halogen atoms include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

[0012] The bonding direction of the divalent group described in this specification is not limited unless otherwise specified. For example, when Y is -COO- in a compound represented by the general formula "XYZ", Y may be -CO-O- or -O-CO-. In addition, the above compound may be "X-CO-OZ" or "XO-CO-Z".

[0013] In this specification, "(meth)acrylic" is a general term including acrylic and methacrylic, and means "at least one of acrylic and methacrylic". Similarly, "(meth)acrylic acid" means "at least one of acrylic acid and methacrylic acid".

[0014] In this specification, "actinic rays" or "radiation" refers to, for example, the bright line spectrum of a mercury lamp, far ultraviolet light represented by an excimer laser, extreme ultraviolet light (EUV light: extreme ultraviolet), X-rays, and electron beams (EB), etc. In this specification, "light" refers to actinic rays or radiation. In this specification, unless otherwise specified, "exposure" includes not only exposure to the emission line spectrum of a mercury lamp, far ultraviolet light represented by an excimer laser (such as an ArF excimer laser), extreme ultraviolet light, X-rays, EUV light, and the like, but also drawing with particle beams such as electron beams and ion beams.

[0015] In this specification, the weight average molecular weight (Mw), number average molecular weight (Mn), and dispersity (also called molecular weight distribution) (Mw / Mn) of a resin are measured by Gel Permeation Chromatography (GPC). It is defined as a polystyrene equivalent value obtained by GPC measurement using a GPC (Tosoh Corporation HLC-8120GPC) (solvent: tetrahydrofuran, flow rate (sample injection amount): 10 μL, column: Tosoh Corporation TSK gel Multipore HXL-M, column temperature: 40°C, flow rate: 1.0 mL / min, detector: refractive index detector).

[0016] 1Å is 1×10 -10 m.

[0017] In this specification, the acid dissociation constant (pKa) refers to the pKa in an aqueous solution, and specifically, is a value calculated based on a database of Hammett's substituent constants and known literature values ​​using the following software package 1. All pKa values ​​described in this specification are values ​​calculated using this software package.

[0018] Software package 1: Advanced Chemistry Development (ACD / Labs) Software V8.14 for Solaris (1994-2007 ACD / Labs).

[0019] On the other hand, pKa can also be calculated by molecular orbital calculations. The specific method is to calculate the pKa of H in a solvent based on the thermodynamic cycle. +A method of calculating the pKa by calculating the dissociation free energy is exemplified. (In this specification, water is usually used as the solvent, and DMSO (dimethyl sulfoxide) is used when the pKa cannot be obtained with water.) H + The dissociation free energy can be calculated, for example, by DFT (density functional theory), but various other methods have been reported in the literature, and the method is not limited to these. There are several software programs that can perform DFT, such as Gaussian16.

[0020] As described above, the pKa in this specification refers to a value calculated using the software package 1 based on the database of Hammett's substituent constants and known literature values. However, when the pKa cannot be calculated by this method, a value obtained by Gaussian 16 based on DFT (density functional theory) is used.

[0021] [Actinic ray-sensitive or radiation-sensitive resin composition] The actinic ray-sensitive or radiation-sensitive resin composition (hereinafter, also referred to as "resist composition") of the present invention will be described. The resist composition of the present invention may be a positive resist composition or a negative resist composition. Furthermore, it may be a resist composition for alkali development or a resist composition for organic solvent development. The composition of the present invention is typically a chemically amplified resist composition.

[0022] The resist composition of the present invention contains one or more specific compounds selected from the group consisting of compounds represented by general formula (1), compounds represented by general formula (2), and compounds represented by general formula (3), and an acid-decomposable resin. The mechanism by which the problem of the present invention is solved by such a configuration is not necessarily clear, but the present inventors consider it as follows. The specific compound is an onium salt containing an organic anion and an organic cation, and usually acts as a photoacid generator. In each specific compound represented by each general formula, the organic cation has a fluorine-containing group (fluorine atom or fluoroalkyl group) and a substituent so as to satisfy the conditions of a predetermined number, position, and / or type. Such a specific compound has excellent decomposition efficiency during exposure and excellent compatibility with acid-decomposable resins, so that the LWR performance of the formed pattern is good. In addition, the electron-withdrawing property of the entire cation is appropriately adjusted and / or the nucleophilicity to the sulfonium atom is reduced, so that the stability of the specific compound is enhanced, and it is believed that the resist composition can maintain good LWR performance even when stored for a long period of time. Hereinafter, in this specification, the ability to obtain a pattern with excellent LWR performance even when the resist composition is stored for an extended period of time is also referred to as the effect of the present invention being excellent.

[0023] [Components of the resist composition] Components that the resist composition may contain will be described in detail below.

[0024] <Specific compound> The resist composition of the present invention contains a specific compound. The specific compound usually acts as a photoacid generator. The photoacid generator is a compound that generates an acid when irradiated (exposed) with actinic rays or radiation (preferably EUV light or ArF). The photoacid generator is preferably in the form of a low molecular weight compound. When the photoacid generator is in the form of a low molecular weight compound, the molecular weight is preferably 3,000 or less, more preferably 2,000 or less, and even more preferably 1,200 or less. The specific compound is preferably a compound that generates an organic acid upon exposure to light. Examples of the organic acid include sulfonic acids (aliphatic sulfonic acids, aromatic sulfonic acids, camphorsulfonic acids, etc.), carboxylic acids (aliphatic carboxylic acids, aromatic carboxylic acids, aralkyl carboxylic acids, etc.), carbonylsulfonylimide acids, bis(alkylsulfonyl)imide acids, and tris(alkylsulfonyl)methide acids.

[0025] The volume of the acid generated by the photoacid generator is not particularly limited. However, in order to suppress the diffusion of the acid generated by exposure to the non-exposed area and to improve the resolution, it is preferable that the volume of the acid be 240 Å or less. 3 More than 305 Å is preferable. 3 More preferably, 350 Å or more 3 More preferably, 400 Å or more. 3 From the viewpoint of sensitivity or solubility in a coating solvent, the volume of the acid generated by the photoacid generator is preferably 1500 Å or less. 3 Preferably less than 1000 Å 3 Less than 700 Å is more preferable. 3 The following is even more preferred: The volume values ​​are calculated using "WinMOPAC" by Fujitsu Ltd. In calculating the volume values, first, the chemical structure of the acid in each example is input, then, using this structure as the initial structure, the most stable conformation of each acid is determined by molecular force field calculation using the MM (Molecular Mechanics)3 method, and then, for these most stable conformations, molecular orbital calculations are performed using the PM (Parameterized Model number)3 method to calculate the "accessible volume" of each acid.

[0026] The structure of the acid generated by the photoacid generator is not particularly limited, but in terms of suppressing the diffusion of the acid and improving the resolution, it is preferable that the interaction between the acid generated by the photoacid generator and the resin (A) described below is strong. From this point of view, when the acid generated by the photoacid generator is an organic acid, it is preferable that it further has a polar group in addition to organic acid groups such as a sulfonic acid group, a carboxylic acid group, a carbonylsulfonylimide acid group, a bissulfonylimide acid group, and a trisulfonylmethide acid group. Examples of the polar group include an ether group, an ester group, an amide group, an acyl group, a sulfo group, a sulfonyloxy group, a sulfonamide group, a thioether group, a thioester group, a urea group, a carbonate group, a carbamate group, a hydroxyl group, and a mercapto group. The number of polar groups possessed by the generated acid is not particularly limited, and is preferably 1 or more, and more preferably 2 or more. However, from the viewpoint of suppressing excessive development, the number of polar groups is preferably less than 6, and more preferably less than 4.

[0027] The photoacid generator is preferably one that generates the acids listed below. Note that the calculated volume (unit: Å) is also shown in some of the examples. 3 ).

[0028] [ka]

[0029] [ka]

[0030] [ka]

[0031] The specific compound is one or more selected from the group consisting of a compound represented by general formula (1), a compound represented by general formula (2), and a compound represented by general formula (3). The compound represented by general formula (1), the compound represented by general formula (2), and the compound represented by general formula (3) will be described below.

[0032] (Compound represented by general formula (1)) General formula (1) is shown below.

[0033] [ka]

[0034] In general formula (1), X - represents an organic anion. The organic anion is preferably a non-nucleophilic anion (an anion having an extremely low ability to cause a nucleophilic reaction).

[0035] Examples of non-nucleophilic anions include sulfonate anions (aliphatic sulfonate anions, aromatic sulfonate anions, camphorsulfonate anions, etc.), carboxylate anions (aliphatic carboxylate anions, aromatic carboxylate anions, aralkyl carboxylate anions, etc.), sulfonylimide anions, bis(alkylsulfonyl)imide anions, tris(alkylsulfonyl)methide anions, etc.

[0036] The aliphatic moiety in the aliphatic sulfonate anion and the aliphatic carboxylate anion may be an alkyl group or a cycloalkyl group, and is preferably a linear or branched alkyl group having 1 to 30 carbon atoms or a cycloalkyl group having 3 to 30 carbon atoms. The alkyl group may be, for example, a fluoroalkyl group (which may or may not have a substituent other than a fluorine atom; it may also be a perfluoroalkyl group).

[0037] The aryl group in the aromatic sulfonate anion and aromatic carboxylate anion is preferably an aryl group having 6 to 14 carbon atoms, and examples thereof include a phenyl group, a tolyl group, and a naphthyl group.

[0038] The alkyl group, cycloalkyl group, and aryl group mentioned above may have a substituent. The substituent is not particularly limited, but specific examples thereof include a nitro group, a halogen atom such as a fluorine atom or a chlorine atom, a carboxy group, a hydroxyl group, an amino group, a cyano group, an alkoxy group (preferably having 1 to 15 carbon atoms), an alkyl group (preferably having 1 to 10 carbon atoms), a cycloalkyl group (preferably having 3 to 15 carbon atoms), an aryl group (preferably having 6 to 14 carbon atoms), an alkoxycarbonyl group (preferably having 2 to 7 carbon atoms), an acyl group (preferably having 2 to 12 carbon atoms), an alkoxycarbonyloxy group (preferably having 2 to 7 carbon atoms), an alkylthio group (preferably having 1 to 15 carbon atoms), an alkylsulfonyl group (preferably having 1 to 15 carbon atoms), an alkyliminosulfonyl group (preferably having 1 to 15 carbon atoms), and an aryloxysulfonyl group (preferably having 6 to 20 carbon atoms).

[0039] The aralkyl group in the aralkyl carboxylate anion is preferably an aralkyl group having 7 to 14 carbon atoms, and examples thereof include a benzyl group, a phenethyl group, a naphthylmethyl group, a naphthylethyl group, and a naphthylbutyl group.

[0040] An example of the sulfonylimide anion is a saccharin anion.

[0041] The alkyl group in the bis(alkylsulfonyl)imide anion and the tris(alkylsulfonyl)methide anion is preferably an alkyl group having a carbon number of 1 to 5. Substituents for these alkyl groups include a halogen atom, an alkyl group substituted with a halogen atom, an alkoxy group, an alkylthio group, an alkyloxysulfonyl group, an aryloxysulfonyl group, and a cycloalkylaryloxysulfonyl group, and a fluorine atom or an alkyl group substituted with a fluorine atom is preferred. In addition, the alkyl groups in the bis(alkylsulfonyl)imide anion may be bonded to each other to form a ring structure, which increases the acid strength.

[0042] Other non-nucleophilic anions include, for example, phosphorus fluorides (e.g., PF6 - ), boron fluorides (e.g., BF4 - ), and antimony fluorides (e.g., SbF6 - ) are mentioned.

[0043] As the non-nucleophilic anion, an aliphatic sulfonate anion in which at least the α-position of the sulfonic acid is substituted with a fluorine atom, an aromatic sulfonate anion in which a fluorine atom or a group having a fluorine atom is substituted, a bis(alkylsulfonyl)imide anion in which an alkyl group is substituted with a fluorine atom, or a tris(alkylsulfonyl)methide anion in which an alkyl group is substituted with a fluorine atom is preferred. Among them, a perfluoroaliphatic sulfonate anion (preferably having 4 to 8 carbon atoms) or a benzenesulfonate anion having a fluorine atom is more preferred, and a nonafluorobutanesulfonate anion, a perfluorooctane sulfonate anion, a pentafluorobenzenesulfonate anion, or a 3,5-bis(trifluoromethyl)benzenesulfonate anion is even more preferred.

[0044] The non-nucleophilic anion is also preferably an anion represented by the following formula (AN1).

[0045] [ka]

[0046] In formula (AN1), o represents an integer of 1 to 3. p represents an integer of 0 to 10. q represents an integer of 0 to 10.

[0047] Xf represents a fluorine atom or an alkyl group substituted with at least one fluorine atom. The number of carbon atoms in this alkyl group is preferably 1 to 10, more preferably 1 to 4. In addition, the alkyl group substituted with at least one fluorine atom is preferably a perfluoroalkyl group. Xf is preferably a fluorine atom or a perfluoroalkyl group having 1 to 4 carbon atoms, more preferably a fluorine atom or CF3. In particular, it is further preferable that both Xf are fluorine atoms.

[0048] R4 and R5 each independently represent a hydrogen atom, a fluorine atom, an alkyl group, or an alkyl group substituted with at least one fluorine atom. When there are a plurality of R4 and R5, R4 and R5 may be the same or different. The alkyl group represented by R4 and R5 may have a substituent and preferably has a carbon number of 1 to 4. R4 and R5 are preferably a hydrogen atom. Specific examples and preferred embodiments of the alkyl group substituted with at least one fluorine atom are the same as the specific examples and preferred embodiments of Xf in formula (AN1).

[0049] L represents a divalent linking group. When a plurality of L's are present, they may be the same or different. Examples of the divalent linking group include -O-CO-O-, -COO-, -OCO-, -CONH-, -NHCO-, -CO-, -O-, -S-, -SO-, -SO2-, an alkylene group (preferably having 1 to 6 carbon atoms), a cycloalkylene group (preferably having 3 to 15 carbon atoms), an alkenylene group (preferably having 2 to 6 carbon atoms), and a divalent linking group formed by combining a plurality of these groups. Among these, -O-CO-O-, -COO-, -OCO-, -CONH-, -NHCO-, -CO-, -O-, -SO2-, -O-CO-O-alkylene group-, -alkylene group-O-CO-O-, -COO-alkylene group-, -OCO-alkylene group-, -CONH-alkylene group-, or -NHCO-alkylene group- are preferred, and -O-CO-O-, -O-CO-O-alkylene group-, -alkylene group-O-CO-O-, -COO-, -OCO-, -CONH-, -SO2-, -COO-alkylene group-, or -OCO-alkylene group- are more preferred.

[0050] W represents an organic group containing a cyclic structure, and is preferably a cyclic organic group. Examples of the cyclic organic group include an alicyclic group, an aryl group, and a heterocyclic group. The alicyclic group may be monocyclic or polycyclic. Examples of the monocyclic alicyclic group include monocyclic cycloalkyl groups such as cyclopentyl, cyclohexyl, and cyclooctyl. Examples of the polycyclic alicyclic group include polycyclic cycloalkyl groups such as norbornyl, tricyclodecanyl, tetracyclodecanyl, tetracyclododecanyl, and adamantyl. Among them, alicyclic groups having a bulky structure with 7 or more carbon atoms, such as norbornyl, tricyclodecanyl, tetracyclodecanyl, tetracyclododecanyl, and adamantyl, are preferred.

[0051] The aryl group may be monocyclic or polycyclic, and examples of the aryl group include phenyl, naphthyl, phenanthryl, and anthryl groups. The heterocyclic group may be monocyclic or polycyclic. The polycyclic group can suppress the diffusion of the acid more effectively. The heterocyclic group may have aromaticity or may not have aromaticity. Examples of heterocyclic rings having aromaticity include furan ring, thiophene ring, benzofuran ring, benzothiophene ring, dibenzofuran ring, dibenzothiophene ring, and pyridine ring. Examples of heterocyclic rings not having aromaticity include tetrahydropyran ring, lactone ring, sultone ring, and decahydroisoquinoline ring. As the heterocyclic ring in the heterocyclic group, a furan ring, a thiophene ring, a pyridine ring, or a decahydroisoquinoline ring is particularly preferred.

[0052] The cyclic organic group may have a substituent. Examples of the substituent include an alkyl group (which may be either linear or branched, and preferably has 1 to 12 carbon atoms), a cycloalkyl group (which may be either monocyclic, polycyclic, or spirocyclic, and preferably has 3 to 20 carbon atoms), an aryl group (which preferably has 6 to 14 carbon atoms), a hydroxyl group, an alkoxy group, an ester group, an amide group, a urethane group, a ureido group, a thioether group, a sulfonamide group, and a sulfonate ester group. The carbon constituting the cyclic organic group (the carbon contributing to the ring formation) may be a carbonyl carbon.

[0053] The anion represented by formula (AN1) is SO3 - -CF2-CH2-OCO-(L)q'-W, SO3 - -CF2-CHF-CH2-OCO-(L)q'-W, SO3 - -CF2-COO-(L)q'-W, SO3 - -CF2-CF2-CH2-CH2-(L)qW or SO3 - -CF2-CH(CF3)-OCO-(L)q'-W is preferred, where L, q and W are the same as in formula (AN1), and q' represents an integer of 0 to 10.

[0054] The non-nucleophilic anion is also preferably an anion represented by the following formula (AN2).

[0055] [ka]

[0056] In formula (AN2), X B1 and X B2 Each of X independently represents a hydrogen atom or a monovalent organic group having no fluorine atom. B1 and X B2 is preferably a hydrogen atom. X B3 and X B4 Each of X independently represents a hydrogen atom or a monovalent organic group. B3 and XB4 At least one of X is preferably a fluorine atom or a monovalent organic group having a fluorine atom, B3 and X B4 It is more preferable that both of X are fluorine atoms or monovalent organic groups having fluorine atoms. B3 and X B4 It is more preferable that both of the above are fluorine-substituted alkyl groups. L, q and W are the same as in formula (AN1).

[0057] The non-nucleophilic anion is preferably an anion represented by the following formula (AN3).

[0058] [ka]

[0059] In formula (AN3), each Xa independently represents a fluorine atom or an alkyl group substituted with at least one fluorine atom. Each Xb independently represents a hydrogen atom or an organic group having no fluorine atom. The definitions and preferred embodiments of o, p, q, R4, R5, L, and W are the same as those of formula (AN1).

[0060] The non-nucleophilic anion is also preferably an anion represented by the following formula (AN4).

[0061] [ka]

[0062] In formula (AN4), R 1 and R 2 each independently represents a substituent which is not an electron-withdrawing group or a hydrogen atom. Examples of the substituent that is not an electron-withdrawing group include a hydrocarbon group, a hydroxyl group, an oxyhydrocarbon group, an oxycarbonylhydrocarbon group, an amino group, a hydrocarbon-substituted amino group, and a hydrocarbon-substituted amide group. Moreover, the substituents that are not electron-withdrawing groups are preferably each independently -R', -OH, -OR', -OCOR', -NH2, -NR'2, -NHR', or -NHCOR', where R' is a monovalent hydrocarbon group.

[0063] Examples of the monovalent hydrocarbon group represented by R' include: Monovalent linear or branched hydrocarbon groups such as alkyl groups such as methyl, ethyl, propyl, and butyl; alkenyl groups such as ethenyl, propenyl, and butenyl; and alkynyl groups such as ethynyl, propynyl, and butynyl; cycloalkyl groups such as a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a norbornyl group, or an adamantyl group; monovalent alicyclic hydrocarbon groups such as a cycloalkenyl group such as a cyclopropenyl group, a cyclobutenyl group, a cyclopentenyl group, or a norbornenyl group; Examples of the aromatic hydrocarbon groups include aryl groups such as a phenyl group, a tolyl group, a xylyl group, a mesityl group, a naphthyl group, a methylnaphthyl group, an anthryl group, and a methylanthryl group; and aralkyl groups such as a benzyl group, a phenethyl group, a phenylpropyl group, a naphthylmethyl group, and an anthrylmethyl group. Among them, R 1 and R 2 are each independently preferably a hydrocarbon group (preferably a cycloalkyl group) or a hydrogen atom.

[0064] In formula (AN4), L represents a divalent linking group formed from a combination of one or more linking groups S and one or more alkylene groups which may have a substituent, or a divalent linking group formed from one or more linking groups S. The linking group S is * A -O-CO-O-* B , * A -CO-* B , * A -CO-O-* B , * A -O-CO-* B , * A -O-* B , * A -S-* B, and * A -SO2-* B is a group selected from the group consisting of: However, when L is a "divalent linking group consisting of one or more linking groups S and one or more unsubstituted alkylene groups", which is one form of the "divalent linking group consisting of one or more linking groups S and one or more alkylene groups which may have a substituent", the linking group S is * A -O-CO-O-* B , * A -CO-* B , * A -O-CO-* B , * A -O-* B , * A -S-* B , and * A -SO2-* B In other words, when the alkylene groups in the "divalent linking group consisting of one or more linking groups S and one or more alkylene groups which may have a substituent" are all unsubstituted alkylene groups, the linking group S is preferably a group selected from the group consisting of: A -O-CO-O-* B , * A -CO-* B , * A -O-CO-* B , * A -O-* B , * A -S-* B , and * A -SO2-* B Preferably, it is a group selected from the group consisting of: * A is R in formula (AN4). 3 represents the bond position on the B is -SO3 in formula (AN4) - The bond position on the side is represented.

[0065] In a divalent linking group consisting of one or more linking groups S and an alkylene group which may have one or more substituents, there may be only one linking group S, or there may be two or more. Similarly, there may be only one alkylene group which may have a substituent, or there may be two or more. When there are a plurality of linking groups S, the plurality of linking groups S may be the same or different. When there are a plurality of alkylene groups, the plurality of alkylene groups may be the same or different. In addition, the linking groups S may be bonded to each other consecutively. A -CO-* B , * A -O-CO-* B , and * A -O-* B The groups selected from the group consisting of are consecutively bonded to form "* A -O-CO-O-* B It is preferable that " is not formed. A -CO-* B and* A -O-* B The groups selected from the group consisting of are consecutively bonded to form "* A -O-CO-* B " and "* A -CO-O-* B " is preferably not formed.

