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

Abstract

The present invention provides an actinic ray-sensitive or radiation-sensitive resin composition that can obtain a pattern with excellent LWR performance. In addition, a resist film, a pattern forming method, and a method for manufacturing an electronic device related to the above-mentioned actinic ray-sensitive or radiation-sensitive resin composition are provided. The actinic ray-sensitive or radiation-sensitive resin composition comprises: a photoacid generator A, which generates an acid represented by general formula (I) and having a pKa of 1.00 or more; a photoacid generator B selected from the group consisting of an acid having a pKa greater than 1.00 or more than the acid generated by the photoacid generator A, and a nitrogen-containing compound C having a pKa greater than 1.00 or more than the acid generated by the photoacid generator A; and an acid-decomposable resin, in the case of a photoacid generator D that generates an acid having a pKa less than 1.00, the ratio of the number of moles of the photoacid generator A to the number of moles of the photoacid generator D is 1.0 or more.

Description

Technical Field

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

[0002] After the KrF excimer laser (248nm) resist is used, a pattern forming method using chemical amplification is used to compensate for the reduction in sensitivity caused by light absorption. For example, in the positive chemical amplification method, first, the photoacid generator contained in the exposure part is decomposed by light irradiation to generate acid. Moreover, in the baking (PEB: Post Exposure Bake) process after exposure, the alkali-insoluble group of the resin contained in the photosensitive or radiation-sensitive resin composition is changed to an alkali-soluble group by the catalytic action of the generated acid, thereby changing the solubility in the developer. Then, for example, an alkaline aqueous solution is used for development. Thus, the exposure part is removed to obtain the desired pattern.

[0003] In order to achieve miniaturization of semiconductor devices, the wavelength of exposure light sources has been shortened and the numerical aperture (NA) of projection lenses has been increased. Currently, exposure machines using ArF excimer lasers with a wavelength of 193 nm as light sources are being developed.

[0004] Based on such current situation, various structures have been proposed as actinic ray-sensitive or radiation-sensitive resin compositions.

[0005] For example, Patent Document 1 discloses a resist composition containing a photodegradable quencher (D0) including a compound represented by the following general formula (d0).

[0006] [Chemical formula 1]

[0007]

[0008] Previous technical literature

[0009] Patent Literature

[0010] Patent Document 1: Japanese Patent Application Laid-Open No. 2014-209167

[0011] As a result of a detailed study of the technology disclosed in Patent Document 1, the present inventors have found that the LWR (line width roughness) performance of the obtained pattern in the resist composition of Patent Document 1 has room for improvement. Summary of the invention

[0012] Technical issues to be solved by the invention

[0013] Therefore, an object of the present invention is to provide an actinic ray-sensitive or radiation-sensitive resin composition capable of obtaining a pattern excellent in LWR performance.

[0014] Furthermore, the present invention aims to provide a resist film, a pattern forming method, and a method for producing an electronic device involving the above-mentioned actinic ray-sensitive or radiation-sensitive resin composition.

[0015] Means for solving technical problems

[0016] The present inventors have conducted intensive studies to solve the above-mentioned problems, and as a result, have found that the above-mentioned problems can be solved by using a photoacid generator with a specific structure, thereby completing the present invention.

[0017] That is, it was found that the above-mentioned problems can be solved by the following structure.

[0018] [1]

[0019] An actinic ray-sensitive or radiation-sensitive resin composition comprising:

[0020] A photoacid generator A which generates an acid represented by the general formula (I) described below and having a pKa of -1.00 or more;

[0021] One or more selected from the group consisting of a photoacid generator B that generates an acid having a pKa greater than that of the acid generated by the photoacid generator A by 1.00 or more, and a nitrogen-containing compound C having a conjugate acid having a pKa greater than that of the acid generated by the photoacid generator A by 1.00 or more; and

[0022] Acid decomposable resins,

[0023] The above-mentioned actinic ray-sensitive or radiation-sensitive resin composition optionally contains a photoacid generator D which is a compound different from the above-mentioned nitrogen-containing compound C and generates an acid having a pKa of less than -1.00.

[0024] When the actinic ray or radiation sensitive resin composition contains the photoacid generator D, the ratio of the molar content of the photoacid generator A to the molar content of the photoacid generator D in the actinic ray or radiation sensitive resin composition is 1.0 or more.

[0025] [2]

[0026] The actinic ray-sensitive or radiation-sensitive resin composition as described in [1], wherein:

[0027] In the general formula (I) described below, L 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.

[0028] 〔3〕

[0029] The actinic ray-sensitive or radiation-sensitive resin composition as described in [1] or [2], wherein:

[0030] In the general formula (I) described below, R 3 It represents an organic group having a ring structure.

[0031] [4]

[0032] The actinic ray-sensitive or radiation-sensitive resin composition according to any one of [1] to [3], wherein the acid-decomposable resin is a methacrylate resin.

[0033] 〔5〕

[0034] A resist film formed using the actinic ray-sensitive or radiation-sensitive resin composition according to any one of [1] to [4].

[0035] [6]

[0036] A pattern forming method comprises the following steps:

[0037] A step of forming a resist film on a support using the actinic ray-sensitive or radiation-sensitive resin composition described in any one of [1] to [4];

[0038] a step of exposing the resist film to light; and

[0039] A step of developing the exposed resist film using a developer.

[0040] 〔7〕

[0041] A method for manufacturing an electronic device, comprising the pattern forming method described in [6].

[0042] Effects of the Invention

[0043] According to the present invention, an actinic ray-sensitive or radiation-sensitive resin composition capable of obtaining a pattern excellent in LWR performance can be provided.

[0044] Furthermore, the present invention aims to provide a resist film, a pattern forming method, and a method for producing an electronic device involving the above-mentioned actinic ray-sensitive or radiation-sensitive resin composition. DETAILED DESCRIPTION

[0045] Hereinafter, the present invention will be described in detail.

[0046] The description of the constituent requirements described below may be based on representative embodiments of the present invention, but the present invention is not limited to such embodiments.

[0047] In the marking of the group (atomic group) in this specification, as long as it does not deviate from the main purpose of the present invention, the marking that does not record substitution and unsubstituted includes groups without substitution and groups with substitution. For example, "alkyl" means not only alkyl without substitution (unsubstituted alkyl) but also alkyl with substitution (substituted alkyl). In addition, "organic group" in this specification refers to a group containing at least one carbon atom.

[0048] "Actinic rays" or "radiation" in this specification refers to, for example, the bright line spectrum of a mercury lamp, far ultraviolet rays represented by excimer lasers, extreme ultraviolet rays (EUV light: Extreme Ultraviolet), X-rays, and electron beams (EB: Electron Beam), etc. "Light" in this specification refers to actinic rays or radiation.

[0049] Unless otherwise specified, "exposure" in this specification includes not only exposure based on the bright line spectrum of a mercury lamp, far ultraviolet rays represented by excimer lasers, extreme ultraviolet rays, X-rays and EUV, but also exposure based on particle rays such as electron beams and ion beams.

[0050] In this specification, "to" is used to mean that the numerical values ​​described before and after it are included as the lower limit and the upper limit.

[0051] In the present specification, (meth)acrylate means acrylate and methacrylate, and (meth)acrylic acid means acrylic acid and methacrylic acid.

[0052] In this specification, the weight average molecular weight (Mw), number average molecular weight (Mn) and dispersion degree (also called molecular weight distribution) (Mw / Mn) of the resin are defined as polystyrene conversion values ​​based on GPC measurement (solvent: tetrahydrofuran, flow rate (sample injection amount): 10 μL, column: TSK gel Multipore HXL-M manufactured by TOSOH CORPORATION, column temperature: 40°C, flow rate: 1.0 mL / min, detector: differential refractive index detector) using a GPC (Gel Permeation Chromatography) apparatus (HLC-8120GPC manufactured by TOSOH CORPORATION).

[0053] In this specification, pKa (acid dissociation constant pKa) represents the acid dissociation constant pKa in aqueous solution, for example, in Chemistry Handbook (II) (revised 4th edition, 1993, Japan Chemical Society, Maruzen Company, Limited). The lower the value of the acid dissociation constant pKa, the greater the acid strength. The value of pKa can be calculated using the following software package 1 to obtain the value of the database based on the Hammett substituent constant and the known literature value. The values ​​of pKa recorded in this specification all represent the values ​​calculated by using the software package.

[0054] Software package 1: Advanced Chemistry Development (ACD / Labs) Software V8.14 for Solaris (1994-2007ACD / Labs).

[0055] In the present specification, examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

[0056] [Acticular ray-sensitive or radiation-sensitive resin composition]

[0057] The actinic ray-sensitive or radiation-sensitive resin composition of the present invention (hereinafter, also simply referred to as "composition" or "composition of the present invention") will be described.

[0058] The composition of the present invention is a so-called resist composition, and may be a positive resist composition or a negative resist composition, and may be a resist composition for alkali development or a resist composition for organic solvent development.

[0059] The composition of the present invention is typically a chemically amplified resist composition.

[0060] The composition of the present invention comprises a photoacid generator A, one or more selected from the group consisting of a photoacid generator B and a nitrogen-containing compound C, and an acid-decomposable resin.

[0061] The photoacid generator A is a compound that generates an acid represented by the general formula (I) described below and has a pKa of -1.00 or more.

[0062] The photoacid generator B is a compound that generates an acid having a pKa greater than that of the acid generated by the photoacid generator A by 1.00 or more.

[0063] The nitrogen-containing compound C is a compound whose conjugate acid has a pKa greater than that of the acid generated by the photoacid generator A by 1.00 or more.

[0064] Furthermore, the composition of the present invention may also contain a photoacid generator D.

[0065] The photoacid generator D is a compound that generates an acid having a pKa of less than -1.00.

[0066] When the composition contains the photoacid generator D, the ratio of the number of moles of the photoacid generator A contained in the composition to the number of moles of the photoacid generator D contained in the composition is 1.0 or more.

[0067] The mechanism by which the problems of the present invention are solved by such a structure is not clear, but the present inventors presume as follows.

[0068] The photoacid generator A that generates a weak acid is less likely to aggregate in the resist film when the composition is used to form a resist film and has good dispersibility. Furthermore, since the composition contains at least one of the photoacid generator B and the nitrogen-containing compound C, the diffusion of the acid generated by the photoacid generator A is controlled.

[0069] Furthermore, when the composition contains the photoacid generator D, the content thereof is less than the content (substance basis) of the photoacid generator A, so the amount of the photoacid generator D present in the resist film due to aggregation is suppressed. It is therefore inferred that the resist film formed using the composition of the present invention is likely to react uniformly during exposure, and the LWR performance of the obtained pattern is improved.

[0070] <Acid-degradable resin (resin A)>

[0071] The composition of the present invention contains an acid-decomposable resin (hereinafter, also referred to as "resin A").

[0072] The acid-decomposable resin generally contains a repeating unit having a group that is decomposed by the action of an acid to increase polarity (hereinafter also referred to as an "acid-decomposable group").

[0073] In the pattern forming method of the present invention, typically, when an alkaline developer is used as a developer, it is preferred to form a positive pattern, and when an organic developer is used as a developer, it is preferred to form a negative pattern.

[0074] (Repeating unit having an acid-decomposable group)

[0075] It is preferred that the resin A contains a repeating unit having an acid-decomposable group.

[0076] The acid-decomposable group preferably has a structure in which a polar group is protected by a group (leaving group) that is decomposed and released by the action of an acid.

[0077] Examples of the polar group include acidic groups (groups that dissociate in a 2.38 mass % tetramethylammonium hydroxide aqueous solution) such as a carboxyl group, a phenolic hydroxyl group, a fluorinated alcohol group, a sulfonic acid 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 tri(alkylcarbonyl)methylene group, and a tri(alkylsulfonyl)methylene group, as well as an alcoholic hydroxyl group and the like.

[0078] In addition, the alcoholic hydroxyl group refers to a hydroxyl group bonded to a hydrocarbon group and excluding a hydroxyl group (phenolic hydroxyl group) directly bonded to an aromatic ring, and as a hydroxyl group, an aliphatic alcohol group (for example, a hexafluoroisopropanol group, etc.) whose α position is substituted with an electron-withdrawing group such as a fluorine atom is excluded. As the alcoholic hydroxyl group, a hydroxyl group having a pKa (acid dissociation constant) of 12 to 20 is preferred.

[0079] As the polar group, a carboxyl group, a phenolic hydroxyl group, a fluorinated alcohol group (preferably a hexafluoroisopropanol group) or a sulfonic acid group is preferred.

[0080] Preferred acid-decomposable groups are groups in which the hydrogen atoms of these groups are substituted with groups that are detached by the action of an acid (leaving group).

[0081] Examples of the group that is released by the action of an acid (releasing group) include -C(R 36 )(R 37 )(R 38 )、-C(R 36 )(R 37 )(OR 39 ) and -C(R 01 )(R 02 )(OR 39 )wait.

[0082] In the formula, R 36 ~R 39 R each independently represents an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group or an alkenyl group. 36 With R 37 They may be bonded to each other to form a ring.

[0083] R 01 and R 02 Each independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group or an alkenyl group.

[0084] Preferred R 36 ~R 39 , R 01 and R 02The alkyl group is an alkyl group having 1 to 8 carbon atoms, and examples thereof include methyl, ethyl, propyl, n-butyl, sec-butyl, hexyl and octyl groups.

[0085] R 36 ~R 39 , R 01 and R 02 The cycloalkyl group may be a monocyclic ring or a polycyclic ring. As a monocyclic ring, a cycloalkyl group having 3 to 8 carbon atoms is preferred, for example, a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, and a cyclooctyl group. As a polycyclic ring, a cycloalkyl group having 6 to 20 carbon atoms is preferred, for example, adamantyl group, norbornyl group, isobornyl group, camphoryl group, dicyclopentyl group, α-pinenyl group, tricyclodecyl group, tetracyclododecyl group, and androstanyl group are preferred. In addition, one or more carbon atoms in the cycloalkyl group may be substituted by heteroatoms such as oxygen atoms.

[0086] Preferred R 36 ~R 39 , R 01 and R 02 The aryl group is an aryl group having 6 to 10 carbon atoms, and examples thereof include phenyl, naphthyl, and anthracenyl.

[0087] Preferred R 36 ~R 39 , R 01 and R 02 The aralkyl group is an aralkyl group having 7 to 12 carbon atoms, and examples thereof include benzyl, phenethyl, and naphthylmethyl.

[0088] Preferred R 36 ~R 39 , R 01 and R 02 The alkenyl group is an alkenyl group having 2 to 8 carbon atoms, and examples thereof include vinyl, allyl, butenyl and cyclohexenyl.

[0089] As R 36 With R 37 The ring formed by bonding to each other is preferably a cycloalkyl group (monocyclic or polycyclic). As the monocyclic cycloalkyl group, cyclopentyl or cyclohexyl is preferred, and as the polycyclic cycloalkyl group, norbornyl, tetracyclodecanyl, tetracyclododecyl or adamantyl is preferred.

[0090] The acid-decomposable group preferably has a tertiary alkyl ester group, an acetal group, a cumyl ester group, an enol ester group or an acetal ester group, and more preferably has an acetal group or a tertiary alkyl ester group.

[0091] As the repeating unit having an acid-decomposable group, the resin A preferably has a repeating unit represented by the following general formula (AI).

[0092] [Chemical formula 2]

[0093]

[0094] In the general formula (AI), T represents a single bond or a divalent linking group.

