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 even under long-term storage. 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 compound represented by the general formula (I) and an acid-decomposable resin. M1 + A ‑ ‑L‑B ‑ M2 + (I)

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 manufacturing an electronic device. Background Art

[0002] In order to compensate for the decrease in sensitivity caused by light absorption after the KrF excimer laser (248nm) resist is used, a pattern forming method using chemical amplification is used. 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. Then, in the post-exposure baking (PEB: Post Exposure Bake) process, the alkali-insoluble groups of the resin contained in the photosensitive or radiation-sensitive resin composition are converted into alkali-soluble groups by the catalytic action of the generated acid, thereby changing the solubility in the developer. After that, development is performed using, for example, an alkaline aqueous solution. Thus, the exposure part is removed to obtain the desired pattern.

[0003] Under such circumstances, various structures have been proposed as actinic ray-sensitive or radiation-sensitive resin compositions in order to miniaturize semiconductor elements.

[0004] For example, Patent Document 1 discloses an acid generator containing a salt represented by the following formula (I) as a component used in a composition.

[0005] [Chemical formula 1]

[0006]

[0007] Previous technical literature

[0008] Patent Literature

[0009] Patent Document 1: Japanese Patent Application Laid-Open No. 2015-024989 Summary of the invention

[0010] Technical issues to be solved by the invention

[0011] The present inventors have specifically studied the technology disclosed in Patent Document 1 and found that there is room for improvement in the LWR (line width roughness) performance of the pattern obtained when the composition of Patent Document 1 is stored for a long period of time (e.g., 3 months) after the composition is manufactured and applied to pattern formation.

[0012] 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 even when stored for a long period of time.

[0013] Furthermore, the present invention aims to provide a resist film, a pattern forming method, and a method for producing an electronic device related to the above-mentioned actinic ray-sensitive or radiation-sensitive resin composition.

[0014] Means for solving technical problems

[0015] The present inventors have conducted intensive studies to solve the above problems, and as a result, have found that the above problems can be solved by the following structure.

[0016] [1]

[0017] An actinic ray-sensitive or radiation-sensitive resin composition comprises a compound represented by the following general formula (I) and an acid-decomposable resin.

[0018] [2]

[0019] The actinic ray-sensitive or radiation-sensitive resin composition according to [1], wherein among the compounds represented by the general formula (I) described below, B - It represents a group represented by any one of the above-mentioned general formulae (B-1) to (B-3) described later.

[0020] 〔3〕

[0021] The actinic ray-sensitive or radiation-sensitive resin composition according to [1] or [2], wherein among the compounds represented by the general formula (I) described below, B - It represents a group represented by any one of the above-mentioned general formulae (B-1) to (B-2) described later.

[0022] [4]

[0023] The actinic ray-sensitive or radiation-sensitive resin composition according to any one of [1] to [3], wherein among the compounds represented by the general formula (I) described below, A - It represents a group represented by any of the general formulae (A-1) to (A-2) described below.

[0024] 〔5〕

[0025] A resist film formed using the actinic ray-sensitive or radiation-sensitive resin composition described in any one of [1] to [4].

[0026] [6]

[0027] A pattern forming method comprises the following steps:

[0028] A process for 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];

[0029] a step of exposing the resist film to light; and

[0030] A step of developing the exposed resist film using a developer.

[0031] 〔7〕

[0032] A method for manufacturing an electronic device, comprising the pattern forming method described in [6].

[0033] Effects of the Invention

[0034] According to the present invention, it is possible to provide an actinic ray-sensitive or radiation-sensitive resin composition capable of obtaining a pattern excellent in LWR performance even when stored for a long period of time.

[0035] Furthermore, the present invention can provide a resist film, a pattern forming method, and a method for producing an electronic device related to the above-mentioned actinic ray-sensitive or radiation-sensitive resin composition. DETAILED DESCRIPTION

[0036] Hereinafter, the present invention will be described in detail.

[0037] The constituent elements described below will be described based on typical embodiments of the present invention, but the present invention is not limited to these embodiments.

[0038] In the marking of the group (atomic group) in this specification, unless it is contrary to the purpose of the present invention, the marking that does not record substitution and unsubstituted includes not only the group without substitution, but also the group with substitution. For example, "alkyl" includes not only the alkyl without substitution (unsubstituted alkyl) but also the alkyl with substitution (substituted alkyl). In addition, the "organic group" in this specification refers to a group containing at least one carbon atom.

[0039] Unless otherwise specified, the substituent is preferably a monovalent substituent.

[0040] The "actinic rays" or "radiation rays" in this specification refer 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. The "light" in this specification refers to actinic rays or radiation rays.

[0041] Unless otherwise specified, "exposure" in this specification includes not only exposure using the bright line spectrum of a mercury lamp, far ultraviolet light represented by excimer laser, extreme ultraviolet light, X-rays and EUV light, but also drawing using particle beams such as electron beams and ion beams.

[0042] 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.

[0043] Unless otherwise specified, the bonding direction of the divalent groups marked in this specification is not limited. For example, when Y in the compound represented by the general formula "XYZ" is -COO-, Y can be -CO-O- or -O-CO-. Furthermore, the above compound can be "X-CO-OZ" or "XO-CO-Z".

[0044] In the present specification, (meth)acrylate means acrylate and methacrylate, and (meth)acrylic acid means acrylic acid and methacrylic acid.

[0045] In this specification, the weight average molecular weight (Mw), number average molecular weight (Mn) and dispersion degree (also referred to as molecular weight distribution) (Mw / Mn) of a resin are defined as polystyrene conversion values ​​obtained by GPC measurement using a GPC (Gel Permeation Chromatography) apparatus (HLC-8120GPC manufactured by TOSOH CORPORATION) (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).

[0046] In this specification, the acid dissociation constant (pKa) means the pKa in aqueous solution, specifically, the value obtained by calculation based on the database of Hammett's substituent constant and known literature values ​​using the following software package 1. The pKa values ​​described in this specification all represent the values ​​obtained by calculation using this software package.

[0047] Software package 1: Advanced Chemistry Development (ACD / Labs) Software V8.14 for Solaris (1994-2007ACD / Labs).

[0048] On the other hand, pKa can also be calculated by molecular orbital algorithm. As a specific method, it can be mentioned that the H in the solvent is calculated based on the thermodynamic cycle. + (In this specification, water is usually used as the solvent, and DMSO (dimethyl sulfoxide) is used when pKa cannot be calculated using water.)

[0049] About H + The calculation method of dissociation free energy can be calculated by DFT (density functional method), for example, but various other methods have been reported in literature, etc., and the method is not limited to this. In addition, there are many software that can realize DFT, for example, Gaussian16 can be cited.

[0050] As described above, the pKa in this specification refers to a value obtained by calculating a value based on Hammett's substituent constant and a database of known literature values ​​using Software Package 1, but when pKa cannot be calculated by this method, a value obtained by Gaussian16 based on DFT (density functional theory) is used.

[0051] In the present specification, examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

[0052] [Acticular ray-sensitive or radiation-sensitive resin composition]

[0053] 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.

[0054] 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 alkaline development or a resist composition for organic solvent development.

[0055] The composition of the present invention is typically a chemically amplified resist composition.

[0056] The composition of the present invention contains a compound represented by the general formula (I) described later (hereinafter, also referred to as a specific compound) and an acid-decomposable resin.

[0057] Although the mechanism by which the problem of the present invention is solved by such a structure is not always clear, the present inventors presume as follows.

[0058] That is, in the conventional compositions, if the photoacid generator and the acid diffusion controller are added to the composition only as separate compounds, the photoacid generators or the acid diffusion controllers are easily condensed. Therefore, in the conventional compositions, there are portions with high (or low) concentrations of the photoacid generator and portions with high (or low) concentrations of the acid diffusion controller in the formed resist film, and the concentration ratio of the photoacid generator to the acid diffusion controller is easily uneven. As a result, when the resist film is exposed, the amount and diffusion of the acid generated in the resist film are also uneven, which is the cause of the uneven width of the pattern obtained after development.

[0059] On the other hand, the specific compound contains a structure having a function equivalent to that of a photoacid generator in one molecule (equivalent to "M1 + A - -" portion), and a structure having a function equivalent to that of a photodisintegrating acid diffusion controller (equivalent to "-B - M2 + ” part) both, so in the resist film, the existence ratio of each of the above structures can be made constant.

[0060] Therefore, the present inventors presumed that even when the resist film is exposed, the amount and diffusion of the acid generated in the resist film are likely to become uniform, and the width of the pattern obtained after development is also stable.

[0061] Furthermore, in the specific compound, B - The nitrogen anion in the group represented by is located inside the organic group, and the specific compound or the acid-decomposable resin is not easily deteriorated due to the interaction between the nitrogen anion and the acid-decomposable resin. Therefore, the present inventors speculate that the composition of the present invention is easily stable even when stored for a long time, and a pattern with excellent LWR performance can be obtained even when stored for a long time.

[0062] Hereinafter, the components of the composition of the present invention will be described.

[0063] 〔Specific compounds〕

[0064] The composition of the present invention comprises a specific compound.

[0065] The specific compound is a compound represented by the general formula (I).

[0066] M1 + A - -LB - M2 + (I)

[0067] In the general formula (I), M1 + and M2 + Each independently represents an organic cation.

[0068] The above-mentioned organic cations will be described later.

[0069] In the general formula (I), L represents a divalent organic group.

[0070] Examples of the above-mentioned divalent organic group include -COO-, -CONH-, -CO-, -O-, alkylene groups (preferably having 1 to 6 carbon atoms. They may be linear or branched), cycloalkylene groups (preferably having 3 to 15 carbon atoms), alkenylene groups (preferably having 2 to 6 carbon atoms), and divalent linking groups formed by combining a plurality of these groups.

[0071] One or more of the methylene groups constituting the cycloalkane ring of the cycloalkylene group may be substituted with a carbonyl carbon and / or a hetero atom (oxygen atom or the like).

[0072] These divalent linking groups further preferably have a group selected from the group consisting of -S-, -SO- and -SO2-.

[0073] Among them, L is preferably a group represented by the following general formula (L).

[0074] * A -LA-LB-LC-LD-LE-* B (L)

[0075] In the general formula (L), * A It represents the same as A in the general formula (I) - bonding position.

[0076] In the general formula (L), * B Indicates that B in the general formula (I) - bonding position.

[0077] In the general formula (L), LA represents -(C(R LA1 )(R LA2 )) XA -.

[0078] The above-mentioned XA represents an integer of 1 or more, preferably 1-10, and more preferably 1-3.

[0079] R LA1 and R LA2 Each independently represents a hydrogen atom or a substituent.

[0080] As R LA1 and R LA2 The substituents are each independently preferably a fluorine atom or a fluoroalkyl group, more preferably a fluorine atom or a perfluoroalkyl group, further preferably a fluorine atom or a perfluoromethyl group.

[0081] When XA is greater than 2, there are XA R LA1 They may be the same or different.

[0082] When XA is greater than 2, there are XA R LA2 They may be the same or different.

[0083] -(C(R LA1 )(R LA2 ))- is preferably -CH2-, -CHF-, -CH(CF3)- or -CF2-.

[0084] Among them, A in the general formula (I) -Directly bonded -(C(R LA1 )(R LA2 ))- is preferably -CH2-, -CHF-, -CH(CF3)- or -CF2-.

[0085] In addition to A in the general formula (I) - Directly bonded -(C(R LA1 )(R LA2 ))-Other-(C(R LA1 )(R LA2 ))- are each independently preferably -CH2-, -CHF- or -CF2-.