[0066] In a divalent linking group consisting of one or more linking groups S, there may be only one linking group S or there may be two or more linking groups S. When there are multiple linking groups S, the multiple linking groups S may be the same or different. Again, * A -CO-* B , * A -O-CO-* B , and * A -O-* B The groups selected from the group consisting of are consecutively bonded to form "* A -O-CO-O-* B It is preferable that " is not formed. A -CO-*B and* A -O-* B The groups selected from the group consisting of are consecutively bonded to form "* A -O-CO-* B " and "* A -CO-O-* B " is preferably not formed.

[0067] However, in either case, -SO3 - The atom at the β-position to is not a carbon atom having a fluorine atom as a substituent. In addition, when the atom at the β-position is a carbon atom, the carbon atom need not be directly substituted with a fluorine atom, and the carbon atom may have a substituent having a fluorine atom (for example, a fluoroalkyl group such as a trifluoromethyl group). The atom at the β-position is, in other words, —C(R 1 )(R 2 )- is an atom in L that is directly bonded to

[0068] Among them, it is preferable that L has only one linking group S. In other words, L preferably represents a divalent linking group consisting of a combination of one linking group S and an alkylene group which may have one or more substituents, or a divalent linking group consisting of one linking group S.

[0069] L is preferably, for example, a group represented by the following formula (AN4-2). * a -(CR 2a 2) X -Q-(CR 2b 2) Y -* b (AN4-2)

[0070] In formula (AN4-2), * a is R in formula (AN4). 3 represents the bonding position with * b is -C(R 1 )(R2 )- represents the bond position. X and Y each independently represent an integer of 0 to 10, and preferably an integer of 0 to 3. R 2a and R 2b each independently represents a hydrogen atom or a substituent. R 2a and R 2b If there are multiple of each, there are multiple R 2a and R 2b may be the same or different, However, when Y is 1 or more, -C(R 1 )(R 2 )- and CR 2b R in 2 2b is other than a fluorine atom. Q is * A -O-CO-O-* B , * A -CO-* B , * A -CO-O-* B , * A -O-CO-* B , * A -O-* B , * A -S-* B , or * A -SO2-* B Represents. However, X+Y in formula (AN4-2) is 1 or more, and R in formula (AN4-2) 2a and R 2b When all of are hydrogen atoms, Q is * A -O-CO-O-* B , * A -CO-* B , * A -O-CO-* B , * A -O-* B , * A -S-* B , or * A -SO2-* B Represents. * A is R in formula (AN4). 3represents the bond position on the B is -SO3 in formula (AN4) - The bond position on the side is represented.

[0071] In formula (AN4), R 3 represents an organic group. The organic group is not limited as long as it has one or more carbon atoms, and may be a straight-chain group (e.g., a straight-chain alkyl group) or a branched-chain group (e.g., a branched-chain alkyl group such as a t-butyl group), or may have a cyclic structure. The organic group may or may not have a substituent. The organic group may or may not have a heteroatom (oxygen atom, sulfur atom, and / or nitrogen atom, etc.).

[0072] Among them, R 3 is preferably an organic group having a cyclic structure. The cyclic structure may be a single ring or multiple rings, and may have a substituent. The ring in the organic group containing a cyclic structure is preferably directly bonded to L in formula (AN4). The organic group having a cyclic structure may or may not have a heteroatom (such as an oxygen atom, a sulfur atom, and / or a nitrogen atom). The heteroatom may substitute for one or more of the carbon atoms forming the cyclic structure. The organic group having a cyclic structure is preferably, for example, a hydrocarbon group having a cyclic structure, a lactone ring group, or a sultone ring group, and among these, the organic group having a cyclic structure is preferably a hydrocarbon group having a cyclic structure. The cyclic hydrocarbon group is preferably a monocyclic or polycyclic cycloalkyl group, which may have a substituent. The cycloalkyl group may be a monocyclic group (such as a cyclohexyl group) or a polycyclic group (such as an adamantyl group), and preferably has 5 to 12 carbon atoms. The lactone group and sultone group are preferably groups in which one hydrogen atom has been removed from a ring atom constituting the lactone structure or sultone structure in any of the structures represented by general formulae (LC1-1) to (LC1-21) and general formulae (SL1-1) to (SL1-3) described below.

[0073] The non-nucleophilic anion may be a benzenesulfonate anion, and is preferably a benzenesulfonate anion substituted with a branched alkyl group or a cycloalkyl group.

[0074] As the non-nucleophilic anion, an aromatic sulfonate anion represented by the following formula (AN5) is also preferred.

[0075] [ka]

[0076] In formula (AN5), Ar represents an aryl group (such as a phenyl group) and may further have a substituent other than the sulfonate anion and the -(DB) group. Examples of the further substituent include a fluorine atom and a hydroxyl group.

[0077] n represents an integer of 0 or more. As n, 1 to 4 is preferable, 2 to 3 is more preferable, and 3 is even more preferable.

[0078] D represents a single bond or a divalent linking group. Examples of the divalent linking group include an ether group, a thioether group, a carbonyl group, a sulfoxide group, a sulfone group, a sulfonate group, an ester group, and a group formed by combining two or more of these groups.

[0079] B represents a hydrocarbon group.

[0080] B is preferably an aliphatic hydrocarbon structure, and more preferably an isopropyl group, a cyclohexyl group, or an aryl group which may further have a substituent (such as a tricyclohexylphenyl group).

[0081] The non-nucleophilic anion is also preferably a disulfonamide anion. The disulfonamide anion is, for example, N - (SO2-R q )2 is the anion. Here, R q represents an alkyl group which may have a substituent, preferably a fluoroalkyl group, more preferably a perfluoroalkyl group. q may be bonded to each other to form a ring. q The group formed by bonding together is preferably an alkylene group which may have a substituent, more preferably a fluoroalkylene group, and further preferably a perfluoroalkylene group. The alkylene group preferably has 2 to 4 carbon atoms.

[0082] Further, examples of the non-nucleophilic anion include anions represented by the following formulas (d1-1) to (d1-3). The specific compounds having anions represented by the following formulas (d1-1) to (d1-3) as anions can also function as an acid diffusion controller described later.

[0083] [ka]

[0084] In formula (d1-1), R 51 represents a hydrocarbon group (for example, an aryl group such as a phenyl group) which may have a substituent (for example, a hydroxyl group). In formula (d1-2), Z 2c represents a hydrocarbon group having 1 to 30 carbon atoms which may have a substituent (with the proviso that the carbon atom adjacent to S is not substituted with a fluorine atom). Z 2c The hydrocarbon group in may be linear or branched, or may have a cyclic structure. In addition, a carbon atom in the hydrocarbon group (preferably, a carbon atom that is a member of the ring when the hydrocarbon group has a cyclic structure) may be a carbonyl carbon (-CO-). Examples of the hydrocarbon group include a group having a norbornyl group that may have a substituent. The carbon atom forming the norbornyl group may be a carbonyl carbon. In addition, "Z 2c -SO3 -" is preferably different from the anions represented by the above formulas (AN1) to (AN5). For example, Z 2c is preferably other than an aryl group. 2c In -SO3 - The atoms at the α-position and β-position to Z are preferably atoms other than carbon atoms having a fluorine atom as a substituent. 2c is -SO3 - The atom at the α-position and / or the atom at the β-position to the above is preferably a ring member atom in a cyclic group. In formula (d1-3), R 52 represents an organic group (preferably a hydrocarbon group having a fluorine atom); Y 3 represents a linear, branched, or cyclic alkylene group, an arylene group, or a carbonyl group, and Rf represents a hydrocarbon group.

[0085] In general formula (1), Ar 1 and Ar 2 each independently represents an aromatic hydrocarbon ring group having at least one (preferably 1 to 5) substituent. Examples of the aromatic hydrocarbon ring group include a benzene ring group, a naphthalene ring group, and an anthracene ring group. Of these, the aromatic hydrocarbon ring group is preferably, independently of the other, a benzene ring group. The aromatic hydrocarbon ring group has at least one (preferably 1 to 5) substituents which are each independently preferably a fluorine atom, a fluoroalkyl group, or an organic group other than an electron-withdrawing group, and more preferably a fluoroalkyl group, or an organic group other than an electron-withdrawing group. Examples of the fluoroalkyl group include the same fluoroalkyl groups as those in the fluorine-containing group described below. The organic groups other than the electron-withdrawing group are preferably each independently a hydrocarbon group, an oxyhydrocarbon group, a hydrocarbon-substituted amino group, or a hydrocarbon-substituted amide group. However, the hydrocarbon group portion in these organic groups does not have a halogen atom as a substituent. In addition, the hydrocarbon group portion in these organic groups may be linear or branched, or may have a cyclic structure as a whole or a part. Among them, the hydrocarbon group portion is preferably linear or branched, and preferably does not have a cyclic structure. In addition, the hydrocarbon group portion is preferably unsubstituted. Moreover, the organic groups other than the electron-withdrawing group are each preferably independently -R', -OR', -NR'2, -NHR', or -NHCOR'. R' is a monovalent hydrocarbon group. However, the hydrocarbon group does not have a halogen atom as a substituent. The hydrocarbon group may be linear or branched, and may have a cyclic structure as a whole or a part. Among them, the hydrocarbon group is preferably linear or branched, and preferably does not have a cyclic structure. It is also preferable that the hydrocarbon group has no substitution. The organic groups other than the electron-withdrawing groups are each independently preferably a hydrocarbon group (-R'), more preferably a linear or branched alkyl group.

[0086] Examples of the monovalent hydrocarbon group represented by R' include: linear or branched hydrocarbon groups such as alkyl groups, e.g., methyl, ethyl, n-propyl, isopropyl, n-butyl, and tert-butyl; alkenyl groups, e.g., ethenyl, propenyl, and butenyl; and alkynyl groups, e.g., ethynyl, propynyl, and butynyl; cycloalkyl groups such as a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a norbornyl group, and an adamantyl group; alicyclic hydrocarbon groups such as a cycloalkenyl group such as a cyclopropenyl group, a cyclobutenyl group, a cyclopentenyl group, and a norbornenyl group; Examples of the alkyl group include aryl groups such as a phenyl group, a tolyl group, a xylyl group, a mesityl group, a naphthyl group, a methylnaphthyl group, an anthryl group, and a methylanthryl group; and aromatic hydrocarbon groups such as aralkyl groups such as a benzyl group, a phenethyl group, a phenylpropyl group, a naphthylmethyl group, and an anthrylmethyl group. The monovalent hydrocarbon group represented by R' preferably has 1 to 10 carbon atoms, more preferably 2 to 8 carbon atoms, and further preferably 3 to 6 carbon atoms.

[0087] When an organic group other than the above-mentioned electron-withdrawing group has a substituent (for example, when the R' portion in -R', -OR', -NR'2, -NHR', or -NHCOR' has a substituent), the substituent is preferably an organic group other than the above-mentioned electron-withdrawing group (-R', -OR', -NR'2, -NHR', and / or -NHCOR', etc.). The total number of carbon atoms in the organic groups other than the electron-withdrawing groups (including the carbon atoms contained in the substituent when the organic group has a substituent) is preferably 1 to 10, more preferably 2 to 8, and further preferably 3 to 6.

[0088] Ar 1 and Ar 2 The aromatic hydrocarbon ring group in may or may not have a substituent other than the organic group other than the electron-withdrawing group described above. 1 and Ar 2 It is preferable that the aromatic hydrocarbon ring group in the formula (I) does not have any substituent other than the organic group other than the above-mentioned electron-withdrawing group. In addition, when the aromatic hydrocarbon group is said to have a substituent (an organic group other than an electron-withdrawing group, etc.), it is intended that the substituent (an organic group other than an electron-withdrawing group, etc.) is directly bonded to a ring atom of the aromatic hydrocarbon group. For example, when the aromatic hydrocarbon group is said to have an organic group other than an electron-withdrawing group, it is intended that the organic group other than the electron-withdrawing group is directly bonded to a ring atom of the aromatic hydrocarbon group, not that an organic group other than an electron-withdrawing group is included in a part of the substituent possessed by the aromatic hydrocarbon group. Hereinafter, when a similar expression is used for a specific compound, it has the same intention.

[0089] In general formula (1), Ar 3 represents an aromatic hydrocarbon ring group (benzene ring group) represented by general formula (1R).

[0090] [ka]

[0091] In formula (1R), * represents a bonding position. In general formula (1R), R 1 ~R 5 each independently represents a hydrogen atom, a fluorine atom, or an alkyl group which may have a substituent. The optionally substituted alkyl group is preferably a fluoroalkyl group. However, R 1 and R 5 At least one of these represents a fluorine-containing group selected from the group consisting of a fluorine atom and a fluoroalkyl group. The fluoroalkyl group in the fluorine-containing group is an alkyl group having at least one fluorine atom as a substituent. The alkyl group in the fluoroalkyl group may be linear or branched. It is also preferable that the alkyl group in the fluoroalkyl group does not have a substituent other than a fluorine atom. The fluoroalkyl group may be a perfluoroalkyl group. The number of carbon atoms in the fluoroalkyl group is preferably 1 to 10, more preferably 1 to 5, independently of each other. Of these, the fluorine-containing group is preferably a fluoroalkyl group. Ar 1 , Ar 2 , and Ar 3 The aromatic hydrocarbon ring group represented by the following formula (I) preferably has a total of 1 to 10 fluorine-containing groups (preferably fluoroalkyl groups).

[0092] In general formula (1), Ar 1 , Ar 2 , and Ar 3 At least two of the groups have different structures. In other words, Ar 1 , Ar2 , and Ar 3 Not all of the groups have the same structure. In addition, Ar 1 , Ar 2 , and Ar 3 are groups having the same structure, for example, Ar 1 and Ar 2 each of the aromatic hydrocarbon ring groups is a benzene ring group, and Ar 1 , Ar 2 , and Ar 3 The types and arrangements (bonding positions) of the groups on the benzene ring groups of Ar 1 , Ar 2 , and Ar 3 Even if the combinations of the types of groups on the benzene ring groups are all the same, if the arrangements of those groups are not all the same, then Ar 1 , Ar 2 , and Ar 3 Not all of the above are necessarily groups having the same structure. Hereinafter, in general formula (2) and general formula (3), similar expressions have the same meaning.

[0093] Among them, the compound represented by the general formula (1) preferably satisfies the following condition A or condition B. When the compound satisfies the condition A or condition B, it may satisfy only one of the conditions A and B, or may satisfy both of them. Condition A: In general formula (1), Ar 1 , Ar 2 , and Ar 3 The aromatic hydrocarbon ring group represented by the following formula (I) has a total of two or more (preferably three or more, more preferably 3 to 10) fluorine-containing groups (preferably fluoroalkyl groups). Condition B: In general formula (1), Ar 1 , Ar 2 , and Ar 3has a total of one or more (preferably 1 to 5, more preferably 2) organic groups other than electron-withdrawing groups (preferably a hydrocarbon group, more preferably an alkyl group; also preferably a linear or branched chain group), and the total number of carbon atoms contained in the total of one or more organic groups other than electron-withdrawing groups is 2 or more (preferably 3 or more, more preferably 3 to 20, even more preferably 6 to 10). Here, the total number of carbon atoms contained in the organic group other than the one or more electron-withdrawing groups is 3 or more, for example, Ar 1 , Ar 2 , and Ar 3 In the case where a plurality of organic groups other than the electron-withdrawing group are present as the substituents of the aromatic hydrocarbon ring group represented by the formula (I), the total number of carbon atoms contained in the plurality of organic groups other than the electron-withdrawing group is 3 or more. 1 , Ar 2 , and Ar 3 In the case where only one organic group other than an electron-withdrawing group is present as a substituent of an aromatic hydrocarbon ring group represented by the formula (I), the total number of carbon atoms contained in the organic group other than the one electron-withdrawing group is 3 or more.

[0094] More specifically, the following compound (A), compound (B), and compound (C) are used for the explanation. - represents an organic anion, and compound (A), compound (B), and compound (C) all correspond to the compound represented by general formula (1). For example, when compound (A), compound (B), and compound (C) are applied to general formula (1), Ar 1 , Ar 2 , and Ar 3 The total number of organic groups other than the electron-withdrawing group contained in the aromatic hydrocarbon ring group represented by the formula (I) is two. In addition, when the compound (A), the compound (B), and the compound (C) are applied to the general formula (1), Ar 1 , Ar 2 , and Ar 3The total numbers of carbon atoms contained in the organic groups other than the electron-withdrawing group of the aromatic hydrocarbon ring group represented by the following formula (1) are 8, 2, and 8, from the left. In addition, when the compound (A), the compound (B), and the compound (C) are applied to the general formula (1), Ar 1 , Ar 2 , and Ar 3 The total number of fluorine-containing groups contained in the aromatic hydrocarbon ring group represented by the following formula (1) is 1, 5, and 2, from the left. Other similar expressions for specific compounds have the same meaning.

[0095] [ka]

[0096] (Compound represented by general formula (2)) General formula (2) is shown below.

[0097] [ka]

[0098] In general formula (2), X - represents an organic anion. X in general formula (2) - As the organic anion represented by the formula (1), for example, - Similarly, organic anions represented by the following formula are also included.

[0099] Ar 4 and Ar 5 each independently represents an aromatic hydrocarbon ring group having at least one substituent. Examples of the aromatic hydrocarbon ring group include a benzene ring group, a naphthalene ring group, and an anthracene ring group. Of these, the aromatic hydrocarbon ring group is preferably, independently of the other, a benzene ring group. The aromatic hydrocarbon ring group has at least one (preferably 1 to 5) substituents which are each independently preferably a fluorine atom, a fluoroalkyl group, or an organic group other than an electron-withdrawing group, and more preferably a fluoroalkyl group, or an organic group other than an electron-withdrawing group. In addition, examples of the fluoroalkyl group in general formula (2) (including general formula (2R)) include the same fluoroalkyl groups as those which can be the fluorine-containing group explained in relation to general formula (1) (including general formula (1R)). Examples of the organic group other than the electron-withdrawing group in general formula (2) (including general formula (2R)) include the organic groups other than the electron-withdrawing group described in relation to general formula (1) (including general formula (1R)). Among them, Ar 4 and Ar 5 The organic group other than the electron-withdrawing group as a substituent of the aromatic hydrocarbon ring group is preferably linear or branched. For example, the organic groups other than the electron-withdrawing group are each independently -R', -OR', -OCOR', -NR'2, -NHR', or -NHCOR', and R' is preferably a linear or branched hydrocarbon group. When the organic group other than the electron-withdrawing group is linear or branched, the compound represented by general formula (2) is likely to have good compatibility with the acid-decomposable resin, and the effect of the present invention is considered to be more excellent.

[0100] In general formula (2), Ar 6 represents an aromatic hydrocarbon ring group (benzene ring group) represented by general formula (2R).

[0101] [ka]

[0102] In formula (2R), * represents the bonding position. In the general formula (2R), each independently represents R 6 , R 7 , R 9 , and R 10 each independently represents a hydrogen atom, a fluorine atom, or an alkyl group which may have a substituent. The optionally substituted alkyl group is preferably a fluoroalkyl group. In other words, R 6 , R 7 , R 9 , and R 10 are each independently preferably a hydrogen atom, a fluorine atom or a fluoroalkyl group, more preferably a hydrogen atom. In general formula (2R), R 8 represents a fluorine-containing group selected from the group consisting of a fluorine atom and a fluoroalkyl group. The fluorine-containing group is preferably a fluoroalkyl group.

[0103] Ar 6 The aromatic hydrocarbon ring group (benzene ring group) represented by general formula (2R) is preferably a group represented by general formula (2S).

[0104] [ka]

[0105] In formula (2S), * represents a bonding position. In general formula (2S), R 8F R represents a fluoroalkyl group. 8F The fluoroalkyl group in the formula (2R) is, for example, 8 The same applies to the fluoroalkyl group in the above.

[0106] Ar in general formula (2) 5 and Ar 6 It is also preferable that both of the above are a group represented by general formula (2S). In this case, Ar 5 and a group represented by general formula (2S) in Ar 6 and the groups represented by general formula (2S) in the above may be the same or different. In addition, Ar in the general formula (2) 5 and Ar 6 are each independently a group represented by general formula (2S), Ar 4It is also preferred that the aromatic hydrocarbon group has at least one (preferably 1 to 5) organic group other than the electron-withdrawing group, and Ar 4 It is also preferable that the aromatic hydrocarbon group has at least two (preferably 2 to 5) substituents.

[0107] In general formula (2), Ar 4 , Ar 5 , and Ar 6 At least two of the groups have different structures. In other words, Ar 4 , Ar 5 , and Ar 6 Not all of the groups have the same structure.

[0108] In general formula (2), Ar 4 , Ar 5 , and Ar 6 The aromatic hydrocarbon ring group represented by the following formula has a total of two or more fluorine-containing groups (preferably fluoroalkyl groups). In addition, Ar 6 The aromatic hydrocarbon ring group represented by the formula (I) may have two or more (e.g., two to three) fluorine-containing groups as substituents, or Ar 6 The aromatic hydrocarbon ring group represented by the formula: 4 and / or an aromatic hydrocarbon ring group represented by Ar 5 The aromatic hydrocarbon ring group represented by the following formula (I) may have one or more (for example, 1 to 3) fluorine-containing groups as substituents.

[0109] Among them, the compound represented by the general formula (2) preferably satisfies the following condition 1 or condition 2. When the compound satisfies the condition 1 or condition 2, the compound may satisfy either one of the conditions 1 or 2, or both of them. Condition 1: In general formula (2), Ar 4 , Ar 5 , and Ar 6 has a total of three or more (preferably 3 to 6) fluorine-containing groups (preferably fluoroalkyl groups). Condition 2: In general formula (2), Ar 4 , Ar5 , and Ar 6 has a total of one or more (preferably 1 to 6) linear or branched organic groups other than electron-withdrawing groups, and the total number of carbon atoms contained in the total of one or more linear or branched organic groups other than electron-withdrawing groups is 2 or more (preferably 3 or more, more preferably 3 to 8).

[0110] The compound represented by general formula (2) is preferably different from the compound represented by general formula (1). For example, the compound represented by the general formula (2) is S + The benzene ring group bonded to S + It is also preferred that the fluorine-containing group is not present at the ortho position relative to the bonding position with the aryl group.

[0111] (Compound represented by general formula (3)) General formula (3) is shown below.

[0112] [ka]

[0113] In general formula (3), X - represents an organic anion. X in general formula (3) - As the organic anion represented by the formula (1), for example, - Similarly, organic anions represented by the following formula are also included.