[0095] Examples of the divalent linking group for T include an alkylene group, an arylene group, -COO-Rt-, and -O-Rt-. In the formula, Rt represents an alkylene group, a cycloalkylene group, or an arylene group.

[0096] T is preferably a single bond or -COO-Rt-. Rt is preferably a chain alkylene group having 1 to 5 carbon atoms, and more preferably -CH2-, -(CH2)2- or -(CH2)3-.

[0097] More preferably, T is a single bond.

[0098] In the general formula (AI), Xa1 represents a hydrogen atom, a halogen atom or a monovalent organic group.

[0099] Xa1 is preferably a hydrogen atom or an alkyl group.

[0100] The alkyl group of Xa1 may have a substituent, and examples of the substituent include a hydroxyl group and a halogen atom (preferably a fluorine atom).

[0101] The alkyl group of Xa1 preferably has 1 to 4 carbon atoms, and examples thereof include methyl, ethyl, propyl, hydroxymethyl, and trifluoromethyl. The alkyl group of Xa1 is preferably a methyl group.

[0102] In the general formula (AI), Rx1 to Rx3 each independently represent an alkyl group or a cycloalkyl group.

[0103] Any two of Rx1 to Rx3 may be bonded to form a ring structure, or may not form a ring structure.

[0104] The alkyl group of Rx1, Rx2 and Rx3 may be linear or branched, and preferably methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl and tert-butyl. The number of carbon atoms in the alkyl group is preferably 1 to 10, more preferably 1 to 5, and further preferably 1 to 3. In the alkyl group of Rx1, Rx2 and Rx3, a part of the carbon-carbon bond may be a double bond.

[0105] The cycloalkyl of Rx1, Rx2 and Rx3 may be monocyclic or polycyclic. Examples of monocyclic cycloalkyl include cyclopentyl and cyclohexyl. Examples of polycyclic cycloalkyl include norbornyl, tetracyclodecyl, tetracyclododecyl and adamantyl.

[0106] The ring formed by bonding two of Rx1, Rx2, and Rx3 may be a monocyclic ring or a polycyclic ring.

[0107] As examples of monocyclic rings, monocyclic cycloalkane rings such as cyclopentyl ring, cyclohexyl ring, cycloheptyl ring and cyclooctane ring can be enumerated. As examples of polycyclic rings, polycyclic cycloalkyl rings such as norbornane ring, tetracyclodecane ring, tetracyclododecane ring and adamantane ring can be enumerated. Among them, cyclopentyl ring, cyclohexyl ring or adamantane ring is preferred.

[0108] Furthermore, as a ring formed by bonding two of Rx1, Rx2, and Rx3, the following rings are also preferred.

[0109] [Chemical formula 3]

[0110]

[0111] Specific examples of the monomer corresponding to the repeating unit represented by the general formula (AI) are given below.

[0112] The following specific examples correspond to the case where Xa1 in the general formula (AI) is a methyl group, and Xa1 may be arbitrarily substituted with a hydrogen atom, a halogen atom or a monovalent organic group.

[0113] [Chemical formula 4]

[0114]

[0115] The resin A also preferably has, as a repeating unit having an acid-decomposable group, a repeating unit described in paragraphs <0336> to <0369> of the specification of US Patent Application Publication No. 2016 / 0070167A1.

[0116] Furthermore, the resin A may have, as a repeating unit having an acid-decomposable group, a repeating unit including a group that generates an alcoholic hydroxyl group by being decomposed by an acid as described in paragraphs <0363> to <0364> of the specification of US Patent Application Publication No. 2016 / 0070167A1.

[0117] The content of the repeating unit having an acid-decomposable group contained in the resin A (the total of the repeating units having an acid-decomposable group when there are multiple repeating units) is preferably 10 to 90 mol %, more preferably 20 to 80 mol %, and further preferably 30 to 70 mol % relative to all repeating units of the resin A.

[0118] The resin A may contain one or more repeating units having an acid-decomposable group. When containing two or more repeating units, the total content thereof is preferably within the above-mentioned preferred content range.

[0119] (having at least one repeating unit selected from the group consisting of a lactone structure, a sultone structure, and a carbonate structure)

[0120] It is preferred that the resin A contains a repeating unit having at least one selected from the group consisting of a lactone structure, a sultone structure, and a carbonate structure.

[0121] The lactone structure or sultone structure may have a lactone ring or a sultone ring, and a lactone structure having a 5- to 7-membered lactone ring or a sultone structure having a 5- to 7-membered sultone ring is preferred.

[0122] A lactone structure in which another ring is fused to a 5- to 7-membered lactone ring to form a bicyclic structure or a spirocyclic structure is also preferred. A sultone structure in which another ring is fused to a 5- to 7-membered sultone ring to form a bicyclic structure or a spirocyclic structure is also preferred.

[0123] Among them, it is preferred that resin A contains repeating units having a lactone structure represented by any of the following general formulae (LC1-1) to (LC1-22) or a sultone structure represented by any of the following general formulae (SL1-1) to (SL1-3). The lactone structure or sultone structure may be directly bonded to the main chain.

[0124] Among them, the lactone structure represented by the general formula (LC1-1), the general formula (LC1-4), the general formula (LC1-5), the general formula (LC1-8), the general formula (LC1-16), the general formula (LC1-21) or the general formula (LC1-22) or the sultone structure represented by the general formula (SL1-1) is preferred.

[0125] [Chemical formula 5]

[0126]

[0127] The lactone structure or the sultone structure may or may not have a substituent (Rb2). As the substituent (Rb2), preferably 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 2 to 8 carbon atoms, a carboxyl group, a halogen atom, a hydroxyl group, a cyano group or an acid-decomposable group, etc., more preferably an alkyl group having 1 to 4 carbon atoms, a cyano group or an acid-decomposable group. n2 represents an integer of 0 to 4. When n2 is 2 or more, the multiple substituents (Rb2) may be the same or different. Furthermore, the multiple substituents (Rb2) may be bonded to each other to form a ring.

[0128] As the repeating unit having a lactone structure or a sultone structure, a repeating unit represented by the following general formula (III) is preferred.

[0129] [Chemical formula 6]

[0130]

[0131] In the above general formula (III),

[0132] A represents an ester bond (a group represented by -COO-) or an amide bond (a group represented by -CONH-).

[0133] n is the number of repetitions of the structure represented by -R0-Z- and represents an integer of 0 to 5, and is preferably 0 or 1, and more preferably 0. When n is 0, (-R0-Z-)n is a single bond.

[0134] R0 represents an alkylene group, a cycloalkylene group or a combination thereof. When there are a plurality of R0, the plurality of R0 may be the same or different.

[0135] The alkylene group or cycloalkylene group of R0 may have a substituent.

[0136] Z represents a single bond, an ether bond, an ester bond, an amide bond, a urethane bond, or a urea bond. When there are plural Zs, the plural Zs may be the same or different.

[0137] Among them, Z is preferably an ether bond or an ester bond, and more preferably an ester bond.

[0138] R8 represents a monovalent organic group having a lactone structure or a sultone structure.

[0139] Among them, a group formed by removing one hydrogen atom from one carbon atom constituting a lactone structure or a sultone structure in any of the structures represented by general formulae (LC1-1) to (LC1-22) and the structures represented by general formulae (SL1-1) to (SL1-3) is preferred.

[0140] In addition, it is preferred that the carbon atom from which one hydrogen atom is removed is not a carbon atom constituting the substituent (Rb2).

[0141] R7 represents a hydrogen atom, a halogen atom or a monovalent organic group (preferably a methyl group).

[0142] The following are examples of monomers corresponding to repeating units having at least one selected from the group consisting of a lactone structure and a sultone structure.

[0143] In the following examples, the methyl group bonded to the vinyl group may be substituted with a hydrogen atom, a halogen atom or a monovalent organic group.

[0144] [Chemical formula 7]

[0145]

[0146] [Chemical formula 8]

[0147]

[0148] The resin A may contain a repeating unit having a carbonate structure. As the carbonate structure, a cyclic carbonate structure is preferred.

[0149] As the repeating unit having a cyclic carbonate structure, a repeating unit represented by the following general formula (A-1) is preferred.

[0150] [Chemical formula 9]

[0151]

[0152] In the general formula (A-1), R A 1 represents a hydrogen atom, a halogen atom or a monovalent organic group (preferably a methyl group).

[0153] n represents an integer greater than or equal to 0.

[0154] R A 2 In the case where n is 2 or more, there are multiple R A 2 They may be the same or different.

[0155] A represents a single bond or a divalent linking group.

[0156] Z represents an atomic group which forms a monocyclic or polycyclic ring together with the group represented by -O-CO-O- in the formula.

[0157] Resin A also preferably has a repeating unit described in paragraphs <0370> to <0414> of US Patent Application Publication No. 2016 / 0070167A1 as a repeating unit having at least one selected from the group consisting of a lactone structure, a sultone structure, and a carbonate structure.

[0158] In the case where resin A contains at least one repeating unit selected from the group consisting of a lactone structure, a sultone structure and a carbonate structure, the content of the repeating unit having at least one selected from the group consisting of a lactone structure, a sultone structure and a carbonate structure contained in resin A is preferably 5 to 70 mol %, more preferably 10 to 65 mol %, and further preferably 20 to 60 mol % relative to all the repeating units in resin A.

[0159] Resin A may have one or more repeating units having at least one selected from the group consisting of a lactone structure, a sultone structure, and a carbonate structure. When having two or more repeating units, the total content thereof is preferably within the above-mentioned preferred content range.

[0160] (Repeating unit having a proton-donating group)

[0161] The resin A contains a repeating unit having a proton-donating group in addition to the above-mentioned repeating units.

[0162] The proton-donating group is not particularly limited, and examples thereof include groups containing hydrogen atoms bonded to heteroatoms such as oxygen atoms, nitrogen atoms, and sulfur atoms. Specifically, examples thereof include sulfonamide groups, carboxyl groups, and hydroxyl groups (preferably, alcoholic hydroxyl groups or fluorinated alcohol groups. In addition, alcoholic hydroxyl groups refer to hydroxyl groups other than hydroxyl groups (phenolic hydroxyl groups) bonded to hydrocarbon groups and directly bonded to aromatic rings, and as hydroxyl groups, aliphatic alcohols (hereinafter also referred to as "fluorinated alcohol groups"). For example, hexafluoroisopropanol groups, etc.) substituted at the α-position with electron-withdrawing groups such as fluorine atoms are excluded. As the alcoholic hydroxyl group, a hydroxyl group having a pKa of 12 or more and 20 or less is preferred. Acidic groups (groups dissociated in a 2.38% by mass aqueous solution of tetramethylammonium hydroxide) such as sulfonic acid group, sulfonyl imide group, (alkylsulfonyl) (alkylcarbonyl) methylene group, (alkylsulfonyl) (alkylcarbonyl) imide group, bis(alkylcarbonyl) methylene group, bis(alkylcarbonyl) imide group, bis(alkylsulfonyl) methylene group, bis(alkylsulfonyl) imide group, tris(alkylcarbonyl) methylene group and tris(alkylsulfonyl) methylene group are preferred.

[0163] As the above-mentioned proton-donating group, a sulfonamide group is preferred (as the above-mentioned sulfonamide group, an alkylsulfonamide group is preferred, and *-NH-SO2-R X (R X represents an alkyl group having 1 to 10 carbon atoms (which may be linear, branched, or cyclic). X The alkyl group represented by R may have a substituent. Examples of the substituent include a halogen atom (for example, a fluorine atom). X The number of carbon atoms of the alkyl group represented by is preferably 1 to 6, more preferably 1 to 3. ) alkylsulfonamide group represented by. ), carboxyl group, hydroxyl group (as the hydroxyl group, alcoholic hydroxyl group or fluorinated alcohol group (for example, hexafluoroisopropanol group, etc.) is preferred.) or sulfonic acid group, more preferably alkylsulfonamide group, carboxyl group or hydroxyl group.

[0164] It is preferred that the repeating unit having a proton-donating group is a repeating unit represented by the general formula (H2).

[0165] [Chemical formula 10]

[0166]

[0167] In the above general formula (H2), R P represents a hydrogen atom, a halogen atom or a monovalent organic group (preferably a methyl group).

[0168] L 102 It represents a substituted or unsubstituted hydrocarbon group having 1 to 30 carbon atoms which may contain a hetero atom.

[0169] As L 102 The substituted or unsubstituted hydrocarbon group having 1 to 30 carbon atoms which may contain a hetero atom is not particularly limited, and examples thereof include -O-, -N(R a )-, -CO-, -S-, -SO2-, or a combination thereof, a substituted or unsubstituted hydrocarbon group having 1 to 30 carbon atoms (preferably 1 to 20 carbon atoms, more preferably 1 to 15 carbon atoms). a It represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms.

[0170] In addition, when the above-mentioned hydrocarbon group contains a hetero atom, -CH2- is substituted by the hetero atom.

[0171] As L 102 The substituted or unsubstituted hydrocarbon group having 1 to 30 carbon atoms which may contain a hetero atom may be linear, branched, or have a cyclic structure.

[0172] As L 102 The substituted or unsubstituted hydrocarbon group having 1 to 30 carbon atoms which may contain heteroatoms preferably has one or more groups selected from the group consisting of alkylene groups and cyclic hydrocarbon groups, and more preferably alkylene groups, cyclic hydrocarbon groups, or groups in combination thereof. Preferably, the alkylene group has 1 to 5 carbon atoms. The cyclic hydrocarbon group may be monocyclic or polycyclic, and is preferably a non-aromatic ring (such as an adamantane ring).

[0173] Q 102 represents a group having a proton-donating group. If possible, Q 102 The proton donating group itself may also be used.

[0174] Examples of the proton-donating group are as described above.

[0175] n represents an integer of 1 or more, preferably 1-5, more preferably 1-2.

[0176] When resin A contains a repeating unit having a proton-donating group, the content of the repeating unit having a proton-donating group contained in resin A is preferably 1 to 50 mol %, more preferably 3 to 40 mol %, and further preferably 5 to 30 mol % based on all repeating units in resin A.

[0177] The resin A may contain one or more types of repeating units having a proton-donating group. When containing two or more types, the total content thereof is preferably within the above-mentioned preferred content range.

[0178] (A repeating unit having no acid-decomposable group or polar group)

[0179] In addition to the above repeating units, resin A may also include repeating units that do not have an acid-decomposable group or a polar group. Preferably, the repeating unit that does not have an acid-decomposable group or a polar group has an alicyclic hydrocarbon structure. As repeating units that do not have an acid-decomposable group or a polar group, for example, the repeating units described in paragraphs <0236> to <0237> of the specification of U.S. Patent Application Publication No. 2016 / 0026083A1 can be cited.

[0180] Preferred examples of the monomer corresponding to the repeating unit having neither an acid-decomposable group nor a polar group are shown below.

[0181] [Chemical formula 11]

[0182]

[0183] In addition, specific examples of repeating units having neither an acid-decomposable group nor a polar group include repeating units disclosed in paragraph <0433> of US Patent Application Publication No. 2016 / 0070167A1.

[0184] When resin A contains repeating units having neither acid-decomposable groups nor polar groups, the content of repeating units having neither acid-decomposable groups nor polar groups is preferably 5 to 40 mol %, more preferably 5 to 30 mol %, and even more preferably 5 to 25 mol % relative to all repeating units in resin A.

[0185] The resin A may contain one or more repeating units having neither an acid-decomposable group nor a polar group. When containing two or more repeating units, the total content thereof is preferably within the above-mentioned preferred content range.