[0086] In the general formula (L), LB represents a single bond, an ester group (—COO—) or a sulfonyl group (—SO 2 —).

[0087] In the general formula (L), LC represents a single bond, an alkylene group, a cycloalkylene group, or a group formed by combining these groups ("-alkylene-cycloalkylene-" etc.).

[0088] The above-mentioned alkylene group may be linear or branched.

[0089] The alkylene group has preferably 1 to 5 carbon atoms, more preferably 1 to 2 carbon atoms, and even more preferably 1 carbon atom.

[0090] The cycloalkylene group has preferably 3 to 15 carbon atoms, more preferably 5 to 10 carbon atoms.

[0091] The cycloalkylene group may be a monocyclic or polycyclic ring.

[0092] Examples of the cycloalkylene group include a norbornanediyl group and an adamantanediyl group.

[0093] As a substituent which the cycloalkylene group may have, an alkyl group (which may be linear or branched and preferably has 1 to 5 carbon atoms) is preferred.

[0094] One or more of the methylene groups constituting the cycloalkane ring of the cycloalkylene group may be substituted with a carbonyl carbon and / or a hetero atom (oxygen atom or the like).

[0095] When LC is "-alkylene-cycloalkylene-", the alkylene moiety is preferably present on the LB side.

[0096] When LB is a single bond, LC is preferably a single bond or a cycloalkylene group.

[0097] In the general formula (L), LD represents a single bond, an ether group (—O—), a carbonyl group (—CO—), or an ester group (—COO—).

[0098] In the general formula (L), LE represents a single bond or -(C(R LE1)(R LE2 )) XE -.

[0099] The above-(C(R LE1 )(R LE2 )) XE XE in - represents an integer of 1 or more, preferably 1-10, more preferably 1-3.

[0100] R LE1 and R LE2 Each independently represents a hydrogen atom or a substituent.

[0101] When XE is greater than 2, there are XE R LE1 They may be the same or different.

[0102] When XE is greater than 2, there are XE R LE2 They may be the same or different.

[0103] Among them, -(C(R LE1 )(R LE2 ))- is preferably -CH2-.

[0104] In the general formula (L), when LB, LC and LD are single bonds, LE is also preferably a single bond.

[0105] In the general formula (I), A - Represents an acidic anionic group.

[0106] The acidic anionic group is a group having an anionic atom.

[0107] Specifically, A - Preferred is a group represented by any of the general formulae (A-1) to (A-2).

[0108] [Chemical formula 2]

[0109]

[0110] In the general formulae (A-1) to (A-2), * represents a bonding position.

[0111] In the general formula (A-2), R A Represents an organic group.

[0112] R A An alkyl group is preferred.

[0113] The above-mentioned alkyl group may be linear or branched.

[0114] The alkyl group preferably has 1 to 10 carbon atoms, and more preferably 1 to 5 carbon atoms.

[0115] As the substituent which the above-mentioned alkyl group may have, a fluorine atom is preferable.

[0116] The above-mentioned alkyl group having a fluorine atom as a substituent may or may not be a perfluoroalkyl group.

[0117] In the general formula (I), B - It represents a group represented by any one of the general formulae (B-1) to (B-4).

[0118] B - The group is preferably a group represented by any one of the general formulae (B-1) to (B-3), and more preferably a group represented by any one of the general formulae (B-1) to (B-2).

[0119] [Chemical formula 3]

[0120]

[0121] In general formulae (B-1) to (B-4), * represents a bonding position.

[0122] In the general formulas (B-1) to (B-4), R B Represents an organic group.

[0123] R B Preferred is a cycloalkyl group, an aromatic ring group or an alkyl group.

[0124] When R B In the case of a cycloalkyl group, the cycloalkyl group preferably has 3 to 15 carbon atoms, and more preferably has 5 to 10 carbon atoms.

[0125] The cycloalkyl group may be a monocyclic or polycyclic ring.

[0126] Examples of the cycloalkyl group include a norbornyl group and an adamantyl group.

[0127] As a substituent which the above-mentioned cycloalkyl group may have, an alkyl group (which may be linear or branched, and preferably has 1 to 5 carbon atoms) is preferred.

[0128] One or more carbon atoms serving as ring members of the cycloalkyl group may be substituted with a carbonyl carbon atom.

[0129] When R B When it is an aromatic ring group, the aromatic ring group may or may not have a hetero atom. The aromatic ring group may be a monocyclic ring or a polycyclic ring. The number of ring members of the aromatic ring group is preferably 5 to 12, more preferably 5 to 6.

[0130] As a substituent which the above-mentioned aromatic ring group may have, an alkyl group which may have a fluorine atom (may be linear or branched, and preferably has 1 to 5 carbon atoms) is preferable.

[0131] When R B In the case of an alkyl group, the alkyl group may be linear or branched.

[0132] The alkyl group preferably has 1 to 10 carbon atoms, and more preferably 1 to 5 carbon atoms.

[0133] As the substituent which the above-mentioned alkyl group may have, a cycloalkyl group, a fluorine atom or a cyano group is preferable.

[0134] As an example of the cycloalkyl group of the above substituent, there can be mentioned: B In the case of a cycloalkyl group, the cycloalkyl group described above.

[0135] When the alkyl group has a fluorine atom as the substituent, the alkyl group may or may not be a perfluoroalkyl group. When the alkyl group has a fluorine atom as the substituent, a part or all of the alkyl group is preferably a perfluoromethyl group.

[0136] In the compound represented by the general formula (I), M1 + and M2 + In the compound represented by HA-L-BH respectively substituted with hydrogen atoms, the pKa of the group represented by HA is lower than the pKa of the group represented by BH.

[0137] More specifically, when the acid dissociation constant of a compound represented by HA-L-BH is determined, "HA-L-BH" is replaced by "A - -L-BH" is set as "the pKa of the group represented by HA", and further "A - -L-BH" becomes "A - -LB - " is set to "pKa of the group represented by BH".

[0138] The "pKa of the group represented by HA" and the "pKa of the group represented by BH" were determined using "Package 1" or "Gaussian 16", respectively.

[0139] Among them, the pKa of the group represented by HA is preferably -12.00 to 1.00, more preferably -7.00 to 0.50, and further preferably -5.00 to 0.00.

[0140] The pKa of the group represented by HB is preferably -4.00 to 14.00, more preferably -2.00 to 12.00, further preferably -1.00 to 5.00.

[0141] The difference between the pKa of the group represented by HB and the pKa of the group represented by HA ("pKa of the group represented by HB" - "pKa of the group represented by HA") is preferably 0.10 to 20.00, more preferably 0.50 to 17.00, further preferably 2.00 to 15.00.

[0142] In the general formula (I), M1 + and M2 + Preferred forms of the organic cations represented will be described in detail.

[0143] By M1 + and M2 + The organic cations represented are each independently preferably a cation represented by the general formula (ZaI) (cation (ZaI)) or a cation represented by the general formula (ZaII) (cation (ZaII)).

[0144] [Chemical formula 4]

[0145]

[0146] R 204 -I + -R 205 (ZaII)

[0147] In the above general formula (ZaI),

[0148] R 201 , R 202 and R 203 Each independently represents an organic group.

[0149] 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 may contain an oxygen atom, a sulfur atom, an ester group, an amide group, or a carbonyl group in the ring. 201 ~R 203 Examples of the group formed by bonding two of the groups include alkylene (e.g., butylene, pentylene, etc.) and -CH2-CH2-O-CH2-CH2-.

[0150] Preferred embodiments of the cation in the general formula (ZaI) include the cation (ZaI-1) and cation (ZaI-2) described later, the cation represented by the general formula (ZaI-3b) (cation (ZaI-3b)), and the cation represented by the general formula (ZaI-4b) (cation (ZaI-4b)).

[0151] First, the cation (ZaI-1) will be described.

[0152] The cation (ZaI-1) is R 201 ~R 203 At least one of the arylsulfonium cations is an aryl group.

[0153] In the arylsulfonium compound, R 201 ~R 203 All are aromatic, and R 201 ~R 203 Part of them is aryl, and the rest is alkyl or cycloalkyl.

[0154] 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-).

[0155] Examples of the arylsulfonium cation include a triarylsulfonium cation, a diarylalkylsulfonium cation, an aryldialkylsulfonium cation, a diarylcycloalkylsulfonium cation, and an aryldicycloalkylsulfonium cation.

[0156] 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 residues, furan residues, thiophene residues, indole residues, benzofuran residues and benzothiophene residues can be cited. When the arylsulfonium cation has two or more aryl groups, the two or more aryl groups may be the same or different.

[0157] The alkyl group or cycloalkyl group that the arylsulfonium cation 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.

[0158] As R 201 ~R 203The substituents that the aryl, alkyl and cycloalkyl groups may have include, independently, alkyl groups (e.g., having 1 to 15 carbon atoms), cycloalkyl groups (e.g., having 3 to 15 carbon atoms), aryl groups (e.g., having 6 to 14 carbon atoms), alkoxy groups (e.g., having 1 to 15 carbon atoms), cycloalkylalkoxy groups (e.g., having 1 to 15 carbon atoms), halogen atoms, hydroxyl groups and phenylthio groups.

[0159] The above-mentioned substituent may further have a substituent if possible. For example, the above-mentioned alkyl group may have a halogen atom as a substituent to become a halogenated alkyl group such as a trifluoromethyl group.

[0160] The substituent is preferably a group having an acid-decomposable group. The acid-decomposable group is the same as the acid-decomposable group described in the <Repeating unit having an acid-decomposable group> described later.

[0161] Next, the cation (ZaI-2) will be described.

[0162] The cation (ZaI-2) is R in the formula (ZaI) 201 ~R 203 Each independently represents a cation of an organic group having no aromatic ring. Here, the aromatic ring also includes an aromatic ring containing a heteroatom.

[0163] As R 201 ~R 203 The organic group having no aromatic ring usually has 1 to 30 carbon atoms, preferably 1 to 20 carbon atoms.

[0164] R 201 ~R 203 Each independently is preferably 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 further preferably a linear or branched 2-oxoalkyl group.

[0165] As R 201 ~R 203 The alkyl group and the cycloalkyl group are preferably a straight-chain alkyl group having 1 to 10 carbon atoms, a branched-chain alkyl group having 3 to 10 carbon atoms (e.g., methyl, ethyl, propyl, butyl and pentyl), or a cycloalkyl group having 3 to 10 carbon atoms (e.g., cyclopentyl, cyclohexyl and norbornyl).

[0166] 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.

[0167] Next, the cation (ZaI-3b) will be described.

[0168] The cation (ZaI-3b) is a cation represented by the following general formula (ZaI-3b).

[0169] [Chemical formula 5]

[0170]

[0171] In the general formula (ZaI-3b),

[0172] R 1c ~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.

[0173] 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.

[0174] 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.

[0175] 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.

[0176] 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- to 10-membered rings, preferably 4- to 8-membered rings, and more preferably 5- or 6-membered rings.

[0177] 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.

[0178] As R5c 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.

[0179] Next, the cation (ZaI-4b) will be described.

[0180] The cation (ZaI-4b) is a cation represented by the following general formula (ZaI-4b).

[0181] [Chemical formula 6]

[0182]

[0183] In the general formula (ZaI-4b),

[0184] l represents an integer from 0 to 2.

[0185] r represents an integer from 0 to 8.

[0186] R 13 The group represents a hydrogen atom, a fluorine atom, a hydroxyl group, an alkyl group, an alkoxy group, an alkoxycarbonyl group, an alkoxyalkoxy 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.

[0187] 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 also have a substituent. 14 , each independently represents the above-mentioned groups such as hydroxyl group.