[0114] In general formula (3), Ar 7 and Ar 8 each independently represents an aromatic hydrocarbon ring group which may have an organic group other than an electron-withdrawing group. Examples of the aromatic hydrocarbon ring group include a benzene ring group, a naphthalene ring group, and an anthracene ring group. Of these, the aromatic hydrocarbon ring group is preferably, independently of the other, a benzene ring group. As described above, the aromatic hydrocarbon ring groups may each independently have an organic group (preferably 1 to 5) other than the electron-withdrawing group. 7 and Ar 8 The aromatic hydrocarbon ring group has no substituents other than the "organic group other than an electron-withdrawing group". However, Ar 7 and Ar 8 The aromatic hydrocarbon ring group represented by the following formula has a total of one or more (preferably 1 to 8) organic groups other than the electron-withdrawing group. In addition, examples of the organic group other than the electron-withdrawing group in general formula (3) (including general formula (3R)) include the organic groups other than the electron-withdrawing group described in relation to general formula (1) (including general formula (1R)).

[0115] In general formula (3), Ar 9 represents an aromatic hydrocarbon ring group (benzene ring group) represented by general formula (3R).

[0116] [ka]

[0117] In formula (3R), * represents the bonding position. In general formula (3R), R 11 , R 13 , and R 15 each independently represents a hydrogen atom, a fluorine atom, or an alkyl group which may have a substituent. The alkyl group which may have a substituent is preferably a fluoroalkyl group. In general formula (3R), R 12 and R 14 Each of the groups independently represents a fluorine-containing group selected from the group consisting of a fluorine atom and a fluoroalkyl group. The fluorine-containing group is preferably a fluoroalkyl group. In addition, examples of the fluoroalkyl group in general formula (3R) include the same fluoroalkyl groups which can be the fluorine-containing group explained in relation to general formula (1) (including general formula (1R)).

[0118] Among them, in the general formula (3), Ar 7 , Ar 8 , and Ar 9 It is preferable that the aromatic hydrocarbon ring group represented by the following formula (I) has a total of one or more (preferably 2 to 5) organic groups other than the electron-withdrawing group, and the total number of carbon atoms contained in the total of one or more organic groups other than the electron-withdrawing group is 2 or more (preferably 3 or more, more preferably 3 to 20, and even more preferably 3 to 12). Ar 7 , Ar 8 , and Ar 9 The aromatic hydrocarbon ring group represented by the following formula (I) preferably has a total of 2 to 5 fluorine-containing groups (preferably fluoroalkyl groups).

[0119] The compound represented by general formula (3) is preferably different from the compound represented by general formula (1) and / or the compound represented by general formula (2). For example, the compound represented by the general formula (3) is S + The benzene ring group bonded to S + It is also preferred that the fluorine-containing group is not present at the ortho-position and / or para-position relative to the bonding position.

[0120] The organic cations that the specific compounds may have (X in the general formulas (1) to (3)) are listed below. - Examples of the parts other than the above are given below.

[0121] [ka]

[0122] [ka]

[0123] [ka]

[0124] In the resist composition, the content of the specific compound is preferably 5% by mass or more, more preferably 9% by mass or more, and even more preferably 10% by mass or more, based on the total solid content of the composition, in terms of superior effects of the present invention. Also, the content is preferably 40% by mass or less, more preferably 35% by mass or less, and even more preferably 33% by mass or less. In addition, when the specific compound includes a specific compound having an anion represented by any one of formulas (d1-1) to (d1-3), the content of the specific compound is preferably 1 to 30 mass%, more preferably 3 to 20 mass%, of the total solid content. When the specific compound contains a specific compound having an anion other than the anion represented by any one of formulas (d1-1) to (d1-3) (for example, an anion represented by formulas (AN1) to (AN5), a disulfonamide anion, and a perfluoroaliphatic sulfonate anion, etc.), the content of the specific compound is preferably 3 to 35 mass%, more preferably 10 to 25 mass%, of the total solid content. The specific compound may be used alone or in combination of two or more. The solid content means all components other than the solvent described below.

[0125] <Acid-decomposable resin (resin (A))>

[0126] The composition of the present invention contains a resin that decomposes under the action of an acid and has an increased polarity (hereinafter, also referred to as "acid-decomposable resin" or "resin (A)"). That is, in the pattern formation method of the present invention, typically, when an alkaline developer is used as the developer, a positive pattern is preferably formed, and when an organic developer is used as the developer, a negative pattern is preferably formed. The resin (A) usually contains a group that decomposes under the action of an acid to increase its polarity (hereinafter also referred to as an "acid-decomposable group"), and preferably contains a repeating unit having an acid-decomposable group.

[0127] (Repeating Unit Having an Acid-Decomposable Group) The acid decomposable group refers to a group that decomposes under the action of an acid to generate a polar group. The acid decomposable group preferably has a structure in which a polar group is protected by a leaving group that is released under the action of an acid. In other words, the resin (A) has a repeating unit that decomposes under the action of an acid to generate a polar group. The polarity of the resin having this repeating unit increases under the action of an acid, increasing its solubility in an alkaline developer and decreasing its solubility in an organic solvent. The polar group is preferably an alkali-soluble group, and examples thereof include acidic groups such as a carboxyl group, a phenolic hydroxyl group, a fluorinated alcohol group, a sulfonic acid group, a phosphate group, a sulfonamide group, a sulfonylimide group, an (alkylsulfonyl)(alkylcarbonyl)methylene group, an (alkylsulfonyl)(alkylcarbonyl)imide group, a bis(alkylcarbonyl)methylene group, a bis(alkylcarbonyl)imide group, a bis(alkylsulfonyl)methylene group, a bis(alkylsulfonyl)imide group, a tris(alkylcarbonyl)methylene group, and a tris(alkylsulfonyl)methylene group, as well as an alcoholic hydroxyl group. Among these, the polar group is preferably a carboxyl group, a phenolic hydroxyl group, a fluorinated alcohol group (preferably a hexafluoroisopropanol group), or a sulfonic acid group.

[0128] Examples of the leaving group which is eliminated by the action of an acid include groups represented by the formulae (Y1) to (Y4). Formula (Y1):-C(Rx1)(Rx2)(Rx3) Formula(Y2):-C(=O)OC(Rx1)(Rx2)(Rx3) Formula(Y3):-C(R 36 )(R 37 )(OR 38 ) Formula (Y4):-C(Rn)(H)(Ar)

[0129] In formula (Y1) and formula (Y2), Rx1 to Rx3 each independently represent an alkyl group (linear or branched), a cycloalkyl group (monocyclic or polycyclic), an alkenyl group (linear or branched), or an aryl group (monocyclic or polycyclic). When all of Rx1 to Rx3 are alkyl groups (linear or branched), it is preferable that at least two of Rx1 to Rx3 are methyl groups. In particular, it is preferable that Rx1 to Rx3 each independently represent a linear or branched alkyl group, and it is more preferable that Rx1 to Rx3 each independently represent a linear alkyl group. Two of Rx1 to Rx3 may be bonded to form a monocycle or polycycle. The alkyl group of Rx1 to Rx3 is preferably an alkyl group having 1 to 5 carbon atoms, such as a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, and a t-butyl group. As the cycloalkyl group of Rx1 to Rx3, a monocyclic cycloalkyl group such as a cyclopentyl group and a cyclohexyl group, and a polycyclic cycloalkyl group such as a norbornyl group, a tetracyclodecanyl group, a tetracyclododecanyl group, and an adamantyl group are preferable. The aryl group of Rx1 to Rx3 is preferably an aryl group having 6 to 10 carbon atoms, and examples thereof include a phenyl group, a naphthyl group, and an anthryl group. The alkenyl group of Rx1 to Rx3 is preferably a vinyl group. The ring formed by combining two of Rx1 to Rx3 is preferably a cycloalkyl group. The cycloalkyl group formed by combining two of Rx1 to Rx3 is preferably a monocyclic cycloalkyl group such as a cyclopentyl group or a cyclohexyl group, or a polycyclic cycloalkyl group such as a norbornyl group, a tetracyclodecanyl group, a tetracyclododecanyl group, or an adamantyl group, and more preferably a monocyclic cycloalkyl group having 5 to 6 carbon atoms. In the cycloalkyl group formed by combining two of Rx1 to Rx3, for example, one of the methylene groups constituting the ring may be replaced with a heteroatom such as an oxygen atom, a group having a heteroatom such as a carbonyl group, or a vinylidene group. In addition, in these cycloalkyl groups, one or more of the ethylene groups constituting the cycloalkane ring may be replaced with a vinylene group. In the group represented by formula (Y1) or formula (Y2), for example, it is preferable that Rx1 is a methyl group or an ethyl group, and Rx2 and Rx3 are bonded to form the above-mentioned cycloalkyl group.

[0130] In formula (Y3), R 36 ~R 38 R each independently represents a hydrogen atom or a monovalent organic group. 37 and R 38 may be bonded to each other to form a ring. Examples of the monovalent organic group include an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, and an alkenyl group. R 36 It is also preferred that is a hydrogen atom. The alkyl group, cycloalkyl group, aryl group, and aralkyl group may contain a group having a heteroatom such as an oxygen atom and / or a heteroatom such as a carbonyl group. For example, the alkyl group, cycloalkyl group, aryl group, and aralkyl group may have one or more methylene groups replaced with a heteroatom such as an oxygen atom and / or a group having a heteroatom such as a carbonyl group. Also, R 38 R may be bonded to another substituent on the main chain of the repeating unit to form a ring. 38 The group formed by bonding together of the repeating unit and another substituent carried by the main chain of the repeating unit is preferably an alkylene group such as a methylene group.

[0131] Formula (Y3) is preferably a group represented by the following formula (Y3-1).

[0132] [ka]

[0133] Here, L1 and L2 each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, or a group formed by combining these (for example, a group formed by combining an alkyl group with an aryl group). M represents a single bond or a divalent linking group. Q represents an alkyl group which may contain a heteroatom, a cycloalkyl group which may contain a heteroatom, an aryl group which may contain a heteroatom, an amino group, an ammonium group, a mercapto group, a cyano group, an aldehyde group, or a group combining these (for example, a group combining an alkyl group and a cycloalkyl group). The alkyl and cycloalkyl groups may, for example, have one of the methylene groups replaced with a heteroatom such as an oxygen atom or a group containing a heteroatom such as a carbonyl group. It is preferable that one of L1 and L2 is a hydrogen atom, and the other is an alkyl group, a cycloalkyl group, an aryl group, or a combination of an alkylene group and an aryl group. At least two of Q, M and L1 may be bonded to form a ring (preferably a 5- or 6-membered ring). From the viewpoint of fine patterning, L2 is preferably a secondary or tertiary alkyl group, more preferably a tertiary alkyl group. Examples of the secondary alkyl group include an isopropyl group, a cyclohexyl group, or a norbornyl group, and examples of the tertiary alkyl group include a tert-butyl group or an adamantane group. In these embodiments, Tg (glass transition temperature) and activation energy are high, so that the film strength is ensured and fogging can be suppressed.

[0134] In formula (Y4), Ar represents an aromatic ring group. Rn represents an alkyl group, a cycloalkyl group, or an aryl group. Rn and Ar may be bonded to each other to form a non-aromatic ring. Ar is more preferably an aryl group.

[0135] In terms of excellent acid decomposition property of the repeating unit, when a non-aromatic ring is directly bonded to the polar group (or a residue thereof) in a leaving group protecting a polar group, it is also preferable that a ring member atom adjacent to the ring member atom directly bonded to the polar group (or a residue thereof) in the non-aromatic ring does not have a halogen atom such as a fluorine atom as a substituent.

[0136] Other examples of the leaving group that is eliminated by the action of an acid include a 2-cyclopentenyl group having a substituent (such as an alkyl group), such as a 3-methyl-2-cyclopentenyl group, and a cyclohexyl group having a substituent (such as an alkyl group), such as a 1,1,4,4-tetramethylcyclohexyl group.

[0137] The repeating unit having an acid-decomposable group is also preferably a repeating unit represented by formula (A).

[0138] [ka]

[0139] L1 represents a divalent linking group which may have a fluorine atom or an iodine atom, R1 represents a hydrogen atom, a fluorine atom, an iodine atom, an alkyl group which may have a fluorine atom or an iodine atom, or an aryl group which may have a fluorine atom or an iodine atom, and R2 represents a leaving group which is eliminated by the action of an acid and which may have a fluorine atom or an iodine atom, provided that at least one of L1, R1, and R2 has a fluorine atom or an iodine atom. L1 represents a divalent linking group which may have a fluorine atom or an iodine atom. Examples of the divalent linking group which may have a fluorine atom or an iodine atom include -CO-, -O-, -S-, -SO-, -SO2-, a hydrocarbon group which may have a fluorine atom or an iodine atom (e.g., an alkylene group, a cycloalkylene group, an alkenylene group, an arylene group, etc.), and a linking group in which a plurality of these are linked together. Among them, L1 is preferably -CO- or -arylene group-alkylene group having a fluorine atom or an iodine atom-. The arylene group is preferably a phenylene group. The alkylene group may be linear or branched. The number of carbon atoms in the alkylene group is not particularly limited, but is preferably 1 to 10, and more preferably 1 to 3. The total number of fluorine atoms and iodine atoms contained in the alkylene group having a fluorine atom or an iodine atom is not particularly limited, but is preferably 2 or more, more preferably 2 to 10, and even more preferably 3 to 6.

[0140] R1 represents a hydrogen atom, a fluorine atom, an iodine atom, an alkyl group which may have a fluorine atom or an iodine atom, or an aryl group which may have a fluorine atom or an iodine atom. The alkyl group may be linear or branched. The number of carbon atoms in the alkyl group is not particularly limited, but is preferably 1 to 10, and more preferably 1 to 3. The total number of fluorine atoms and iodine atoms contained in the alkyl group having a fluorine atom or an iodine atom is not particularly limited, but is preferably 1 or more, more preferably 1 to 5, and even more preferably 1 to 3. The alkyl group may contain a heteroatom other than a halogen atom, such as an oxygen atom.

[0141] R2 represents a leaving group which is eliminated by the action of an acid and which may have a fluorine atom or an iodine atom. Among them, examples of the leaving group include groups represented by formulae (Z1) to (Z4). Formula (Z1):-C(Rx 11 )(Rx 12 )(Rx 13 ) Formula (Z2):-C(=O)OC(Rx 11 )(Rx 12 )(Rx 13 ) Formula (Z3):-C(R 136 )(R 137 )(OR 138 ) Formula (Z4):-C(Rn1)(H)(Ar1)

[0142] In formulas (Z1) and (Z2), Rx 11 ~Rx 13Rx each independently represents an alkyl group (linear or branched) which may have a fluorine atom or an iodine atom, a cycloalkyl group (monocyclic or polycyclic) which may have a fluorine atom or an iodine atom, an alkenyl group (linear or branched) which may have a fluorine atom or an iodine atom, or an aryl group (monocyclic or polycyclic) which may have a fluorine atom or an iodine atom. 11 ~Rx 13 When all of Rx are alkyl groups (linear or branched), 11 ~Rx 13 At least two of these are preferably methyl groups. Rx 11 ~Rx 13 are the same as Rx1 to Rx3 in (Y1) and (Y2) described above, except that they may have a fluorine atom or an iodine atom, and have the same definitions and preferred ranges as the alkyl group, the cycloalkyl group, the alkenyl group, and the aryl group.

[0143] In formula (Z3), R 136 ~R 138 R each independently represents a hydrogen atom or a monovalent organic group which may have a fluorine atom or an iodine atom. 137 and R 138 and may be bonded to each other to form a ring. Examples of the monovalent organic group which may have a fluorine atom or an iodine atom include an alkyl group which may have a fluorine atom or an iodine atom, a cycloalkyl group which may have a fluorine atom or an iodine atom, an aryl group which may have a fluorine atom or an iodine atom, an aralkyl group which may have a fluorine atom or an iodine atom, and groups which combine these (for example, a group which combines an alkyl group and a cycloalkyl group). The alkyl group, cycloalkyl group, aryl group, and aralkyl group may contain a heteroatom such as an oxygen atom in addition to a fluorine atom and an iodine atom. That is, the alkyl group, cycloalkyl group, aryl group, and aralkyl group may have, for example, one methylene group replaced with a heteroatom such as an oxygen atom or a group having a heteroatom such as a carbonyl group. Also, R 138 may be bonded to another substituent on the main chain of the repeating unit to form a ring. In this case, R 138 The group formed by bonding together of the repeating unit and another substituent carried by the main chain of the repeating unit is preferably an alkylene group such as a methylene group.

[0144] Formula (Z3) is preferably a group represented by the following formula (Z3-1).

[0145] [ka]

[0146] Here, L 11 and L 12 each independently represents a hydrogen atom; an alkyl group which may have a heteroatom selected from the group consisting of a fluorine atom, an iodine atom, and an oxygen atom; a cycloalkyl group which may have a heteroatom selected from the group consisting of a fluorine atom, an iodine atom, and an oxygen atom; an aryl group which may have a heteroatom selected from the group consisting of a fluorine atom, an iodine atom, and an oxygen atom; or a group combining these (for example, a group combining an alkyl group and a cycloalkyl group which may have a heteroatom selected from the group consisting of a fluorine atom, an iodine atom, and an oxygen atom). M1 represents a single bond or a divalent linking group. Q1 represents an alkyl group which may have a heteroatom selected from the group consisting of a fluorine atom, an iodine atom, and an oxygen atom; a cycloalkyl group which may have a heteroatom selected from the group consisting of a fluorine atom, an iodine atom, and an oxygen atom; an aryl group which is selected from the group consisting of a fluorine atom, an iodine atom, and an oxygen atom; an amino group; an ammonium group; a mercapto group; a cyano group; an aldehyde group; or a group combining these (for example, a group combining an alkyl group and a cycloalkyl group which may have a heteroatom selected from the group consisting of a fluorine atom, an iodine atom, and an oxygen atom).

[0147] In formula (Y4), Ar1 represents an aromatic ring group which may have a fluorine atom or an iodine atom. Rn1 represents an alkyl group which may have a fluorine atom or an iodine atom, a cycloalkyl group which may have a fluorine atom or an iodine atom, or an aryl group which may have a fluorine atom or an iodine atom. Rn1 and Ar1 may be bonded to each other to form a non-aromatic ring.

[0148] The repeating unit having an acid-decomposable group is also preferably a repeating unit represented by formula (AI).

[0149] [ka]

[0150] In general formula (AI), Xa1 represents a hydrogen atom or an alkyl group which may have a substituent. T represents a single bond or a divalent linking group. Rx1 to Rx3 each independently represent an alkyl group (linear or branched), a cycloalkyl group (monocyclic or polycyclic), an alkenyl group (linear or branched), or an aryl group (monocyclic or polycyclic). However, when all of Rx1 to Rx3 are alkyl groups (linear or branched), it is preferable that at least two of Rx1 to Rx3 are methyl groups. Two of Rx1 to Rx3 may be bonded to form a monocyclic or polycyclic ring (such as a monocyclic or polycyclic cycloalkyl group).

[0151] The alkyl group represented by Xa1, which may have a substituent, is, for example, a methyl group or -CH2-R 11 Examples of the group represented by R 11 represents a halogen atom (such as a fluorine atom), a hydroxyl group, or a monovalent organic group, and examples thereof include an alkyl group having 5 or less carbon atoms which may be substituted with a halogen atom, an acyl group having 5 or less carbon atoms which may be substituted with a halogen atom, and an alkoxy group having 5 or less carbon atoms which may be substituted with a halogen atom, preferably an alkyl group having 3 or less carbon atoms, and more preferably a methyl group. Xa1 is preferably a hydrogen atom, a methyl group, a trifluoromethyl group, or a hydroxymethyl group.

[0152] Examples of the divalent linking group for T include an alkylene group, an aromatic ring group, a -COO-Rt- group, and a -O-Rt- group, in which Rt represents an alkylene group or a cycloalkylene group. T is preferably a single bond or a -COO-Rt- group. When T represents a -COO-Rt- group, Rt is preferably an alkylene group having 1 to 5 carbon atoms, more preferably a -CH2- group, a -(CH2)2- group, or a -(CH2)3- group.

[0153] The alkyl group of Rx1 to Rx3 is preferably an alkyl group having 1 to 4 carbon atoms, such as a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, and a t-butyl group. The cycloalkyl group of Rx1 to Rx3 is preferably a monocyclic cycloalkyl group such as a cyclopentyl group or a cyclohexyl group, or a polycyclic cycloalkyl group such as a norbornyl group, a tetracyclodecanyl group, a tetracyclododecanyl group, or an adamantyl group. The aryl group of Rx1 to Rx3 is preferably an aryl group having 6 to 10 carbon atoms, and examples thereof include a phenyl group, a naphthyl group, and an anthryl group. The alkenyl group of Rx1 to Rx3 is preferably a vinyl group. The cycloalkyl group formed by combining two of Rx1 to Rx3 is preferably a monocyclic cycloalkyl group such as a cyclopentyl group or a cyclohexyl group, and is preferably a polycyclic cycloalkyl group such as a norbornyl group, a tetracyclodecanyl group, a tetracyclododecanyl group, or an adamantyl group. Among them, a monocyclic cycloalkyl group having 5 to 6 carbon atoms is preferable. In the cycloalkyl group formed by combining two of Rx1 to Rx3, for example, one of the methylene groups constituting the ring may be replaced with a heteroatom such as an oxygen atom, a group having a heteroatom such as a carbonyl group, or a vinylidene group. In addition, in these cycloalkyl groups, one or more of the ethylene groups constituting the cycloalkane ring may be replaced with a vinylene group. In the repeating unit represented by general formula (AI), for example, Rx1 is preferably a methyl group or an ethyl group, and Rx2 and Rx3 are bonded to form the above-mentioned cycloalkyl group.

[0154] When each of the above groups has a substituent, examples of the substituent include an alkyl group (having 1 to 4 carbon atoms), a halogen atom, a hydroxyl group, an alkoxy group (having 1 to 4 carbon atoms), a carboxyl group, and an alkoxycarbonyl group (having 2 to 6 carbon atoms), etc. The number of carbon atoms in the substituent is preferably 8 or less.

[0155] The repeating unit represented by general formula (AI) is preferably an acid-decomposable (meth)acrylic acid tertiary alkyl ester repeating unit (a repeating unit in which Xa1 represents a hydrogen atom or a methyl group, and T represents a single bond).