[0186] In order to adjust dry etching resistance, compatibility with standard developer, substrate adhesion, resist profile or further adjust generally necessary properties of resist, i.e., resolution, heat resistance, sensitivity, etc., resin A may have various repeating structural units in addition to the above-mentioned repeating structural units.

[0187] Examples of such a repeating structural unit include repeating structural units that conform to prescribed monomers, but the repeating structural units are not limited to these.

[0188] Examples of the predetermined monomer include compounds having one addition-polymerizable unsaturated bond selected from acrylates, methacrylates, acrylamides, methacrylamides, allyl compounds, vinyl ethers, and vinyl esters.

[0189] In addition, an addition-polymerizable unsaturated compound copolymerizable with the monomers corresponding to the above-mentioned various repeating structural units may also be used.

[0190] In the resin A, the molar ratio of each repeating structural unit can be appropriately set in order to adjust various properties.

[0191] When the composition of the present invention is a composition for ArF exposure, it is preferred that the resin A substantially does not have an aromatic group from the viewpoint of the transmittance of ArF light. More specifically, the repeating unit having an aromatic group is preferably 5 mol% or less, more preferably 3 mol% or less, and ideally 0 mol% relative to all repeating units in the resin A. That is, it is further preferred that the repeating unit having an aromatic group is not included. In addition, the resin A preferably has a monocyclic or polycyclic alicyclic hydrocarbon structure.

[0192] The resin A is preferably a (meth)acrylate resin, and more preferably a methacrylate resin.

[0193] Regarding the (meth)acrylate resin (or methacrylate resin), the content of the (meth)acrylate repeating unit (or methacrylate repeating unit) is 80 mol% or more, preferably 90 mol% or more, more preferably 95 mol% or more, and further preferably 99 mol% or more, relative to all repeating units of resin A.

[0194] Regarding resin A, all repeating units may be composed of (meth)acrylate repeating units. In this case, all repeating units may be methacrylate repeating units, all repeating units may be acrylate repeating units, or all repeating units may be a combination of methacrylate repeating units and acrylate repeating units. Among them, it is preferred that the content of acrylate repeating units is 50 mol% or less relative to all repeating units of resin A.

[0195] In addition, a known resin can be appropriately used as the resin A. For example, the known resins disclosed in paragraphs <0055> to <0191> of U.S. Patent Application Publication No. 2016 / 0274458A1, paragraphs <0035> to <0085> of U.S. Patent Application Publication No. 2015 / 0004544A1, and paragraphs <0045> to <0090> of U.S. Patent Application Publication No. 2016 / 0147150A1 can be preferably used as the resin A.

[0196] When the composition of the present invention is for KrF exposure, EB exposure or EUV exposure, it is preferred that the resin A contains a repeating unit having an aromatic hydrocarbon group, and it is more preferred that the resin A contains a repeating unit containing a phenolic hydroxyl group. Examples of the repeating unit containing a phenolic hydroxyl group include hydroxystyrene repeating units and hydroxystyrene (meth)acrylate repeating units.

[0197] When the composition of the present invention is for KrF exposure, EB exposure or EUV exposure, the resin A preferably has a structure in which the hydrogen atom of the phenolic hydroxyl group is protected by a group (leaving group) that is decomposed and released by the action of an acid.

[0198] In this case, the content of the repeating unit having an aromatic hydrocarbon group contained in the resin A is preferably 30 to 100 mol % based on all the repeating units in the resin A, more preferably 40 to 100 mol %, and further preferably 50 to 100 mol %.

[0199] The weight average molecular weight of resin A is preferably 1,000 to 200,000, more preferably 2,000 to 20,000, further preferably 3,000 to 15,000, and particularly preferably 3,000 to 12,000. The degree of dispersion (Mw / Mn) is usually 1.0 to 3.0, preferably 1.0 to 2.6, more preferably 1.0 to 2.0, and further preferably 1.1 to 2.0.

[0200] The resin A may be used alone or in combination of two or more.

[0201] The content of resin A in the composition is usually 20% by mass or more, preferably 40% by mass or more, more preferably 60% by mass or more, and further preferably 75% by mass or more relative to the total solid content in the composition. The upper limit is not particularly limited, but is preferably 95% by mass or less, and more preferably 90% by mass or less.

[0202] When two or more types of resins A are used in the composition, the total content thereof is preferably within the above-mentioned preferred content range.

[0203] In addition, the solid content refers to the components excluding the solvent in the composition, and any components other than the solvent, even if they are liquid components, are regarded as solid components.

[0204] <Photoacid generator A>

[0205] The composition of the present invention comprises a photoacid generator A.

[0206] The photoacid generator A is a compound that generates an acid upon irradiation with actinic rays or radiation.

[0207] The pKa of the acid generated by the photoacid generator A is -1.00 or higher (preferably -1.00 to 5.00, more preferably -0.50 to 3.00, and even more preferably 0.00 to 2.00).

[0208] Furthermore, the acid generated by the photoacid generator A is a compound represented by the following general formula (I).

[0209] [Chemical formula 12]

[0210]

[0211] In the general formula (I), R 1 and R 2 Each independently represents a substituent which is not an electron withdrawing group or a hydrogen atom.

[0212] Examples of the substituent other than the electron withdrawing group include a hydrocarbon group, a hydroxyl group, an oxyhydrocarbonyl group, an oxycarbonylhydrocarbon group, an amino group, a hydrocarbon-substituted amino group, and a hydrocarbon-substituted amide group.

[0213] Furthermore, as the substituent which is not an electron withdrawing group, each independently preferably is -R', -OH, -OR', -OCOR', -NH2, -NR'2, -NHR', or -NHCOR'. R' is a monovalent hydrocarbon group.

[0214] Examples of the monovalent hydrocarbon group represented by R' include:

[0215] Alkyl groups such as methyl, ethyl, propyl, and butyl; alkenyl groups such as vinyl, propenyl, and butenyl; monovalent chain hydrocarbon groups such as alkynyl groups such as ethynyl, propynyl, and butynyl;

[0216] Cycloalkyl groups such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, norbornyl and adamantyl; monovalent alicyclic hydrocarbon groups such as cycloalkenyl groups such as cyclopropenyl, cyclobutenyl, cyclopentenyl and norbornyl;

[0217] Aryl groups such as phenyl, tolyl, xylyl, methyl, naphthyl, methylnaphthyl, anthracenyl, methylanthryl; and monovalent aromatic hydrocarbon groups such as aralkyl groups such as benzyl, phenethyl, phenylpropyl, naphthylmethyl, anthracenylmethyl.

[0218] Among them, R is preferred 1 and R 2 Each is independently a hydrocarbon group (preferably a cycloalkyl group) or a hydrogen atom.

[0219] In the general formula (I), L represents a divalent linking group including a combination of one or more linking groups S and an alkylene group which may have one or more substituents, or a divalent linking group including one or more linking groups S.

[0220] The linker S is selected from * 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 The groups in the group.

[0221] In the case where L is one form of "a divalent linking group comprising a combination of one or more linking groups S and an alkylene group which may have one or more substituents", that is, "a divalent linking group comprising a combination of one or more linking groups S and an alkylene group which does not have one or more substituents", the linking group S is selected from * 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 all alkylene groups in the "divalent linking group comprising a combination of one or more linking groups S and an alkylene group which may have one or more substituents" are unsubstituted alkylene groups, the linking group S is 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 The groups in the group.

[0222] * A represents R in the general formula (I) 3 Bonding position on the side, * B It represents the bonding position to the -SO3H side in the general formula (I).

[0223] In a divalent linking group including a combination 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 two or more. Similarly, there may be only one alkylene group which may have a substituent or two or more. In the case where there are multiple linking groups S, the multiple linking groups S may be the same or different. In the case where there are multiple alkylene groups, the multiple alkylene groups may be the same or different.

[0224] In addition, the linking groups S may be continuously bonded to each other. Among them, preferably selected from * A -CO-* B ,* A -O-CO-* B and* A -O-* B The groups in the group are bonded continuously without forming "* A -O-CO-O-* B "And, preferably selected from * A -CO-* B and* A -O-* B The groups in the group are bonded continuously without forming "* A -O-CO-* B "and"* A -CO-O-* B ”.

[0225] In the divalent linking group including 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 a plurality of linking groups S, the linking groups S in the case of the plurality of linking groups S may be the same or different.

[0226] At this time, preferably selected from * A -CO-* B ,* A -O-CO-* B and* A -O-* B The groups in the group are bonded continuously without forming "* A -O-CO-O-* B "And, preferably selected from * A -CO-* B and* A -O-* B The groups in the group are bonded continuously without forming "* A -O-CO-* B "and"* A -CO-O-* B”.

[0227] However, in any case, in L, the atom at the β-position relative to -SO3H is not a carbon atom having a fluorine atom as a substituent.

[0228] When the atom at the β-position is a carbon atom, the carbon atom may have a substituent having a fluorine atom (for example, a fluoroalkyl group such as a trifluoromethyl group) as long as the carbon atom is not directly substituted with a fluorine atom.

[0229] In addition, the atom at the β position refers to the atom at the same position as -C(R 1 )(R 2 )-directly bonded to an atom in L.

[0230] Among them, it is preferred that L has only one linking group S.

[0231] That is, L preferably represents a divalent linking group including a combination of one linking group S and an alkylene group which may have one or more substituents, or a divalent linking group including one linking group S.

[0232] For example, L is preferably a group represented by the following general formula (II).

[0233] * a -(CR 2a 2) X -Q-(CR 2b 2) Y -* b (II)

[0234] In the general formula (II), * a It represents the same as R in the general formula (I) 3 bonding position.

[0235] * b represents the same as -C(R 1 )(R 2 )-bonding position.

[0236] X and Y each independently represent an integer of 0-10, and preferably an integer of 0-3.

[0237] R 2a and R 2b Each independently represents a hydrogen atom or a substituent.

[0238] There are multiple R 2a and R 2b In the case of multiple R 2a and R 2b They may be the same or different.

[0239] When Y is 1 or more, the -C(R 1 )(R 2 )- Direct Bonding CR 2b R in 2 2b is other than a fluorine atom.

[0240] Q stands for * 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 .

[0241] Wherein, X+Y in the general formula (II) is 1 or more, and R in the general formula (II) is 2a and R 2b When all of the atoms in are hydrogen atoms, Q represents * A -O-CO-O-* B ,* A -CO-* B ,* A -O-CO-* B ,* A -O-* B ,* A -S-* B or* A -SO2-* B .

[0242] * A represents R in the general formula (I) 3 Bonding position on the side, * B It represents the bonding position to the -SO3H side in the general formula (I).

[0243] In the general formula (I), R 3 Represents an organic group.

[0244] As long as the organic group has more than one carbon atom, there is no particular limitation, and it can be a straight-chain group (for example, a straight-chain alkyl group such as a methyl group, an ethyl group, a n-propyl group or a n-butyl group), a branched group (for example, a branched alkyl group such as an isopropyl group or a tert-butyl group), or a cyclic structure. The organic group may or may not have a substituent. The organic group may or may not have a heteroatom (an oxygen atom, a sulfur atom and / or a nitrogen atom, etc.).

[0245] Among them, R is preferred 3 It is an organic group having a cyclic structure. The cyclic structure may be monocyclic or polycyclic and may have a substituent. It is preferred that the ring in the organic group having a cyclic structure is directly bonded to L in the general formula (I).

[0246] The organic group having the above-mentioned cyclic structure may or may not have, for example, a heteroatom (oxygen atom, sulfur atom and / or nitrogen atom). The heteroatom may substitute with one or more carbon atoms forming the cyclic structure.

[0247] The organic group having the cyclic structure is preferably, for example, a hydrocarbon group having a cyclic structure, a lactone ring group, and a sultone ring group. Among them, the organic group having the cyclic structure is preferably a hydrocarbon group having a cyclic structure.

[0248] The hydrocarbon group having a cyclic structure is preferably a monocyclic or polycyclic cycloalkyl group. These groups may have a substituent.

[0249] The cycloalkyl group may be monocyclic (cyclohexyl group, etc.) or polycyclic (adamantyl group, etc.), and preferably has 5 to 12 carbon atoms.

[0250] As the above-mentioned lactone group and sultone group, for example, in any of the structures represented by the above-mentioned general formulas (LC1-1) to (LC1-22) and the structures represented by general formulas (SL1-1) to (SL1-3), a group formed by removing one hydrogen atom from one carbon atom constituting the lactone structure or the sultone structure is preferred.

[0251] In addition, it is preferred that the carbon atom from which one hydrogen atom is removed is not a carbon atom constituting the substituent (Rb2).

[0252] The photoacid generator A is not particularly limited as long as the generated acid satisfies the above-mentioned requirements, and may be an onium salt compound or a zwitterion.

[0253] Among them, it is preferred that the photoacid generator A is an onium salt compound having an anion and a cation.

[0254] The photoacid generator is preferably a compound represented by the general formula (ZaI) (compound (ZaI)) or a compound represented by the general formula (ZaII) (compound (ZaII)).

[0255] [Chemical formula 13]

[0256]

[0257] R in the general formula (ZaI) 1 , R 2 , L and R 3 Respectively with R in the above general formula (I) 1 , R 2 , L and R 3 have the same meaning.

[0258] In the above general formula (ZaI),

[0259] R 201 , R 202 and R 203 Each independently represents an organic group.

[0260] As R 201 , R 202 and R 203 The number of carbon atoms of the organic group is usually 1 to 30, preferably 1 to 20. 201 ~R 203 Two of them 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 the group formed by bonding two of the groups include alkylene (e.g., butylene, pentylene) and -CH2-CH2-O-CH2-CH2-.

[0261] Preferred forms of the cation in the general formula (ZaI) include the corresponding groups in the compound (ZaI-1) described later, the compound (ZaI-2), the compound represented by the general formula (ZaI-3b) (compound (ZaI-3b)), and the compound represented by the general formula (ZaI-4b) (compound (ZaI-4b)).

[0262] The photoacid generator A may be a compound having a plurality of structures represented by the general formula (ZaI). For example, the photoacid generator A may be a compound having R 2 and R 3 of the compound represented by the general formula (ZaI) bonded to the compound via a single bond or a linking group. 201 ~R 203 At least one of them and R of another compound represented by general formula (ZaI) 201 ~R 203 A compound having a structure consisting of at least one of the following.

[0263] First, the compound (ZaI-1) will be described.

[0264] Compound (ZaI-1) is R 201 ~R 203 An arylsulfonium compound in which at least one of the groups is an aryl group, that is, a compound having an arylsulfonium cation.

[0265] In arylsulfonium compounds, R 201 ~R 203 All of R 201 ~R 203 A portion of may be an aryl group, and the remainder may be an alkyl group or a cycloalkyl group.

[0266] And, R 201 ~R 203 One of them is an aryl group, R 201 ~R 203 The remaining two of R may be bonded to form a ring structure, and may contain an oxygen atom, a sulfur atom, an ester group, an amide group, or a carbonyl group in the ring. 201 ~R 203 In the group formed by two bonds, for example, one or more methylene groups may be substituted by an oxygen atom, a sulfur atom, an ester group, an amide group and / or a carbonyl group (for example, a butylene group, a pentylene group or -CH2-CH2-O-CH2-CH2-).

[0267] Examples of the arylsulfonium compound include triarylsulfonium compounds, diarylalkylsulfonium compounds, aryldialkylsulfonium compounds, diarylcycloalkylsulfonium compounds, and aryldicycloalkylsulfonium compounds.