[0188] R 15 Each independently represents an alkyl group, a cycloalkyl group or a naphthyl group. These groups may also have a substituent. 15 Can bond to each other to form a ring. 15 When they are bonded to each other to form a ring (preferably a 5- to 8-membered ring, more preferably a 5- or 6-membered ring), in addition to S + In addition, it may contain heteroatoms such as oxygen atoms and nitrogen atoms. 15 The alkylene groups are preferably bonded to each other to form a ring structure.

[0189] 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.

[0190] Next, the general formula (ZaII) will be described.

[0191] In the general formula (ZaII), R 204 and R 205 Each independently represents an aryl group, an alkyl group or a cycloalkyl group.

[0192] 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.

[0193] As R 204 and R 205 The alkyl group and cycloalkyl group are preferably a straight-chain alkyl group having 1 to 10 carbon atoms, a branched-chain 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).

[0194] 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 substituents that the aryl group, alkyl group and cycloalkyl group may have include, for example, 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 15 carbon atoms), an alkoxy group (e.g., having 1 to 15 carbon atoms), a halogen atom, a hydroxyl group and a phenylthio group.

[0195] The molecular weight of the compound (DD) is preferably 300 to 3,000, more preferably 500 to 2,000, and even more preferably 700 to 1,500.

[0196] The content of the specific photoacid generator is preferably 0.1 to 35% by mass, more preferably 1 to 30% by mass, and even more preferably 5 to 25% by mass, based on the total solid content of the composition.

[0197] The solid content refers to the components that form the resist film, excluding the solvent. Furthermore, as long as it is a component that forms the resist film, it is considered to be a solid content even if it is in a liquid state.

[0198] The specific compound may be used alone or in combination of two or more. When two or more are used, the total content thereof is preferably within the above-mentioned preferred content range.

[0199] Preferred examples of specific compounds are shown below. In the following examples, anions (equivalent to A - -LB - part) and cation (equivalent to M1 + or M2 + The combination of parts) can be exchanged appropriately.

[0200] The numerical value additionally described in each specific compound is the M1 of each specific compound. + and M2 + When the compounds are substituted with hydrogen atoms to form the compounds HA-L-BH, the pKa of the group represented by HA (the numerical value shown on the left) and the pKa of the group represented by BH (the numerical value shown on the right) are shown.

[0201] [Chemical formula 7]

[0202]

[0203] [Chemical formula 8]

[0204]

[0205] [Chemical formula 9]

[0206]

[0207] [Chemical formula 10]

[0208]

[0209] [Chemical formula 11]

[0210]

[0211] [Acid-decomposable resin (resin (A))]

[0212] The composition of the present invention contains a resin that decomposes and increases in polarity by the action of an acid (hereinafter, also referred to as an "acid-decomposable resin" or "resin (A)").

[0213] That is, in the pattern forming method of the present invention, typically, when an alkaline developer is used as a developer, a positive pattern is preferably formed, and when an organic developer is used as a developer, a negative pattern is preferably formed.

[0214] The resin (A) generally contains a group that is decomposed by the action of an acid to increase polarity (hereinafter also referred to as an "acid-decomposable group"), and preferably contains a repeating unit having an acid-decomposable group.

[0215] <Repeating unit having an acid-decomposable group>

[0216] The acid-decomposable group refers to a group that is decomposed by the action of an acid to generate a polar group. The acid-decomposable group preferably has a structure in which the polar group is protected by a dissociating group that is dissociated by the action of an acid. That is, the resin (A) contains a repeating unit having a group that is decomposed by the action of an acid to generate a polar group. The polarity of the resin having this repeating unit increases by the action of an acid, thereby increasing the solubility in an alkaline developer and reducing the solubility in an organic solvent.

[0217] The polar group is preferably an alkali-soluble group, for example, a carboxyl group, a phenolic hydroxyl group, a fluorinated alcohol group, a sulfonic acid group, a phosphoric 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 tris(alkylcarbonyl) methylene group, a tris(alkylsulfonyl) methylene group and other acidic groups and an alcoholic hydroxyl group can be mentioned.

[0218] Among them, the polar group is preferably a carboxyl group, a phenolic hydroxyl group, a fluorinated alcohol group (preferably a hexafluoroisopropanol group), or a sulfonic acid group.

[0219] Examples of the leaving group that leaves by the action of an acid include groups represented by formulae (Y1) to (Y4).

[0220] Formula (Y1): -C(Rx1)(Rx2)(Rx3)

[0221] Formula (Y2): -C(=O)OC(Rx1)(Rx2)(Rx3)

[0222] Formula (Y3): -C(R 36 )(R 37 )(OR 38 )

[0223] Formula (Y4): -C(Rn)(H)(Ar)

[0224] In formula (Y1) and formula (Y2), Rx1 to Rx3 each independently represent an alkyl group (straight chain or branched chain), a cycloalkyl group (monocyclic or polycyclic), an alkenyl group (straight chain or branched chain), or an aryl group (monocyclic or polycyclic). In addition, when all of Rx1 to Rx3 are alkyl groups (straight chain or branched chain), it is preferred that at least two of Rx1 to Rx3 are methyl groups.

[0225] Among them, it is preferred that Rx1 to Rx3 each independently represent a linear or branched alkyl group, and it is more preferred that Rx1 to Rx3 each independently represent a linear alkyl group.

[0226] Two of Rx1 to Rx3 may be bonded to form a monocyclic or polycyclic ring.

[0227] The alkyl group for Rx1 to Rx3 is preferably an alkyl group having 1 to 5 carbon atoms, such as methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group and tert-butyl group.

[0228] The cycloalkyl group for Rx1 to Rx3 is preferably a monocyclic cycloalkyl group such as a cyclopentyl group and a cyclohexyl group, or a polycyclic cycloalkyl group such as a norbornyl group, a tetracyclodecyl group, a tetracyclododecyl group, and an adamantyl group.

[0229] As the aryl group for Rx1 to Rx3, an aryl group having 6 to 10 carbon atoms is preferred, and examples thereof include phenyl, naphthyl, and anthracenyl.

[0230] As the alkenyl group of Rx1 to Rx3, a vinyl group is preferable.

[0231] The ring formed by two of Rx1 to Rx3 being bonded together is preferably a cycloalkyl group. The cycloalkyl group formed by two of Rx1 to Rx3 being bonded together is preferably a monocyclic cycloalkyl group such as a cyclopentyl group or a cyclohexyl group, or a polycyclic cycloalkyl group such as a norbornyl group, a tetracyclodecyl group, a tetracyclododecyl group or an adamantyl group, and more preferably a monocyclic cycloalkyl group having 5 to 6 carbon atoms.

[0232] In the cycloalkyl group formed by bonding two of Rx1 to Rx3, for example, one of the methylene groups constituting the ring may be substituted by a group having a hetero atom such as an oxygen atom, a hetero atom such as a carbonyl group, or a vinylene group. Furthermore, in these cycloalkyl groups, one or more of the ethylene groups constituting the cycloalkyl ring may be substituted by a vinylene group.

[0233] The group represented by the formula (Y1) or (Y2) is preferably a mode in which, for example, Rx1 is a methyl group or an ethyl group, and Rx2 and Rx3 are bonded to form the above-mentioned cycloalkyl group.

[0234] In formula (Y3), R 36 ~R 38 R each independently represents a hydrogen atom or a monovalent organic group. 37 With R 38 They may be bonded to each other to form a ring. Examples of the monovalent organic group include an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, and an alkenyl group. 36 A hydrogen atom is also preferred.

[0235] Furthermore, the above-mentioned alkyl, cycloalkyl, aryl and aralkyl groups may also contain groups having heteroatoms such as oxygen atoms and / or heteroatoms such as carbonyl groups. For example, in the above-mentioned alkyl, cycloalkyl, aryl and aralkyl groups, for example, one or more methylene groups may be substituted by groups having heteroatoms such as oxygen atoms and / or heteroatoms such as carbonyl groups.

[0236] And, R 38 R may bond with another substituent on the main chain of the repeating unit to form a ring. 38 The group formed by mutually bonding with another substituent possessed by the main chain of the repeating unit is preferably an alkylene group such as a methylene group.

[0237] As the formula (Y3), a group represented by the following formula (Y3-1) is preferred.

[0238] [Chemical formula 12]

[0239]

[0240] Here, L1 and L2 each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, or a group formed by combining these groups (for example, a group formed by combining an alkyl group and an aryl group).

[0241] M represents a single bond or a divalent linking group.

[0242] Q represents an alkyl group which may contain a heteroatom, a cycloalkyl group which may contain a heteroatom, an aryl group which may contain a heteroatom, an amino group, an ammonium group, a mercapto group, a cyano group, an aldehyde group, or a group formed by combining these groups (for example, a group formed by combining an alkyl group and a cycloalkyl group).

[0243] In the alkyl group and the cycloalkyl group, for example, one of the methylene groups may be substituted with a group having a hetero atom such as an oxygen atom or a hetero atom such as a carbonyl group.

[0244] It is also preferred that one of L1 and L2 is a hydrogen atom, and the other is an alkyl group, a cycloalkyl group, an aryl group, or a group formed by combining an alkylene group and an aryl group.

[0245] At least two of Q, M and L1 may be bonded to form a ring (preferably a 5-membered ring or a 6-membered ring).

[0246] From the viewpoint of pattern miniaturization, L2 is preferably a secondary alkyl group or a tertiary alkyl group, and more preferably a tertiary alkyl group. As the secondary alkyl group, isopropyl, cyclohexyl or norbornyl can be mentioned, and as the tertiary alkyl group, tert-butyl or adamantyl can be mentioned. In these modes, since Tg (glass transition temperature) and activation energy increase, it is possible to ensure film strength and suppress blurring.

[0247] In formula (Y4), Ar represents an aromatic ring group. Rn represents an alkyl group, a cycloalkyl group or an aryl group. Rn and Ar may be bonded to each other to form a non-aromatic ring. Ar is more preferably an aryl group.

[0248] From the viewpoint of excellent acid decomposability of the repeating unit, it is also preferred that when a non-aromatic ring is directly bonded to a polar group (or its residue) in a leaving group protecting a polar group, the ring atoms in the non-aromatic ring adjacent to the ring atoms directly bonded to the polar group (or its residue) do not have a halogen atom such as a fluorine atom as a substituent.

[0249] In addition, the leaving group that is released by the action of the acid may be a 2-cyclopentenyl group having a substituent (alkyl group, etc.) such as a 3-methyl-2-cyclopentenyl group, or a cyclohexyl group having a substituent (alkyl group, etc.) such as a 1,1,4,4-tetramethylcyclohexyl group.

[0250] As the repeating unit having an acid-decomposable group, a repeating unit represented by the formula (A) is also preferred.

[0251] [Chemical formula 13]

[0252]

[0253] L1 represents a divalent linking group which may have a fluorine atom or an iodine atom, R1 represents a hydrogen atom, a fluorine atom, an iodine atom, an alkyl group which may have a fluorine atom or an iodine atom, or an aryl group which may have a fluorine atom or an iodine atom, and R2 represents a leaving group which is released by the action of an acid and may have a fluorine atom or an iodine atom. At least one of L1, R1, and R2 has a fluorine atom or an iodine atom.

[0254] L1 represents a divalent linking group that can have a fluorine atom or an iodine atom. As a divalent linking group that can have a fluorine atom or an iodine atom, -CO-, -O-, -S-, -SO-, -SO2-, a hydrocarbon group (e.g., an alkylene group, a cycloalkylene group, an alkenylene group, an arylene group, etc.) that can have a fluorine atom or an iodine atom, and a linking group formed by connecting a plurality of them, etc. can be cited. Among them, as L1, preferably -CO-, an arylene group, an alkylene group having a fluorine atom or an iodine atom, or -arylene group-alkylene group having a fluorine atom or an iodine atom-.