[0156] The content of the repeating unit having an acid-decomposable group is preferably from 15 to 80 mol %, more preferably from 20 to 70 mol %, and even more preferably from 20 to 65 mol %, based on all repeating units in the resin (A).

[0157] Specific examples of repeating units having an acid-decomposable group are shown below, but the present invention is not limited thereto. In the formula, Xa1 represents any one of H, F, CH3, CF3, and CH2OH, and Rxa and Rxb each represent a linear or branched alkyl group having 1 to 5 carbon atoms.

[0158] [ka]

[0159] [ka]

[0160] [ka]

[0161] [ka]

[0162] [ka]

[0163] The resin (A) may contain repeating units other than the repeating units mentioned above. For example, the resin (A) may contain at least one type of repeating unit selected from the group consisting of Group A below, and / or at least one type of repeating unit selected from the group consisting of Group B below. Group A: A group consisting of the following repeating units (20) to (29). (20) A repeating unit having an acid group, as described below (21) A repeating unit having a fluorine atom or an iodine atom, as described below. (22) A repeating unit having a lactone group, a sultone group, or a carbonate group, as described below. (23) A repeating unit having a photoacid generating group, which will be described later (24) A repeating unit represented by the following general formula (V-1) or the following general formula (V-2) (25) A repeating unit represented by the following formula (A) (26) A repeating unit represented by formula (B) described below. (27) A repeating unit represented by formula (C) described below. (28) A repeating unit represented by formula (D) described below. (29) Group B of repeating units represented by formula (E) described below: a group consisting of the following repeating units (30) to (32). (30) A repeating unit having at least one group selected from a lactone group, a sultone group, a carbonate group, a hydroxyl group, a cyano group, and an alkali-soluble group, as described below. (31) A repeating unit having an alicyclic hydrocarbon structure and not exhibiting acid decomposition, which will be described later (32) A repeating unit represented by the general formula (III) described below, which does not have either a hydroxyl group or a cyano group.

[0164] When the composition of the present invention is used as an actinic ray-sensitive or radiation-sensitive resin composition for EUV, the resin (A) preferably has at least one repeating unit selected from the group consisting of Group A above. In addition, when the composition is used as an actinic ray-sensitive or radiation-sensitive resin composition for EUV, the resin (A) preferably contains at least one of a fluorine atom and an iodine atom. When the resin (A) contains both a fluorine atom and an iodine atom, the resin (A) may have one repeating unit containing both a fluorine atom and an iodine atom, or the resin (A) may contain two types of repeating units, a repeating unit containing a fluorine atom and a repeating unit containing an iodine atom. When the composition is used as an actinic ray-sensitive or radiation-sensitive resin composition for EUV, it is also preferred that the resin (A) has a repeating unit having an aromatic group. When the composition of the present invention is used as an actinic ray-sensitive or radiation-sensitive resin composition for ArF, the resin (A) preferably has at least one repeating unit selected from the group consisting of Group B above. When the composition of the present invention is used as an actinic ray-sensitive or radiation-sensitive resin composition for ArF, it is preferred that the resin (A) contains neither fluorine atoms nor silicon atoms. In addition, when the composition is used as an actinic ray-sensitive or radiation-sensitive resin composition for ArF, it is preferable that the resin (A) does not have an aromatic group.

[0165] (Repeating unit having an acid group) The resin (A) may have a repeating unit having an acid group. The acid group is preferably an acid group having a pKa of 13 or less. The acid group is preferably, for example, a carboxyl group, a phenolic hydroxyl group, a fluorinated alcohol group (preferably a hexafluoroisopropanol group), a sulfonic acid group, a sulfonamide group, or an isopropanol group. In addition, in the above hexafluoroisopropanol group, one or more (preferably one or two) of the fluorine atoms may be substituted with a group other than a fluorine atom (such as an alkoxycarbonyl group). The thus formed -C(CF3)(OH)-CF2- is also preferable as an acid group. In addition, one or more of the fluorine atoms may be substituted with a group other than a fluorine atom to form a ring containing -C(CF3)(OH)-CF2-. The repeating unit having an acid group is preferably a repeating unit different from the repeating unit having a structure in which a polar group is protected with a leaving group that is eliminated by the action of an acid as described above, and a repeating unit having a lactone group, a sultone group, or a carbonate group as described below.

[0166] The repeating unit having an acid group may have a fluorine atom or an iodine atom.

[0167] The repeating unit having an acid group is preferably a repeating unit represented by formula (B).

[0168] [ka]

[0169] R3 represents a hydrogen atom or a monovalent organic group which may have a fluorine atom or an iodine atom. The monovalent organic group which may have a fluorine atom or an iodine atom is preferably a group represented by -L4-R8. L4 represents a single bond or an ester group. R8 may be an alkyl group which may have a fluorine atom or an iodine atom, a cycloalkyl group which may have a fluorine atom or an iodine atom, an aryl group which may have a fluorine atom or an iodine atom, or a group which combines these groups.

[0170] R4 and R5 each independently represent a hydrogen atom, a fluorine atom, an iodine atom, or an alkyl group which may have a fluorine atom or an iodine atom.

[0171] L2 represents a single bond or an ester group. L3 represents an aromatic hydrocarbon ring group having a valence of (n+m+1) or an alicyclic hydrocarbon ring group having a valence of (n+m+1). Examples of the aromatic hydrocarbon ring group include a benzene ring group and a naphthalene ring group. Examples of the alicyclic hydrocarbon ring group include a monocyclic or polycyclic ring group, such as a cycloalkyl ring group. R6 represents a hydroxyl group or a fluorinated alcohol group (preferably a hexafluoroisopropanol group). When R6 is a hydroxyl group, L3 is preferably an aromatic hydrocarbon ring group having a valence of (n+m+1). R7 represents a halogen atom, such as a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom. m represents an integer of 1 or more. m is preferably an integer of 1 to 3, and more preferably an integer of 1 to 2. n represents an integer of 0 or greater than 1. n is preferably an integer of 1 to 4. Incidentally, (n+m+1) is preferably an integer of 1 to 5.

[0172] As the repeating unit having an acid group, a repeating unit represented by the following general formula (I) is also preferred.

[0173] [ka]

[0174] In general formula (I), R 41 , R 42 and R 43 each independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, a cyano group, or an alkoxycarbonyl group. 42 may be bonded to Ar4 to form a ring, in which case R 42 represents a single bond or an alkylene group. X4 is a single bond, -COO-, or -CONR 64 - represents R 64 represents a hydrogen atom or an alkyl group. L4 represents a single bond or an alkylene group. Ar4 represents an (n+1)-valent aromatic ring group; R 42 When it bonds with the ring, it represents an (n+2)-valent aromatic ring group. n represents an integer of 1 to 5.

[0175] R in general formula (I) 41 , R 42 , and R 43 As the alkyl group, an alkyl group having 20 or less carbon atoms, such as a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, a hexyl group, a 2-ethylhexyl group, an octyl group, or a dodecyl group, is preferable, an alkyl group having 8 or less carbon atoms is more preferable, and an alkyl group having 3 or less carbon atoms is even more preferable.

[0176] R in general formula (I) 41 , R 42 , and R 43 The cycloalkyl group may be a monocyclic or polycyclic group, and among these, a monocyclic cycloalkyl group having 3 to 8 carbon atoms, such as a cyclopropyl group, a cyclopentyl group, and a cyclohexyl group, is preferred. R in general formula (I) 41 , R 42 , and R 43Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, with a fluorine atom being preferred. R in general formula (I) 41 , R 42 , and R 43 The alkyl group contained in the alkoxycarbonyl group of R 41 , R 42 , R 43 The same alkyl groups as those in the above are preferred.

[0177] Preferred examples of the substituent in each of the above groups include an alkyl group, a cycloalkyl group, an aryl group, an amino group, an amide group, a ureido group, a urethane group, a hydroxyl group, a carboxyl group, a halogen atom, an alkoxy group, a thioether group, an acyl group, an acyloxy group, an alkoxycarbonyl group, a cyano group, and a nitro group. The number of carbon atoms in the substituent is preferably 8 or less.

[0178] Ar4 represents an aromatic ring group having a valence of (n+1). When n is 1, the divalent aromatic ring group is preferably an arylene group having 6 to 18 carbon atoms, such as a phenylene group, a tolylene group, a naphthylene group, or an anthracenylene group, or a divalent aromatic ring group containing a heterocycle, such as a thiophene ring, a furan ring, a pyrrole ring, a benzothiophene ring, a benzofuran ring, a benzopyrrole ring, a triazine ring, an imidazole ring, a benzimidazole ring, a triazole ring, a thiadiazole ring, or a thiazole ring. The aromatic ring group may have a substituent.

[0179] Specific examples of the (n+1)-valent aromatic ring group when n is an integer of 2 or more include groups obtained by removing any (n-1) hydrogen atoms from the above-mentioned specific examples of the divalent aromatic ring group. The (n+1)-valent aromatic ring group may further have a substituent.

[0180] Examples of the substituent that the above-mentioned alkyl group, cycloalkyl group, alkoxycarbonyl group, alkylene group, and (n+1)-valent aromatic ring group may have include R 41 , R42 , and R 43 Examples of the alkyl group include the alkyl groups listed above, alkoxy groups such as a methoxy group, an ethoxy group, a hydroxyethoxy group, a propoxy group, a hydroxypropoxy group, and a butoxy group; and aryl groups such as a phenyl group. -CONR represented by X4 64 -(R 64 represents a hydrogen atom or an alkyl group) 64 Examples of the alkyl group include alkyl groups having 20 or less carbon atoms, such as a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, a hexyl group, a 2-ethylhexyl group, an octyl group, and a dodecyl group, and an alkyl group having 8 or less carbon atoms is preferred. X4 is preferably a single bond, -COO- or -CONH-, more preferably a single bond or -COO-.

[0181] The alkylene group in L4 is preferably an alkylene group having 1 to 8 carbon atoms, such as a methylene group, an ethylene group, a propylene group, a butylene group, a hexylene group, or an octylene group. Ar4 is preferably an aromatic ring group having 6 to 18 carbon atoms, and more preferably a benzene ring group, a naphthalene ring group, or a biphenylene ring group. The repeating unit represented by formula (I) preferably has a hydroxystyrene structure, that is, Ar4 is preferably a benzene ring group.

[0182] The repeating unit represented by formula (I) is preferably a repeating unit represented by the following formula (1).

[0183] [ka]

[0184] In general formula (1), A represents a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, or a cyano group. R represents a halogen atom, an alkyl group, a cycloalkyl group, an aryl group, an alkenyl group, an aralkyl group, an alkoxy group, an alkylcarbonyloxy group, an alkylsulfonyloxy group, an alkyloxycarbonyl group, or an aryloxycarbonyl group, and when there are a plurality of R, they may be the same or different. When there are a plurality of R, they may be combined together to form a ring. R is preferably a hydrogen atom. a represents an integer of 1 to 3. b represents an integer of 0 to (5-a).

[0185] Examples of repeating units having an acid group are shown below: In the formula, a represents 1 or 2.

[0186] [ka]

[0187] [ka]

[0188] [ka]

[0189] Among the above repeating units, the repeating units specifically described below are preferred: In the formula, R represents a hydrogen atom or a methyl group, and a represents 2 or 3.

[0190] [ka]

[0191] [ka]

[0192] The content of the repeating unit having an acid group is preferably from 10 to 70 mol %, more preferably from 15 to 65 mol %, and even more preferably from 20 to 60 mol %, based on all repeating units in the resin (A).

[0193] (Repeating units having fluorine or iodine atoms) The resin (A) may have a repeating unit having a fluorine atom or an iodine atom in addition to the above-mentioned <repeating unit having an acid-decomposable group> and <repeating unit having an acid group>. The <repeating unit having a fluorine atom or an iodine atom> referred to here is preferably different from other types of repeating units belonging to Group A, such as the <repeating unit having a lactone group, a sultone group, or a carbonate group> and the <repeating unit having a photoacid generating group> described below.

[0194] The repeating unit having a fluorine atom or an iodine atom is preferably a repeating unit represented by formula (C).

[0195] [ka]

[0196] L5 represents a single bond or an ester group. R9 represents a hydrogen atom, or an alkyl group which may have a fluorine atom or an iodine atom. R 10 represents a hydrogen atom, an alkyl group which may have a fluorine atom or an iodine atom, a cycloalkyl group which may have a fluorine atom or an iodine atom, an aryl group which may have a fluorine atom or an iodine atom, or a group combining these.

[0197] Examples of repeating units having a fluorine atom or an iodine atom are shown below.

[0198] [ka]

[0199] The content of the repeating units having a fluorine atom or an iodine atom is preferably from 0 to 50 mol %, more preferably from 5 to 45 mol %, and even more preferably from 10 to 40 mol %, based on all repeating units in the resin (A). As described above, the repeating units having a fluorine atom or an iodine atom do not include <repeating units having an acid decomposable group> and <repeating units having an acid group>. Therefore, the content of the repeating units having a fluorine atom or an iodine atom also refers to the content of repeating units having a fluorine atom or an iodine atom excluding <repeating units having an acid decomposable group> and <repeating units having an acid group>.

[0200] Among the repeating units of the resin (A), the total content of repeating units containing at least one of a fluorine atom and an iodine atom is preferably 20 to 100 mol %, more preferably 30 to 100 mol %, and even more preferably 40 to 100 mol %, based on all repeating units of the resin (A). Examples of the repeating unit containing at least one of a fluorine atom and an iodine atom include a repeating unit having a fluorine atom or an iodine atom and an acid-decomposable group, a repeating unit having a fluorine atom or an iodine atom and an acid group, and a repeating unit having a fluorine atom or an iodine atom.

[0201] (Repeating units having a lactone group, a sultone group, or a carbonate group) Resin (A) may have a repeating unit having at least one type selected from the group consisting of a lactone group, a sultone group, and a carbonate group (hereinafter, collectively referred to as a "repeating unit having a lactone group, a sultone group, or a carbonate group"). It is also preferred that the repeating units having a lactone group, a sultone group, or a carbonate group do not have an acid group such as a hexafluoropropanol group.

[0202] The lactone group or sultone group may have a lactone structure or a sultone structure. The lactone structure or the sultone structure is preferably a 5- to 7-membered lactone structure or a 5- to 7-membered sultone structure. Among them, a 5- to 7-membered lactone structure having another ring structure condensed thereto in the form of a bicyclo structure or a spiro structure, or a 5- to 7-membered sultone structure having another ring structure condensed thereto in the form of a bicyclo structure or a spiro structure, is more preferred. Resin (A) preferably has a repeating unit having a lactone structure represented by any one of the following general formulas (LC1-1) to (LC1-21), or a lactone group or sultone group formed by removing one or more hydrogen atoms from a ring member atom of a sultone structure represented by any one of the following general formulas (SL1-1) to (SL1-3). Furthermore, the lactone group or sultone group may be directly bonded to the main chain. For example, the ring atoms of the lactone group or sultone group may constitute the main chain of the resin (A).

[0203] [ka]

[0204] The lactone structure or sultone structure portion may have a substituent (Rb2). Preferred examples of the substituent (Rb2) include an alkyl group having 1 to 8 carbon atoms, a cycloalkyl group having 4 to 7 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, an alkoxycarbonyl group having 1 to 8 carbon atoms, a carboxyl group, a halogen atom, a hydroxyl group, a cyano group, and an acid-decomposable group. n2 represents an integer of 0 to 4. When n2 is 2 or more, the multiple Rb2 may be different from each other, and the multiple Rb2 may be bonded to each other to form a ring.

[0205] Examples of the repeating unit having a group having a lactone structure represented by any of general formulas (LC1-1) to (LC1-21) or a sultone structure represented by any of general formulas (SL1-1) to (SL1-3) include a repeating unit represented by the following general formula (AI):

[0206] [ka]

[0207] In general formula (AI), Rb0 represents a hydrogen atom, a halogen atom, or an alkyl group having 1 to 4 carbon atoms. Preferred examples of the substituent that the alkyl group of Rb0 may have include a hydroxyl group and a halogen atom. Examples of the halogen atom of Rb0 include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. Rb0 is preferably a hydrogen atom or a methyl group. Ab represents a single bond, an alkylene group, a divalent linking group having a monocyclic or polycyclic alicyclic hydrocarbon structure, an ether group, an ester group, a carbonyl group, a carboxyl group, or a divalent group combining these. Among these, a single bond or a linking group represented by -Ab1-CO2- is preferred. Ab1 represents a linear or branched alkylene group, or a monocyclic or polycyclic cycloalkylene group, and is preferably a methylene group, an ethylene group, a cyclohexylene group, an adamantylene group, or a norbornylene group. V represents a group obtained by removing one hydrogen atom from a ring member atom of a lactone structure represented by any of the general formulas (LC1-1) to (LC1-21), or a group obtained by removing one hydrogen atom from a ring member atom of a sultone structure represented by any of the general formulas (SL1-1) to (SL1-3).

[0208] When optical isomers exist in the repeating unit having a lactone group or a sultone group, any optical isomer may be used. In addition, one type of optical isomer may be used alone, or a mixture of multiple optical isomers may be used. When one type of optical isomer is mainly used, its optical purity (ee) is preferably 90 or more, more preferably 95 or more.

[0209] The carbonate group is preferably a cyclic carbonate group. The repeating unit having a cyclic carbonate group is preferably a repeating unit represented by the following general formula (A-1).

[0210] [ka]

[0211] In general formula (A-1), R A 1 represents a hydrogen atom, a halogen atom, or a monovalent organic group (preferably a methyl group). n represents an integer of 0 or greater. R A 2 represents a substituent. When n is 2 or more, multiple R A 2 may be the same or different. A represents a single bond or a divalent linking group. The divalent linking group is preferably an alkylene group, a divalent linking group having a monocyclic or polycyclic alicyclic hydrocarbon structure, an ether group, an ester group, a carbonyl group, a carboxyl group, or a divalent group formed by combining these groups. Z represents an atomic group which forms a monocyclic or polycyclic ring together with the group represented by -O-CO-O- in the formula.

[0212] Examples of repeating units having a lactone group, a sultone group, or a carbonate group are shown below.

[0213] [ka]

[0214] [ka]

[0215] [ka]

[0216] The content of repeating units having a lactone group, a sultone group, or a carbonate group is preferably from 1 to 70 mol %, more preferably from 5 to 65 mol %, and even more preferably from 5 to 60 mol %, based on all repeating units in the resin (A).

[0217] (Repeating unit having a photoacid generating group) The resin (A) may contain, as a repeating unit other than those mentioned above, a repeating unit having a group that generates an acid upon irradiation with actinic rays or radiation (hereinafter also referred to as a "photoacid generating group"). In this case, the repeating unit having the photoacid generating group can be considered to correspond to a compound (also called a "photoacid generator") that generates an acid when exposed to actinic rays or radiation, which will be described later. An example of such a repeating unit is a repeating unit represented by the following general formula (4).

[0218] [ka]

[0219] R 41 represents a hydrogen atom or a methyl group. 41 represents a single bond or a divalent linking group. 42 R represents a divalent linking group. 40 represents a structural portion that is decomposed by irradiation with actinic rays or radiation to generate an acid in the side chain.

[0220] Examples of the repeating unit having a photoacid generating group are shown below.

[0221] [ka]

[0222] [ka]

[0223] Other examples of the repeating unit represented by formula (4) include the repeating units described in paragraphs

[0094] to

[0105] of JP2014-041327A.

[0224] The content of the repeating unit having a photoacid generating group is preferably from 1 to 40 mol %, more preferably from 5 to 35 mol %, and even more preferably from 5 to 30 mol %, based on all repeating units in the resin (A).

[0225] (Repeating unit represented by general formula (V-1) or the following general formula (V-2)) The resin (A) may have a repeating unit represented by the following general formula (V-1) or the following general formula (V-2). The repeating units represented by the following general formula (V-1) and the following general formula (V-2) are preferably repeating units different from the repeating units described above.

[0226] [ka]

[0227] During the ceremony, R6 and R7 each independently represent a hydrogen atom, a hydroxyl group, an alkyl group, an alkoxy group, an acyloxy group, a cyano group, a nitro group, an amino group, a halogen atom, an ester group (-OCOR or -COOR: R is an alkyl group or a fluorinated alkyl group having 1 to 6 carbon atoms), or a carboxyl group. The alkyl group is preferably a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms. n3 represents an integer of 0 to 6. n4 represents an integer of 0 to 4. X 4 is a methylene group, an oxygen atom, or a sulfur atom. Examples of the repeating unit represented by formula (V-1) or (V-2) are shown below.

[0228] [ka]

[0229] (Repeating unit for reducing the mobility of the main chain) Resin (A) preferably has a high glass transition temperature (Tg) from the viewpoint of suppressing excessive diffusion of generated acid or pattern collapse during development. Tg is preferably higher than 90° C., more preferably higher than 100° C., even more preferably higher than 110° C., and particularly preferably higher than 125° C. An excessively high Tg leads to a decrease in the dissolution rate in the developer, so Tg is preferably 400° C. or lower, more preferably 350° C. or lower. In this specification, the glass transition temperature (Tg) of a polymer such as resin (A) is calculated by the following method. First, the Tg of a homopolymer consisting of each repeating unit contained in the polymer is calculated by the Bicerano method. Hereinafter, the calculated Tg is referred to as the "Tg of the repeating unit". Next, the mass ratio (%) of each repeating unit to the total repeating units in the polymer is calculated. Next, the Tg at each mass ratio is calculated using the Fox formula (described in Materials Letters 62 (2008) 3152, etc.), and these are summed up to obtain the Tg (°C) of the polymer. The Bicerano method is described in, for example, Prediction of Polymer Properties, Marcel Dekker Inc., New York (1993). Calculation of Tg by the Bicerano method can be performed using polymer property estimation software MDL Polymer (MDL Information Systems, Inc.).

[0230] In order to increase the Tg of the resin (A) (preferably to make the Tg exceed 90° C.), it is preferable to reduce the mobility of the main chain of the resin (A). Methods for reducing the mobility of the main chain of the resin (A) include the following methods (a) to (e). (a) Introduction of bulky substituents into the main chain (b) Introduction of multiple substituents into the main chain (c) Introduction of a substituent group that induces interactions between resins (A) near the main chain (d) Main chain formation in a cyclic structure (e) Linking a cyclic structure to the main chain The resin (A) preferably has a repeating unit that exhibits a homopolymer Tg of 130° C. or higher. The type of repeating unit exhibiting a homopolymer Tg of 130° C. or higher is not particularly limited, and may be any repeating unit exhibiting a homopolymer Tg of 130° C. or higher as calculated by the Bicerano method. Depending on the type of functional group in the repeating units represented by formulae (A) to (E) described below, the repeating units may be considered to exhibit a homopolymer Tg of 130° C. or higher.