[0268] As the aryl group contained in the arylsulfonium compound, phenyl or naphthyl is preferred, and phenyl is more preferred. The aryl group may be an aryl group containing a heterocyclic structure having an oxygen atom, a nitrogen atom or a sulfur atom. As the heterocyclic structure, pyrrole residue, furan residue, thiophene residue, indole residue, benzofuran residue and benzothiophene residue can be cited. In the case where the arylsulfonium compound has two or more aryl groups, the two or more aryl groups may be the same or different.

[0269] The alkyl group or cycloalkyl group which the arylsulfonium compound has as required 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 methyl, ethyl, propyl, n-butyl, sec-butyl, tert-butyl, cyclopropyl, cyclobutyl and cyclohexyl.

[0270] R 201 ~R 203The aryl group, alkyl group and cycloalkyl group may each independently have 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 halogen atom, a hydroxyl group or a phenylthio group as a substituent.

[0271] Next, compound (ZaI-2) is described.

[0272] Compound (ZaI-2) is a compound wherein R 201 ~R 203 Each independently represents a compound of an organic group having no aromatic ring, wherein the aromatic ring also includes an aromatic ring containing a heteroatom.

[0273] As R 201 ~R 203 The organic group having no aromatic ring generally has 1 to 30 carbon atoms, preferably 1 to 20 carbon atoms.

[0274] Preferred R 201 ~R 203 Each independently represents an alkyl group, a cycloalkyl group, an allyl group or a vinyl group, more preferably a linear or branched 2-oxoalkyl group, a 2-oxocycloalkyl group or an alkoxycarbonylmethyl group, and still more preferably a linear or branched 2-oxoalkyl group.

[0275] As R 201 ~R 203 The alkyl group and the cycloalkyl group may preferably include a straight-chain alkyl group having 1 to 10 carbon atoms or a branched-chain alkyl group having 3 to 10 carbon atoms (for example, methyl, ethyl, propyl, butyl and pentyl), and a cycloalkyl group having 3 to 10 carbon atoms (for example, cyclopentyl, cyclohexyl and norbornyl).

[0276] R 201 ~R 203 It may be further substituted by a halogen atom, an alkoxy group (for example, having 1 to 5 carbon atoms), a hydroxyl group, a cyano group or a nitro group.

[0277] Next, compound (ZaI-3b) is described.

[0278] Compound (ZaI-3b) is a compound having a phenacylsulfonium salt structure represented by the following general formula (ZaI-3b).

[0279] [Chemical formula 14]

[0280]

[0281] In the general formula (ZaI-3b),

[0282] R1c ~R 5c Each independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an alkoxy group, an aryloxy group, an alkoxycarbonyl group, an alkylcarbonyloxy group, a cycloalkylcarbonyloxy group, a halogen atom, a hydroxyl group, a nitro group, an alkylthio group or an arylthio group.

[0283] R 6c and R 7c Each independently represents a hydrogen atom, an alkyl group (such as tert-butyl group), a cycloalkyl group, a halogen atom, a cyano group or an aryl group.

[0284] R x and R y Each independently represents an alkyl group, a cycloalkyl group, a 2-oxoalkyl group, a 2-oxocycloalkyl group, an alkoxycarbonylalkyl group, an allyl group or a vinyl group.

[0285] R 1c ~R 5c Any two or more of R 5c With R 6c , R 6c With R 7c , R 5c With R x and R x With R y They may be bonded to form a ring, and the ring may independently contain an oxygen atom, a sulfur atom, a keto group, an ester bond, or an amide bond.

[0286] Examples of the ring include aromatic or non-aromatic hydrocarbon rings, aromatic or non-aromatic heterocyclic rings, and polycyclic condensed rings formed by combining two or more of these rings. Examples of the ring include 3-10 membered rings, preferably 4-8 membered rings, and more preferably 5- or 6-membered rings.

[0287] As R 1c ~R 5c Any two or more of R 6c With R 7c , and R x With R y Examples of the group formed by bonding include alkylene groups such as butylene and pentylene. The methylene group in the alkylene group may be substituted with a hetero atom such as an oxygen atom.

[0288] As R 5c With R 6c , and R 5c With R x The group formed by bonding is preferably a single bond or an alkylene group. Examples of the alkylene group include a methylene group and an ethylene group.

[0289] Zac - The "R 3 -LC(R 1)(R 2 )-SO3 - ” have the same meaning.

[0290] Next, compound (ZaI-4b) is described.

[0291] Compound (ZaI-4b) is a compound represented by the following general formula (ZaI-4b).

[0292] [Chemical formula 15]

[0293]

[0294] In the general formula (ZaI-4b),

[0295] l represents an integer from 0 to 2.

[0296] r represents an integer from 0 to 8.

[0297] R 13 represents a hydrogen atom, a fluorine atom, a hydroxyl group, an alkyl group, an alkoxy group, an alkoxycarbonyl group, or a group having a cycloalkyl group (it may be a cycloalkyl group itself or a group partially containing a cycloalkyl group). These groups may have a substituent.

[0298] R 14 represents a hydroxyl group, an alkyl group, an alkoxy group, an alkoxycarbonyl group, an alkylcarbonyl group, an alkylsulfonyl group, a cycloalkylsulfonyl group, or a group having a cycloalkyl group (which may be a cycloalkyl group itself or a group partially containing a cycloalkyl group). These groups may have a substituent. 14 When there are plural groups, each independently represents the above-mentioned group such as a hydroxyl group.

[0299] R 15 Each of R independently represents an alkyl group, a cycloalkyl group or a naphthyl group. These groups may have a substituent. 15 They may be bonded to each other to form a ring. 15 When they are bonded to each other to form a ring, heteroatoms such as oxygen atoms and nitrogen atoms may be contained in the ring skeleton. 15 are alkylene groups, and are bonded to each other to form a ring structure.

[0300] Za - The "R 3 -LC(R 1 )(R 2 )-SO3 - ” have the same meaning.

[0301] In the general formula (ZaI-4b), R 13 , R 14 and R 15The alkyl group is linear or branched. The number of carbon atoms in the alkyl group is preferably 1 to 10. As the alkyl group, a methyl group, an ethyl group, an n-butyl group, a tert-butyl group, or the like is more preferred.

[0302] Next, the general formula (ZaII) will be described.

[0303] In the general formula (ZaII), R 204 and R 205 Each independently represents an aryl group, an alkyl group or a cycloalkyl group.

[0304] As R 204 and R 205 R is an aryl group, preferably a phenyl group or a naphthyl group, more preferably a phenyl group. 204 and R 205 The aryl group may be an aryl group containing a heterocyclic ring having an oxygen atom, a nitrogen atom, a sulfur atom, etc. Examples of the skeleton of the aryl group having a heterocyclic ring include pyrrole, furan, thiophene, indole, benzofuran, and benzothiophene.

[0305] As R 204 and R 205 The alkyl group and the cycloalkyl group are preferably a linear alkyl group having 1 to 10 carbon atoms, a branched alkyl group having 3 to 10 carbon atoms (e.g., methyl, ethyl, propyl, butyl or pentyl) or a cycloalkyl group having 3 to 10 carbon atoms (e.g., cyclopentyl, cyclohexyl or norbornyl).

[0306] R 204 and R 205 The aryl group, alkyl group and cycloalkyl group of R may each independently have a substituent. 204 and R 205 The aryl group, alkyl group and cycloalkyl group may have a substituent, for example, an alkyl group (for example, having 1 to 15 carbon atoms), a cycloalkyl group (for example, having 3 to 15 carbon atoms), an aryl group (for example, having 6 to 15 carbon atoms), an alkoxy group (for example, having 1 to 15 carbon atoms), a halogen atom, a hydroxyl group and a phenylthio group.

[0307] In the general formula (ZaII), "R 3 -LC(R 1 )(R 2 )-SO3 - " is an anion, and is related to "R 3 -LC(R 1 )(R 2 )-SO3 - ” have the same meaning.

[0308] Preferred examples of anions and cations when the photoacid generator A includes an onium salt compound of an anion and a cation are shown below.

[0309] The following cations and anions can be used as the photoacid generator A in any combination.

[0310] [Chemical formula 16]

[0311]

[0312] [Chemical formula 17]

[0313]

[0314] [Chemical formula 18]

[0315]

[0316] [Chemical formula 19]

[0317]

[0318] [Chemical formula 20]

[0319]

[0320] The photoacid generator A may be in the form of a low molecular weight compound or in the form of being incorporated into a part of a polymer. Furthermore, the form of a low molecular weight compound and the form of being incorporated into a part of a polymer may be used in combination.

[0321] The photoacid generator A is preferably in the form of a low molecular weight compound.

[0322] 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 1,000 or less.

[0323] The content of the photoacid generator A is preferably 0.1 to 35% by mass, more preferably 0.5 to 25% by mass, further preferably 3 to 20% by mass, and particularly preferably 3 to 18% by mass, based on the total solid content of the composition.

[0324] The content of the photoacid generator A is preferably 0.01 to 1.00 mmol, more preferably 0.05 to 0.70 mmol, and even more preferably 0.10 to 0.40 mmol, based on 1 g of the solid content of the composition.

[0325] The photoacid generator A may be used alone or in combination of two or more. When two or more photoacid generators are used, the total content thereof is preferably within the above-mentioned preferred content range.

[0326] <Photoacid generator B>

[0327] The composition further comprises at least one of a photoacid generator B and a nitrogen-containing compound C.

[0328] The photoacid generator B is a compound that generates an acid upon irradiation with actinic rays or radiation.

[0329] The photoacid generator B is a compound that generates an acid having a pKa greater than that of the acid generated by the photoacid generator A by 1.00 or more.

[0330] The difference between the pKa of the acid generated by the photoacid generator B and the pKa of the acid generated by the photoacid generator A is preferably 1.00 to 12.00, more preferably 1.00 to 5.00, and even more preferably 1.00 to 3.00.

[0331] The pKa of the acid generated by the photoacid generator B varies depending on the type of the photoacid generator A used, but is, for example, preferably 0.00 to 12.00, more preferably 0.50 to 6.00, and even more preferably 1.00 to 4.00.

[0332] The photoacid generator B is an onium salt compound preferably including an anion and a cation. As such an onium salt compound, compounds represented by general formulae (d1-1) to (d1-3) are preferred.

[0333] [Chemical formula 21]

[0334]

[0335] In formula (d1-1), R 51 It represents a hydrocarbon group (for example, an aryl group such as a phenyl group) which may have a substituent (for example, a hydroxyl group).

[0336] In formula (d1-2), Z 2c It represents a hydrocarbon group having 1 to 30 carbon atoms which may have a substituent (but the carbon atom adjacent to S is not substituted with a fluorine atom).

[0337] Z 2c The hydrocarbon group in the above-mentioned hydrocarbon group may be straight-chain, branched, or have a cyclic structure. Furthermore, the carbon atom in the above-mentioned hydrocarbon group (preferably the carbon atom forming the cyclic structure when the above-mentioned hydrocarbon group has a cyclic structure) may be a carbonyl carbon (-CO-). As the above-mentioned hydrocarbon group, for example, a norbornyl group may be cited which may have a substituent. The carbon atom forming the above-mentioned norbornyl group may be a carbonyl carbon.

[0338] Furthermore, it is preferred that "Z" in the general formula (d1-2) 2c -SO3 - " and "R 3 -LC(R 1 )(R 2 )-SO3 - "different.

[0339] In formula (d1-3), R 52represents an organic group. The organic group is preferably an alkyl group, more preferably an alkyl group having 1 to 10 carbon atoms. The alkyl group may be linear, branched, or cyclic. As a substituent that the alkyl group may have, a fluorine atom is preferred. The alkyl group may be a perfluoroalkyl group.

[0340] Y 3 represents a single bond, -CO-, an alkylene group or an arylene group. The alkylene group may be linear, branched or cyclic. The alkylene group preferably has 1 to 7 carbon atoms. The arylene group preferably has 6 to 15 carbon atoms.

[0341] Rf represents a hydrocarbon group. Preferably, the number of carbon atoms of the above hydrocarbon group is 1 to 30. It may be straight chain, branched, or have a cyclic structure. Furthermore, the carbon atom in the above hydrocarbon group (preferably the carbon atom forming a cyclic structure when the above hydrocarbon group has a cyclic structure) may be a carbonyl carbon (-CO-). As the above hydrocarbon group, for example, a norbornyl group which may have a substituent may be mentioned. The carbon atom forming the above norbornyl group may be a carbonyl carbon. As the above hydrocarbon group, an alkyl group such as a methyl group is also preferred.

[0342] Examples of the substituent which the above hydrocarbon group may have include a fluorine atom.

[0343] In formulas (d1-1) to (d1-3), M + are each independently an ammonium cation, a sulfonium cation or an iodonium cation.

[0344] As the sulfonium cation and the iodonium cation, for example, the sulfonium cation and the iodonium cation which may be included in the photoacid generator A (more specifically, the cation in the compound represented by the general formula (ZaI) and the compound represented by the general formula (ZaII)) can be used in the same manner.

[0345] The photoacid generator B may be a compound having a cationic site and an anionic site in the same molecule, wherein the cationic site and the anionic site are bonded to each other via a covalent bond.

[0346] As the above-mentioned compound, a compound represented by the general formula (C-1) or a compound represented by the general formula (C-2) is preferred.

[0347] [Chemical formula 22]

[0348]

[0349] In the general formulas (C-1) to (C-3),

[0350] R1, R2, and R3 each independently represent a substituent having 1 or more carbon atoms.

[0351] L1 represents a cationic group (S + ,I + or N + ) and -X - A divalent linking group or a single bond for bonding.

[0352] -X - Representation-COO - 、-SO3 - 、-SO2 - or -N - -R4.

[0353] R4 represents a monovalent substituent having at least one of a carbonyl group (-CO-), a sulfonyl group (-SO2-) and a sulfinyl group (-S(=O)-) at the bonding site to the adjacent N atom.

[0354] R1, R2, R3, R4 and L1 may be bonded to each other to form a ring.

[0355] Furthermore, in the general formula (C-3), two of R1 to R3 together represent one divalent substituent, which may be bonded to a double bond via a N atom.

[0356] Examples of the substituent having 1 or more carbon atoms in R1 to R3 include alkyl, cycloalkyl, aryl (preferably having 6 to 15 carbon atoms), alkoxycarbonyl, cycloalkyloxycarbonyl, aryloxycarbonyl, alkylaminocarbonyl, cycloalkylaminocarbonyl, and arylaminocarbonyl. Among them, alkyl, cycloalkyl, and aryl are preferred.

[0357] As the divalent linking group L1, there can be mentioned a linear or branched alkylene group, a cycloalkylene group, an arylene group (preferably having 6 to 15 carbon atoms), a carbonyl group, an ether bond, an ester bond, an amide bond, a carbamate bond, a urea bond, and a group formed by combining two or more of them, etc. Among them, an alkylene group, an arylene group, an ether bond, an ester bond, or a group formed by combining two or more of them is preferred.

[0358] Photoacid generator B may be a compound that generates an acid having a pKa greater than 1.00 or more than that of the acid generated by photoacid generator A and may be an onium salt compound having a nitrogen atom in the cation part. Preferably, the onium salt compound having a nitrogen atom in the cation part has a basic site containing a nitrogen atom in the cation part.

[0359] Preferably, the basic site is an amino group, more preferably an aliphatic amino group. Furthermore, preferably, all the atoms adjacent to the nitrogen atom in the basic site are hydrogen atoms or carbon atoms. Furthermore, from the viewpoint of improving basicity, preferably, an electron-withdrawing functional group (carbonyl, sulfonyl, cyano, halogen atom, etc.) is not directly bonded to the nitrogen atom.