[0255] The arylene group is preferably a phenylene group.

[0256] The alkylene group may be linear or branched. The number of carbon atoms in the alkylene group is not particularly limited, but is preferably 1 to 10, more preferably 1 to 3.

[0257] The total number of fluorine atoms and iodine atoms contained in the alkylene group having fluorine atoms or iodine atoms is not particularly limited, but is preferably 2 or more, more preferably 2 to 10, and even more preferably 3 to 6.

[0258] R1 represents a hydrogen atom, a fluorine atom, an iodine atom, an alkyl group which may have a fluorine atom or an iodine atom, or an aryl group which may have a fluorine atom or an iodine atom.

[0259] The alkyl group may be linear or branched. The number of carbon atoms in the alkyl group is not particularly limited, but is preferably 1 to 10, more preferably 1 to 3.

[0260] The total number of fluorine atoms and iodine atoms contained in the alkyl group having fluorine atoms or iodine atoms is not particularly limited, but is preferably 1 or more, more preferably 1 to 5, and even more preferably 1 to 3.

[0261] The above-mentioned alkyl group may contain heteroatoms such as oxygen atoms in addition to halogen atoms.

[0262] R2 represents a leaving group which is released by the action of an acid and may have a fluorine atom or an iodine atom.

[0263] Examples of the leaving group include groups represented by formulae (Z1) to (Z4).

[0264] Formula (Z1): -C(Rx 11 )(Rx 12 )(Rx 13 )

[0265] Formula (Z2): -C(=O)OC(Rx 11 )(Rx 12 )(Rx 13 )

[0266] Formula (Z3): -C(R 136 )(R 137 )(OR 138 )

[0267] Formula (Z4): -C(Rn1)(H)(Ar1)

[0268] In formula (Z1) and (Z2), Rx 11 ~Rx 13 Each independently represents an alkyl group (straight chain or branched chain) which may have a fluorine atom or an iodine atom, a cycloalkyl group (monocyclic or polycyclic) which may have a fluorine atom or an iodine atom, an alkenyl group (straight chain or branched chain) which may have a fluorine atom or an iodine atom, or an aryl group (monocyclic or polycyclic) which may have a fluorine atom or an iodine atom. 11 ~Rx 13 When all of them are alkyl groups (linear or branched), preferably Rx11 ~Rx 13 At least 2 of them are methyl groups.

[0269] Rx 11 ~Rx 13 In the formula (Y1), (Y2), except that it may have a fluorine atom or an iodine atom, it is the same as Rx1 to Rx3 in the above formula (Y1) and (Y2), and has the same definitions and preferred ranges as an alkyl group, a cycloalkyl group, an alkenyl group and an aryl group.

[0270] In formula (Z3), R 136 ~R 138 R each independently represents a hydrogen atom or a monovalent organic group which may have a fluorine atom or an iodine atom. 137 With R 138 As the monovalent organic group which may have a fluorine atom or an iodine atom, there can be mentioned an alkyl group which may have a fluorine atom or an iodine atom, a cycloalkyl group which may have a fluorine atom or an iodine atom, an aryl group which may have a fluorine atom or an iodine atom, an aralkyl group which may have a fluorine atom or an iodine atom, and a group formed by combining them (for example, a group formed by combining an alkyl group and a cycloalkyl group).

[0271] In addition to fluorine atoms and iodine atoms, the above-mentioned alkyl, cycloalkyl, aryl and aralkyl groups may also contain heteroatoms such as oxygen atoms. That is, in the above-mentioned alkyl, cycloalkyl, aryl and aralkyl groups, for example, one of the methylene groups may be substituted by a group having heteroatoms such as oxygen atoms or heteroatoms such as carbonyl groups.

[0272] And, R 138 It can be bonded to another substituent on the main chain of the repeating unit to form a ring. 138 The group formed by mutually bonding with another substituent possessed by the main chain of the repeating unit is preferably an alkylene group such as a methylene group.

[0273] As the formula (Z3), a group represented by the following formula (Z3-1) is preferred.

[0274] [Chemical formula 14]

[0275]

[0276] Here, L 11 and L 12Each independently represents a hydrogen atom; an alkyl group which may have a heteroatom selected from the group consisting of a fluorine atom, an iodine atom and an oxygen atom; a cycloalkyl group which may have a heteroatom selected from the group consisting of a fluorine atom, an iodine atom and an oxygen atom; an aryl group which may have a heteroatom selected from the group consisting of a fluorine atom, an iodine atom and an oxygen atom; or a group formed by combining them (for example, a group formed by combining an alkyl group and a cycloalkyl group which may have a heteroatom selected from the group consisting of a fluorine atom, an iodine atom and an oxygen atom).

[0277] M1 represents a single bond or a divalent linking group.

[0278] Q1 represents an alkyl group which may have a heteroatom selected from the group consisting of fluorine atoms, iodine atoms and oxygen atoms; a cycloalkyl group which may have a heteroatom selected from the group consisting of fluorine atoms, iodine atoms and oxygen atoms; an aryl group which may have a heteroatom selected from the group consisting of fluorine atoms, iodine atoms and oxygen atoms; an amino group; an ammonium group; a mercapto group; a cyano group; an aldehyde group; or a group formed by combining them (for example, a group formed by combining an alkyl group and a cycloalkyl group which may have a heteroatom selected from the group consisting of fluorine atoms, iodine atoms and oxygen atoms).

[0279] In formula (Z4), Ar1 represents an aromatic ring group which may have a fluorine atom or an iodine atom. Rn1 represents an alkyl group which may have a fluorine atom or an iodine atom, a cycloalkyl group which may have a fluorine atom or an iodine atom, or an aryl group which may have a fluorine atom or an iodine atom. Rn1 and Ar1 may be bonded to each other to form a non-aromatic ring.

[0280] As the repeating unit having an acid-decomposable group, a repeating unit represented by the general formula (AI) is also preferred.

[0281] [Chemical formula 15]

[0282]

[0283] In the general formula (AI),

[0284] Xa1 represents a hydrogen atom or an alkyl group which may have a substituent.

[0285] T represents a single bond or a divalent linking group.

[0286] Rx1 to Rx3 each independently represent an alkyl group (straight chain or branched), a cycloalkyl group (monocyclic or polycyclic), an alkenyl group (straight chain or branched) or an aryl group (monocyclic or polycyclic). When all of Rx1 to Rx3 are alkyl groups (straight chain or branched), it is preferred that at least two of Rx1 to Rx3 are methyl groups.

[0287] Two of Rx1 to Rx3 may be bonded to form a monocyclic or polycyclic ring (monocyclic or polycyclic cycloalkyl group).

[0288] As the alkyl group which may have a substituent represented by Xa1, for example, there can be mentioned a methyl group or a -CH2-R 11 Represents a group. 11 represents a halogen atom (fluorine atom, etc.), a hydroxyl group or a monovalent organic group, for example, an alkyl group having 5 or less carbon atoms which may be substituted by a halogen atom, an acyl group having 5 or less carbon atoms which may be substituted by a halogen atom, and an alkoxy group having 5 or less carbon atoms which may be substituted by a halogen atom, preferably an alkyl group having 3 or less carbon atoms, and more preferably a methyl group. Xa1 is preferably a hydrogen atom, a methyl group, a trifluoromethyl group or a hydroxymethyl group.

[0289] Examples of the divalent linking group for T include an alkylene group, an aromatic ring group, a -COO-Rt- group, and a -O-Rt- group. In the formula, Rt represents an alkylene group or a cycloalkylene group.

[0290] T is preferably a single bond or a -COO-Rt- group. When T represents a -COO-Rt- group, Rt is preferably an alkylene group having 1 to 5 carbon atoms, more preferably a -CH2- group, a -(CH2)2- group or a -(CH2)3- group.

[0291] The alkyl group for Rx1 to Rx3 is preferably an alkyl group having 1 to 4 carbon atoms, such as methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group and tert-butyl group.

[0292] The cycloalkyl group for Rx1 to Rx3 is preferably a monocyclic cycloalkyl group such as a cyclopentyl group and a cyclohexyl group, or a polycyclic cycloalkyl group such as a norbornyl group, a tetracyclodecyl group, a tetracyclododecyl group, and an adamantyl group.

[0293] As the aryl group for Rx1 to Rx3, an aryl group having 6 to 10 carbon atoms is preferred, and examples thereof include phenyl, naphthyl, and anthracenyl.

[0294] As the alkenyl group of Rx1 to Rx3, a vinyl group is preferable.

[0295] The cycloalkyl group formed by bonding two of Rx1 to Rx3 is preferably a monocyclic cycloalkyl group such as cyclopentyl and cyclohexyl, and is also preferably a polycyclic cycloalkyl group such as norbornyl, tetracyclodecyl, tetracyclododecyl and adamantyl. Among them, a monocyclic cycloalkyl group having 5 to 6 carbon atoms is preferred.

[0296] In the cycloalkyl group formed by bonding two of Rx1 to Rx3, for example, one of the methylene groups constituting the ring may be substituted by a group having a hetero atom such as an oxygen atom, a hetero atom such as a carbonyl group, or a vinylene group. Furthermore, in these cycloalkyl groups, one or more of the ethylene groups constituting the cycloalkyl ring may be substituted by a vinylene group.

[0297] The repeating unit represented by the general formula (AI) is preferably a mode in which, for example, Rx1 is a methyl group or an ethyl group, and Rx2 and Rx3 are bonded to form the above-mentioned cycloalkyl group.

[0298] When the above groups have a substituent, examples of the substituent include an alkyl group (having 1 to 4 carbon atoms), a halogen atom, a hydroxyl group, an alkoxy group (having 1 to 4 carbon atoms), a carboxyl group, and an alkoxycarbonyl group (having 2 to 6 carbon atoms). The number of carbon atoms in the substituent is preferably 8 or less.

[0299] The repeating unit represented by the general formula (AI) is preferably an acid-decomposable tertiary alkyl (meth)acrylate repeating unit (a repeating unit in which Xa1 represents a hydrogen atom or a methyl group, and T represents a single bond).

[0300] The content of repeating units having an acid-decomposable group is preferably 15 mol% or more, more preferably 20 mol% or more, and further preferably 30 mol% or more relative to all repeating units in the resin (A). The upper limit is preferably 80 mol% or less, more preferably 70 mol% or less, and particularly preferably 60 mol% or less.

[0301] Specific examples of repeating units having an acid-decomposable group are shown below, but the present invention is not limited thereto. In the formula, Xa1 represents any one of H, CH3, CF3 and CH2OH, and Rxa and Rxb represent a linear or branched alkyl group having 1 to 5 carbon atoms.

[0302] [Chemical formula 16]

[0303]

[0304] [Chemical formula 17]

[0305]

[0306] [Chemical formula 18]

[0307]

[0308] [Chemical formula 19]

[0309]

[0310] [Chemical formula 20]

[0311]

[0312] [Chemical formula 21]

[0313]

[0314] The resin (A) may contain repeating units other than the above-mentioned repeating units.

[0315] For example, the resin (A) may also contain at least one repeating unit selected from the group consisting of the following Group A and / or at least one repeating unit selected from the group consisting of the following Group B.

[0316] Group A: A group consisting of the following repeating units (20) to (29).