[0231] (Repeating unit represented by formula (A)) One example of a specific means for achieving the above (a) is a method in which a repeating unit represented by formula (A) is introduced into resin (A).

[0232] [ka]

[0233] Formula (A), R A R represents a group having a polycyclic structure. x represents a hydrogen atom, a methyl group, or an ethyl group. The group having a polycyclic structure is a group having a plurality of ring structures, and the plurality of ring structures may or may not be condensed. Specific examples of the repeating unit represented by formula (A) include the following repeating units.

[0234] [ka]

[0235] [ka]

[0236] [ka]

[0237] In the above formula, R represents a hydrogen atom, a methyl group, or an ethyl group. Ra represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, an alkenyl group, a hydroxyl group, an alkoxy group, an acyloxy group, a cyano group, a nitro group, an amino group, a halogen atom, an ester group (-OCOR''' or -COOR''':R''' is an alkyl group or a fluorinated alkyl group having 1 to 20 carbon atoms), or a carboxyl group. The alkyl group, the cycloalkyl group, the aryl group, the aralkyl group, and the alkenyl group may each have a substituent. In addition, a hydrogen atom bonded to a carbon atom in the group represented by Ra may be substituted with a fluorine atom or an iodine atom. R' and R" each independently represent an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, an alkenyl group, a hydroxyl group, an alkoxy group, an acyloxy group, a cyano group, a nitro group, an amino group, a halogen atom, an ester group (-OCOR''' or -COOR''':R''' is an alkyl group or a fluorinated alkyl group having 1 to 20 carbon atoms), or a carboxyl group. The alkyl group, the cycloalkyl group, the aryl group, the aralkyl group, and the alkenyl group may each have a substituent. The hydrogen atom bonded to the carbon atom in the group represented by R' and R'' may be substituted with a fluorine atom or an iodine atom. L represents a single bond or a divalent linking group. Examples of the divalent linking group include -COO-, -CO-, -O-, -S-, -SO-, -SO2-, an alkylene group, a cycloalkylene group, an alkenylene group, and a linking group in which a plurality of these groups are linked together. m and n each independently represent an integer of 0 or more. There is no particular upper limit to m and n, but they are often 2 or less, and more often 1 or less.

[0238] (Repeating unit represented by formula (B)) One example of a specific means for achieving the above (b) is a method in which a repeating unit represented by formula (B) is introduced into resin (A).

[0239] [ka]

[0240] In formula (B), R b1 ~R b4 each independently represents a hydrogen atom or an organic group; R b1 ~R b4 At least two of the groups represent organic groups. In addition, when at least one of the organic groups is a group in which a ring structure is directly linked to the main chain in the repeating unit, the type of the other organic groups is not particularly limited. Furthermore, when none of the organic groups has a ring structure directly linked to the main chain in the repeating unit, at least two of the organic groups are substituents having three or more constituent atoms excluding hydrogen atoms.

[0241] Specific examples of the repeating unit represented by formula (B) include the following repeating units.

[0242] [ka]

[0243] In the above formula, each R independently represents a hydrogen atom or an organic group, such as an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, or an alkenyl group, each of which may have a substituent. Each R' independently represents an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, an alkenyl group, a hydroxyl group, an alkoxy group, an acyloxy group, a cyano group, a nitro group, an amino group, a halogen atom, an ester group (-OCOR'' or -COOR'': R'' is an alkyl group or a fluorinated alkyl group having 1 to 20 carbon atoms), or a carboxyl group. The alkyl group, the cycloalkyl group, the aryl group, the aralkyl group, and the alkenyl group may each have a substituent. In addition, a hydrogen atom bonded to a carbon atom in the group represented by R' may be substituted with a fluorine atom or an iodine atom. m represents an integer of 0 or more. There is no particular upper limit to m, but it is often 2 or less, and more often 1 or less.

[0244] (Repeating unit represented by formula (C)) One example of a specific means for achieving the above (c) is a method in which a repeating unit represented by formula (C) is introduced into resin (A).

[0245] [ka]

[0246] In formula (C), R c1 ~R c4 each independently represents a hydrogen atom or an organic group; R c1 ~R c4 At least one of the above is a group having a hydrogen-bonding hydrogen atom within three atoms from the main chain carbon. Among these, in order to induce interactions between the main chains of the resin (A), it is preferable to have a hydrogen-bonding hydrogen atom within two atoms (closer to the main chain).

[0247] Specific examples of the repeating unit represented by formula (C) include the following repeating units.

[0248] [ka]

[0249] In the above formula, R represents an organic group. Examples of the organic group include an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, an alkenyl group, and an ester group (-OCOR or -COOR: R is an alkyl group or a fluorinated alkyl group having 1 to 20 carbon atoms), each of which may have a substituent. R' represents a hydrogen atom or an organic group. Examples of the organic group include an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, and an alkenyl group. The hydrogen atom in the organic group may be substituted with a fluorine atom or an iodine atom.

[0250] (Repeating unit represented by formula (D)) One example of a specific means for achieving the above (d) is a method in which a repeating unit represented by formula (D) is introduced into resin (A).

[0251] [ka]

[0252] In formula (D), "cyclic" refers to a group that forms a main chain with a ring structure. The number of constituent atoms of the ring is not particularly limited.

[0253] Specific examples of the repeating unit represented by formula (D) include the following repeating units.

[0254] [ka]

[0255] In the above formula, each R independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, an alkenyl group, a hydroxyl group, an alkoxy group, an acyloxy group, a cyano group, a nitro group, an amino group, a halogen atom, an ester group (-OCOR" or -COOR'': R" is an alkyl group or a fluorinated alkyl group having 1 to 20 carbon atoms), or a carboxyl group. The alkyl group, the cycloalkyl group, the aryl group, the aralkyl group, and the alkenyl group may each have a substituent. In addition, the hydrogen atom bonded to the carbon atom in the group represented by R may be substituted with a fluorine atom or an iodine atom. In the above formula, R' each independently represents an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, an alkenyl group, a hydroxyl group, an alkoxy group, an acyloxy group, a cyano group, a nitro group, an amino group, a halogen atom, an ester group (-OCOR" or -COOR'': R" is an alkyl group or a fluorinated alkyl group having 1 to 20 carbon atoms), or a carboxyl group. The alkyl group, the cycloalkyl group, the aryl group, the aralkyl group, and the alkenyl group may each have a substituent. In addition, a hydrogen atom bonded to a carbon atom in the group represented by R' may be substituted with a fluorine atom or an iodine atom. m represents an integer of 0 or more. There is no particular upper limit to m, but it is often 2 or less, and more often 1 or less.

[0256] (Repeating unit represented by formula (E)) One example of a specific means for achieving the above (e) is a method in which a repeating unit represented by formula (E) is introduced into resin (A).

[0257] [ka]

[0258] In formula (E), each Re independently represents a hydrogen atom or an organic group, such as an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, or an alkenyl group, each of which may have a substituent. "Cyclic" refers to a ring-shaped group that contains carbon atoms in the main chain. There is no particular restriction on the number of atoms contained in the cyclic group.

[0259] Specific examples of the repeating unit represented by formula (E) include the following repeating units.

[0260] [ka]

[0261] [ka]

[0262] In the above formula, each R independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, an alkenyl group, a hydroxyl group, an alkoxy group, an acyloxy group, a cyano group, a nitro group, an amino group, a halogen atom, an ester group (-OCOR" or -COOR'': R" is an alkyl group or a fluorinated alkyl group having 1 to 20 carbon atoms), or a carboxyl group. The alkyl group, the cycloalkyl group, the aryl group, the aralkyl group, and the alkenyl group may each have a substituent. In addition, the hydrogen atom bonded to the carbon atom in the group represented by R may be substituted with a fluorine atom or an iodine atom. Each R' independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, an alkenyl group, a hydroxyl group, an alkoxy group, an acyloxy group, a cyano group, a nitro group, an amino group, a halogen atom, an ester group (-OCOR'' or -COOR'': R'' is an alkyl group or a fluorinated alkyl group having 1 to 20 carbon atoms), or a carboxyl group. The alkyl group, the cycloalkyl group, the aryl group, the aralkyl group, and the alkenyl group may each have a substituent. In addition, the hydrogen atom bonded to the carbon atom in the group represented by R' may be substituted with a fluorine atom or an iodine atom. m represents an integer of 0 or more. There is no particular upper limit to m, but it is often 2 or less, and more often 1 or less. In addition, two Rs bonded to the same carbon atom may be bonded to each other to form a ring. In formulae (E-2), (E-4), (E-6), and (E-8), two R may join together to form "=O".

[0263] The content of the repeating unit represented by formula (E) is preferably 5 mol % or more, more preferably 10 mol % or more, based on the total repeating units in the resin (A), and the upper limit is preferably 60 mol % or less, more preferably 55 mol % or less.

[0264] (Repeating units having at least one type of group selected from a lactone group, a sultone group, a carbonate group, a hydroxyl group, a cyano group, and an alkali-soluble group) The resin (A) may have a repeating unit having at least one type of group selected from a lactone group, a sultone group, a carbonate group, a hydroxyl group, a cyano group, and an alkali-soluble group. Examples of the repeating unit having a lactone group, a sultone group, or a carbonate group contained in the resin (A) include the repeating units described above in <Repeat units having a lactone group, a sultone group, or a carbonate group>. The preferred content is also as described above in <Repeat units having a lactone group, a sultone group, or a carbonate group>.

[0265] The resin (A) may contain a repeating unit having a hydroxyl group or a cyano group, which improves the adhesion to the substrate and the affinity for the developer. The repeating unit having a hydroxyl group or a cyano group is preferably a repeating unit having an alicyclic hydrocarbon structure substituted with a hydroxyl group or a cyano group. It is preferable that the repeating unit having a hydroxyl group or a cyano group does not have an acid-decomposable group. Examples of the repeating unit having a hydroxyl group or a cyano group include repeating units represented by the following general formulas (AIIa) to (AIId).

[0266] [ka]

[0267] In general formulae (AIIa) to (AIId), R 1c represents a hydrogen atom, a methyl group, a trifluoromethyl group, or a hydroxymethyl group. R 2c ~R 4c each independently represents a hydrogen atom, a hydroxyl group, or a cyano group. 2c ~R 4cAt least one of R represents a hydroxyl group or a cyano group. 2c ~R 4c One or two of R are hydroxyl groups and the rest are hydrogen atoms. More preferably, R 2c ~R 4c Two of them are hydroxyl groups and the rest are hydrogen atoms.

[0268] The content of the repeating units having a hydroxyl group or a cyano group is preferably 5 mol % or more, more preferably 10 mol % or more, based on the total repeating units in the resin (A), and the upper limit is preferably 60 mol % or less, more preferably 55 mol % or less, and even more preferably 50 mol % or less.

[0269] Specific examples of the repeating unit having a hydroxyl group or a cyano group are listed below, but the present invention is not limited to these.

[0270] [ka]

[0271] The resin (A) may have a repeating unit having an alkali-soluble group. Examples of the alkali-soluble group include a carboxyl group, a sulfonamide group, a sulfonylimide group, a bisulfonylimide group, and an aliphatic alcohol group (e.g., a hexafluoroisopropanol group) substituted with an electron-withdrawing group at the α-position, and the carboxyl group is preferred. The resin (A) contains a repeating unit having an alkali-soluble group, which increases the resolution in contact hole applications. Examples of the repeating unit having an alkali-soluble group include a repeating unit having an alkali-soluble group bonded directly to the main chain of a resin, such as a repeating unit of acrylic acid or methacrylic acid, or a repeating unit having an alkali-soluble group bonded to the main chain of a resin via a linking group, which may have a monocyclic or polycyclic cyclic hydrocarbon structure. The repeating unit having an alkali-soluble group is preferably a repeating unit derived from acrylic acid or methacrylic acid.

[0272] The content of the repeating unit having an alkali-soluble group is preferably 0 mol% or more, more preferably 3 mol% or more, and even more preferably 5 mol% or more, based on the total repeating units in the resin (A).The upper limit is preferably 20 mol% or less, more preferably 15 mol% or less, and even more preferably 10 mol% or less.

[0273] Specific examples of repeating units having an alkali-soluble group are shown below, but the present invention is not limited thereto. In the specific examples, Rx represents H, CH3, CH2OH, or CF3.

[0274] [ka]

[0275] As a repeating unit having at least one type of group selected from a lactone group, a hydroxyl group, a cyano group, and an alkali-soluble group, a repeating unit having at least two selected from a lactone group, a hydroxyl group, a cyano group, and an alkali-soluble group is preferable, a repeating unit having a cyano group and a lactone group is more preferable, and a repeating unit having a structure in which a cyano group is substituted on a lactone structure represented by general formula (LC1-4) is even more preferable.

[0276] (Repeating unit having an alicyclic hydrocarbon structure and not showing acid decomposition) The resin (A) may have an alicyclic hydrocarbon structure and a repeating unit that does not exhibit acid decomposition. This can reduce the elution of low molecular weight components from the resist film into the immersion liquid during immersion exposure. Examples of such repeating units include repeating units derived from 1-adamantyl (meth)acrylate, diadamantyl (meth)acrylate, tricyclodecanyl (meth)acrylate, or cyclohexyl (meth)acrylate.

[0277] (Repeating unit represented by formula (III) having neither a hydroxyl group nor a cyano group) The resin (A) may have a repeating unit represented by general formula (III) which does not have either a hydroxyl group or a cyano group.

[0278] [ka]

[0279] In general formula (III), R5 represents a hydrocarbon group having at least one cyclic structure and having neither a hydroxyl group nor a cyano group. Ra represents a hydrogen atom, an alkyl group, or a -CH2-O-Ra2 group, where Ra2 represents a hydrogen atom, an alkyl group, or an acyl group.

[0280] The cyclic structure of R5 includes a monocyclic hydrocarbon group and a polycyclic hydrocarbon group. Examples of the monocyclic hydrocarbon group include a cycloalkyl group having 3 to 12 carbon atoms (more preferably 3 to 7 carbon atoms) and a cycloalkenyl group having 3 to 12 carbon atoms.

[0281] Examples of the polycyclic hydrocarbon group include a ring assembly hydrocarbon group and a bridged cyclic hydrocarbon group. Examples of the bridged cyclic hydrocarbon ring include a bicyclic hydrocarbon ring, a tricyclic hydrocarbon ring, and a tetracyclic hydrocarbon ring. In addition, the bridged cyclic hydrocarbon ring also includes a fused ring in which multiple 5- to 8-membered cycloalkane rings are fused. The bridged cyclic hydrocarbon group is a norbornyl group, an adamantyl group, a bicyclooctanyl group, or a tricyclo[5, 2, 1, 0 2,6 ]decanyl group is preferred, and norbornyl or adamantyl group is more preferred.

[0282] The alicyclic hydrocarbon group may have a substituent, and examples of the substituent include a halogen atom, an alkyl group, a hydroxyl group protected by a protecting group, and an amino group protected by a protecting group. The halogen atom is preferably a bromine atom, a chlorine atom or a fluorine atom. The alkyl group is preferably a methyl group, an ethyl group, a butyl group, or a t-butyl group. The alkyl group may further have a substituent, and the substituent may be a halogen atom, an alkyl group, a hydroxyl group protected by a protecting group, or an amino group protected by a protecting group.

[0283] Examples of the protecting group include an alkyl group, a cycloalkyl group, an aralkyl group, a substituted methyl group, a substituted ethyl group, an alkoxycarbonyl group, and an aralkyloxycarbonyl group. The alkyl group is preferably an alkyl group having 1 to 4 carbon atoms. The substituted methyl group is preferably a methoxymethyl group, a methoxythiomethyl group, a benzyloxymethyl group, a t-butoxymethyl group, or a 2-methoxyethoxymethyl group. The substituted ethyl group is preferably a 1-ethoxyethyl group or a 1-methyl-1-methoxyethyl group. The acyl group is preferably an aliphatic acyl group having 1 to 6 carbon atoms, such as a formyl group, an acetyl group, a propionyl group, a butyryl group, an isobutyryl group, a valeryl group, or a pivaloyl group. The alkoxycarbonyl group is preferably an alkoxycarbonyl group having 1 to 4 carbon atoms.

[0284] The content of the repeating unit represented by formula (III) having neither a hydroxyl group nor a cyano group is preferably from 0 to 40 mol %, more preferably from 0 to 20 mol %, based on all repeating units in the resin (A). Specific examples of the repeating unit represented by formula (III) include, but are not limited to, the following: In the formula, Ra represents H, CH3, CH2OH, or CF3.

[0285] [ka]

[0286] (Other repeating units) Furthermore, the resin (A) may have a repeating unit other than the repeating units mentioned above. For example, resin (A) may have a repeating unit selected from the group consisting of a repeating unit having an oxathiane ring group, a repeating unit having an oxazolone ring group, a repeating unit having a dioxane ring group, and a repeating unit having a hydantoin ring group. Examples of such repeating units are shown below.

[0287] [ka]

[0288] In addition to the above repeating structural units, the resin (A) may have various repeating structural units for the purpose of adjusting dry etching resistance, suitability for a standard developer, substrate adhesion, resist profile, resolution, heat resistance, sensitivity, and the like.

[0289] It is also preferable that all of the repeating units of the resin (A) are composed of (meth)acrylate repeating units (particularly when the composition is used as an ArF actinic ray-sensitive or radiation-sensitive resin composition). In this case, any of those in which all of the repeating units are methacrylate repeating units, all of the repeating units are acrylate repeating units, and all of the repeating units are a combination of methacrylate repeating units and acrylate repeating units can be used, and it is preferable that the acrylate repeating units account for 50 mol % or less of the total repeating units.

[0290] The resin (A) can be synthesized according to a conventional method (for example, radical polymerization). The weight average molecular weight of the resin (A), as a polystyrene equivalent value by the GPC method, is preferably 1,000 to 200,000, more preferably 3,000 to 20,000, and even more preferably 5,000 to 15,000. By making the weight average molecular weight of the resin (A) 1,000 to 200,000, deterioration of heat resistance and dry etching resistance can be further suppressed. In addition, deterioration of developability and deterioration of film formability due to high viscosity can be further suppressed. The dispersity (molecular weight distribution) of the resin (A) is usually 1 to 5, preferably 1 to 3, more preferably 1.2 to 3.0, and even more preferably 1.2 to 2.0. The smaller the dispersity, the better the resolution and resist shape, and further the smoother the side walls of the resist pattern and the better the roughness.

[0291] In the composition of the present invention, the content of the resin (A) is preferably from 50 to 99.9 mass %, more preferably from 60 to 99.0 mass %, based on the total solid content of the composition. The solid content refers to the components in the composition excluding the solvent, and any components other than the solvent are considered to be solids even if they are liquid components. The resin (A) may be used alone or in combination of two or more kinds.

[0292] <Other photoacid generators> The resist composition may contain other photoacid generators that do not fall under the specific compounds (compounds that generate an acid upon exposure to actinic rays or radiation that do not fall under the specific compounds). The other photoacid generators are compounds that generate an acid upon exposure (preferably exposure to EUV light and / or ArF light). The other photoacid generator may be in the form of a low molecular weight compound, may be incorporated into a part of a polymer, or may be in the form of a low molecular weight compound and a form of being incorporated into a part of a polymer in combination. When the other photoacid generator is in the form of a low molecular weight compound, the molecular weight is preferably 3,000 or less, more preferably 2,000 or less, and even more preferably 1,000 or less. When the other photoacid generator is in a form incorporated into a part of a polymer, it may be incorporated into a part of the resin (A) or into a resin different from the resin (A). In the present invention, the photoacid generator is preferably in the form of a low molecular weight compound. The other photoacid generators are not particularly limited, and among them, compounds that generate organic acids are preferred. Examples of the organic acids include the organic acids described as the organic acids that the specific compounds can generate.

[0293] Other examples of photoacid generators include "M + X - " is an onium salt. "M + X - In the compound represented by X - represents an organic anion. "M + X - X in " - is X as described in relation to general formula (1) in a specific compound. - Organic anions represented by the formula: "M + X - In the compound represented by the formula "M + represents an organic cation. The organic cations are preferably each independently a cation represented by general formula (ZaI) (cation (ZaI)) or a cation represented by general formula (ZaII) (cation (ZaII)). However, the cation represented by the general formula (ZaI) is a cation (X - This is different from the parts other than the above.

[0294] [ka]

[0295] In the above general formula (ZaI), R 201 , R 202 , and R 203 each independently represents an organic group. R 201 , R 202 , and R 203 The carbon number of the organic group represented by R is usually 1 to 30, and preferably 1 to 20. 201 ~R 203 Two of these may be bonded to form a ring structure, and the ring may contain an oxygen atom, a sulfur atom, an ester group, an amide group, or a carbonyl group. 201 ~R 203Examples of groups formed by combining two of these include alkylene groups (such as butylene and pentylene groups) and -CH2-CH2-O-CH2-CH2-.

[0296] An example of the cation in general formula (ZaI) is the cation (ZaI-1) described below.

[0297] The cation (ZaI-1) is R 201 ~R 203 is an arylsulfonium cation, in which at least one of the groups is an aryl group. The arylsulfonium cation is R 201 ~R 203 may all be aryl groups, or R 201 ~R 203 A part of the group may be an aryl group, and the remainder may be an alkyl group or a cycloalkyl group. Also, R 201 ~R 203 is an aryl group, and R 201 ~R 203 The remaining two of R may be bonded to form a ring structure, and the ring may contain an oxygen atom, a sulfur atom, an ester group, an amide group, or a carbonyl group. 201 ~R 203 Examples of groups formed by combining two of these groups include alkylene groups in which one or more methylene groups may be substituted with oxygen atoms, sulfur atoms, ester groups, amide groups, and / or carbonyl groups (e.g., butylene groups, pentylene groups, or -CH2-CH2-O-CH2-CH2-). Examples of the arylsulfonium cation include triarylsulfonium cation, diarylalkylsulfonium cation, aryldialkylsulfonium cation, diarylcycloalkylsulfonium cation, and aryldicycloalkylsulfonium cation.