[0360] The acid generator B may be in the form of a low molecular weight compound or in the form of being incorporated into a part of a polymer. Furthermore, the form of a low molecular weight compound and the form of being incorporated into a part of a polymer may be used in combination.

[0361] The photoacid generator B is preferably in the form of a low molecular weight compound.

[0362] When the photoacid generator B 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 further preferably 1,000 or less.

[0363] When the composition contains the photoacid generator B, the content thereof is preferably 0.1 to 15% by mass, more preferably 0.5 to 10% by mass, and even more preferably 1 to 5% by mass, based on the total solid content of the composition.

[0364] When the composition contains the photoacid generator B, the content thereof is preferably 0.005 to 0.50 mmol, more preferably 0.01 to 0.10 mmol, and even more preferably 0.01 to 0.05 mmol, based on 1 g of the solid content of the composition.

[0365] The photoacid generator B may be used alone or in combination of two or more. When two or more photoacid generators B are used in the composition, the total content thereof is preferably within the above-mentioned preferred content range.

[0366] <Nitrogen-containing compound C>

[0367] The composition comprises at least one of a photoacid generator B and a nitrogen-containing compound C.

[0368] The nitrogen-containing compound C is a compound different from the photoacid generator A.

[0369] The nitrogen-containing compound C has at least one nitrogen atom and is a compound having a conjugate acid with a pKa greater than that of the acid generated by the photoacid generator A by 1.00 or more.

[0370] As long as the necessary condition that the pKa of the conjugate acid is greater than that of the acid generated by the photoacid generator A by 1.00 or more is satisfied, the nitrogen-containing compound C may be a compound that generates an acid by irradiation with actinic rays or radiation.

[0371] In addition, if it is a compound having a nitrogen atom and the pKa of the conjugate acid is 1.00 or more larger than the acid generated by the photoacid generator A, then even if it is a compound that generates an acid with a pKa that is 1.00 or more larger than the acid generated by the photoacid generator A, the above compound is equivalent to the nitrogen-containing compound C and not to the photoacid generator B.

[0372] Preferably, the nitrogen atom contained in the nitrogen-containing compound C is a nitrogen anion (N - ) and / or nitrogen cations (N+ That is, in the nitrogen-containing compound containing nitrogen anions (N - ) and / or nitrogen cations (N + ) is preferably further provided with a nitrogen anion (N - ) and / or nitrogen cations (N + ) other than nitrogen atoms.

[0373] The difference between the pKa of the conjugate acid of the nitrogen-containing compound C and the pKa of the acid generated by the photoacid generator A is preferably 1.00 to 14.00, more preferably 2.00 to 13.00, and even more preferably 3.00 to 12.00.

[0374] The pKa of the conjugate acid of the nitrogen-containing compound C varies depending on the type of the photoacid generator A used, but is, for example, preferably 0.00 to 14.00, more preferably 3.00 to 13.00, and even more preferably 3.50 to 12.50.

[0375] The nitrogen-containing compound C captures the acid generated by the photoacid generator A or the like during exposure, and functions as a quencher that suppresses the reaction of the acid-decomposable resin in the unexposed portion due to the excess generated acid.

[0376] Examples of the nitrogen-containing compound C include a basic compound having a nitrogen atom (DA), a basic compound having a nitrogen atom and whose basicity decreases or disappears by irradiation with actinic rays or radiation (DB), a low molecular weight compound having a nitrogen atom and a group that is detached by the action of an acid (DD), and an onium salt compound having a nitrogen atom in the cation portion (DE).

[0377] (Basic Compound (DA))

[0378] Examples of the basic compound (DA) include compounds having structures represented by general formulae (A) to (E).

[0379] [Chemical formula 23]

[0380]

[0381] In the general formulas (A) and (E),

[0382] R 200 , R 201 , and R 202 R may be the same or different and each independently 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). 201 With R 202 They may be bonded to each other to form a ring.

[0383] R 203 , R 204 , R 205 and R 206 The groups may be the same or different and each independently represents an alkyl group having 1 to 20 carbon atoms.

[0384] The alkyl group in the general formula (A) and (E) may have a substituent or may be unsubstituted.

[0385] As for the alkyl group having a substituent, 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 is preferred.

[0386] More preferably, the alkyl groups in the general formulae (A) and (E) are unsubstituted.

[0387] As the basic compound (DA), guanidine, aminopyrrolidine, pyrazole, pyrazoline, piperazine, aminomorpholine, aminoalkylmorpholine or piperidine are preferred, and compounds having an imidazole structure, a diazabicyclic 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 group, or an aniline derivative having a hydroxyl group and / or an ether group are more preferred.

[0388] (Compound (DB))

[0389] The nitrogen-containing compound C may be a basic compound (DB) (hereinafter also referred to as "compound (DB)") having a nitrogen atom and whose basicity is reduced or eliminated by irradiation with actinic rays or radiation. The compound (DB) is a compound having a proton accepting functional group and whose proton accepting property is reduced or eliminated or changes from proton accepting property to acidic property by decomposition by irradiation with actinic rays or radiation.

[0390] The proton accepting functional group refers to a functional group having a group or electron that can electrostatically interact with a proton, for example, a functional group having a macrocyclic structure such as a cyclic polyether, or a functional group having a nitrogen atom containing 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 refers to, for example, a nitrogen atom having a partial structure shown in the following formula.

[0391] [Chemical formula 24]

[0392]

[0393] Preferred partial structures of the proton accepting functional group include, for example, crown ether, azacrown ether, primary to tertiary amine, pyridine, imidazole and pyrazine structures.

[0394] Compound (DB) generates a compound whose proton accepting property decreases, disappears, or changes from proton accepting property to acidic property by decomposition upon irradiation with actinic rays or radiation. Here, the decrease or disappearance of proton accepting property, or the change from proton accepting property to acidic property, refers to the change of proton accepting property caused by the addition of proton to the proton accepting functional group, specifically, when a proton adduct is generated from a compound (DB) having a proton accepting functional group and a proton, the equilibrium constant under chemical equilibrium decreases.

[0395] Proton acceptor properties can be confirmed by performing pH measurements.

[0396] The pKa of the compound generated by decomposition of the compound (DB) by irradiation with actinic rays or radiation is preferably pKa<-1, more preferably -13<pKa<-1, and even more preferably -13<pKa<-3.

[0397] The compound produced in this way can be neutralized intramolecularly and its pKa becomes -1 or higher.

[0398] Preferably, the compound (DB) is a compound represented by the general formula (c-1).

[0399] RBXA-W1-N - -W2-R f [C + ] (c-1)

[0400] In the general formula (c-1),

[0401] W1 and W2 each independently represent -SO2- or -CO-.

[0402] R f It represents an alkyl group which may have a substituent, a cycloalkyl group which may have a substituent, or an aryl group which may have a substituent.

[0403] A represents a single bond or a divalent linking group.

[0404] X represents a single bond, -SO2- or -CO-.

[0405] B represents a single bond, an oxygen atom or -N(Rx)Ry-.

[0406] Rx represents a hydrogen atom or an organic group.

[0407] Ry represents a single bond or a divalent organic group.

[0408] R represents an organic group having a proton accepting functional group.

[0409] Rx may be bonded to Ry to form a ring, or may be bonded to R to form a ring.

[0410] [C + ] represents a counter cation.

[0411] It is preferred that at least one of W1 and W2 is -SO2-, and it is more preferred that both of them are -SO2-.

[0412] Preferred R f The alkyl group may have a fluorine atom having 1 to 6 carbon atoms, more preferably a perfluoroalkyl group having 1 to 6 carbon atoms, and still more preferably a perfluoroalkyl group having 1 to 3 carbon atoms.

[0413] As the divalent linking group in A, a divalent linking group having 2 to 12 carbon atoms is preferred, for example, an alkylene group and a phenylene group can be cited. Among them, an alkylene group having at least one fluorine atom is preferred, preferably having 2 to 6 carbon atoms, more preferably 2 to 4. The alkylene chain may have a linking group such as an oxygen atom or a sulfur atom. Preferably, the alkylene group is an alkylene group in which 30 to 100% of the number of hydrogen atoms are substituted by fluorine atoms, and more preferably, the carbon atom bonded to the X and / or W1 portion has a fluorine atom. Among them, the divalent linking group in A is preferably a perfluoroalkylene group, more preferably a perfluoroethylene group, a perfluoropropylene group or a perfluorobutylene group.

[0414] When B represents -N(Rx)Ry-, the organic group in Rx preferably has 2 to 30 carbon atoms, and examples thereof include alkyl groups, cycloalkyl groups which may have an oxygen atom in the ring, aryl groups, aralkyl groups, and alkenyl groups.

[0415] The alkyl group in Rx may have a substituent, and is preferably a linear or branched alkyl group having 1 to 20 carbon atoms. The alkyl group may have an oxygen atom, a sulfur atom and / or a nitrogen atom in the alkyl chain.

[0416] Examples of the alkyl group having a substituent include a group in which a cycloalkyl group is substituted in a linear or branched alkyl group (for example, adamantylmethyl, adamantylethyl, cyclohexylethyl, camphor residue, etc.).

[0417] The cycloalkyl group in Rx may have a substituent, and is preferably a cycloalkyl group having 3 to 20 carbon atoms. The cycloalkyl group may have an oxygen atom in the ring.

[0418] The aryl group in Rx may have a substituent, and is preferably an aryl group having 6 to 14 carbon atoms.

[0419] The aralkyl group in Rx may have a substituent, and preferably an aralkyl group having 7 to 20 carbon atoms is used.

[0420] The alkenyl group in Rx may have a substituent, and examples thereof include groups having a double bond at any position of the alkyl group exemplified as Rx.

[0421] When B represents -N(Rx)Ry-, the divalent organic group in Ry is preferably an alkylene group. In this case, as a ring that can be formed by bonding Rx and Ry to each other, for example, a 5- to 8-membered ring containing a nitrogen atom can be mentioned, and a 6-membered ring is particularly preferred. The nitrogen atom contained in the ring may be a nitrogen atom other than the nitrogen atom directly bonded to X in -N(Rx)Ry-.

[0422] When B represents -N(Rx)Ry-, it is preferred that R and Rx are bonded to each other to form a ring. If a ring is formed, the stability is improved, and the storage stability of the composition using this is improved. The number of carbon atoms forming the ring is preferably 4 to 20, and it may be a monocyclic ring or a polycyclic ring, and may contain an oxygen atom, a sulfur atom and / or a nitrogen atom in the ring. The nitrogen atom contained in the ring may be a nitrogen atom other than the nitrogen atom directly bonded to X in -N(Rx)Ry-.

[0423] As a monocyclic ring, a 4-membered ring, a 5-membered ring, a 6-membered ring, a 7-membered ring and an 8-membered ring containing a nitrogen atom can be mentioned. As such a ring structure, for example, a piperazine ring and a piperidine ring can be mentioned. As a polycyclic ring, a structure containing a combination of two or more monocyclic structures can be mentioned. The monocyclic ring and the polycyclic ring can each have a substituent, for example, preferably, a halogen atom, a hydroxyl group, a cyano group, a carboxyl group, a carbonyl group, a cycloalkyl group (preferably a carbon number of 3 to 10), an aryl group (preferably a carbon number of 6 to 14), an alkoxy group (preferably a carbon number of 1 to 10), an acyl group (preferably a carbon number of 2 to 15), an acyloxy group (preferably a carbon number of 2 to 15), an alkoxycarbonyl group (preferably a carbon number of 2 to 15), an aminoacyl group (preferably a carbon number of 2 to 20), or a lactone ring group (preferably a group formed by removing one hydrogen atom from a lactone structure represented by any one of the general formulas (LC1-1) to (LC1-22) above). If possible, these substituents can further have a substituent. Examples of the case where the aryl group and the cycloalkyl group further have a substituent include an alkyl group (preferably having 1 to 15 carbon atoms). Examples of the substituent that the aminoacyl group may further have include an alkyl group (preferably having 1 to 15 carbon atoms).

[0424] As the proton accepting functional group in R, as described above, preferably, as a partial structure, for example, a structure having a crown ether, a primary or tertiary amine, and a nitrogen-containing heterocyclic ring (pyridine, imidazole, pyrazine, etc.) is used.

[0425] In addition, as a proton accepting functional group, a functional group having a nitrogen atom is preferred, and a group having a primary to tertiary amino group or a nitrogen-containing heterocyclic group is more preferred. In these structures, it is preferred that all atoms adjacent to the nitrogen atom contained in the structure are carbon atoms or hydrogen atoms. Furthermore, it is preferred that the electron-withdrawing functional group (carbonyl, sulfonyl, cyano, halogen atom, etc.) is not directly bonded to the nitrogen atom.

[0426] The organic group in the organic group (group R) containing such a proton accepting functional group preferably has 2 to 30 carbon atoms, and examples thereof include alkyl, cycloalkyl, aryl, aralkyl and alkenyl groups, and each group may have a substituent.

[0427] The alkyl, cycloalkyl, aryl, aralkyl and alkenyl groups of the alkyl, cycloalkyl, aryl, aralkyl and alkenyl groups containing a proton accepting functional group in R include the same groups as those exemplified as Rx.

[0428] Examples of substituents that the above groups may have include halogen atoms, hydroxyl groups, nitro groups, cyano groups, carboxyl groups, cycloalkyl groups (preferably having 3 to 10 carbon atoms, which may be partially substituted with heteroatoms or groups having heteroatoms (ester groups, etc.)), aryl groups (preferably having 6 to 14 carbon atoms), alkoxy groups (preferably having 1 to 10 carbon atoms), acyl groups (preferably having 2 to 20 carbon atoms), acyloxy groups (preferably having 2 to 10 carbon atoms), alkoxycarbonyl groups (preferably having 2 to 20 carbon atoms), and aminoacyl groups (preferably having 2 to 20 carbon atoms). Examples of substituents that cyclic groups such as aryl groups and cycloalkyl groups may include alkyl groups (preferably having 1 to 20 carbon atoms). Examples of substituents that aminoacyl groups may have include 1 or 2 alkyl groups (preferably having 1 to 20 carbon atoms).

[0429] [C + As the counter cation, a sulfonium cation or an iodonium cation is preferred. As the sulfonium cation and the iodonium cation, for example, the sulfonium cation and the iodonium cation among the cations that the photoacid generator A may have (more specifically, the cations in the compound represented by the general formula (ZaI) and the cations in the compound represented by the general formula (ZaII) etc.) can be used in the same manner.

[0430] (Compound (DD))

[0431] The nitrogen-containing compound C may be a low molecular weight compound (DD) having a nitrogen atom and a group that is detached by the action of an acid (hereinafter also referred to as "compound (DD)"). Preferably, the compound (DD) is an amine derivative having a group that is detached by the action of an acid on the nitrogen atom.

[0432] The group that is released 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 hemiamalin ether group, and more preferably a carbamate group or a hemiamalin ether group.

[0433] The molecular weight of the compound (DD) is preferably 100 to 1,000, more preferably 100 to 700, and even more preferably 100 to 500.

[0434] Compound (DD) may have a carbamate group having a protecting group on the nitrogen atom. As the protecting group constituting the carbamate group, a group represented by the following general formula (d-1) is preferred.