[0317] (20) Repeating unit having an acid group as described below

[0318] (21) The repeating unit having a fluorine atom or an iodine atom described below

[0319] (22) Repeating units having a lactone group, a sultone group or a carbonate group as described below

[0320] (23) The repeating unit having a photoacid generating group described below

[0321] (24) A repeating unit represented by the general formula (V-1) or the following general formula (V-2)

[0322] (25) The repeating unit represented by the formula (A) described below

[0323] (26) The repeating unit represented by the formula (B) described below

[0324] (27) The repeating unit represented by the formula (C) described below

[0325] (28) The repeating unit represented by the formula (D) described below

[0326] (29) The repeating unit represented by the formula (E) described below

[0327] Group B: A group consisting of the following repeating units (30) to (32).

[0328] (30) the repeating unit described later having at least one group selected from the group consisting of a lactone group, a sultone group, a carbonate group, a hydroxyl group, a cyano group and an alkali-soluble group

[0329] (31) A repeating unit having an alicyclic hydrocarbon structure and not being acid-decomposable as described below

[0330] (32) a repeating unit having neither a hydroxyl group nor a cyano group and represented by the general formula (III) described below

[0331] When the composition of the present invention is used as an actinic ray-sensitive or radiation-sensitive resin composition for EUV, the resin (A) preferably has at least one repeating unit selected from the group consisting of the above-mentioned Group A.

[0332] Furthermore, when the composition is used as an EUV-sensitive or radiation-sensitive resin composition, the resin (A) preferably contains at least one of a fluorine atom and an iodine atom. When the resin (A) contains both a fluorine atom and an iodine atom, the resin (A) may have one repeating unit containing both a fluorine atom and an iodine atom, or the resin (A) may contain two types of repeating units containing fluorine atoms and repeating units containing iodine atoms.

[0333] Furthermore, when the composition is used as an actinic ray-sensitive or radiation-sensitive resin composition for EUV, the resin (A) preferably further contains a repeating unit having an aromatic group.

[0334] When the composition of the present invention is used as an actinic ray-sensitive or radiation-sensitive resin composition for ArF, the resin (A) preferably has at least one repeating unit selected from the group consisting of the above-mentioned Group B.

[0335] When the composition of the present invention is used as an actinic ray-sensitive or radiation-sensitive resin composition for ArF, the resin (A) preferably contains neither a fluorine atom nor a silicon atom.

[0336] Furthermore, when the composition is used as an actinic ray-sensitive or radiation-sensitive resin composition for ArF, the resin (A) preferably has no aromatic group.

[0337] <Repeating unit having an acid group>

[0338] The resin (A) may contain a repeating unit having an acid group.

[0339] As the acid group, an acid group having a pKa of 13 or less is preferred.

[0340] As the acid group, for example, a carboxyl group, a phenolic hydroxyl group, a fluorinated alcohol group (preferably a hexafluoroisopropanol group), a sulfonic acid group, a sulfonamide group, or an isopropanol group is preferable.

[0341] Furthermore, in the above-mentioned hexafluoroisopropanol group, one or more (preferably 1 to 2) fluorine atoms may be substituted by groups other than fluorine atoms (such as alkoxycarbonyl groups). The -C(CF3)(OH)-CF2- formed in this way is also preferably used as an acid group. Furthermore, one or more fluorine atoms may be substituted by groups other than fluorine atoms to form a ring containing -C(CF3)(OH)-CF2-.

[0342] The repeating unit having an acid group is preferably a repeating unit different from the repeating unit having a structure in which a polar group is protected by a leaving group that is released by the action of the acid and the repeating unit having a lactone group, a sultone group or a carbonate group described later.

[0343] The repeating unit having an acid group may have a fluorine atom or an iodine atom.

[0344] As the repeating unit having an acid group, a repeating unit represented by the formula (B0) is preferred.

[0345] [Chemical formula 22]

[0346]

[0347] R3 represents a hydrogen atom or a monovalent organic group which may have a fluorine atom or an iodine atom.

[0348] As the monovalent organic group which may have a fluorine atom or an iodine atom, a group represented by -L4-R8 is preferred. L4 represents a single bond or an ester group. R8 may include an alkyl group which may have a fluorine atom or an iodine atom, a cycloalkyl group which may have a fluorine atom or an iodine atom, an aryl group which may have a fluorine atom or an iodine atom, or a group formed by combining these.

[0349] R4 and R5 each independently represent a hydrogen atom, a fluorine atom, an iodine atom, or an alkyl group which may have a fluorine atom or an iodine atom.

[0350] L2 represents a single bond or an ester group.

[0351] L3 represents an (n+m+1)-valent aromatic hydrocarbon ring group or an (n+m+1)-valent alicyclic hydrocarbon ring group. As the aromatic hydrocarbon ring group, a benzene ring group and a naphthalene ring group can be mentioned. As the alicyclic hydrocarbon ring group, it can be a monocyclic ring or a polycyclic ring, for example, a cycloalkyl ring group can be mentioned.

[0352] R6 represents a hydroxyl group or a fluorinated alcohol group (preferably a hexafluoroisopropanol group). When R6 is a hydroxyl group, L3 is preferably an aromatic hydrocarbon ring group having a valence of (n+m+1).

[0353] R7 represents a halogen atom. Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.

[0354] m represents an integer greater than or equal to 1. m is preferably an integer of 1-3, and more preferably an integer of 1-2.

[0355] n represents an integer greater than or equal to 0 or 1. n is preferably an integer of 1-4.

[0356] In addition, (n+m+1) is preferably an integer of 1-5.

[0357] As the repeating unit having an acid group, a repeating unit represented by the following general formula (I) is also preferred.

[0358] [Chemical formula 23]

[0359]

[0360] In the general formula (I),

[0361] R 41 , R 42 and R 43 Each independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, a cyano group or an alkoxycarbonyl group. 42 It can bond with Ar4 to form a ring. In this case, R 42 represents a single bond or an alkylene group.

[0362] X4 represents a single bond, -COO- or -CONR 64 -, R 64 represents a hydrogen atom or an alkyl group.

[0363] L4 represents a single bond or an alkylene group.

[0364] Ar4 represents an (n+1) valent aromatic ring group. 42 When they are bonded to form a ring, they represent an (n+2)-valent aromatic ring group.

[0365] n represents an integer of 1-5.

[0366] As R in the general formula (I) 41 , R 42 and R 43 The alkyl group is preferably an alkyl group having 20 or less carbon atoms, such as methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, hexyl, 2-ethylhexyl, octyl and dodecyl, more preferably an alkyl group having 8 or less carbon atoms, and further preferably an alkyl group having 3 or less carbon atoms.

[0367] As R in the general formula (I) 41 , R 42 and R 43 The cycloalkyl group may be monocyclic or polycyclic. Among them, preferred are monocyclic cycloalkyl groups having 3 to 8 carbon atoms, such as cyclopropyl, cyclopentyl and cyclohexyl.

[0368] As R in the general formula (I) 41 , R 42 and R 43 The halogen atom includes a fluorine atom, a chlorine atom, a bromine atom and an iodine atom, and a fluorine atom is preferred.

[0369] As R in the general formula (I) 41 , R 42 and R 43 The alkyl group contained in the alkoxycarbonyl group is preferably the same as the above R 41 , R 42 and R 43 The alkyl group in is the same as the alkyl group.

[0370] Preferred substituents in the above groups include, for example, alkyl, cycloalkyl, aryl, amino, amide, urea, carbamate, hydroxy, carboxyl, halogen, alkoxy, thioether, acyl, acyloxy, alkoxycarbonyl, cyano, and nitro. The substituent preferably has 8 or less carbon atoms.

[0371] Ar4 represents an (n+1)-valent aromatic ring group. When n is 1, the divalent aromatic ring group is preferably an arylene group having 6 to 18 carbon atoms such as phenylene, tolylene, naphthylene and anthracene, or a divalent aromatic ring group containing a heterocycle such as a thiophene ring, a furan ring, a pyrrole ring, a benzothiophene ring, a benzofuran ring, a benzopyrrole ring, a triazine ring, an imidazole ring, a benzimidazole ring, a triazole ring, a thiadiazole ring and a thiazole ring. In addition, the above aromatic ring group may have a substituent.

[0372] Specific examples of the (n+1)-valent aromatic ring group when n is an integer of 2 or more include groups obtained by removing (n-1) arbitrary hydrogen atoms from the above-mentioned specific examples of the divalent aromatic ring group.

[0373] The (n+1)-valent aromatic ring group may further have a substituent.

[0374] Examples of the substituents that the alkyl group, cycloalkyl group, alkoxycarbonyl group, alkylene group, and (n+1)-valent aromatic ring group may have include R 41 , R 42 and R 43 The alkyl groups mentioned above, alkoxy groups such as methoxy, ethoxy, hydroxyethoxy, propoxy, hydroxypropoxy and butoxy; aryl groups such as phenyl; and the like.

[0375] As -CONR represented by X4 64 -(R 64 represents a hydrogen atom or an alkyl group) 64 The alkyl group includes alkyl groups having 20 or less carbon atoms, such as methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, hexyl, 2-ethylhexyl, octyl and dodecyl, and preferably alkyl groups having 8 or less carbon atoms.

[0376] X4 is preferably a single bond, -COO- or -CONH-, and more preferably a single bond or -COO-.

[0377] The alkylene group in L4 is preferably an alkylene group having 1 to 8 carbon atoms, such as a methylene group, an ethylene group, a propylene group, a butylene group, a hexylene group, and an octylene group.

[0378] Ar4 is preferably an aromatic ring group having 6 to 18 carbon atoms, and more preferably a benzene ring group, a naphthyl ring group, and a biphenylene ring group.

[0379] The repeating unit represented by the general formula (I) preferably has a hydroxystyrene structure. That is, Ar4 is preferably a benzene ring group.

[0380] The repeating unit represented by the general formula (I) is preferably a repeating unit represented by the following general formula (1).

[0381] [Chemical formula 24]

[0382]

[0383] In the general formula (1),

[0384] A represents a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom or a cyano group.

[0385] R represents a halogen atom, an alkyl group, a cycloalkyl group, an aryl group, an alkenyl group, an aralkyl group, an alkoxy group, an alkylcarbonyloxy group, an alkylsulfonyloxy group, an alkoxycarbonyl group or an aryloxycarbonyl group, and when there are a plurality of them, they may be the same or different. When there are a plurality of R groups, they may form a ring together. As R, a hydrogen atom is preferred.

[0386] a represents an integer of 1-3.

[0387] b represents an integer from 0 to (5-a).

[0388] The repeating unit having an acid group is exemplified below.

[0389] [Chemical formula 25]

[0390]

[0391] [Chemical formula 26]

[0392]

[0393] [Chemical formula 27]

[0394]

[0395] Among the above-mentioned repeating units, the repeating units specifically described below are preferred. In the formula, R represents a hydrogen atom or a methyl group, and a represents 2 or 3.

[0396] [Chemical formula 28]

[0397]

[0398] [Chemical formula 29]

[0399]

[0400] The content of repeating units having an acid group is preferably 10 mol% or more, more preferably 15 mol% or more, relative to all repeating units in the resin (A). And, as its upper limit, it is preferably 70 mol% or less, more preferably 65 mol% or less, and further preferably 60 mol% or less.

[0401] <Repeating unit having fluorine atom or iodine atom>

[0402] The resin (A) may contain repeating units having fluorine atoms or iodine atoms, other than the <repeating units having an acid-decomposable group> and <repeating units having an acid group> described above. Furthermore, the <repeating units having fluorine atoms or iodine atoms> mentioned here are preferably different from other types of repeating units belonging to Group A, such as the <repeating units having a lactone group, a sultone group or a carbonate group> and the <repeating units having a photoacid generating group> described later.

[0403] As the repeating unit having a fluorine atom or an iodine atom, a repeating unit represented by the formula (C0) is preferred.