[0298] The aryl group contained in the arylsulfonium cation is preferably a phenyl group or a naphthyl group, more preferably a phenyl group. The aryl group may be an aryl group having a heterocyclic structure with an oxygen atom, a nitrogen atom, or a sulfur atom. Examples of the heterocyclic structure include a pyrrole residue, a furan residue, a thiophene residue, an indole residue, a benzofuran residue, and a benzothiophene residue. When the arylsulfonium cation has two or more aryl groups, the two or more aryl groups may be the same or different. The alkyl group or cycloalkyl group that the arylsulfonium cation has as necessary is preferably a linear alkyl group having 1 to 15 carbon atoms, a branched alkyl group having 3 to 15 carbon atoms, or a cycloalkyl group having 3 to 15 carbon atoms, and examples thereof include a methyl group, an ethyl group, a propyl group, an n-butyl group, a sec-butyl group, a t-butyl group, a cyclopropyl group, a cyclobutyl group, and a cyclohexyl group.

[0299] R 201 ~R 203 The substituents which the aryl group, alkyl group and cycloalkyl group may have are each independently preferably an alkyl group (e.g., having 1 to 15 carbon atoms), a cycloalkyl group (e.g., having 3 to 15 carbon atoms), an aryl group (e.g., having 6 to 14 carbon atoms), an alkoxy group (e.g., having 1 to 15 carbon atoms), a cycloalkylalkoxy group (e.g., having 1 to 15 carbon atoms), a halogen atom, a hydroxyl group, or a phenylthio group. The above-mentioned substituents may further have a substituent if possible. For example, the above-mentioned alkyl group may have a halogen atom as a substituent to form a halogenated alkyl group such as a trifluoromethyl group.

[0300] When the resist composition contains another photoacid generator, the content is not particularly limited, but in terms of the effect of the present invention being more excellent, the content is preferably 0.5% by mass or more, more preferably 1% by mass or more, and even more preferably 2% by mass or more, based on the total solid content of the composition. Also, the content is preferably 40% by mass or less, more preferably 35% by mass or less, and even more preferably 30% by mass or less. The photoacid generator may be used alone or in combination of two or more kinds.

[0301] <Solvent> The resist composition may contain a solvent. The solvent preferably contains (M1) propylene glycol monoalkyl ether carboxylate and (M2) at least one selected from the group consisting of propylene glycol monoalkyl ether, lactate ester, acetate ester, alkoxypropionate ester, linear ketone, cyclic ketone, lactone, and alkylene carbonate. The solvent may further contain components other than the components (M1) and (M2).

[0302] The present inventors have found that the use of such a solvent in combination with the above-mentioned resin improves the coatability of the composition and enables the formation of a pattern with fewer development defects. Although the reason for this is not entirely clear, the present inventors believe that this is due to the fact that these solvents have a good balance of the solubility, boiling point, and viscosity of the above-mentioned resin, and therefore can suppress unevenness in the film thickness of the composition film and the occurrence of precipitates during spin coating.

[0303] The component (M1) is preferably at least one selected from the group consisting of propylene glycol monomethyl ether acetate (PGMEA), propylene glycol monomethyl ether propionate, and propylene glycol monoethyl ether acetate, and is more preferably propylene glycol monomethyl ether acetate (PGMEA).

[0304] Component (M2) is preferably the following solvent: The propylene glycol monoalkyl ether is preferably propylene glycol monomethyl ether (PGME) or propylene glycol monoethyl ether (PGEE). The lactate ester is preferably ethyl lactate, butyl lactate or propyl lactate. The acetate ester is preferably methyl acetate, ethyl acetate, butyl acetate, isobutyl acetate, propyl acetate, isoamyl acetate, methyl formate, ethyl formate, butyl formate, propyl formate, or 3-methoxybutyl acetate. Also preferred is butyl butyrate. The alkoxypropionate is preferably methyl 3-methoxypropionate (MMP) or ethyl 3-ethoxypropionate (EEP). The chain ketone is preferably 1-octanone, 2-octanone, 1-nonanone, 2-nonanone, acetone, 2-heptanone, 4-heptanone, 1-hexanone, 2-hexanone, diisobutyl ketone, phenylacetone, methyl ethyl ketone, methyl isobutyl ketone, acetylacetone, acetonylacetone, ionone, diacetonyl alcohol, acetylcarbinol, acetophenone, methyl naphthyl ketone, or methyl amyl ketone. The cyclic ketone is preferably methylcyclohexanone, isophorone, cyclopentanone, or cyclohexanone. The lactone is preferably γ-butyrolactone. The alkylene carbonate is preferably propylene carbonate.

[0305] More preferably, component (M2) is propylene glycol monomethyl ether (PGME), ethyl lactate, ethyl 3-ethoxypropionate, methyl amyl ketone, cyclohexanone, butyl acetate, pentyl acetate, γ-butyrolactone, or propylene carbonate.

[0306] In addition to the above components, it is preferable to use an ester-based solvent having 7 or more carbon atoms (preferably 7 to 14, more preferably 7 to 12, and even more preferably 7 to 10) and 2 or less heteroatoms.

[0307] Examples of ester-based solvents having 7 or more carbon atoms and 2 or less heteroatoms include amyl acetate, 2-methylbutyl acetate, 1-methylbutyl acetate, hexyl acetate, pentyl propionate, hexyl propionate, butyl propionate, isobutyl isobutyrate, heptyl propionate, and butyl butanoate, with isoamyl acetate being preferred.

[0308] Component (M2) is preferably a solvent having a flash point (hereinafter also referred to as fp) of 37°C or higher. Component (M2) is preferably propylene glycol monomethyl ether (fp: 47°C), ethyl lactate (fp: 53°C), ethyl 3-ethoxypropionate (fp: 49°C), methyl amyl ketone (fp: 42°C), cyclohexanone (fp: 44°C), pentyl acetate (fp: 45°C), methyl 2-hydroxyisobutyrate (fp: 45°C), γ-butyrolactone (fp: 101°C), or propylene carbonate (fp: 132°C). Among these, propylene glycol monoethyl ether, ethyl lactate, pentyl acetate, or cyclohexanone are more preferred, and propylene glycol monoethyl ether or ethyl lactate are even more preferred. The "flash point" used herein refers to the value listed in the reagent catalog of Tokyo Chemical Industry Co., Ltd. or Sigma-Aldrich Co.

[0309] The solvent preferably contains component (M1). More preferably, the solvent consists essentially of component (M1) alone, or is a mixed solvent of component (M1) and other components. In the latter case, the solvent further preferably contains both component (M1) and component (M2).

[0310] The mass ratio (M1 / M2) of the component (M1) to the component (M2) is preferably from 100 / 0 to 0 / 10, more preferably from 100 / 0 to 15 / 85, still more preferably from 100 / 0 to 40 / 60, and particularly preferably from 100 / 0 to 60 / 40. That is, when the solvent contains both the component (M1) and the component (M2), the mass ratio of the component (M1) to the component (M2) is preferably 15 / 85 or more, more preferably 40 / 60 or more, and even more preferably 60 / 40 or more. By adopting such a constitution, the number of development defects can be further reduced.

[0311] When the solvent contains both the component (M1) and the component (M2), the mass ratio of the component (M1) to the component (M2) is, for example, 99 / 1 or less.

[0312] As described above, the solvent may further contain components other than the components (M1) and (M2). In this case, the content of the components other than the components (M1) and (M2) is preferably 5 to 30 mass % based on the total amount of the solvent.

[0313] The content of the solvent in the resist composition is preferably determined so that the solids concentration is 0.5 to 30 mass %, and more preferably 1 to 20 mass %, which further improves the coatability of the resist composition. The solid content means all components other than the solvent.

[0314] <Acid diffusion control agent> The resist composition may further contain an acid diffusion controller. The acid diffusion controller acts as a quencher that traps the acid generated from the photoacid generator, and plays a role in controlling the diffusion of acid in the resist film. The acid diffusion controller may be, for example, a basic compound. The basic compound is preferably a compound having a structure represented by the following general formulae (A) to (E).

[0315] [ka]

[0316] In the general formula (A) and the general formula (E), R 200 , R 201 and R 202may be the same or different, and each represents a hydrogen atom, an alkyl group (preferably having 1 to 20 carbon atoms), a cycloalkyl group (preferably having 3 to 20 carbon atoms), or an aryl group (preferably having 6 to 20 carbon atoms), where R 201 and R 202 may be bonded to each other to form a ring.

[0317] Regarding the above alkyl group, the alkyl group having a substituent is preferably an aminoalkyl group having 1 to 20 carbon atoms, a hydroxyalkyl group having 1 to 20 carbon atoms, or a cyanoalkyl group having 1 to 20 carbon atoms. R 203 , R 204 , R 205 and R 206 may be the same or different and represent an alkyl group having 1 to 20 carbon atoms. The alkyl groups in the general formulae (A) and (E) are more preferably unsubstituted.

[0318] As the basic compound, guanidine, aminopyrrolidine, pyrazole, pyrazoline, piperazine, aminomorpholine, aminoalkylmorpholine (the alkyl group portion may be linear or branched, and may be partially replaced with an ether group and / or an ester group. The total number of all atoms other than hydrogen atoms in the alkyl group portion is preferably 1 to 17), piperidine, etc. Among them, compounds having an imidazole structure, a diazabicyclo structure, an onium hydroxide structure, an onium carboxylate structure, a trialkylamine structure, an aniline structure, or a pyridine structure, an alkylamine derivative having a hydroxyl group and / or an ether bond, or an aniline derivative having a hydroxyl group and / or an ether bond, etc. are more preferred.

[0319] Examples of compounds having an imidazole structure include imidazole, 2,4,5-triphenylimidazole, and benzimidazole. Examples of compounds having a diazabicyclo structure include 1,4-diazabicyclo[2,2,2]octane, 1,5-diazabicyclo[4,3,0]non-5-ene, and 1,8-diazabicyclo[5,4,0]undec-7-ene. Examples of compounds having an onium hydroxide structure include triarylsulfonium hydroxide, phenacylsulfonium hydroxide, and sulfonium hydroxide having a 2-oxoalkyl group. Specific examples include triphenylsulfonium hydroxide, tris(t-butylphenyl)sulfonium hydroxide, bis(t-butylphenyl)iodonium hydroxide, phenacylsulfonium hydroxide, and 2-oxopropylthiophenium hydroxide. Compounds having an onium carboxylate structure include compounds having an onium hydroxide structure in which the anion portion is carboxylate, such as acetate, adamantane-1-carboxylate, and perfluoroalkyl carboxylate. Compounds having a trialkylamine structure include tri(n-butyl)amine and tri(n-octyl)amine. Aniline compounds include 2,6-diisopropylaniline, N,N-dimethylaniline, N,N-dibutylaniline, and N,N-dihexylaniline. Alkylamine derivatives having a hydroxyl group and / or ether bond include ethanolamine, diethanolamine, triethanolamine, tris(methoxyethoxyethyl)amine, and "(HO-C2H4-O-C2H4)2N(-C3H6-O-CH3)". Aniline derivatives having a hydroxyl group and / or ether bond include N,N-bis(hydroxyethyl)aniline.

[0320] Preferred examples of the basic compound include an amine compound having a phenoxy group and an ammonium salt compound having a phenoxy group.

[0321] As the amine compound, for example, primary, secondary, and tertiary amine compounds can be used, and an amine compound having at least one alkyl group bonded to a nitrogen atom is preferred. The amine compound is more preferably a tertiary amine compound. As long as the amine compound has at least one alkyl group (preferably having 1 to 20 carbon atoms) bonded to a nitrogen atom, a cycloalkyl group (preferably having 3 to 20 carbon atoms) or an aryl group (preferably having 6 to 12 carbon atoms) may be bonded to the nitrogen atom in addition to the alkyl group. The amine compound preferably has an oxyalkylene group. The number of oxyalkylene groups in the molecule is preferably 1 or more, more preferably 3 to 9, and even more preferably 4 to 6. Among the oxyalkylene groups, an oxyethylene group (-CH2CH2O-) or an oxypropylene group (-CH(CH3)CH2O- or CH2CH2CH2O-) is preferred, and an oxyethylene group is more preferred.

[0322] Examples of the ammonium salt compound include primary, secondary, tertiary, and quaternary ammonium salt compounds, and ammonium salt compounds having at least one alkyl group bonded to a nitrogen atom are preferred. In the ammonium salt compound, as long as at least one alkyl group (preferably having 1 to 20 carbon atoms) is bonded to a nitrogen atom, a cycloalkyl group (preferably having 3 to 20 carbon atoms) or an aryl group (preferably having 6 to 12 carbon atoms) may be bonded to the nitrogen atom in addition to the alkyl group. The ammonium salt compound preferably has an oxyalkylene group. The number of oxyalkylene groups in a molecule is preferably 1 or more, more preferably 3 to 9, and even more preferably 4 to 6. Among the oxyalkylene groups, an oxyethylene group (-CH2CH2O-) or an oxypropylene group (-CH(CH3)CHO- or -CH2CH2CH2O-) is preferred, and an oxyethylene group is more preferred. Examples of the anion of the ammonium salt compound include halogen atoms, sulfonates, borates, and phosphates, among which halogen atoms or sulfonates are preferred. The halogen atoms are preferably chlorine atoms, bromine atoms, or iodine atoms. The sulfonates are preferably organic sulfonates having 1 to 20 carbon atoms. Examples of the organic sulfonates include alkyl sulfonates and aryl sulfonates having 1 to 20 carbon atoms. The alkyl group of the alkyl sulfonate may have a substituent, and examples of the substituent include a fluorine atom, a chlorine atom, a bromine atom, an alkoxy group, an acyl group, and an aromatic ring group. Examples of the alkyl sulfonate include methane sulfonate, ethane sulfonate, butane sulfonate, hexane sulfonate, octane sulfonate, benzyl sulfonate, trifluoromethane sulfonate, pentafluoroethane sulfonate, and nonafluorobutane sulfonate. Examples of the aryl group of the arylsulfonate include a benzene ring group, a naphthalene ring group, and an anthracene ring group. The substituent that the benzene ring group, the naphthalene ring group, and the anthracene ring group may have are preferably a linear or branched alkyl group having 1 to 6 carbon atoms, or a cycloalkyl group having 3 to 6 carbon atoms. Examples of the linear or branched alkyl group and the cycloalkyl group include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an i-butyl group, a t-butyl group, an n-hexyl group, and a cyclohexyl group. Examples of other substituents include an alkoxy group having 1 to 6 carbon atoms, a halogen atom, a cyano group, a nitro group, an acyl group, and an acyloxy group.

[0323] The amine compound having a phenoxy group and the ammonium salt compound having a phenoxy group are amine compounds or ammonium salt compounds having a phenoxy group at the terminal opposite to the nitrogen atom of the alkyl group. Examples of the substituent of the phenoxy group include an alkyl group, an alkoxy group, a halogen atom, a cyano group, a nitro group, a carboxylic acid group, a carboxylic acid ester group, a sulfonic acid ester group, an aryl group, an aralkyl group, an acyloxy group, and an aryloxy group. The substitution position of the substituent may be any of the 2-6 positions. The number of the substituent may be any of the 1-5 positions.

[0324] It is preferable that at least one oxyalkylene group is present between the phenoxy group and the nitrogen atom. The number of oxyalkylene groups in the molecule is preferably 1 or more, more preferably 3 to 9, and even more preferably 4 to 6. Among the oxyalkylene groups, an oxyethylene group (-CH2CH2O-) or an oxypropylene group (-CH(CH3)CHO- or -CH2CH2CH2O-) is preferable, and an oxyethylene group is more preferable.

[0325] The amine compound having a phenoxy group can be obtained by heating a primary or secondary amine having a phenoxy group and a haloalkyl ether to react with each other, adding an aqueous solution of a strong base (e.g., sodium hydroxide, potassium hydroxide, tetraalkylammonium, etc.) to the reaction system, and further extracting the reaction product with an organic solvent (e.g., ethyl acetate, chloroform, etc.). Alternatively, the amine compound having a phenoxy group can be obtained by heating a primary or secondary amine and a haloalkyl ether having a phenoxy group at the end to react with each other, adding an aqueous solution of a strong base to the reaction system, and further extracting the reaction product with an organic solvent.

[0326] (Compound (PA) that has a proton-accepting functional group and that decomposes upon exposure to actinic rays or radiation to reduce or eliminate the proton-accepting property, or to generate a compound that has changed from a proton-accepting property to an acidic property) The resist composition may contain, as an acid diffusion controller, a compound (hereinafter, also referred to as compound (PA)) that has a proton acceptor functional group and that decomposes upon irradiation with actinic rays or radiation to reduce or eliminate the proton acceptor property, or to generate a compound that has changed from proton acceptor property to acidic property.

[0327] The proton acceptor functional group means a group capable of electrostatically interacting with a proton or a functional group having electrons, for example, a functional group having a macrocyclic structure such as a cyclic polyether, or a functional group having a nitrogen atom having an unshared electron pair that does not contribute to π conjugation. The nitrogen atom having an unshared electron pair that does not contribute to π conjugation is, for example, a nitrogen atom having a partial structure represented by the following general formula:

[0328] [ka]

[0329] Preferred partial structures of the proton acceptor functional group include, for example, a crown ether structure, an azacrown ether structure, a primary to tertiary amine structure, a pyridine structure, an imidazole structure, and a pyrazine structure.

[0330] When exposed to actinic rays or radiation, the compound (PA) decomposes to generate a compound in which the proton acceptor property is reduced or eliminated, or which has changed from proton acceptor property to acidity. Here, the reduction or elimination of proton acceptor property, or the change from proton acceptor property to acidity, refers to a change in proton acceptor property caused by the addition of a proton to a proton acceptor functional group. Specifically, this means that when a proton adduct is generated from the compound (PA) having a proton acceptor functional group and a proton, the equilibrium constant in the chemical equilibrium decreases.

[0331] As the compound (PA), for example, those described in paragraphs

[0421] to

[0428] of JP 2014-41328 A and paragraphs

[0108] to

[0116] of JP 2014-134686 A can be used, the contents of which are incorporated herein by reference.

[0332] A low molecular weight compound having a nitrogen atom and a group that is cleaved by the action of an acid can also be used as the acid diffusion controller. The low molecular weight compound is preferably an amine derivative having, on a nitrogen atom, a group that is cleaved by the action of an acid. The group which is eliminated by the action of an acid is preferably an acetal group, a carbonate group, a carbamate group, a tertiary ester group, a tertiary hydroxyl group, or a hemiaminal ether group, more preferably a carbamate group or a hemiaminal ether group. The molecular weight of the low molecular weight compound is preferably 100-1,000, more preferably 100-700, and even more preferably 100-500. The small molecule compound may have a carbamate group with a protecting group on the nitrogen atom.

[0333] Specific examples of the acid diffusion controller are shown below, but the present invention is not limited thereto.

[0334] [ka]

[0335] [ka]

[0336] [ka]

[0337] [ka]

[0338] When the resist composition contains an acid diffusion controller, the content of the acid diffusion controller is preferably from 0.001 to 15 mass %, and more preferably from 0.01 to 8 mass %, relative to the total solid content of the resist composition. The acid diffusion controller may be used alone or in combination of two or more kinds. In addition, when the resist composition contains a specific compound having an anion represented by any one of formulas (d1-1) to (d1-3) and / or another photoacid generator having an anion represented by any one of formulas (d1-1) to (d1-3) (collectively referred to as "d1-based photoacid generator"), the d1-based photoacid generator can also function as an acid diffusion controller. When the resist composition contains a d1-based photoacid generator, it is also preferable that the resist composition does not substantially contain an acid diffusion controller. Here, "substantially does not contain an acid diffusion controller" means that the content of the acid diffusion controller is 5 mass% or less with respect to the total content of the d1-based photoacid generator. Furthermore, when the resist composition contains both a d1-based photoacid generator and an acid diffusion controller, the total content thereof is preferably from 1 to 30 mass %, and more preferably from 3 to 20 mass %.

[0339] The ratio of the photoacid generator to the acid diffusion controller in the resist composition is preferably photoacid generator / acid diffusion controller (molar ratio) = 2.5 to 300. From the viewpoints of sensitivity and resolution, the molar ratio is preferably 2.5 or more, and from the viewpoint of suppressing a decrease in resolution due to thickening of the resist pattern over time until heat treatment after exposure, the molar ratio is preferably 300 or less. The photoacid generator / acid diffusion controller (molar ratio) is more preferably 5.0 to 200, and even more preferably 7.0 to 150.

[0340] Examples of the acid diffusion controller include compounds described in paragraphs

[0140] to

[0144] of JP2013-11833A (such as amine compounds, amide group-containing compounds, urea compounds, and nitrogen-containing heterocyclic compounds).

[0341] <Hydrophobic resin> The resist composition may contain, in addition to the resin (A), a hydrophobic resin different from the resin (A). The hydrophobic resin is preferably designed to be unevenly distributed on the surface of the resist film, but unlike a surfactant, it does not necessarily have to have a hydrophilic group in the molecule, and does not necessarily have to contribute to uniform mixing of polar and non-polar substances. The effects of adding a hydrophobic resin include control of the static and dynamic contact angle of the resist film surface with water, and suppression of outgassing.

[0342] From the viewpoint of uneven distribution on the membrane surface layer, the hydrophobic resin preferably has one or more of "fluorine atoms", "silicon atoms" and "CH3 partial structures contained in the side chain portion of the resin", and more preferably has two or more of them. In addition, the hydrophobic resin preferably has a hydrocarbon group having 5 or more carbon atoms. These groups may be present in the main chain of the resin or may be substituted on the side chain.

[0343] When the hydrophobic resin contains a fluorine atom and / or a silicon atom, the fluorine atom and / or the silicon atom in the hydrophobic resin may be contained in the main chain or in the side chain of the resin.

[0344] When the hydrophobic resin contains a fluorine atom, the partial structure having a fluorine atom is preferably an alkyl group having a fluorine atom, a cycloalkyl group having a fluorine atom, or an aryl group having a fluorine atom. The alkyl group having a fluorine atom (preferably having 1 to 10 carbon atoms, more preferably having 1 to 4 carbon atoms) is a linear or branched alkyl group in which at least one hydrogen atom is substituted with a fluorine atom, and may further have a substituent other than a fluorine atom. The cycloalkyl group having a fluorine atom is a monocyclic or polycyclic cycloalkyl group in which at least one hydrogen atom is substituted with a fluorine atom, and may further have a substituent other than a fluorine atom. Examples of aryl groups having a fluorine atom include aryl groups in which at least one hydrogen atom of an aryl group, such as a phenyl group or a naphthyl group, is substituted with a fluorine atom, and the aryl group may further have a substituent other than a fluorine atom. Examples of the repeating unit having a fluorine atom or a silicon atom include the repeating units exemplified in paragraph

[0519] of US2012 / 0251948A1.