[0435] [Chemical formula 25]

[0436]

[0437] In the general formula (d-1),

[0438] R b Each independently represents a hydrogen atom, an alkyl group (preferably having 1 to 10 carbon atoms), a cycloalkyl group (preferably having 3 to 30 carbon atoms), an aryl group (preferably having 3 to 30 carbon atoms), an aralkyl group (preferably having 1 to 10 carbon atoms), or an alkoxyalkyl group (preferably having 1 to 10 carbon atoms). b They may be linked to each other to form a ring.

[0439] R b The alkyl, cycloalkyl, aryl and aralkyl groups represented may be independently substituted by a hydroxyl, cyano, amino, pyrrolidinyl, piperidinyl, morpholinyl, oxo or other functional groups, an alkoxy group or a halogen atom. b The same applies to the alkoxyalkyl groups represented.

[0440] As R b , preferably a linear or branched alkyl group, a cycloalkyl group or an aryl group, more preferably a linear or branched alkyl group or a cycloalkyl group.

[0441] As 2 R b Examples of the ring formed by mutually linking include alicyclic hydrocarbons, aromatic hydrocarbons, heterocyclic hydrocarbons, and derivatives thereof.

[0442] Examples of specific structures of the group represented by general formula (d-1) include structures disclosed in paragraph <0466> of US Patent Publication No. US2012 / 0135348A1, but the present invention is not limited thereto.

[0443] The compound (DD) is preferably a compound having a structure represented by the following general formula (6).

[0444] [Chemical formula 26]

[0445]

[0446] In general formula (6),

[0447] l represents an integer from 0 to 2, m represents an integer from 1 to 3, and l+m=3 is satisfied.

[0448] R arepresents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group or an aralkyl group. a Can be the same or different, 2 R a They may be linked to each other to form a heterocyclic ring together with the nitrogen atom in the formula. The heterocyclic ring may contain a hetero atom other than the nitrogen atom in the formula.

[0449] R b and R in the above general formula (d-1) b The meanings are the same, and the preferred examples are also the same.

[0450] In the general formula (6), as R a The alkyl, cycloalkyl, aryl and aralkyl groups may be substituted independently by the same groups as those mentioned above. The aforementioned groups are, as R b The alkyl group, cycloalkyl group, aryl group and aralkyl group may be substituted.

[0451] As the above R a Specific examples of the alkyl, cycloalkyl, aryl and aralkyl groups (these groups may be substituted by the above groups) include the same as those for R b The same groups as the above-mentioned specific examples.

[0452] (Compound (DE))

[0453] The nitrogen-containing compound C may be an onium salt compound (DE) having a nitrogen atom in the cation portion (hereinafter also referred to as "compound (DE)"). When compound (DE) generates an acid by irradiation with actinic rays or radiation, the pKa of the generated acid is smaller than the pKa of the acid generated by the photoacid generator A plus 1.

[0454] The compound (DE) is preferably a compound having a basic site containing a nitrogen atom in the cation portion.

[0455] Preferably, the basic site is an amino group, more preferably an aliphatic amino group. Furthermore, preferably, all the atoms adjacent to the nitrogen atom in the basic site are hydrogen atoms or carbon atoms. Furthermore, from the viewpoint of improving basicity, preferably, an electron-withdrawing functional group (carbonyl, sulfonyl, cyano, halogen atom, etc.) is not directly bonded to the nitrogen atom.

[0456] When the composition contains the nitrogen-containing compound C, the content of the nitrogen-containing compound C in the composition is preferably 0.1 to 15% by mass, more preferably 0.1 to 10% by mass, and even more preferably 0.5 to 8.0% by mass, based on the total solid content of the composition.

[0457] The nitrogen-containing compound C may be used alone or in combination of two or more. When two or more nitrogen-containing compounds C are used in the composition, the total content thereof is preferably within the above-mentioned preferred content range.

[0458] The composition may contain at least one selected from the group consisting of the photoacid generator B and the nitrogen-containing compound C, and may contain only one or two.

[0459] <Photoacid generator D>

[0460] The composition of the present invention may or may not contain a photoacid generator D that generates an acid with a pKa of less than -1.00.

[0461] The photoacid generator D is a compound different from the nitrogen-containing compound C described above.

[0462] That is, even if it is a compound that generates an acid with a pKa of less than -1.00 by irradiation with actinic rays or radiation, if the above compound has a nitrogen atom and the pKa of the conjugate acid is 1.00 or more greater than that of the acid generated by the photoacid generator A, the above compound is equivalent to the above nitrogen-containing compound C, and not to the photoacid generator D.

[0463] When the composition contains the photoacid generator D, the ratio of the molar number of the photoacid generator A to the molar number of the photoacid generator D in the composition (the content of the photoacid generator A / the content of the photoacid generator D (molar ratio)) is 1.0 or more, preferably 1.5 or more, more preferably 2.0 or more, further preferably 5.0 or more, and particularly preferably 10 or more. The upper limit is not particularly limited, and is, for example, 20 or less.

[0464] When the composition contains a photoacid generator D, the content of the photoacid generator D is preferably 15% by mass or less, more preferably 7% by mass or less, further preferably 4% by mass or less, and particularly preferably 1% by mass or less relative to the total solid content of the composition. The lower limit is not particularly limited, and is, for example, 0.1% by mass or more.

[0465] When the composition contains the photoacid generator D, the content of the photoacid generator D is preferably 0.13 mmol or less, more preferably 0.10 mmol or less, further preferably 0.07 mmol or less, and particularly preferably 0.03 mmol or less, based on 1 g of the solid content of the composition. The lower limit is not particularly limited, and is, for example, 0.001 mmol or more.

[0466] <Hydrophobic resin>

[0467] The composition of the present invention may contain a hydrophobic resin. In addition, the hydrophobic resin is preferably a resin different from the resin A.

[0468] When the composition of the present invention contains a hydrophobic resin, it is easy to control the static and / or dynamic contact angle on the surface of the resist film (actinic ray or radiation-sensitive film), thereby improving the development characteristics, suppressing degassing, improving the immersion liquid followability in immersion exposure, and reducing immersion defects.

[0469] The hydrophobic resin is preferably designed so as to be localized on the surface of the resist film, but unlike a surfactant, it is not necessarily required to have a hydrophilic group in the molecule and may not contribute to uniform mixing of polar and nonpolar substances.

[0470] From the viewpoint of partial localization to the film surface, the hydrophobic resin is preferably a resin having at least one repeating unit selected from the group consisting of "fluorine atom", "silicon atom" and "CH3 partial structure contained in the side chain part of the resin". In the case where the hydrophobic resin contains fluorine atoms and / or silicon atoms, the above-mentioned fluorine atoms and / or silicon atoms in the hydrophobic resin may be contained in the main chain of the resin or in the side chain.

[0471] When the hydrophobic resin contains a fluorine atom, a resin containing an alkyl group having a fluorine atom, a cycloalkyl group having a fluorine atom, or an aryl group having a fluorine atom as a partial structure having a fluorine atom is preferred.

[0472] It is preferred that the hydrophobic resin has at least one group selected from the following groups (x) to (z).

[0473] (x) Acid group

[0474] (y) a group that is decomposed by the action of an alkaline developer and has increased solubility in an alkaline developer (hereinafter also referred to as a polarity conversion group)

[0475] (z) Groups that decompose by the action of an acid

[0476] Examples of the acid group (x) include a phenolic hydroxyl group, a carboxyl group, a fluorinated alcohol group, a sulfonic acid group, a sulfonamide group, a sulfonimide 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 tri(alkylcarbonyl) methylene group, and a tri(alkylsulfonyl) methylene group. Preferred acid groups include a fluorinated alcohol group (preferably hexafluoroisopropanol), a sulfonimide group, or a bis(alkylcarbonyl) methylene group.

[0477] As the group (y) that is decomposed by the action of the alkaline developer and has increased solubility in the alkaline developer, for example, there can be mentioned a lactone group, a carboxyl ester group (-COO-), an anhydride group (-CO-O-CO-), an acid imide group (-NHCONH-), a carboxyl thioester group (-COS-), a carbonate group (-O-CO-O-), a sulfate group (-OSO2O-), and a sulfonate group (-SO2O-), preferably a lactone group or a carboxyl ester group (-COO-).

[0478] As repeating units containing these groups, for example, repeating units in which these groups are directly bonded to the main chain of the resin, for example, repeating units based on acrylate and methacrylate, etc. can be cited. In the repeating unit, these groups can be bonded to the main chain of the resin via a linking group. Alternatively, the repeating unit can be used when polymerizing a polymerization initiator or chain transfer agent having these groups and introduced into the terminal of the resin.

[0479] Examples of the repeating unit having a lactone group include the same repeating units as those described above in the section of the resin A as the repeating units having a lactone structure.

[0480] When the hydrophobic resin contains a repeating unit having a group (y) which is decomposed by the action of an alkaline developer and has increased solubility in an alkaline developer, the content thereof is preferably 1 to 100 mol %, more preferably 3 to 98 mol %, and further preferably 5 to 95 mol % relative to all repeating units in the hydrophobic resin.

[0481] The repeating unit having a group (z) decomposed by the action of an acid in the hydrophobic resin may include the same repeating unit as the repeating unit having an acid-decomposable group listed in the resin A. The repeating unit having a group (z) decomposed by the action of an acid may have at least one of a fluorine atom and a silicon atom. When the hydrophobic resin contains a repeating unit having a group (z) decomposed by the action of an acid, the content thereof is preferably 1 to 80 mol %, more preferably 10 to 80 mol %, and further preferably 15 to 60 mol % relative to all repeating units in the hydrophobic resin.

[0482] The hydrophobic resin may further have a repeating unit different from the above-mentioned repeating units.

[0483] When the hydrophobic resin has a repeating unit containing a fluorine atom, the content thereof is preferably 10 to 100 mol %, more preferably 30 to 100 mol % relative to all repeating units in the hydrophobic resin. Furthermore, when the hydrophobic resin has a repeating unit containing a silicon atom, the content thereof is preferably 10 to 100 mol %, more preferably 20 to 100 mol % relative to all repeating units in the hydrophobic resin.

[0484] On the other hand, especially when the hydrophobic resin contains a CH3 partial structure in the side chain part, it is also preferred that the hydrophobic resin does not substantially contain fluorine atoms and silicon atoms. In addition, it is preferred that the hydrophobic resin is substantially composed of repeating units consisting of atoms selected from carbon atoms, oxygen atoms, hydrogen atoms, nitrogen atoms and sulfur atoms.

[0485] The weight average molecular weight of the hydrophobic resin in terms of standard polystyrene is preferably from 1,000 to 100,000, more preferably from 1,000 to 50,000.

[0486] The total content of residual monomers and / or oligomer components contained in the hydrophobic resin is preferably 0.01 to 5% by mass, more preferably 0.01 to 3% by mass. The degree of dispersion (Mw / Mn) is preferably 1.0 to 5.0, more preferably 1.0 to 3.0.

[0487] As the hydrophobic resin, known resins can be appropriately selected and used alone or as a mixture of these. For example, known resins disclosed in sections <0451> to <0704> of U.S. Patent Application Publication No. 2015 / 0168830A1 and sections <0340> to <0356> of U.S. Patent Application Publication No. 2016 / 0274458A1 can be preferably used as hydrophobic resins. In addition, it is preferred that the repeating units disclosed in sections <0177> to <0258> of U.S. Patent Application Publication No. 2016 / 0237190A1 are also used as repeating units constituting the hydrophobic resin.

[0488] Preferred examples of monomers corresponding to the repeating units constituting the hydrophobic resin are shown below.

[0489] [Chemical formula 27]

[0490]

[0491] [Chemical formula 28]

[0492]

[0493] The hydrophobic resin may be used alone or in combination of two or more.

[0494] From the viewpoint of achieving both immersion liquid followability and development characteristics in immersion exposure, it is also preferred to use two or more hydrophobic resins having different surface energies in combination.

[0495] The content of the hydrophobic resin in the composition is preferably 0.01 to 10% by mass, more preferably 0.03 to 8.0% by mass, and even more preferably 0.10 to 1.0% by mass relative to the total solid content in the composition of the present invention. When two or more hydrophobic resins are used, the total content is preferably within the above-mentioned preferred content range.

[0496] <Solvent>

[0497] The composition of the present invention may contain a solvent.

[0498] In the composition of the present invention, known resist solvents can be used appropriately. For example, known solvents disclosed in paragraphs <0665> to <0670> of U.S. Patent Application Publication No. 2016 / 0070167A1, paragraphs <0210> to <0235> of U.S. Patent Application Publication No. 2015 / 0004544A1, paragraphs <0424> to <0426> of U.S. Patent Application Publication No. 2016 / 0237190A1, and paragraphs <0357> to <0366> of U.S. Patent Application Publication No. 2016 / 0274458A1 can be preferably used.

[0499] Examples of the solvent that can be used when preparing the composition include organic solvents such as alkylene glycol monoalkyl ether carboxylates, alkylene glycol monoalkyl ethers, alkyl lactates, alkyl alkoxypropionates, cyclic lactones (preferably having 4 to 10 carbon atoms), monoketone compounds that may have a ring (preferably having 4 to 10 carbon atoms), alkylene carbonates, alkyl alkoxy acetates, and alkyl pyruvates.

[0500] As the organic solvent, a mixed solvent of a solvent having a hydroxyl group in its structure and a solvent having no hydroxyl group can be used.

[0501] As a solvent having a hydroxyl group and a solvent not having a hydroxyl group, the aforementioned exemplary compounds can be appropriately selected. As a solvent containing a hydroxyl group, alkylene glycol monoalkyl ether or lactic acid alkyl ester is preferred, and propylene glycol monomethyl ether (PGME), propylene glycol monoethyl ether (PGEE), 2-hydroxyisobutyric acid methyl ester or ethyl lactate is more preferred. In addition, as a solvent not having a hydroxyl group, alkylene glycol monoalkyl ether acetate, alkyl alkoxy propionate, a monoketone compound that may have a ring, a cyclic lactone, or alkyl acetate is preferred. Among these, propylene glycol monomethyl ether acetate (PGMEA), ethyl ethoxy propionate, 2-heptanone, γ-butyrolactone, cyclohexanone, cyclopentanone or butyl acetate is more preferred, and propylene glycol monomethyl ether acetate, γ-butyrolactone, ethyl ethoxy propionate, cyclohexanone, cyclopentanone or 2-heptanone is further preferred. As a solvent not having a hydroxyl group, propylene carbonate is also preferred.

[0502] The mixing ratio (mass ratio) of the solvent having hydroxyl group to the solvent having no hydroxyl group is preferably 1 / 99 to 99 / 1, more preferably 10 / 90 to 90 / 10, and further preferably 20 / 80 to 60 / 40. From the viewpoint of coating uniformity, a mixed solvent containing 50% by mass or more of the solvent having no hydroxyl group is preferred.

[0503] The solvent preferably contains propylene glycol monomethyl ether acetate. In this case, the solvent may be a single solvent of propylene glycol monomethyl ether acetate or a mixed solvent of two or more solvents containing propylene glycol monomethyl ether acetate.

[0504] The solid content concentration of the composition of the present invention is preferably 1.0 to 10% by mass, more preferably 2.0 to 5.7% by mass, and further preferably 2.0 to 5.3% by mass. That is, the content of the solvent in the composition when the composition contains a solvent is preferably adjusted to a preferred range satisfying the above-mentioned solid content concentration. In addition, the solid content concentration refers to the mass percentage of the mass of other resist components other than the solvent relative to the total mass of the composition.