[0404] [Chemical formula 30]

[0405]

[0406] L5 represents a single bond or an ester group.

[0407] R9 represents a hydrogen atom or an alkyl group which may have a fluorine atom or an iodine atom.

[0408] R 10 It represents a hydrogen atom, an alkyl group which may have a fluorine atom or an iodine atom, a cycloalkyl group which may have a fluorine atom or an iodine atom, an aryl group which may have a fluorine atom or an iodine atom, or a group composed of a combination of these.

[0409] The repeating unit having a fluorine atom or an iodine atom is exemplified below.

[0410] [Chemical formula 31]

[0411]

[0412] The content of the repeating unit having a fluorine atom or an iodine atom is preferably 0 mol% or more, more preferably 5 mol% or more, and further preferably 10 mol% or more relative to all the repeating units in the resin (A). The upper limit thereof is preferably 50 mol% or less, more preferably 45 mol% or less, and further preferably 40 mol% or less.

[0413] In addition, as described above, since the repeating units having fluorine atoms or iodine atoms do not include <repeating units having an acid-decomposable group> and <repeating units having an acid group>, the content of the repeating units having fluorine atoms or iodine atoms mentioned above also means the content of repeating units having fluorine atoms or iodine atoms other than <repeating units having an acid-decomposable group> and <repeating units having an acid group>.

[0414] Relative to all repeating units of resin (A), the total content of repeating units containing at least one of fluorine atoms and iodine atoms in the repeating units of resin (A) is preferably 20 mol% or more, more preferably 30 mol% or more, and further preferably 40 mol% or more. The upper limit is not particularly limited, for example, 100 mol% or less.

[0415] In addition, examples of repeating units containing at least one of a fluorine atom and an iodine atom include repeating units having a fluorine atom or an iodine atom and an acid-decomposable group, repeating units having a fluorine atom or an iodine atom and an acid group, and repeating units having a fluorine atom or an iodine atom.

[0416] <Repeating unit having a lactone group, a sultone group or a carbonate group>

[0417] The resin (A) may contain a repeating unit having at least one selected from the group consisting of a lactone group, a sultone group and a carbonate group (hereinafter also collectively referred to as “a repeating unit having a lactone group, a sultone group or a carbonate group”).

[0418] It is also preferred that the repeating unit having a lactone group, a sultone group or a carbonate group does not have an acid group such as a hexafluoropropanol group.

[0419] The lactone group or sultone group may have a lactone structure or a sultone structure. The lactone structure or sultone structure is preferably a 5- to 7-membered ring lactone structure or a 5- to 7-membered ring sultone structure. Among them, a structure in which another ring structure is fused to a 5- to 7-membered ring lactone structure in the form of a bicyclic structure or a spirocyclic structure, or a structure in which another ring structure is fused to a 5- to 7-membered ring sultone structure in the form of a bicyclic structure or a spirocyclic structure is more preferably used.

[0420] The resin (A) preferably contains a repeating unit having a lactone group or a sultone group, wherein one or more hydrogen atoms are extracted from ring atoms of a lactone structure represented by any one of the following general formulas (LC1-1) to (LC1-21) or a sultone structure represented by any one of the following general formulas (SL1-1) to (SL1-3).

[0421] Furthermore, the lactone group or the sultone group may be directly bonded to the main chain. For example, the ring atoms of the lactone group or the sultone group may constitute the main chain of the resin (A).

[0422] [Chemical formula 32]

[0423]

[0424] The lactone structure or sultone structure may have a substituent (Rb2). Preferred substituents (Rb2) include alkyl groups having 1 to 8 carbon atoms, cycloalkyl groups having 4 to 7 carbon atoms, alkoxy groups having 1 to 8 carbon atoms, alkoxycarbonyl groups having 1 to 8 carbon atoms, carboxyl groups, halogen atoms, hydroxyl groups, cyano groups, and acid-decomposable groups. n2 represents an integer of 0 to 4. When n2 is 2 or more, multiple Rb2 may be different, and multiple Rb2 may be bonded to each other to form a ring.

[0425] Examples of the repeating unit containing a group having a lactone structure represented by any of the general formulae (LC1-1) to (LC1-21) or a sultone structure represented by any of the general formulae (SL1-1) to (SL1-3) include repeating units represented by the following general formula (AI).

[0426] [Chemical formula 33]

[0427]

[0428] In the general formula (AI), Rb0 represents a hydrogen atom, a halogen atom or an alkyl group having 1 to 4 carbon atoms.

[0429] Preferred substituents that the alkyl group of Rb0 may have include a hydroxyl group and a halogen atom.

[0430] Examples of the halogen atom of Rb0 include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. Rb0 is preferably a hydrogen atom or a methyl group.

[0431] Ab represents a single bond, an alkylene group, a divalent linking group having a monocyclic or polycyclic alicyclic hydrocarbon structure, an ether group, an ester group, a carbonyl group, a carboxyl group, or a divalent group formed by combining them. Among them, a single bond or a linking group represented by -Ab1-CO2- is preferred. Ab1 is a linear or branched alkylene group, or a monocyclic or polycyclic cycloalkylene group, preferably a methylene group, an ethylene group, a cyclohexylene group, an adamantylene group, or a norbornylene group.

[0432] V represents a group formed by extracting one hydrogen atom from a ring atom of a lactone structure represented by any of the general formulae (LC1-1) to (LC1-21), or a group formed by extracting one hydrogen atom from a ring atom of a sultone structure represented by any of the general formulae (SL1-1) to (SL1-3).

[0433] When optical isomers exist in the repeating unit having a lactone group or a sultone group, any optical isomer may be used. Furthermore, one optical isomer may be used alone or a plurality of optical isomers may be used in combination. When one optical isomer is mainly used, its optical purity (ee) is preferably 90 or more, more preferably 95 or more.

[0434] As the carbonate group, a cyclic carbonate group is preferred.

[0435] As the repeating unit having a cyclic carbonate group, a repeating unit represented by the following general formula (A-1) is preferred.

[0436] [Chemical formula 34]

[0437]

[0438] 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).

[0439] n represents an integer greater than or equal to 0.

[0440] R A 2 represents a substituent. When n is 2 or more, there are multiple R A 2 They may be the same or different.

[0441] A represents a single bond or a divalent linking group. The linking group is preferably an alkylene group, a divalent linking group having a monocyclic or polycyclic alicyclic hydrocarbon structure, an ether group, an ester group, a carbonyl group, a carboxyl group, or a divalent group composed of a combination thereof.

[0442] Z represents an atomic group which forms a monocyclic or polycyclic ring together with the group represented by -O-CO-O- in the formula.

[0443] The repeating unit having a lactone group, a sultone group or a carbonate group is exemplified below.

[0444] [Chemical formula 35]

[0445] (where Rx is H, CH3, CH2OH or CF3)

[0446]

[0447] [Chemical formula 36]

[0448] (where Rx is H, CH3, CH2OH or CF3)

[0449]

[0450] [Chemical formula 37]

[0451] (where Rx is H, CH3, CH2OH or CF3)

[0452]

[0453] The content of the repeating unit having a lactone group, a sultone group or a carbonate group is preferably 1 mol% or more, more preferably 10 mol% or more, relative to all repeating units in the resin (A). And, as its upper limit, it is preferably 85 mol% or less, more preferably 80 mol% or less, further preferably 70 mol% or less, and particularly preferably 60 mol% or less.

[0454] <Repeating Unit Having a Photoacid Generating Group>

[0455] The resin (A) may contain, as a repeating unit other than the above, a repeating unit having a group that generates an acid by irradiation with actinic rays or radiation (hereinafter, also referred to as a "photoacid generating group").

[0456] In this case, the repeating unit having the photoacid generating group can be considered to correspond to a compound that generates an acid by irradiation with actinic rays or radiation (also referred to as a "photoacid generator") as described later.

[0457] Examples of such a repeating unit include a repeating unit represented by the following general formula (4).

[0458] [Chemical formula 38]

[0459]

[0460] R 41 represents a hydrogen atom or a methyl group. 41 represents a single bond or a divalent linking group. 42 represents a divalent linking group. 40 It indicates a structural site that is decomposed by irradiation with actinic rays or radiation to generate an acid in the side chain.

[0461] The repeating unit having a photoacid generating group is exemplified below.

[0462] [Chemical formula 39]

[0463]

[0464] [Chemical formula 40]

[0465]

[0466] Examples of the repeating unit represented by the general formula (4) include the repeating units described in paragraphs <0094> to <0105> of JP-A-2014-041327.

[0467] The content of the repeating unit having a photoacid generating group is preferably 1 mol% or more, more preferably 5 mol% or more, relative to all repeating units in the resin (A), and its upper limit is preferably 40 mol% or less, more preferably 35 mol% or less, and further preferably 30 mol% or less.

[0468] <Repeating unit represented by general formula (V-1) or the following general formula (V-2)>

[0469] The resin (A) may have a repeating unit represented by the following general formula (V-1) or the following general formula (V-2).

[0470] The repeating units represented by the following general formula (V-1) and the following general formula (V-2) are preferably repeating units different from the above-mentioned repeating units.

[0471] [Chemical formula 41]

[0472]

[0473] In the formula,

[0474] R6 and R7 each independently represent a hydrogen atom, a hydroxyl group, an alkyl group, an alkoxy group, an acyloxy group, a cyano group, a nitro group, an amino group, a halogen atom, an ester group (-OCOR or -COOR: R is an alkyl group or a fluorinated alkyl group having 1 to 6 carbon atoms) or a carboxyl group. As the alkyl group, a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms is preferred.

[0475] n3 represents an integer from 0 to 6.

[0476] n4 represents an integer from 0 to 4.

[0477] X 4 It is a methylene group, an oxygen atom or a sulfur atom.

[0478] The repeating unit represented by the general formula (V-1) or (V-2) is exemplified below.

[0479] [Chemical formula 42]

[0480]

[0481] <Repeating unit for reducing the mobility of the main chain>

[0482] From the viewpoint of being able to suppress excessive diffusion of the generated acid or pattern collapse during development, the resin (A) preferably has a high glass transition temperature (Tg). Tg is preferably greater than 90°C, more preferably greater than 100°C, further preferably greater than 110°C, and particularly preferably greater than 125°C. In addition, too high Tg will lead to a decrease in the dissolution rate in the developer, so Tg is preferably 400°C or less, more preferably 350°C or less.

[0483] In addition, in this specification, the glass transition temperature (Tg) of a polymer such as resin (A) is calculated by the following method. First, the Tg of a homopolymer consisting only of each repeating unit contained in the polymer is calculated separately by the Bicerano method. Thereafter, the calculated Tg is referred to as the "repeating unit Tg". Next, the mass ratio (%) of each repeating unit relative to all repeating units in the polymer is calculated. Next, the Tg in each mass ratio is calculated using the Fox formula (described in Materials Letters 62 (2008) 3152, etc.), and their sum is set as the Tg (°C) of the polymer.

[0484] The Bicerano method is described in Prediction of polymer properties, Marcel Dekker Inc, New York (1993), etc. In addition, the calculation of Tg by the Bicerano method can be performed using polymer property estimation software MDL Polymer (MDL Information Systems, Inc.).

[0485] In order to increase the Tg of the resin (A) (preferably to make the Tg exceed 90°C), it is preferred to reduce the mobility of the main chain of the resin (A). The following methods (a) to (e) can be mentioned as methods for reducing the mobility of the main chain of the resin (A).