[0345] As described above, the hydrophobic resin also preferably contains a CH3 partial structure in the side chain portion. Here, the CH3 partial structure possessed by the side chain portion in the hydrophobic resin includes the CH3 partial structures possessed by an ethyl group, a propyl group, and the like. On the other hand, methyl groups directly bonded to the main chain of a hydrophobic resin (e.g., α-methyl groups of a repeating unit having a methacrylic acid structure) are not included in the CH3 partial structure of the present invention because they contribute little to the surface uneven distribution of the hydrophobic resin due to the influence of the main chain.

[0346] The hydrophobic resin may have a repeating unit having an acid-decomposable group.

[0347] Regarding hydrophobic resins, see paragraph 2 of JP 2014-010245 A.

[0348] Please refer to the descriptions in

[0415] below, the contents of which are incorporated into the present specification.

[0348] In addition to the hydrophobic resin, the resins described in JP-A-2011-248019, JP-A-2010-175859, and JP-A-2012-032544 can also be preferably used.

[0349] Preferred examples of the monomers corresponding to the repeating units constituting the hydrophobic resin are shown below.

[0350] [ka]

[0351] [ka]

[0352] When the resist composition contains a hydrophobic resin, the content of the hydrophobic resin is preferably from 0.01 to 20 mass %, and more preferably from 0.1 to 15 mass %, relative to the total solid content of the resist composition.

[0353] <Surfactant> The resist composition may contain a surfactant, which can provide a pattern with better adhesion and fewer development defects. The surfactant is preferably a fluorine-based and / or silicon-based surfactant. Examples of fluorine-based and / or silicon-based surfactants include those described in paragraph

[0276] of the specification of U.S. Patent Application Publication No. 2008 / 0248425. In addition, there are also surfactants such as EFTOP EF301 or EF303 (manufactured by Shin-Akita Chemical Industry Co., Ltd.); Fluorad FC430, 431, and 4430 (manufactured by Sumitomo 3M Limited); Megafac F171, F173, F176, F189, F113, F110, F177, F120, and R08 (manufactured by DIC Corporation); Surflon S-382, SC101, 102, 103, 104, 105, and 106 (manufactured by Asahi Glass Co., Ltd.); Troysol S-366 (manufactured by Troy Chemical Co., Ltd.); GF-300 or GF-150 (manufactured by Toa Gosei Chemical Co., Ltd.), and SALON S-382, ... Flon S-393 (manufactured by Seimi Chemical Co., Ltd.); F-top EF121, EF122A, EF122B, RF122C, EF125M, EF135M, EF351, EF352, EF801, EF802, or EF601 (manufactured by JEMCO Co., Ltd.); PF636, PF656, PF6320, and PF6520 (manufactured by OMNOVA Co., Ltd.); KH-20 (manufactured by Asahi Kasei Co., Ltd.); FTX-204G, 208G, 218G, 230G, 204D, 208D, 212D, 218D, and 222D (manufactured by Neos Co., Ltd.). Polysiloxane polymer KP-341 (manufactured by Shin-Etsu Chemical Co., Ltd.) can also be used as a silicone surfactant.

[0354] In addition to the above-mentioned known surfactants, the surfactant may be synthesized using a fluoroaliphatic compound produced by telomerization method (also called telomer method) or oligomerization method (also called oligomer method).Specifically, a polymer having a fluoroaliphatic group derived from the fluoroaliphatic compound may be used as the surfactant.The fluoroaliphatic compound can be synthesized by the method described in JP-A-2002-90991, for example. In addition, surfactants other than the fluorine-based and / or silicone-based surfactants described in paragraph

[0280] of the specification of US Patent Application Publication No. 2008 / 0248425 may be used.

[0355] These surfactants may be used alone or in combination of two or more.

[0356] When the resist composition contains a surfactant, the content of the surfactant is preferably from 0.0001 to 2 mass %, and more preferably from 0.0005 to 1 mass %, relative to the total solid content of the composition.

[0357] <Other additives> The resist composition may further contain a dissolution inhibiting compound, a dye, a plasticizer, a photosensitizer, a light absorber, and / or a compound that promotes solubility in a developer (for example, a phenol compound having a molecular weight of 1000 or less, or an alicyclic or aliphatic compound containing a carboxylic acid group).

[0358] The resist composition may further contain a dissolution inhibiting compound. Here, the term "dissolution inhibiting compound" refers to a compound with a molecular weight of 3000 or less that is decomposed by the action of an acid and has a reduced solubility in an organic developer.

[0359] [Resist film and pattern forming method] The procedure for forming a pattern using the resist composition is not particularly limited, but it is preferable for the method to include the following steps. Step 1: forming a resist film on a substrate using a resist composition Step 2: Exposing the resist film to light Step 3: A step of developing the exposed resist film using a developer to form a pattern. The procedures for each of the above steps will be described in detail below.

[0360] <Step 1: Resist film formation step> Step 1 is a step of forming a resist film on a substrate using a resist composition. The resist composition is as defined above.

[0361] An example of a method for forming a resist film on a substrate using a resist composition is a method in which the resist composition is applied onto a substrate. It is preferable to filter the resist composition before coating as necessary. The pore size of the filter is preferably 0.1 μm or less, more preferably 0.05 μm or less, and even more preferably 0.03 μm or less. The filter is preferably made of polytetrafluoroethylene, polyethylene, or nylon.

[0362] The resist composition can be applied onto a substrate (e.g., silicon, silicon dioxide coating) used in the manufacture of integrated circuit elements by a suitable application method such as a spinner or coater. The application method is preferably spin coating using a spinner. The rotation speed when spin coating using a spinner is preferably 1000 to 3000 rpm. After coating the resist composition, the substrate may be dried to form a resist film. If necessary, various undercoats (inorganic films, organic films, anti-reflective films) may be formed under the resist film.

[0363] An example of a drying method is a method of drying by heating. Heating can be performed by a means provided in a normal exposure machine and / or a developing machine, and may be performed using a hot plate or the like. The heating temperature is preferably 80 to 150° C., more preferably 80 to 140° C., and even more preferably 80 to 130° C. The heating time is preferably 30 to 1000 seconds, more preferably 60 to 800 seconds, and even more preferably 60 to 600 seconds.

[0364] The thickness of the resist film is not particularly limited, but from the viewpoint of forming a fine pattern with higher accuracy, the thickness is preferably from 10 to 65 nm, and more preferably from 15 to 50 nm.

[0365] A top coat may be formed on the resist film using a top coat composition. It is preferable that the top coat composition does not mix with the resist film and can be applied uniformly over the resist film. The topcoat composition includes, for example, a resin, an additive, and a solvent. The resin may be the same as the hydrophobic resin described above. The content of the resin is preferably 50 to 99.9 mass %, more preferably 60 to 99.7 mass %, based on the total solid content of the top coat composition. The additives may be the acid diffusion controller and d1-based photoacid generator described above. Compounds having a radical trap group, such as compounds having an N-oxyl free radical group, may also be used. Examples of such compounds include the [4-(benzoyloxy)-2,2,6,6-tetramethylpiperidinooxy] radical. The content of the additive is preferably 0.01 to 20% by mass, more preferably 0.1 to 15% by mass, based on the total solid content of the top coat composition. The above solvent preferably does not dissolve the resist film, and examples thereof include alcohol-based solvents (such as 4-methyl-2-pentanol), ether-based solvents (such as diisoamyl ether), ester-based solvents, fluorine-based solvents, and hydrocarbon-based solvents (such as n-decane). The content of the solvent in the top coat composition is preferably determined so that the solid content concentration is 0.5 to 30 mass %, and more preferably 1 to 20 mass %. The top coat composition may contain a surfactant in addition to the above-mentioned additives, and the surfactant may be any surfactant that may be contained in the composition of the present invention. The content of the surfactant is preferably 0.0001 to 2 mass %, more preferably 0.0005 to 1 mass %, based on the total solid content of the top coat composition. In addition, the top coat is not particularly limited, and a conventionally known top coat can be formed by a conventionally known method. For example, a top coat can be formed based on the description in paragraphs

[0072] to

[0082] of JP2014-059543A. For example, it is preferable to form a top coat containing a basic compound such as that described in JP 2013-61648 A on the resist film. Specific examples of the basic compound that the top coat may contain include basic compounds that may be contained in the resist composition. The top coat also preferably contains a compound containing at least one group or bond selected from the group consisting of an ether bond, a thioether bond, a hydroxyl group, a thiol group, a carbonyl bond, and an ester bond.

[0366] <Step 2: Exposure step> Step 2 is a step of exposing the resist film to light. An example of the exposure method is a method in which the formed resist film is irradiated with EUV light through a predetermined mask.

[0367] After exposure, it is preferable to bake (heat) the film before developing it, since baking promotes the reaction of the exposed area and improves the sensitivity and pattern shape. The heating temperature is preferably from 80 to 150°C, more preferably from 80 to 140°C, and even more preferably from 80 to 130°C. The heating time is preferably from 10 to 1000 seconds, more preferably from 10 to 180 seconds, and further preferably from 30 to 120 seconds. Heating can be carried out by a means provided in a normal exposure machine and / or developing machine, and may also be carried out using a hot plate or the like. This step is also called post-exposure bake.

[0368] <Process 3: Development process> Step 3 is a step of developing the exposed resist film with a developer to form a pattern. The developer may be an alkaline developer or a developer containing an organic solvent (hereinafter, also referred to as an organic developer).

[0369] Development methods include, for example, a method in which a substrate is immersed in a tank filled with developer for a certain period of time (dip method), a method in which developer is piled up on the substrate surface by surface tension and left stationary for a certain period of time for development (paddle method), a method in which developer is sprayed onto the substrate surface (spray method), and a method in which developer is continuously dispensed while a developer dispensing nozzle is scanned at a constant speed onto a substrate rotating at a constant speed (dynamic dispense method). After the developing step, a step of stopping the development while replacing the solvent with another solvent may be carried out. The development time is not particularly limited as long as the resin in the unexposed area is sufficiently dissolved, and is preferably from 10 to 300 seconds, more preferably from 20 to 120 seconds. The temperature of the developer is preferably from 0 to 50°C, and more preferably from 15 to 35°C.

[0370] The alkaline developer is preferably an aqueous alkaline solution containing an alkali. The type of the aqueous alkaline solution is not particularly limited, but examples include an aqueous alkaline solution containing a quaternary ammonium salt such as tetramethylammonium hydroxide, an inorganic alkali, a primary amine, a secondary amine, a tertiary amine, an alcohol amine, or a cyclic amine. Among them, the alkaline developer is preferably an aqueous solution of a quaternary ammonium salt such as tetramethylammonium hydroxide (TMAH). The alkaline developer may contain an appropriate amount of alcohols, surfactants, etc. The alkali concentration of the alkaline developer is usually 0.1 to 20% by mass. The pH of the alkaline developer is usually 10.0 to 15.0.

[0371] The organic developer is preferably a developer containing at least one organic solvent selected from the group consisting of ketone-based solvents, ester-based solvents, alcohol-based solvents, amide-based solvents, ether-based solvents, and hydrocarbon-based solvents.

[0372] Examples of ketone solvents include 1-octanone, 2-octanone, 1-nonanone, 2-nonanone, acetone, 2-heptanone (methyl amyl ketone), 4-heptanone, 1-hexanone, 2-hexanone, diisobutyl ketone, cyclohexanone, methylcyclohexanone, phenylacetone, methyl ethyl ketone, methyl isobutyl ketone, acetylacetone, acetonylacetone, ionone, diacetonyl alcohol, acetylcarbinol, acetophenone, methyl naphthyl ketone, isophorone, and propylene carbonate.

[0373] Examples of ester-based solvents include methyl acetate, butyl acetate, ethyl acetate, isopropyl acetate, pentyl acetate, isopentyl acetate, amyl acetate, propylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, diethylene glycol monoethyl ether acetate, ethyl-3-ethoxypropionate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, methyl formate, ethyl formate, butyl formate, propyl formate, ethyl lactate, butyl lactate, propyl lactate, butyl butanoate, methyl 2-hydroxyisobutyrate, isoamyl acetate, isobutyl isobutyrate, and butyl propionate.

[0374] Examples of the alcohol-based solvent, amide-based solvent, ether-based solvent, and hydrocarbon-based solvent that can be used include the solvents disclosed in paragraphs

[0715] to

[0718] of the specification of U.S. Patent Application Publication No. 2016 / 0070167A1.

[0375] The above solvents may be mixed in combination, or may be mixed with a solvent other than the above or with water. The water content of the developer as a whole is preferably less than 50% by mass, more preferably less than 20% by mass, even more preferably less than 10% by mass, and particularly preferably substantially free of water. The content of the organic solvent in the organic developer is preferably 50% by mass or more and 100% by mass or less, more preferably 80% by mass or more and 100% by mass or less, still more preferably 90% by mass or more and 100% by mass or less, and particularly preferably 95% by mass or more and 100% by mass or less, based on the total amount of the developer.

[0376] <Other processes> The above pattern formation method preferably includes, after step 3, a step of washing with a rinsing liquid.

[0377] The rinse liquid used in the rinse step following the step of developing with an alkaline developer may be, for example, pure water, to which an appropriate amount of a surfactant may be added. A suitable amount of a surfactant may be added to the rinse solution.

[0378] The rinse liquid used in the rinse step after the development step using an organic developer is not particularly limited as long as it does not dissolve the pattern, and a solution containing a general organic solvent can be used. The rinse liquid is preferably a rinse liquid containing at least one organic solvent selected from the group consisting of hydrocarbon solvents, ketone solvents, ester solvents, alcohol solvents, amide solvents, and ether solvents. Examples of the hydrocarbon-based solvents, ketone-based solvents, ester-based solvents, alcohol-based solvents, amide-based solvents, and ether-based solvents include those similar to those described in the developer containing an organic solvent.

[0379] The method of the rinsing step is not particularly limited, and examples thereof include a method of continuously discharging a rinsing liquid onto a substrate rotating at a constant speed (spin coating method), a method of immersing a substrate in a tank filled with the rinsing liquid for a certain period of time (dip method), and a method of spraying the rinsing liquid onto the substrate surface (spray method). The pattern forming method of the present invention may also include a heating step (Post Bake) after the rinsing step. This step removes the developer and rinsing solution remaining between and inside the patterns due to baking. This step also has the effect of annealing the resist pattern and improving the surface roughness of the pattern. The heating step after the rinsing step is usually performed at 40 to 250°C (preferably 90 to 200°C) for usually 10 seconds to 3 minutes (preferably 30 seconds to 120 seconds).

[0380] Furthermore, the substrate may be etched using the formed pattern as a mask. That is, the substrate (or the underlayer film and the substrate) may be processed using the pattern formed in step 3 as a mask to form a pattern on the substrate. The method for processing the substrate (or the underlayer film and the substrate) is not particularly limited, but a method of forming a pattern on the substrate by dry etching the substrate (or the underlayer film and the substrate) using the pattern formed in step 3 as a mask is preferred. The dry etching may be a single-stage etching or a multi-stage etching. When the etching is a multi-stage etching, each stage of the etching may be the same process or different processes. Any known method can be used for the etching, and various conditions, etc. are appropriately determined depending on the type or use of the substrate, etc. For example, etching can be performed according to the method described in "Chapter 4 Etching" of "Semiconductor Processing Textbook, 4th Edition, published in 2007, published by SEMI Japan", etc. Among them, the dry etching is preferably oxygen plasma etching.

[0381] The resist composition and various materials used in the pattern forming method of the present invention (e.g., solvent, developer, rinse, anti-reflective film forming composition, top coat forming composition, etc.) preferably do not contain impurities such as metals. The content of impurities contained in these materials is preferably 1 mass ppm or less, more preferably 10 mass ppb or less, even more preferably 100 mass ppt or less, particularly preferably 10 mass ppt or less, and most preferably 1 mass ppt or less. Here, examples of metal impurities include Na, K, Ca, Fe, Cu, Mg, Al, Li, Cr, Ni, Sn, Ag, As, Au, Ba, Cd, Co, Pb, Ti, V, W, and Zn.

[0382] Examples of methods for removing impurities such as metals from various materials include filtration using a filter. The filter pore size is preferably less than 100 nm, more preferably 10 nm or less, and even more preferably 5 nm or less. The filter is preferably made of polytetrafluoroethylene, polyethylene, or nylon. The filter may be made of a composite material combining the above filter material with an ion exchange medium. The filter may be a filter that has been washed in advance with an organic solvent. In the filter filtration process, multiple types of filters may be connected in series or parallel. When multiple types of filters are used, filters with different pore sizes and / or materials may be used in combination. In addition, various materials may be filtered multiple times, and the process of filtering multiple times may be a circulation filtration process. In the manufacture of the resist composition, for example, each component such as a resin and a photoacid generator is dissolved in a solvent, and then circulation filtration is preferably performed using a plurality of filters made of different materials. For example, it is preferable to connect a polyethylene filter with a pore size of 50 nm, a nylon filter with a pore size of 10 nm, and a polyethylene filter with a pore size of 3 nm in series, and perform circulation filtration 10 times or more. The smaller the pressure difference between the filters, the more preferable, and generally 0.1 MPa or less, preferably 0.05 MPa or less, and more preferably 0.01 MPa or less. The smaller the pressure difference between the filter and the filling nozzle, the more preferable, and generally 0.5 MPa or less, preferably 0.2 MPa or less, and more preferably 0.1 MPa or less. The interior of the resist composition production apparatus is preferably replaced with an inert gas such as nitrogen, which makes it possible to prevent active gases such as oxygen from dissolving in the resist composition. The resist composition is filtered through a filter and then filled into a clean container. The resist composition filled into the container is preferably stored in a refrigerator. This prevents deterioration of performance over time. The shorter the time from the completion of filling the composition into the container to the start of refrigerated storage, the better, and is generally within 24 hours, preferably within 16 hours, more preferably within 12 hours, and even more preferably within 10 hours. The storage temperature is preferably 0 to 15°C, more preferably 0 to 10°C, and even more preferably 0 to 5°C.

[0383] Methods for reducing impurities such as metals contained in various materials include, for example, selecting raw materials with low metal content as the raw materials constituting the various materials, filtering the raw materials constituting the various materials, and performing distillation under conditions that minimize contamination as much as possible, for example by lining the inside of the apparatus with Teflon (registered trademark).

[0384] In addition to the filter filtration, the impurities may be removed by an adsorbent, or the filter filtration and the adsorbent may be used in combination. As the adsorbent, a known adsorbent may be used, for example, an inorganic adsorbent such as silica gel and zeolite, and an organic adsorbent such as activated carbon. In order to reduce impurities such as metals contained in the above various materials, it is necessary to prevent the incorporation of metal impurities in the manufacturing process. Whether or not metal impurities have been sufficiently removed from the manufacturing equipment can be confirmed by measuring the content of metal components contained in the cleaning solution used to clean the manufacturing equipment. The content of metal components contained in the cleaning solution after use is preferably 100 parts per trillion (ppt) by mass or less, more preferably 10 ppt by mass or less, and even more preferably 1 ppt by mass or less.

[0385] A conductive compound may be added to an organic processing liquid such as a rinse liquid in order to prevent breakdown of chemical piping and various parts (filters, O-rings, tubes, etc.) due to static electricity buildup and subsequent static electricity discharge. The conductive compound is not particularly limited, but an example thereof is methanol. The amount added is not particularly limited, but in terms of maintaining favorable development characteristics or rinsing characteristics, it is preferably 10% by mass or less, more preferably 5% by mass or less. For example, SUS (stainless steel), or various pipes coated with antistatic polyethylene, polypropylene, or fluororesin (polytetrafluoroethylene, perfluoroalkoxy resin, etc.) can be used as the chemical liquid pipe. Similarly, for the filter and O-ring, antistatic polyethylene, polypropylene, or fluororesin (polytetrafluoroethylene, perfluoroalkoxy resin, etc.) can be used.

[0386] A method for improving the surface roughness of a pattern may be applied to the pattern formed by the method of the present invention. Examples of the method for improving the surface roughness of a pattern include a method of treating the pattern with plasma of a gas containing hydrogen, as disclosed in International Publication No. 2014 / 002808. Other known methods include those described in JP 2004-235468 A, U.S. Patent Application Publication No. 2010 / 0020297 A, JP 2008-83384 A, and Proc. of SPIE Vol. 8328 83280N-1 "EUV Resist Curing Technique for LWR Reduction and Etch Selectivity Enhancement".

[0387] When the pattern to be formed is in the form of lines, the aspect ratio, calculated by dividing the pattern height by the line width, is preferably 2.5 or less, more preferably 2.1 or less, and even more preferably 1.7 or less. When the pattern to be formed is a trench (groove) pattern or a contact hole pattern, the aspect ratio calculated by dividing the pattern height by the trench width or hole diameter is preferably 4.0 or less, more preferably 3.5 or less, and even more preferably 3.0 or less.

[0388] The pattern formation method of the present invention can also be used for guide pattern formation in DSA (Directed Self-Assembly) (see, for example, ACS Nano Vol. 4 No. 8 Pages 4815-4823).

[0389] Furthermore, the pattern formed by the above method can be used as a core for the spacer process disclosed in, for example, JP-A-3-270227 and JP-A-2013-164509.

[0390] The present invention also relates to a method for manufacturing an electronic device, which includes the above-mentioned pattern formation method, and an electronic device manufactured by this manufacturing method. The electronic device of the present invention is suitably mounted in electric and electronic equipment (such as home appliances, OA (Office Automation), media-related equipment, optical equipment, and communication equipment). EXAMPLES

[0391] The present invention will be described in more detail below based on examples. The materials, amounts, ratios, processing contents, processing procedures, etc. shown in the following examples can be appropriately changed without departing from the spirit of the present invention. Therefore, the scope of the present invention should not be interpreted as being limited by the following examples.

[0392] [Preparation of Composition] The components contained in the actinic ray-sensitive or radiation-sensitive resin compositions (hereinafter also referred to as "resist compositions") used in the examples and comparative examples and the procedures for producing them are shown below.