[0505] The solid content concentration in the composition is set within an appropriate range to have an appropriate viscosity to improve coating properties or film-forming properties, thereby adjusting the film thickness of a resist film (actinic ray-sensitive or radiation-sensitive film) comprising the composition of the present invention.

[0506] <Surfactant>

[0507] The compositions of the present invention may contain a surfactant.

[0508] The surfactant is preferably a fluorine-based and / or silicon-based surfactant (specifically, a fluorine-based surfactant, a silicon-based surfactant, or a surfactant having both a fluorine atom and a silicon atom).

[0509] When the composition of the present invention contains a surfactant, when an exposure light source of 250 nm or less, particularly 220 nm or less is used, a pattern having good sensitivity and resolution and few adhesion and development defects can be easily obtained.

[0510] Examples of the fluorine-based and / or silicon-based surfactant include the surfactants described in paragraph <0276> of US Patent Application Publication No. 2008 / 0248425.

[0511] Furthermore, surfactants other than fluorine-based and / or silicon-based surfactants described in paragraph <0280> of US Patent Application Publication No. 2008 / 0248425 may be used.

[0512] The surfactant may be used alone or in combination of two or more.

[0513] When the composition of the present invention contains a surfactant, the content of the surfactant is preferably 0.0001 to 2% by mass, more preferably 0.0005 to 1% by mass, based on the total solid content of the composition.

[0514] The surfactant may be used alone or in combination of two or more. When two or more surfactants are used, the total content thereof is preferably within the above-mentioned preferred content range.

[0515] On the other hand, when the content of the surfactant is 10 ppm by mass or more relative to the total solid content of the composition, the surface localization of the hydrophobic resin is improved, thereby making the surface of the resist film more hydrophobic and improving the water followability during immersion exposure.

[0516] <Other additives>

[0517] The composition of the present invention may further contain resins other than those mentioned above, crosslinking agents, acid multipliers, dyes, plasticizers, photosensitizers, light absorbers, alkali-soluble resins, dissolution inhibitors or dissolution accelerators, and the like.

[0518] <Preparation method>

[0519] The composition of the present invention is preferably used by dissolving the above-mentioned components in a predetermined organic solvent (preferably the above-mentioned mixed solvent), filtering the dissolved organic solvent with a filter, and then applying the dissolved organic solvent on a predetermined support (substrate).

[0520] The pore size of the filter used in the filter filtration is preferably 0.1 μm or less, more preferably 0.05 μm or less, and further preferably 0.03 μm or less. In addition, when the solid content concentration of the composition is high (for example, 25% by mass or more), the pore size of the filter used for the filter filtration is preferably 3 μm or less, more preferably 0.5 μm or less, and further preferably 0.3 μm or less. Preferably, the filter is a filter made of polytetrafluoroethylene, polyethylene or nylon. In the filter filtration, for example, as disclosed in Japanese Patent Application Publication No. 2002-062667 (Japanese Patent Application Publication No. 2002-062667), cyclic filtration can be performed, and multiple filters can be connected in series or in parallel for filtration. In addition, the composition can be filtered multiple times. Furthermore, before and after the filter filtration, the composition can be degassed, etc.

[0521] <Application>

[0522] The composition of the present invention relates to an actinic ray or radiation-sensitive resin composition that reacts and changes its properties by irradiation with actinic rays or radiation. More specifically, the composition of the present invention relates to an actinic ray or radiation-sensitive resin composition used in semiconductor manufacturing processes such as IC (Integrated Circuit), the manufacture of circuit substrates of liquid crystals or thermal heads, the preparation of mold structures for stamping, other photosensitive etching processes, and the manufacture of lithographic printing plates or acid-curable compositions. The pattern formed in the present invention can be used in etching processes, ion implantation processes, bump electrode formation processes, rewiring formation processes, and MEMS (Micro Electro Mechanical Systems).

[0523] [Pattern forming method, resist film]

[0524] The present invention also relates to a pattern forming method using the above-mentioned photosensitive ray or radiation-sensitive resin composition. The pattern forming method of the present invention is described below. In addition, the resist film (photosensitive ray or radiation-sensitive film) of the present invention is described together with the description of the pattern forming method.

[0525] The pattern forming method of the present invention has the following characteristics:

[0526] (i) a step of forming a resist film (actinic ray-sensitive or radiation-sensitive film) on a support using the above-mentioned actinic ray-sensitive or radiation-sensitive resin composition (resist film forming step (film forming step));

[0527] (ii) a step of exposing the resist film to light (irradiating it with actinic rays or radiation) (exposure step); and

[0528] (iii) A step of developing the exposed resist film using a developer (development step).

[0529] The pattern forming method of the present invention is not particularly limited as long as it includes the above steps (i) to (iii), and may further include the following steps.

[0530] In the pattern forming method of the present invention, the exposure method in the (ii) exposure step may be liquid immersion exposure.

[0531] The pattern forming method of the present invention preferably includes a (iv) preheating (PB: PreBake) step before the (ii) exposure step.

[0532] The pattern forming method of the present invention preferably includes a (v) post-exposure baking (PEB: Post Exposure Bake) step after the (ii) exposure step and before the (iii) development step.

[0533] In the pattern forming method of the present invention, (ii) may include a plurality of exposure steps.

[0534] In the pattern forming method of the present invention, (iv) may include a plurality of preheating steps.

[0535] In the pattern forming method of the present invention, (v) may include a plurality of post-exposure heating steps.

[0536] In the pattern forming method of the present invention, the (i) resist film forming step (film forming step), (ii) exposure step, and (iii) development step can be performed by generally known methods.

[0537] From the viewpoint of improving the resolution, the film thickness of the resist film is preferably 110 nm or less, and more preferably 95 nm or less.

[0538] Furthermore, a resist underlayer film (e.g., SOG (Spin On Glass), SOC (Spin On Carbon) and an antireflection film) may be formed between the resist film and the support as necessary. As a material constituting the resist underlayer film, a known organic or inorganic material may be used as appropriate.

[0539] A protective film (top coat) can be formed on the upper layer of the resist film. As a protective film, known materials can be used appropriately. For example, it is possible to preferably use a protective film forming composition disclosed in U.S. Patent Application Publication No. 2007 / 0178407, U.S. Patent Application Publication No. 2008 / 0085466, U.S. Patent Application Publication No. 2007 / 0275326, U.S. Patent Application Publication No. 2016 / 0299432, U.S. Patent Application Publication No. 2013 / 0244438, and International Patent Application Publication No. 2016 / 157988A. As a protective film forming composition, it is preferred to include the above-mentioned acid diffusion control agent.

[0540] A protective film may be formed on the upper layer of the resist film including the hydrophobic resin.

[0541] The support is not particularly limited, and in addition to the manufacturing process of semiconductors such as ICs or the manufacturing process of circuit substrates of liquid crystals or thermal heads, it is also possible to use a substrate commonly used in the photolithography process of other photosensitive etching processes. As specific examples of the support, inorganic substrates such as silicon, SiO2 and SiN can be cited.

[0542] The heating temperature is preferably 70 to 130° C., more preferably 80 to 120° C., in both the (iv) preheating step and the (v) post-exposure heating process.

[0543] The heating time is preferably 30 to 300 seconds, more preferably 30 to 180 seconds, and even more preferably 30 to 90 seconds in either the (iv) preheating step or the (v) post-exposure heating step.

[0544] Heating is performed by a mechanism provided in the exposure device and the developing device, and a heating plate or the like may be used.

[0545] The wavelength of the light source used in the exposure process is not particularly limited, and for example, infrared light, visible light, ultraviolet light, far ultraviolet light, extreme ultraviolet light (EUV), X-rays, and electron beams can be cited. Among these, far ultraviolet light is preferred, and its wavelength is preferably 250 nm or less, more preferably 220 nm or less, and further preferably 1 to 200 nm. Specifically, KrF excimer laser (248 nm), ArF excimer laser (193 nm), F2 excimer laser (157 nm), X-rays, EUV (13 nm), or electron beams are preferred, and KrF excimer laser, ArF excimer laser, EUV, or electron beams are more preferred.

[0546] In the development step (iii), an alkali developer may be used, or a developer containing an organic solvent (hereinafter also referred to as an organic developer) may be used.

[0547] As the alkaline developer, a quaternary ammonium salt represented by tetramethylammonium hydroxide is generally used, and other alkaline aqueous solutions such as inorganic bases, primary to tertiary amines, alcoholamines, and cyclic amines can also be used.

[0548] Furthermore, the alkaline developer may contain an appropriate amount of alcohol and / or surfactant. The alkaline developer generally has an alkali concentration of 0.1 to 20% by mass and a pH of 10 to 15.

[0549] The development time using the alkaline developer is usually 10 to 300 seconds.

[0550] The alkali concentration, pH, and development time of the alkali developer can be appropriately adjusted according to the pattern to be formed.

[0551] The organic developer is preferably a developer containing at least one organic solvent selected from the group consisting of ketone solvents, ester solvents, alcohol solvents, amide solvents, ether solvents, and hydrocarbon solvents.

[0552] Examples of the ketone solvent 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, diacetone alcohol, acetyl carbinol, acetophenone, methyl naphthyl ketone, isophorone, and propyl carbonate.

[0553] Examples of the ester solvent include methyl acetate, butyl acetate, ethyl acetate, isopropyl acetate, pentyl acetate, isoamyl 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 butyrate, methyl 2-hydroxyisobutyrate, isoamyl acetate, isobutyl isobutyrate, and butyl propionate.

[0554] As the alcohol solvent, amide solvent, ether solvent, and hydrocarbon solvent, solvents disclosed in paragraphs <0715> to <0718> of the specification of US Patent Application Publication No. 2016 / 0070167A1 can be used.

[0555] The above solvents may be mixed with multiple types, or may be mixed with solvents other than the above solvents or water. The water content of the developer as a whole is preferably less than 50% by mass, more preferably less than 20% by mass, further preferably less than 10% by mass, and particularly preferably substantially free of water.

[0556] The content of the organic solvent in the organic developer is preferably 50 to 100% by mass, more preferably 80 to 100% by mass, further preferably 90 to 100% by mass, and particularly preferably 95 to 100% by mass, based on the total amount of the developer.

[0557] The developer may contain an appropriate amount of a known surfactant as required.

[0558] The content of the surfactant is usually 0.001 to 5% by mass, preferably 0.005 to 2% by mass, and more preferably 0.01 to 0.5% by mass, based on the total amount of the developer.

[0559] The organic developer may contain an acid diffusion controller.

[0560] As the developing method, for example, there can be cited: a method of immersing a substrate in a tank filled with a developer for a certain period of time (immersion method); a method of depositing the developer by surface tension and allowing it to remain stationary on the surface of the substrate for a certain period of time (spin-over immersion method); a method of spraying the developer on the surface of the substrate (spraying method); and a method of continuously spraying the developer onto a substrate rotating at a certain speed while scanning a developer spray nozzle at a certain speed (dynamic distribution method), etc.

[0561] The step of developing with an aqueous alkali solution (alkali developing step) and the step of developing with a developer containing an organic solvent (organic solvent developing step) can be combined. This allows only the region with the intermediate exposure intensity to be insoluble and form a pattern, thereby enabling a finer pattern to be formed.

[0562] After the (iii) development step, it is preferable to include a step of washing with a washing liquid (washing step).

[0563] The rinse liquid used in the rinse process after the development process using an alkali developer can be, for example, pure water. The pure water may contain an appropriate amount of a surfactant. In addition, after the development process or the rinse process, a treatment of removing the developer or rinse liquid attached to the pattern by a supercritical fluid may be performed. Furthermore, in order to remove the water remaining in the pattern, a heat treatment may be performed after the rinse treatment or the treatment with the supercritical fluid.

[0564] The rinse solution used in the rinse step after the development step using a developer containing an organic solvent is not particularly limited as long as it does not dissolve the pattern, and a solution containing a common organic solvent, pure water, etc. can be used. As the rinse solution, a rinse solution containing at least one organic solvent selected from the group consisting of a hydrocarbon solvent, a ketone solvent, an ester solvent, an alcohol solvent, an amide solvent, and an ether solvent is preferably used.

[0565] Specific examples of the hydrocarbon solvent, ketone solvent, ester solvent, alcohol solvent, amide solvent, and ether solvent include the same solvents as described for the developer containing an organic solvent.

[0566] As the rinsing liquid used in the rinsing step in this case, a rinsing liquid containing a monohydric alcohol is more preferably used.

[0567] Examples of the monohydric alcohol used in the rinsing step include linear, branched or cyclic monohydric alcohols, and specifically include 1-butanol, 2-butanol, 3-methyl-1-butanol, tert-butanol, 1-pentanol, 2-pentanol, 1-hexanol, 4-methyl-2-pentanol, 1-heptanol, 1-octanol, 2-hexanol, cyclopentanol, 2-heptanol, 2-octanol, 3-hexanol, 3-heptanol, 3-octanol, 4-octanol and methyl isobutyl carbinol.

[0568] The monohydric alcohol may have 5 or more carbon atoms, and examples thereof include 1-hexanol, 2-hexanol, 4-methyl-2-pentanol, 1-pentanol, 3-methyl-1-butanol, and methyl isobutyl carbinol.

[0569] The components may be mixed in plural types or may be mixed with organic solvents other than those mentioned above.

[0570] The water content of the rinse solution used in the rinse step after the development step using a developer containing an organic solvent is preferably 10% by mass or less, more preferably 5% by mass or less, and further preferably 3% by mass or less. When the water content is 10% by mass or less, good development characteristics can be obtained.

[0571] The rinse solution after the development step using a developer containing an organic solvent may contain an appropriate amount of a surfactant.

[0572] In the rinsing process, the developed substrate is cleaned with a rinse liquid. The method of the cleaning process is not particularly limited, and for example, there can be cited a method of continuously spraying a rinse liquid on a substrate rotating at a certain speed (spin coating method), a method of immersing a substrate in a tank filled with a rinse liquid for a certain period of time (immersion method), or a method of spraying a rinse liquid on the surface of a substrate (spraying method). Among them, it is preferred to use a spin coating method for cleaning, and after cleaning, the substrate is rotated at a speed of 2,000 to 4,000 rpm to remove the rinse liquid from the substrate. In addition, it is also preferred to include a heating process (Post Bake) after the rinsing process. The developer and rinse liquid remaining between and inside the pattern are removed by this heating process. In the heating process after the rinsing process, the heating temperature is generally 40 to 160°C, preferably 70 to 95°C, and the heating time is generally 10 seconds to 3 minutes, preferably 30 seconds to 90 seconds.

[0573] It is preferred that the various materials used in the actinic ray-sensitive or radiation-sensitive resin composition of the present invention and the pattern forming method of the present invention (e.g., resist solvent, developer, rinse solution, antireflection film forming composition or topcoat layer forming composition, etc.) do not contain impurities such as metal components, isomers, and residual monomers. The content of these impurities contained in the above-mentioned various materials is preferably 1 mass ppm or less, more preferably 100 mass ppt or less, further preferably 10 mass ppt or less, and particularly preferably substantially free (below the detection limit of the measuring device).

[0574] As a method for removing impurities such as metals from the above-mentioned various materials, for example, filtration using a filter can be cited. As the filter pore size, the preferred pore size is less than 10nm, more preferably less than 5nm, and further preferably less than 3nm. As the material of the filter, a filter made of polytetrafluoroethylene, polyethylene or nylon is preferred. The filter can use a filter pre-cleaned with an organic solvent. In the filter filtering process, a variety of filters can be connected in series or in parallel for use. When using a variety of filters, filters with different pore sizes and / or materials can be used in combination. In addition, various materials can be filtered multiple times, and the process of filtering multiple times can be a circulating filtration process. As a filter, a filter with reduced dissolution as disclosed in Japanese Patent Application Publication No. 2016-201426 (Japanese Patent Application Publication No. 2016-201426) is preferred.