[0486] (a) Introducing bulky substituents into the main chain

[0487] (b) Introducing multiple substituents into the main chain

[0488] (c) Introducing a substituent that induces interaction between the resins (A) near the main chain

[0489] (d) Forming the main chain in the ring structure

[0490] (e) Connecting the ring structure to the main chain

[0491] The resin (A) preferably has a repeating unit having a homopolymer Tg of 130° C. or higher.

[0492] The type of repeating unit showing a homopolymer Tg of 130°C or higher is not particularly limited, as long as it is a repeating unit showing a homopolymer Tg of 130°C or higher calculated by the Bicerano method. In addition, depending on the type of functional group in the repeating unit represented by formula (A) to formula (E) described later, it is equivalent to a repeating unit showing a homopolymer Tg of 130°C or higher.

[0493] (Repeating unit represented by formula (A))

[0494] As an example of a specific means for realizing the above-mentioned (a), there is mentioned a method of introducing a repeating unit represented by the formula (A) into the resin (A).

[0495] [Chemical formula 43]

[0496]

[0497] In formula (A), R A represents a group having a polycyclic structure. x represents a hydrogen atom, a methyl group or an ethyl group. A group having a polycyclic structure is a group having a plurality of ring structures, and the plurality of ring structures may or may not be condensed.

[0498] Specific examples of the repeating unit represented by formula (A) include the following repeating units.

[0499] [Chemical formula 44]

[0500]

[0501] [Chemical formula 45]

[0502]

[0503] [Chemical formula 46]

[0504]

[0505] In the above formula, R represents a hydrogen atom, a methyl group or an ethyl group.

[0506] Ra represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, an alkenyl group, a hydroxyl group, an alkoxy group, an acyloxy group, a cyano group, a nitro group, an amino group, a halogen atom, an ester group (-OCOR"' or -COOR"': R"' is an alkyl group or a fluorinated alkyl group having 1 to 20 carbon atoms) or a carboxyl group. In addition, the above-mentioned alkyl group, the above-mentioned cycloalkyl group, the above-mentioned aryl group, the above-mentioned aralkyl group and the above-mentioned alkenyl group may each have a substituent. Furthermore, a hydrogen atom bonded to a carbon atom in the group represented by Ra may be substituted by a fluorine atom or an iodine atom.

[0507] Furthermore, R' and R" independently represent an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, an alkenyl group, a hydroxyl group, an alkoxy group, an acyloxy group, a cyano group, a nitro group, an amino group, a halogen atom, an ester group (-OCOR"' or -COOR"': R"' is an alkyl group or a fluorinated alkyl group having 1 to 20 carbon atoms) or a carboxyl group. In addition, the above-mentioned alkyl group, the above-mentioned cycloalkyl group, the above-mentioned aryl group, the above-mentioned aralkyl group and the above-mentioned alkenyl group may also have substituents, respectively. Furthermore, the hydrogen atoms bonded to the carbon atoms in the groups represented by R' and R" may also be substituted by fluorine atoms or iodine atoms.

[0508] L represents a single bond or a divalent linking group. Examples of the divalent linking group include -COO-, -CO-, -O-, -S-, -SO-, -SO2-, an alkylene group, a cycloalkylene group, an alkenylene group, and a linking group formed by connecting a plurality of these groups.

[0509] m and n each independently represent an integer greater than 0. The upper limits of m and n are not particularly limited, but are usually 2 or less, and often 1 or less.

[0510] (Repeating unit represented by formula (B))

[0511] As an example of a specific means for realizing the above-mentioned (b), there is mentioned a method of introducing a repeating unit represented by the formula (B) into the resin (A).

[0512] [Chemical formula 47]

[0513]

[0514] In formula (B), R b1 ~R b4 Each independently represents a hydrogen atom or an organic group, R b1 ~R b4 At least two of them represent organic groups.

[0515] Furthermore, when at least one of the organic groups is a group having a ring structure directly connected to the main chain of the repeating unit, the types of the other organic groups are not particularly limited.

[0516] Furthermore, when any of the organic groups is not a group having a ring structure directly connected to the main chain in the repeating unit, at least two or more of the organic groups are substituents having three or more constituent atoms excluding hydrogen atoms.

[0517] Specific examples of the repeating unit represented by formula (B) include the following repeating units.

[0518] [Chemical formula 48]

[0519]

[0520] In the above formula, R each independently represents a hydrogen atom or an organic group. Examples of the organic group include organic groups such as an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, and an alkenyl group which may have a substituent.

[0521] R' independently represents an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, an alkenyl group, a hydroxyl group, an alkoxy group, an acyloxy group, a cyano group, a nitro group, an amino group, a halogen atom, an ester group (-OCOR" or -COOR": R" is an alkyl group or a fluorinated alkyl group having 1 to 20 carbon atoms) or a carboxyl group. In addition, the above-mentioned alkyl group, the above-mentioned cycloalkyl group, the above-mentioned aryl group, the above-mentioned aralkyl group and the above-mentioned alkenyl group may each have a substituent. Furthermore, a hydrogen atom bonded to a carbon atom in the group represented by R' may be substituted by a fluorine atom or an iodine atom.

[0522] m represents an integer greater than or equal to 0. The upper limit of m is not particularly limited, but is usually 2 or less, and often 1 or less.

[0523] (Repeating unit represented by formula (C))

[0524] As an example of a specific means for realizing the above-mentioned (c), there is mentioned a method of introducing a repeating unit represented by the formula (C) into the resin (A).

[0525] [Chemical formula 49]

[0526]

[0527] In formula (C), R c1 ~R c4 Each independently represents a hydrogen atom or an organic group, R c1 ~R c4 At least one of them is a group having a hydrogen-bonding hydrogen atom within 3 atoms from the main chain carbon. Among them, it is preferred to have a hydrogen-bonding hydrogen atom within 2 atoms (closer to the main chain) in order to cause interaction between the main chains of the resin (A).

[0528] Specific examples of the repeating unit represented by the formula (C) include the following repeating units.

[0529] [Chemical formula 50]

[0530]

[0531] In the above formula, R represents an organic group, which may be substituted, such as an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, an alkenyl group, and an ester group (-OCOR or -COOR: R is an alkyl group or a fluorinated alkyl group having 1 to 20 carbon atoms).

[0532] R' represents a hydrogen atom or an organic group. Examples of the organic group include alkyl, cycloalkyl, aryl, aralkyl and alkenyl groups. In addition, the hydrogen atom in the organic group may be substituted by a fluorine atom or an iodine atom.

[0533] (Repeating unit represented by formula (D))

[0534] As an example of a specific means for realizing the above-mentioned (d), there is mentioned a method of introducing a repeating unit represented by the formula (D) into the resin (A).

[0535] [Chemical formula 51]

[0536]

[0537] In formula (D), "Cyclic" means a group whose main chain is formed by a cyclic structure. The number of atoms constituting the ring is not particularly limited.

[0538] Specific examples of the repeating unit represented by the formula (D) include the following repeating units.

[0539] [Chemical formula 52]

[0540]

[0541] In the above formula, R each independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, an alkenyl group, a hydroxyl group, an alkoxy group, an acyloxy group, a cyano group, a nitro group, an amino group, a halogen atom, an ester group (-OCOR" or -COOR": R" is an alkyl group or a fluorinated alkyl group having 1 to 20 carbon atoms) or a carboxyl group. In addition, the above alkyl group, the above cycloalkyl group, the above aryl group, the above aralkyl group and the above alkenyl group may each have a substituent. Furthermore, a hydrogen atom bonded to a carbon atom in the group represented by R may be substituted by a fluorine atom or an iodine atom.

[0542] In the above formula, R' independently represents an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, an alkenyl group, a hydroxyl group, an alkoxy group, an acyloxy group, a cyano group, a nitro group, an amino group, a halogen atom, an ester group (-OCOR" or -COOR": R" is an alkyl group or a fluorinated alkyl group having 1 to 20 carbon atoms) or a carboxyl group. In addition, the above alkyl group, the above cycloalkyl group, the above aryl group, the above aralkyl group and the above alkenyl group may each have a substituent. Furthermore, a hydrogen atom bonded to a carbon atom in the group represented by R' may be substituted by a fluorine atom or an iodine atom.

[0543] m represents an integer greater than or equal to 0. The upper limit of m is not particularly limited, but is usually 2 or less, and often 1 or less.

[0544] (Repeating unit represented by formula (E))

[0545] As an example of a specific means for realizing the above-mentioned (e), there is mentioned a method of introducing a repeating unit represented by the formula (E) into the resin (A).

[0546] [Chemical formula 53]

[0547]

[0548] In formula (E), Re each independently represents a hydrogen atom or an organic group. Examples of the organic group include an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, and an alkenyl group which may have a substituent.

[0549] "Cyclic" is a cyclic group containing carbon atoms in the main chain. The number of atoms contained in the cyclic group is not particularly limited.

[0550] Specific examples of the repeating unit represented by formula (E) include the following repeating units.

[0551] [Chemical formula 54]

[0552]

[0553] [Chemical formula 55]

[0554]

[0555] In the above formula, R each independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, an alkenyl group, a hydroxyl group, an alkoxy group, an acyloxy group, a cyano group, a nitro group, an amino group, a halogen atom, an ester group (-OCOR" or -COOR": R" is an alkyl group or a fluorinated alkyl group having 1 to 20 carbon atoms) or a carboxyl group. In addition, the above alkyl group, the above cycloalkyl group, the above aryl group, the above aralkyl group and the above alkenyl group may each have a substituent. Furthermore, a hydrogen atom bonded to a carbon atom in the group represented by R may be substituted by a fluorine atom or an iodine atom.

[0556] R' independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, an alkenyl group, a hydroxyl group, an alkoxy group, an acyloxy group, a cyano group, a nitro group, an amino group, a halogen atom, an ester group (-OCOR" or -COOR": R" is an alkyl group or a fluorinated alkyl group having 1 to 20 carbon atoms) or a carboxyl group. In addition, the above-mentioned alkyl group, the above-mentioned cycloalkyl group, the above-mentioned aryl group, the above-mentioned aralkyl group and the above-mentioned alkenyl group may each have a substituent. Furthermore, a hydrogen atom bonded to a carbon atom in the group represented by R' may be substituted by a fluorine atom or an iodine atom.

[0557] m represents an integer greater than or equal to 0. The upper limit of m is not particularly limited, but is usually 2 or less, and often 1 or less.

[0558] Furthermore, in formula (E-2), formula (E-4), formula (E-6) and formula (E-8), two Rs may be bonded to each other to form a ring.

[0559] The content of the repeating unit represented by formula (E) is preferably 5 mol% or more, more preferably 10 mol% or more, relative to all repeating units in resin (A), and its upper limit is preferably 60 mol% or less, more preferably 55 mol% or less.

[0560] <Repeating unit having at least one group selected from a lactone group, a sultone group, a carbonate group, a hydroxyl group, a cyano group, and an alkali-soluble group>

[0561] The resin (A) may include a repeating unit having at least one group selected from the group consisting of a lactone group, a sultone group, a carbonate group, a hydroxyl group, a cyano group, and an alkali-soluble group.

[0562] Examples of the repeating unit having a lactone group, a sultone group or a carbonate group in the resin (A) include the repeating units described in the above <Repeating unit having a lactone group, a sultone group or a carbonate group>. The preferred content is also the same as described in the above <Repeating unit having a lactone group, a sultone group or a carbonate group>.

[0563] The resin (A) may contain a repeating unit having a hydroxyl group or a cyano group. This improves substrate adhesion and developer affinity.

[0564] The repeating unit having a hydroxyl group or a cyano group is preferably a repeating unit having an alicyclic hydrocarbon structure substituted with a hydroxyl group or a cyano group.