[0393] <Photoacid generators (specific compounds and comparative compounds)> (Synthesis of specific compound A-3) Specific compound A-3 was synthesized based on the following scheme.

[0394] [ka]

[0395] Magnesium (18.0 g) was added to tetrahydrofuran (500 mL) to obtain a mixture. 4-Bromobenzenetrifluoride (151.5 g) was added dropwise to the obtained mixture. Then, the mixture was stirred for 1 hour to prepare Grignard reagent A. Thionyl chloride (37.7 g) was added to tetrahydrofuran (500 mL) to obtain a mixture. The mixture was cooled to 0° C., and the previously prepared Grignard reagent A was added dropwise to the mixture. After stirring the mixture for 1 hour, 1N hydrochloric acid (600 mL) was added to the mixture while maintaining the temperature of the mixture at 0° C. The reaction product produced in the mixture was extracted with ethyl acetate (600 mL). The organic phase was washed with saturated aqueous sodium bicarbonate solution (500 mL) and water (500 mL), and then the solvent was distilled off from the organic phase. The concentrate was washed with hexane (300 mL) and filtered to obtain intermediate A (60 g) as a residue (yield 56%).

[0396] [ka]

[0397] Magnesium (5.0 g) was added to tetrahydrofuran (170 mL) to obtain a mixture. 1-Bromo-3,5-bis(trifluoromethyl)benzene (52.0 g) was added dropwise to the obtained mixture. Then, the mixture was stirred for 1 hour to prepare Grignard reagent B. Intermediate A (20.0 g) was added to tetrahydrofuran (170 mL) to obtain a mixed solution. The resulting mixed solution was cooled to 0° C., and trimethylsilyl trifluoromethanesulfonate (91.9 g) was added dropwise to the mixed solution. Then, the previously prepared Grignard reagent B was added dropwise to the mixed solution, and the mixed solution was stirred for 1 hour. Water (500 mL) was added to the mixture while maintaining the temperature of the mixture at 0° C., and the reaction product formed in the mixture was extracted with methylene chloride (500 mL). The obtained organic phase was washed with water (500 mL), and then the solvent was distilled off from the organic phase. The obtained concentrate was washed with diisopropyl ether (300 mL) and filtered to obtain intermediate B (20 g) as a residue (yield 58%).

[0398] [ka]

[0399] Methylene chloride (100 mL) and water (100 mL) were mixed to obtain a mixed solution. Triethylamine hydrochloride Q (10.0 g) and intermediate B (16.1 g) were added to the mixed solution. The mixed solution was stirred for 1 hour, and then the aqueous phase was removed from the mixed solution. The remaining organic layer was washed with 1 mass% potassium carbonate aqueous solution (100 mL), 0.01N hydrochloric acid (100 mL), and water (100 mL). The solvent was distilled off from the organic phase to obtain specific compound A-3 (20 g) (yield 99%).

[0400] Other specific compounds were synthesized with reference to the above synthesis method. The photoacid generators used in the examples are shown below. It should be noted that A-1 to A-13 and B-2 to B-5 are specific compounds, while B-1 and Z-1 to Z-2 are not specific compounds.

[0401] [ka]

[0402] [ka]

[0403] [ka]

[0404] [ka]

[0405] <Acid-decomposable resin (resin (A))> The acid-decomposable resin (resin (A)) used in the production of the resist composition is shown below.

[0406] [ka]

[0407] [ka]

[0408] The molar ratio of the repeating units constituting each of the above-mentioned resins (corresponding in order from the left), the weight average molecular weight (Mw) of each resin, and the dispersity (Mw / Mn) are shown in the table below.

[0409] [Table 1]

[0410] <Acid diffusion control agent> When the resist composition contained an acid diffusion controller, the following acid diffusion controller was used.

[0411] [ka]

[0412] <Hydrophobic resin> In cases where the resist composition contained a hydrophobic resin, a hydrophobic resin having a repeating unit based on the following monomer was used.

[0413] [ka]

[0414] The molar ratio of repeating units based on each monomer in the hydrophobic resin used in the composition, the weight average molecular weight (Mw) of each resin, and the dispersity (Mw / Mn) are shown in the table below.

[0415] [Table 2]

[0416] <Surfactant> When the composition contained a surfactant, the following surfactants were used: E-1: Megafac F176 (DIC Corporation, fluorosurfactant) E-2: Megafac R08 (DIC Corporation, fluorine and silicone surfactant) E-3: PF656 (OMNOVA, fluorosurfactant)

[0417] <Solvent> The solvents contained in the composition are shown below. F-1: Propylene glycol monomethyl ether acetate (PGMEA) F-2: Propylene glycol monomethyl ether (PGME) F-3: Propylene glycol monoethyl ether (PGEE) F-4: Cyclohexanone F-5: Cyclopentanone F-6: 2-heptanone F-7: Ethyl lactate F-8: γ-butyrolactone F-9: Propylene carbonate

[0418] <Preparation of Composition>

[0419] (Preparation of compositions for EUV exposure test (Re-1 to Re-22)) The components shown in the table below were mixed to a solid content of 2% by mass. The resulting mixture was then filtered, in this order, first through a polyethylene filter having a pore size of 50 nm, then through a nylon filter having a pore size of 10 nm, and finally through a polyethylene filter having a pore size of 5 nm, to prepare a resist composition (actinic ray-sensitive or radiation-sensitive resin composition) to be used in a test involving EUV exposure. In addition, in the resist composition, the solid content means all components other than the solvent. The obtained resist composition was used in the examples and comparative examples. In the following table, the content (mass%) of each component means the content relative to the total solid content.

[0420] (Preparation of compositions for ArF exposure test (Re-23 to Re-34)) The components shown in the table below were mixed to a solid content of 4% by mass. The resulting mixture was then filtered, in this order, first through a polyethylene filter having a pore size of 50 nm, then through a nylon filter having a pore size of 10 nm, and finally through a polyethylene filter having a pore size of 5 nm, to prepare a resist composition (actinic ray-sensitive or radiation-sensitive resin composition) to be used in a test using ArF exposure.

[0421] The formulation of each composition is shown below.

[0422] [Table 3]

[0423] [Preparation of Top Coat Composition] In this example, when a resist film was formed using the above resist composition, a top coat was further formed on the resist film as desired. The components and manufacturing procedure of the topcoat composition used to form the topcoat are shown below.

[0424] <Resin> The molar fraction of repeating units based on each monomer for the resins used in the top coat composition, the weight average molecular weight (Mw) of each resin, and the dispersity (Mw / Mn) are shown in the table below. For the structures of the monomers corresponding to the repeating units shown in the table, refer to the monomers shown in the above description of <Hydrophobic Resin>.

[0425] [Table 4]

[0426] <Additives> The topcoat composition contains the following additives:

[0427] [ka]

[0428] <Surfactant> When the topcoat composition contained a surfactant, the following surfactants were used: E-3: PF656 (OMNOVA, fluorosurfactant)

[0429] <Solvent> The solvents contained in the top coat composition are shown below. FT-1: 4-Methyl-2-pentanol (MIBC) FT-2: n-Decane FT-3: Diisoamyl ether

[0430] <Preparation of Top Coat Composition> A solution was prepared by dissolving each component in a solvent so as to satisfy the composition shown in the table below and to have a solid content concentration of 3.8 mass %. The resulting solution was then filtered through a polyethylene filter having a pore size of 0.1 μm to prepare a topcoat composition.

[0431] [Table 5] 〔test〕 Using the resist composition prepared as described above, the LWR of the patterns developed under the following conditions was evaluated. In any of the tests, as the resist composition (photosensitive or radiation-sensitive resin composition) used for pattern formation, the resist composition after being left standing in an environment at 4°C for 3 months after production was used.

[0432] <EUV Exposure, Organic Solvent Development> (Pattern Formation) A composition for forming an underlayer film AL412 (manufactured by Brewer Science) was applied onto a silicon wafer and baked at 205°C for 60 seconds to form an underlayer film with a film thickness of 20 nm. On top of that, the resist composition shown in Table 6 was applied and baked at 100°C for 60 seconds to form a resist film with a film thickness of 30 nm. Using an EUV exposure apparatus (manufactured by Exitech, Micro Exposure Tool, NA0.3, Quadrupole, Outer Sigma 0.68, Inner Sigma 0.36), pattern irradiation was performed on the silicon wafer having the obtained resist film. As for the reticle, a mask with a line size of 20 nm and a line:space ratio of 1:1 was used. After baking the exposed resist film at 90°C for 60 seconds, it was developed with n-butyl acetate for 30 seconds and spin-dried to obtain a negative-type pattern.

[0433] (Evaluation) For a 20 nm (1:1) line-and-space pattern resolved at the optimum exposure dose when resolving a line pattern with an average line width of 20 nm, observation was made from the top of the pattern using a length-measuring scanning electron microscope (SEM (Hitachi, Ltd. S-9380II)). The line width of the pattern was observed at arbitrary points (100 points), and the measurement variation was evaluated with 3σ and taken as the LWR. A smaller value of the LWR indicates better LWR performance. The LWR (nm) is preferably 4.5 nm or less, more preferably 3.9 nm or less, and still more preferably 3.5 nm or less.

[0434] The results are shown in the following table. The "Formula" column in the table indicates which of general formulas (1) to (3) the specific compound used corresponds to. The "F-AL" column indicates whether the cation in the specific compound used has a fluorine-containing group that is a fluoroalkyl group. If this requirement is met, it is marked as "A", and if not, it is marked as "B". The "Condition X" column indicates whether the specific compound used satisfies any of the following conditions X1 to X3. If the compound satisfies this requirement, it is marked as "A," and if it does not, it is marked as "B." Condition X1: The specific compound used is a compound represented by the general formula (1), Ar 1 , Ar 2 , and Ar 3 The aromatic hydrocarbon ring group represented by the formula: has a total of three or more fluoroalkyl groups, or The compound has a total of one or more organic groups other than the electron-withdrawing group, and the total number of carbon atoms contained in the total of one or more organic groups other than the electron-withdrawing group is 3 or more. Condition X2: The specific compound used is a compound represented by the general formula (2), Ar 4 , Ar 5 , and Ar 6 The aromatic hydrocarbon ring group represented by the formula (I) has a total of three or more fluorine-containing groups, or Ar 4 , Ar 5 , and Ar 6 has a total of one or more organic groups other than linear or branched electron-withdrawing groups, and the total number of carbon atoms contained in the total of one or more linear or branched organic groups other than electron-withdrawing groups is 3 or more. Condition X3: The specific compound used is a compound represented by the general formula (3), Ar 7 , Ar 8 , and Ar 9 The total number of carbon atoms contained in the organic groups other than the electron-withdrawing group contained in the aromatic hydrocarbon ring group represented by the formula (I) is 3 or more.

[0435] [Table 6]

[0436] As shown in the table, when obtaining a pattern by EUV exposure and organic solvent development, it was confirmed that the resist composition of the present invention can form a pattern excellent in LWR performance even when using a resist composition stored for a long time. In addition, when using a specific compound in which the fluorine-containing group is a fluoroalkyl group, it was confirmed that the effect of the present invention is more excellent (see, for example, comparison between examples using specific compounds that satisfy the requirements in the "F-AL" column in the table and examples using specific compounds that do not satisfy the requirements). When using a specific compound that satisfies condition X, it was confirmed that the effect of the present invention is even more excellent (see, for example, comparison between examples using specific compounds that satisfy the requirements in the "condition X" column in the table and examples using specific compounds that do not satisfy the requirements).

[0437] <EUV exposure, alkaline development> (Pattern formation) A composition AL412 (manufactured by Brewer Science) for forming an underlayer film was applied onto a silicon wafer and baked at 205°C for 60 seconds to form an underlayer film with a film thickness of 20 nm. On top of this, the resist composition shown in Table 7 was applied and baked at 100°C for 60 seconds to form a resist film with a film thickness of 30 nm. Pattern irradiation was performed on the silicon wafer having the obtained resist film using an EUV exposure apparatus (manufactured by Exitech, Micro Exposure Tool, NA0.3, Quadrupol, outer sigma 0.68, inner sigma 0.36). Note that as the reticle, a mask with a line size of 20 nm and a line:space ratio of 1:1 was used. After baking the exposed resist film at 90°C for 60 seconds, it was developed with an aqueous solution of tetramethylammonium hydroxide (2.38% by mass) for 30 seconds, and then rinsed with pure water for 30 seconds. Thereafter, this was spin-dried to obtain a positive pattern.

[0438] (Evaluation) The obtained pattern was evaluated in the same manner as for evaluating the LWR of the pattern by <EUV exposure, organic solvent development>. The results are shown in the following table. The meanings of the respective columns in the table are as described above.

[0439]

Table 7

[0440] As shown in the table, in the case of obtaining a pattern by EUV exposure and alkali development, it was confirmed that the resist composition of the present invention can form a pattern excellent in LWR performance even when using a resist composition stored for a long period of time. In addition, it was confirmed that the effect of the present invention is more excellent when using a specific compound in which the fluorine-containing group is a fluoroalkyl group (see, for example, the comparison between examples using specific compounds that satisfy the requirements in the "F-AL" column in the table and examples using specific compounds that do not satisfy the requirements). When using a specific compound that satisfies condition X, it was confirmed that the effect of the present invention is even more excellent (see, for example, the comparison between examples using specific compounds that satisfy the requirements in the "condition X" column in the table and examples using specific compounds that do not satisfy the requirements).

[0441] <ArF immersion exposure, organic solvent development> (Pattern formation) A composition for forming an organic antireflection film ARC29SR (manufactured by Brewer Science) was applied onto a silicon wafer and baked at 205 °C for 60 seconds to form an antireflection film with a film thickness of 98 nm. On top of that, the resist composition shown in Table 8 was applied and baked at 100 °C for 60 seconds to form a resist film (a photosensitive or radiation-sensitive film) with a film thickness of 90 nm. For Examples 3-8, 3-9, and 3-10, a topcoat film was formed on the resist film (the types of topcoat compositions used are shown in Table 8). The film thickness of the topcoat film was 100 nm in each case. The resist film was exposed to light through a 6% halftone mask with a 1:1 line and space pattern of 45 nm line width using an ArF excimer laser immersion scanner (ASML; XT1700i, NA 1.20, Dipole, outer sigma 0.950, inner sigma 0.850, Y deflection). Ultrapure water was used as the immersion liquid. The exposed resist film was baked at 90°C for 60 seconds, developed with n-butyl acetate for 30 seconds, rinsed with 4-methyl-2-pentanol for 30 seconds, and then spin-dried to obtain a negative pattern.

[0442] (evaluation) A 45 nm (1:1) line and space pattern resolved with the optimal exposure dose for resolving a line pattern with an average line width of 45 nm was observed from above using a critical dimension scanning electron microscope (SEM (Hitachi, Ltd. S-9380II)). The line width of the pattern was observed at arbitrary points (100 points), and the measurement variation was evaluated at 3σ to determine the LWR. A smaller LWR value indicates better LWR performance. LWR (nm) is preferably 4.0 nm or less, more preferably 3.5 nm or less, and even more preferably 3.0 nm or less. The results are shown in the table below, where the meanings of each column are as described above.

[0443] [Table 8]

[0444] As shown in the table, when a pattern is obtained by ArF exposure and organic solvent development, it was confirmed that the resist composition of the present invention can form a pattern with excellent LWR performance, even when a resist composition that has been stored for a long period of time is used. It was also confirmed that the effects of the present invention are superior when a specific compound in which the fluorine-containing group is a fluoroalkyl group is used (see the comparison between examples in the "F-AL" column in the table in which a specific compound satisfying the requirements is used and examples in which a specific compound not satisfying the requirements is used). When using a specific compound that satisfies condition X, it was confirmed that the effects of the present invention are further excellent (see, for example, the comparison between the examples using the specific compound that satisfies the requirements in the "condition X" column in the table and the examples using the specific compound that does not satisfy the requirements).

[0445] <ArF Immersion Lithography, Alkaline Development> (Pattern Formation) A composition for forming an organic antireflection film ARC29SR (manufactured by Brewer Science) was applied onto a silicon wafer and baked at 205 °C for 60 seconds to form an antireflection film with a film thickness of 98 nm. On top of that, the resist composition shown in Table 9 was applied and baked at 100 °C for 60 seconds to form a resist film with a film thickness of 90 nm. For Examples 4-8, Example 4-9, and Example 4-10, a topcoat film was formed on the upper layer of the resist film (the types of the topcoat compositions used are shown in Table 9). The film thickness of the topcoat film was 100 nm in all cases. The resist film was exposed through a 6% halftone mask of a 1:1 line and space pattern with a line width of 45 nm using an ArF excimer laser immersion scanner (manufactured by ASML; XT1700i, NA 1.20, Dipole, outer sigma 0.950, inner sigma 0.890, Y deflection). Ultrapure water was used as the immersion liquid. After baking the exposed resist film at 90 °C for 60 seconds, it was developed with an aqueous solution of tetramethylammonium hydroxide (2.38 mass%) for 30 seconds and then rinsed with pure water for 30 seconds. Then, it was spin-dried to obtain a positive pattern.

[0446] (Evaluation) The obtained pattern was evaluated in the same manner as evaluating the LWR of the pattern by <ArF Immersion Lithography, Organic Solvent Development>. The results are shown in the following table. The meanings of each column in the table are as described above.

[0447]

Table 9

[0448] As shown in the table, when a pattern is obtained by ArF exposure and alkaline development, it was confirmed that the resist composition of the present invention can form a pattern with excellent LWR performance even when a resist composition that has been stored for a long period of time is used. It was also confirmed that the effects of the present invention are superior when a specific compound in which the fluorine-containing group is a fluoroalkyl group is used (see the comparison between examples in the "F-AL" column in the table in which a specific compound satisfying the requirements is used and examples in which a specific compound not satisfying the requirements is used). It was confirmed that the effects of the present invention are even better when a specific compound satisfying condition X is used (see the comparison between an example using a specific compound satisfying the requirements in the "Condition X" column and an example using a specific compound not satisfying the requirements in the table).

Claims

1. One or more specific compounds selected from the group consisting of a compound represented by general formula (1), a compound represented by general formula (2), and a compound represented by general formula (3), and an acid-decomposable resin. 【Chemistry 1】 In general formula (1), X － represents an organic anion. Ar １ and Ar ２ each independently represents an aromatic hydrocarbon ring group having at least one substituent. Ar ３ represents an aromatic hydrocarbon ring group represented by general formula (1R). In formula (1R), * represents a bonding position. R １ ~R ５ each independently represents a hydrogen atom, a fluorine atom, or an alkyl group which may have a substituent. However, R １ and R ５ At least one of these represents a fluorine-containing group selected from the group consisting of a fluorine atom and a fluoroalkyl group. In general formula (1), Ar １ , Ar ２ , and Ar ３ At least two of these represent groups having different structures. 【Chemistry 2】 In general formula (2), X － represents an organic anion. Ar ４ and Ar ５ each independently represents an aromatic hydrocarbon ring group having at least one substituent. Ar ６ represents an aromatic hydrocarbon ring group represented by general formula (2R). In formula (2R), * represents a bonding position. R ６ , R ７ , R ９ , and R １０ each independently represents a hydrogen atom, a fluorine atom, or an alkyl group which may have a substituent. R ８ represents a fluorine-containing group selected from the group consisting of a fluorine atom and a fluoroalkyl group. In the general formula (2), Ar ４ , Ar ５ , and Ar ６ At least two of these represent groups having different structures. In addition, in the general formula (2), Ar ４ , Ar ５ , and Ar ６ The aromatic hydrocarbon ring group represented by the following formula (I) has a total of two or more fluorine-containing groups. 【Chemistry 3】 In general formula (3), X － represents an organic anion. Ar ７ and Ar ８ each independently represents an aromatic hydrocarbon ring group which may have an organic group other than an electron-withdrawing group. However, Ar ７ and Ar ８ The aromatic hydrocarbon ring group represented by the following formula (I) has one or more organic groups other than the electron-withdrawing group. Ar ９ represents an aromatic hydrocarbon ring group represented by general formula (3R). In formula (3R), * represents a bonding position. R １１ , R １３ , and R １５ each independently represents a hydrogen atom, a fluorine atom, or an alkyl group which may have a substituent. R １２ and R １４ each independently represents a fluorine-containing group selected from the group consisting of a fluorine atom and a fluoroalkyl group.

2. 2. The actinic ray-sensitive or radiation-sensitive resin composition according to claim 1, wherein the fluorine-containing group in the general formulas (1) to (3) is a fluoroalkyl group.

3. In the general formula (1), Ar １ , Ar ２ , and Ar ３ the aromatic hydrocarbon ring group represented by the formula (I) has a total of three or more fluoroalkyl groups, or a total of one or more organic groups other than electron-withdrawing groups, and the total number of carbon atoms contained in the total of one or more organic groups other than electron-withdrawing groups is 3 or more; In the general formula (2), Ar ４ , Ar ５ , and Ar ６ The aromatic hydrocarbon ring group represented by the formula (I) has a total of three or more fluorine-containing groups, or Ar ４ , Ar ５ , and Ar ６ the aromatic hydrocarbon ring group represented by the formula (I) has a total of one or more linear or branched organic groups other than electron-withdrawing groups, the total number of carbon atoms contained in the total of one or more linear or branched organic groups other than electron-withdrawing groups is 3 or more, In the general formula (3), Ar ７ , Ar ８ , and Ar ９ 3. The actinic ray-sensitive or radiation-sensitive resin composition according to claim 1 , wherein the total number of carbon atoms contained in the organic group other than the electron-withdrawing group, which is contained in the aromatic hydrocarbon ring group represented by the formula:

4. Ar ６ The actinic ray-sensitive or radiation-sensitive resin composition according to any one of claims 1 to 3, wherein represents a group represented by general formula (2S): 【Chemistry 4】 In formula (2S), * represents a bonding position. R ８Ｆ represents a fluoroalkyl group.

5. Ar ５ and Ar ６ The actinic ray-sensitive or radiation-sensitive resin composition according to claim 4 , wherein

6. A resist film formed using the actinic ray-sensitive or radiation-sensitive resin composition according to any one of claims 1 to 5.

7. A step of forming a resist film on a substrate using the actinic ray-sensitive or radiation-sensitive resin composition according to any one of claims 1 to 5; exposing the resist film to light; and developing the exposed resist film with a developer to form a pattern.

8. A method for manufacturing an electronic device, comprising the pattern formation method according to claim 7.

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