[0575] In addition to filtering, an adsorbent material can also be used to remove impurities, or a combination of filtering and adsorbent material can be used. As the adsorbent material, a known adsorbent material can be used, for example, an inorganic adsorbent material such as silica gel or zeolite or an organic adsorbent material such as activated carbon can be used. As a metal adsorbent, for example, the material disclosed in Japanese Patent Application Publication No. 2016-206500 (Japanese Patent Application Publication No. 2016-206500) can be cited.

[0576] Furthermore, as methods for reducing impurities such as metals contained in the above-mentioned various materials, there can be cited methods such as selecting raw materials with low metal content as raw materials constituting various materials, filtering the raw materials constituting various materials, or lining the inside of the device with Teflon (registered trademark) to perform distillation under conditions that suppress contamination as much as possible. In order to reduce the metal to the ppt level, it is also preferred to implement glass lining and other treatments in all processes of the manufacturing equipment of various materials (adhesives, PAG, etc.) for synthesizing resist components. The preferred conditions for filtering the raw materials constituting various materials are the same as the above conditions.

[0577] In order to prevent the mixing of impurities, the above-mentioned various materials are preferably stored in containers described in U.S. Patent Application Publication No. 2015 / 0227049, Japanese Patent Application Publication No. 2015-123351 (Japanese Patent Application No. 2015-123351), and Japanese Patent Application Publication No. 2017-013804 (Japanese Patent Application No. 2017-013804).

[0578] The method for improving the surface roughness of the pattern formed by the pattern forming method of the present invention can be applied. As a method for improving the surface roughness of the pattern, for example, the method for treating the pattern by a plasma containing a hydrogen gas disclosed in the specification of U.S. Patent Application Publication No. 2015 / 0104957 can be cited. In addition, the known methods described in the specification of Japanese Patent Application Publication No. 2004-235468 (Japanese Patent Application Publication No. 2004-235468), the specification of U.S. Patent Application Publication No. 2010 / 0020297 and Proc. of SPIE Vol. 8328 83280N-1 "EUV Resist Curing Techniquefor LWR Reduction and Etch Selectivity Enhancement" can be applied.

[0579] Furthermore, the pattern formed by the above method can be used as a core material (Core) of the spacer process disclosed in, for example, Japanese Patent Application Publication No. 1991-270227 (Japanese Patent Application Laid-Open No. 3-270227) and US Patent Application Publication No. 2013 / 0209941.

[0580] [Method for manufacturing electronic device]

[0581] The present invention also relates to a method for manufacturing an electronic device including the above-mentioned pattern forming method. The electronic device manufactured by the method for manufacturing an electronic device of the present invention is suitably mounted on electrical and electronic equipment (e.g., home appliances, OA (Office Automation) related equipment, media related equipment, optical equipment, and communication equipment, etc.).

[0582] Example

[0583] Below, the present invention is further described in detail based on embodiment.As long as the material, usage amount, ratio, processing content and processing sequence etc. shown in the following embodiment do not depart from the gist of the present invention, then can be changed appropriately.Therefore, the scope of the present invention is not interpreted by the restrictiveness of the embodiment shown below.

[0584] [Acticular ray-sensitive or radiation-sensitive resin composition]

[0585] [Element]

[0586] Components contained in the actinic ray-sensitive or radiation-sensitive resin composition (hereinafter also referred to as “composition”) used in Examples and Comparative Examples are shown below.

[0587] <Acid-degradable resin (resin A)>

[0588] The acid-decomposable resin (resin A) used for the preparation of the composition is shown below. In the following formula, * represents a bonding position.

[0589] The numbers added to the repeating units of each resin represent the molar fraction of each repeating unit.

[0590] [Chemical formula 29]

[0591]

[0592] [Chemical formula 30]

[0593]

[0594] <Photoacid generator>

[0595] (PAG-1)

[0596] PAG-1 was synthesized according to the following scheme.

[0597] [Chemical formula 31]

[0598]

[0599] A mixed solution prepared by mixing 1-acetyl adamantane (75 g), N-bromosuccinimide (90 g), methanol (450 mL) and hexane (75 mL) was stirred at 60° C. for 2 hours. After the mixed solution was cooled to room temperature, the mixed solution was filtered, the filtrate was recovered and the solvent was distilled off. The obtained residue was recrystallized from ethanol to obtain 1-adamantyl bromomethyl ketone (70 g) as a white solid (yield 65%).

[0600] The obtained 1-adamantyl bromomethyl ketone (white solid) was analyzed by NMR (nuclear magnetic resonance) method. The results are as follows.

[0601] 1 H NMR (400MHz, CDCl3) δ1.69-1.78 (m, 6H), 1.89 (s, 6H), 2.07 (s, 3H), 4.14 (s, 2H).

[0602] [Chemical formula 32]

[0603]

[0604] A mixed solution prepared by mixing 1-adamantyl bromomethyl ketone (65 g), sodium sulfite (38.2 g), acetonitrile (200 mL) and water (130 mL) was stirred at 85°C for 6 hours. The mixed solution was transferred to a separatory funnel, and the aqueous phase was washed twice with hexane to obtain an aqueous solution. Triphenylsulfonium bromide (60.8 g) and chloroform (130 mL) were added to the obtained aqueous solution and stirred for 1 hour as a reaction solution. The reaction solution was transferred to a separatory funnel, and the organic phase was washed three times with water (65 mL). The solvent was distilled off from the organic phase with an evaporator to obtain PAG-1 (92.1 g) as a white solid (yield 70%) as the target compound.

[0605] The obtained PAG-1 (white solid) was analyzed by NMR method, and the results were as follows.

[0606] 1 H NMR (400MHz, CDCl3) δ1.63-1.71 (m, 6H), 1.87-1.88 (m, 6H), 2.00 (s, 3H), 4.10 (s, 2H), 7.65-7.74 (m, 9H), 7.84-7.86 (m, 6H).

[0607] (PAG-2~PAG-6)

[0608] PAG-2~PAG-6, PAG-10~PAG-20 were synthesized with reference to the synthesis method of PAG-1.

[0609] The photoacid generator used for preparing the composition is shown below.

[0610] Among the following photoacid generators, PAG-1 to PAG-6 and PAG-10 to PAG-20 correspond to photoacid generator A. PAG-7 to PAG-8 and PAG-21 to PAG-23 correspond to photoacid generator B in relation to photoacid generator A used in this example. PAG-9 corresponds to photoacid generator D.

[0611] The pKa value indicated in each photoacid generator indicates the pKa of the acid generated by the photoacid generator.

[0612] [Chemical formula 33]

[0613]

[0614] [Chemical formula 34]

[0615]

[0616] <Nitrogen-containing compounds>

[0617] The nitrogen-containing compounds (nitrogen-containing compounds C) used for preparing the composition are shown below. The pKaH value indicated in each nitrogen-containing compound represents the pKa value of the conjugate acid of the nitrogen-containing compound.

[0618] [Chemical formula 35]

[0619]

[0620] <Hydrophobic resin>

[0621] The hydrophobic resin used for preparing the composition is shown below.

[0622] In the following formulae, * represents a bonding position.

[0623] The numbers added to the repeating units of each hydrophobic resin represent the molar fraction of each repeating unit.

[0624] [Chemical formula 36]

[0625]

[0626] <Surfactant>

[0627] The solvents used for preparing the composition are shown below.

[0628] W-1: MEGAFACE F176 (manufactured by DIC Corporation; fluorine-based surfactant)

[0629] W-2: PolyFox PF-6320 (manufactured by OMNOVA Solutions Inc.; fluorine-based surfactant)

[0630] <Solvent>

[0631] The solvents used for preparing the composition are shown below.

[0632] SL-1: Propylene glycol monomethyl ether acetate (PGMEA)

[0633] SL-2: Propylene glycol monomethyl ether (PGME)

[0634] SL-3: Cyclohexanone

[0635] SL-4: γ-Butyrolactone

[0636] [Preparation of composition]

[0637] Each component shown in the table of the latter section is dissolved in a solvent to a composition described in the table of the latter section, and a solution having a solid content concentration of 3.8% by mass is prepared. Then, the obtained solution is filtered using a polyethylene filter having a pore size of 0.1 μm to prepare an actinic ray-sensitive or radiation-sensitive resin composition (composition). In addition, in the resist composition, the solid content refers to all components except the solvent. The obtained resist composition was used in the examples and comparative examples.

[0638] 〔evaluate〕

[0639] <Formation of Pattern>

[0640] An organic antireflection film-forming composition ARC29SR (manufactured by NISSAN CHEMICAL CORPORATION) was applied to a silicon wafer and baked at 205°C for 60 seconds to form an antireflection film having a thickness of 95 nm. A resist composition was applied to the obtained antireflection film and baked at 100°C for 60 seconds (PB: Prebake) to form a resist film having a thickness of 85 nm.

[0641] The obtained wafer was exposed using an ArF excimer laser immersion scanner (manufactured by ASML; XT1700i, NA1.20, C-Quad, outer sigma 0.900, inner sigma 0.812, XY deflection) through a 6% halftone mask of a 1:1 line and space pattern with a line width of 44nm. Ultrapure water was used as the immersion liquid. Then, it was heated at 105°C (PEB: Post Exposure Bake) for 60 seconds.

[0642] Then, in Examples 1 to 24 and Comparative Examples 1 to 3, development was performed with a negative-type developer (butyl acetate) with stirring for 30 seconds, and further rinsed with pure water to form a 1:1 line and space pattern (negative pattern) with a line width of 44 nm.

[0643] In Examples 25 to 30 and Comparative Examples 4 and 5, development was performed with a positive developer (2.38 mass % ammonium hydroxide aqueous solution) and further rinsed with pure water to form a 1:1 line and space pattern (positive pattern) with a line width of 44 nm.

[0644] <LWR performance>

[0645] The obtained 1:1 line and space pattern with a line width of 44 nm was observed. When observing the pattern, observation was performed from the top of the pattern using a length-measuring scanning electron microscope (SEM (Hitachi, Ltd. S-9380II)).

[0646] The line widths of 50 points in the 2 μm range in the length direction of the line pattern were also measured at equal intervals, and 3σ (nm) was calculated from the standard deviation. The smaller the value, the better the LWR performance of the pattern.

[0647] 〔result〕

[0648] The formulations of the compositions and the results of the evaluations conducted using these compositions are shown in the following table.

[0649] In the column of "solid content", the numbers below the names of the components indicate the added amounts (g) of the components. In each composition, 10 g of the resin, 0.05 g of the hydrophobic resin, and 0.03 g of the surfactant were added.

[0650] Furthermore, 5 g of each of the resins P-3 and P-6 was added to the composition of Example 13, making a total of 10 g. 5 g of each of the resins P-7 and P-9 was added to the composition of Example 30, making a total of 10 g.

[0651] In the table, when the acid generated by the photoacid generator corresponding to the photoacid generator A in each composition corresponds to the general formula (I), "cyclic R 3 " indicates the equivalent of R 3 Whether the group is an organic group containing a ring structure. When the above-mentioned necessary conditions are met, it is recorded as A, and when the necessary conditions are not met, it is recorded as B.

[0652] The description of the numerical value in parentheses in the column of "Solvent" represents the mixing ratio (mass ratio) of each solvent contained in each composition.

[0653] The column of “A / D molar ratio” shows the ratio of the molar number of the photoacid generator A to the molar number of the photoacid generator D in the composition when the composition contains the photoacid generator D.

[0654] [Table 1]

[0655]

[0656] [Table 2]

[0657]

[0658] From the results shown in the table, it was confirmed that the composition of the present invention can obtain a pattern excellent in LWR performance.

[0659] Furthermore, the acid generated by the photoacid generator A is equivalent to R 3 When the group is an organic group containing a ring structure, the LWR of the obtained pattern is more excellent (comparison between Example 1 and Example 2, etc.).

[0660] It was confirmed that when the composition contained the photoacid generator D, when the ratio of the molar number of the photoacid generator A to the molar number of the photoacid generator D in the composition (the content of the photoacid generator A / the content of the photoacid generator D (molar ratio)) was 1.5 times or more (more preferably 5 times or more), the LWR of the obtained pattern was more excellent (comparison with Example 11, Example 12, Example 23, etc.).

Claims

1. An actinic ray-sensitive or radiation-sensitive resin composition comprising: A photoacid generator A that generates an acid represented by the general formula (I) and having a pKa of 0.09 or more; One or more selected from the group consisting of a photoacid generator B that generates an acid with a pKa greater than that of the acid generated by the photoacid generator A by 1.00 or more, and a nitrogen-containing compound C having a conjugate acid with a pKa greater than that of the acid generated by the photoacid generator A by 1.00 or more; and Acid decomposable resins, The actinic ray-sensitive or radiation-sensitive resin composition optionally comprises a photoacid generator D which is a compound different from the nitrogen-containing compound C and generates an acid having a pKa of less than -1.00, When the actinic ray-sensitive or radiation-sensitive resin composition contains the photoacid generator D, the ratio of the molar number of the photoacid generator A to the molar number of the photoacid generator D in the actinic ray-sensitive or radiation-sensitive resin composition is 5.0 or more. In the general formula (I), R 1 and R 2 Each independently represents a substituent of a non-electron-withdrawing group or a hydrogen atom, L is represented by the following general formula (II), * a -(CR 2a 2) X -Q-(CR 2b 2) Y -* b (II) In the general formula (II), * a It represents the same as R in the general formula (I) 3 The bonding position of * b represents the same as -C(R 1 )(R 2 )-bonding position, X and Y each independently represent an integer of 0 to 10, R 2a represents a hydrogen atom or a substituent, R 2b represents a hydrogen atom, There are multiple R 2a In the case of multiple R 2a Same or different, Q means selected from* 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 The groups in * A represents R in the general formula (I) 3 Bonding position on the side, * B represents the bonding position to the -SO3H side in the general formula (I), in, X+Y in the general formula (II) is 1 or more, and R in the general formula (II) is 2a and R 2b When all of are hydrogen atoms, Q represents a member selected from * A -O-CO-O-* B ,* A -CO-* B ,* A -O-CO-* B ,* A -O-* B ,* A -S-* B and* A -SO2-* B The groups in R 3 Represents an organic group.

2. The actinic ray-sensitive or radiation-sensitive resin composition according to claim 1, wherein R 3 It represents an organic group having a ring structure.

3. The actinic ray-sensitive or radiation-sensitive resin composition according to claim 1 or 2, wherein The acid-decomposable resin is a methacrylate resin.

4. The actinic ray-sensitive or radiation-sensitive resin composition according to claim 1 or 2, wherein Q is for free choice* A -O-CO-O-* B ,* A -CO-* B ,* A -O-CO-* B ,* A -O-* B ,* A -S-* B and* A -SO2-* B The groups in the group. 5 . A resist film formed using the actinic ray-sensitive or radiation-sensitive resin composition according to claim 1 .

6. A pattern forming method comprising the following steps: A step of forming a resist film on a support using the actinic ray-sensitive or radiation-sensitive resin composition according to any one of claims 1 to 4; a step of exposing the resist film to light; and A step of developing the exposed resist film using a developer.

7. A method for manufacturing an electronic device, comprising the pattern forming method according to claim 6.

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