[0565] The repeating unit having a hydroxyl group or a cyano group preferably has no acid-decomposable group.

[0566] Examples of the repeating unit having a hydroxyl group or a cyano group include repeating units represented by the following general formulae (AIIa) to (AIId).

[0567] [Chemical formula 56]

[0568]

[0569] In general formula (AIIa) to general formula (AIId),

[0570] R 1c represents a hydrogen atom, a methyl group, a trifluoromethyl group or a hydroxymethyl group.

[0571] R 2c ~R 4c Each independently represents a hydrogen atom, a hydroxyl group or a cyano group. 2c ~R 4c At least one of represents a hydroxyl group or a cyano group. 2c~R 4c One or two of them are hydroxyl groups, and the rest are hydrogen atoms. 2c ~R 4c Two of them are hydroxyl groups and the rest are hydrogen atoms.

[0572] The content of the repeating unit having a hydroxyl group or a cyano group is preferably 5 mol% or more, more preferably 10 mol% or more, relative to all the repeating units in the resin (A). And, as an upper limit, it is preferably 40 mol% or less, more preferably 35 mol% or less, and further preferably 30 mol% or less.

[0573] Specific examples of the repeating unit having a hydroxyl group or a cyano group are given below, but the present invention is not limited to these.

[0574] [Chemical formula 57]

[0575]

[0576] The resin (A) may contain a repeating unit having an alkali-soluble group.

[0577] Examples of the alkali-soluble group include carboxyl, sulfonamide, sulfonimide, bissulfonimide, and aliphatic alcohol groups substituted with electron-withdrawing groups at the α position (e.g., hexafluoroisopropanol), preferably carboxyl. When the resin (A) contains a repeating unit having an alkali-soluble group, the resolution in contact hole applications is improved.

[0578] Examples of the repeating unit having an alkali-soluble group include a repeating unit in which an alkali-soluble group is directly bonded to the main chain of the resin, such as a repeating unit formed of acrylic acid and methacrylic acid, or a repeating unit in which an alkali-soluble group is bonded to the main chain of the resin via a linking group. In addition, the linking group may have a monocyclic or polycyclic cyclic hydrocarbon structure.

[0579] As the repeating unit having an alkali-soluble group, a repeating unit composed of acrylic acid or methacrylic acid is preferred.

[0580] The content of the repeating unit having an alkali-soluble group is preferably 0 mol% or more, more preferably 3 mol% or more, and further preferably 5 mol% or more relative to all repeating units in the resin (A). As its upper limit, it is preferably 20 mol% or less, more preferably 15 mol% or less, and further preferably 10 mol% or less.

[0581] Specific examples of the repeating unit having an alkali-soluble group are shown below, but the present invention is not limited thereto. In the specific examples, Rx represents H, CH3, CH2OH or CF3.

[0582] [Chemical formula 58]

[0583]

[0584] As a repeating unit having at least one group selected from a lactone group, a hydroxyl group, a cyano group and an alkali-soluble group, it is preferably a repeating unit having at least two groups selected from a lactone group, a hydroxyl group, a cyano group and an alkali-soluble group, more preferably a repeating unit having a cyano group and a lactone group, and further preferably a repeating unit having a structure substituted by a cyano group in the lactone structure represented by the general formula (LC1-4).

[0585] <Repeating unit having an alicyclic hydrocarbon structure and not showing acid decomposability>

[0586] The resin (A) may also contain a repeating unit having an alicyclic hydrocarbon structure and not showing acid decomposability. Thus, it is possible to reduce the dissolution of low molecular weight components from the resist film into the immersion liquid during immersion exposure. Examples of such repeating units include repeating units derived from 1-adamantyl (meth)acrylate, diamantyl (meth)acrylate, tricyclodecyl (meth)acrylate, or cyclohexyl (meth)acrylate.

[0587] <Repeating unit having neither a hydroxyl group nor a cyano group and represented by the general formula (III)>

[0588] The resin (A) may include a repeating unit having neither a hydroxyl group nor a cyano group and represented by the general formula (III).

[0589] [Chemical formula 59]

[0590]

[0591] In the general formula (III), R5 represents a hydrocarbon group having at least one cyclic structure and having neither a hydroxyl group nor a cyano group.

[0592] Ra represents a hydrogen atom, an alkyl group or a -CH2-O-Ra2 group. In the formula, Ra2 represents a hydrogen atom, an alkyl group or an acyl group.

[0593] The cyclic structure of R5 includes monocyclic hydrocarbon groups and polycyclic hydrocarbon groups. Examples of the monocyclic hydrocarbon group include cycloalkyl groups having 3 to 12 carbon atoms (more preferably 3 to 7 carbon atoms) or cycloalkenyl groups having 3 to 12 carbon atoms.

[0594] Examples of the polycyclic hydrocarbon group include a ring-aggregated hydrocarbon group and a cross-linked cyclic hydrocarbon group.

[0595] Examples of the crosslinked hydrocarbon ring include a bicyclic hydrocarbon ring, a tricyclic hydrocarbon ring, and a tetracyclic hydrocarbon ring, etc. Furthermore, the crosslinked hydrocarbon ring may include a condensed ring in which a plurality of 5- to 8-membered cycloalkane rings are condensed.

[0596] As the cross-linked cyclic hydrocarbon group, it is preferred to use a norbornyl group, an adamantyl group, a bicyclooctyl group or a tricyclo[5,2,1,0 2,6 ]decyl, more preferably norbornyl or adamantyl.

[0597] The alicyclic hydrocarbon group may have a substituent, and examples of the substituent include a halogen atom, an alkyl group, a hydroxyl group protected by a protecting group, and an amino group protected by a protecting group.

[0598] The halogen atom is preferably a bromine atom, a chlorine atom or a fluorine atom.

[0599] The alkyl group is preferably a methyl group, an ethyl group, a butyl group or a tert-butyl group.

[0600] The above-mentioned alkyl group may further have a substituent, and examples of the substituent include a halogen atom, an alkyl group, a hydroxyl group protected by a protecting group, or an amino group protected by a protecting group.

[0601] Examples of the protecting group include an alkyl group, a cycloalkyl group, an aralkyl group, a substituted methyl group, a substituted ethyl group, an alkoxycarbonyl group, and an aralkyloxycarbonyl group.

[0602] The alkyl group is preferably an alkyl group having 1 to 4 carbon atoms.

[0603] The substituted methyl group is preferably a methoxymethyl group, a methoxythiomethyl group, a benzyloxymethyl group, a tert-butoxymethyl group or a 2-methoxyethoxymethyl group.

[0604] As the substituted ethyl group, 1-ethoxyethyl or 1-methyl-1-methoxyethyl is preferred.

[0605] The acyl group is preferably an aliphatic acyl group having 1 to 6 carbon atoms, such as formyl, acetyl, propionyl, butyryl, isobutyryl, valeryl and pivaloyl.

[0606] The alkoxycarbonyl group is preferably an alkoxycarbonyl group having 1 to 4 carbon atoms.

[0607] The content of the repeating unit having neither a hydroxyl group nor a cyano group and represented by the general formula (III) is preferably 0 to 40 mol %, more preferably 0 to 20 mol %, based on all the repeating units in the resin (A).

[0608] Specific examples of the repeating unit represented by the general formula (III) are given below, but the present invention is not limited thereto. In the specific examples, Ra represents H, CH3, CH2OH or CF3.

[0609] [Chemical formula 60]

[0610]

[0611] <Other repeating units>

[0612] The resin (A) may contain repeating units other than the above-mentioned repeating units.

[0613] For example, the resin (A) may include a repeating unit selected from the group consisting of a repeating unit having an oxathiane ring group, a repeating unit having an oxazorone ring group, a repeating unit having a dioxane ring group, and a repeating unit having a hydantoin ring group.

[0614] Such repeating units are exemplified below.

[0615] [Chemical formula 61]

[0616]

[0617] In addition to the above-mentioned repeating structural units, the resin (A) may have various repeating structural units for the purpose of adjusting dry etching resistance, compatibility with standard developer, substrate adhesion, resist profile, resolution, heat resistance, sensitivity, etc.

[0618] As the resin (A), (especially when the composition is used as an ArF photosensitive ray or radiation-sensitive resin composition) it is also preferred that all repeating units consist of (meth)acrylate repeating units. In this case, any one of the following repeating units can be used, namely, a repeating unit in which all repeating units are methacrylate repeating units, a repeating unit in which all repeating units are acrylate repeating units, and a repeating unit in which all repeating units are composed of methacrylate repeating units and acrylate repeating units, and the acrylate repeating units are preferably 50 mol% or less of all repeating units.

[0619] The resin (A) can be synthesized according to a conventional method (eg, radical polymerization).

[0620] The weight average molecular weight of the resin (A) is preferably 1,000 to 200,000, more preferably 3,000 to 20,000, and even more preferably 5,000 to 15,000 as a polystyrene conversion value based on the GPC method. By setting the weight average molecular weight of the resin (A) to 1,000 to 200,000, it is possible to further suppress the deterioration of heat resistance and dry etching resistance. In addition, it is possible to further suppress the deterioration of film forming properties due to deterioration of developability and increased viscosity.

[0621] The dispersity (molecular weight distribution) of the resin (A) is usually 1 to 5, preferably 1 to 3, more preferably 1.2 to 3.0, and further preferably 1.2 to 2.0. The smaller the dispersity, the better the resolution and resist shape, and the smoother the sidewall of the resist pattern and the better the roughness.

[0622] In the composition of the present invention, the content of the resin (A) is preferably 50 to 99.9% by mass, more preferably 60 to 99.0% by mass, based on the total solid content of the composition.

[0623] In addition, the solid content means the components other than the solvent in the composition, and any component other than the solvent, even if it is a liquid component, is regarded as a solid content.

[0624] Furthermore, the resin (A) may be used alone or in combination of two or more.

[0625] 〔Photoacid generator〕

[0626] The composition of the present invention may include a compound that generates an acid by irradiation with actinic rays or radiation (hereinafter, also referred to as an "acid generator").

[0627] The photoacid generator referred to herein corresponds to an acid generator generally used to cause a deprotection reaction of a resin component (deprotection reaction of an acid-decomposable resin) or to cause a cross-linking reaction of a resin component.

[0628] The photoacid generator is preferably a compound that generates an organic acid by irradiation with actinic rays or radiation, for example, sulfonium salt compounds, iodonium salt compounds, diazonium salt compounds, phosphonium salt compounds, imide sulfonate compounds, oxime sulfonate compounds, diazodisulfone compounds, disulfone compounds and o-nitrobenzylsulfonate compounds.

[0629] As the photoacid generator, a known compound that generates an acid by irradiation with actinic rays or radiation can be appropriately selected and used alone or as a mixture thereof. For example, known compounds disclosed in paragraphs <0125> to <0319> in U.S. Patent Application Publication No. 2016 / 0070167A1, paragraphs <0086> to <0094> in U.S. Patent Application Publication No. 2015 / 0004544A1, and paragraphs <0323> to <0402> in U.S. Patent Application Publication No. 2016 / 0237190A1 can be preferably used as the photoacid generator.

[0630] As the photoacid generator, for example, a compound represented by the following formula (ZI), formula (ZII) or formula (ZIII) is preferred.

[0631] [Chemical formula 62]

[0632]

[0633] In the above general formulae (ZI) and (ZII), R 201 , R 202 , R 203 , R204 and R 205 The same as R in the general formula (ZaI) and (ZaII) described in the description of the specific compound 201 , R 202 , R 203 , R 204 and R 205 Respectively the same.

[0634] In other words, the cation moieties in the above general formulae (ZI) and (ZII) are the same as the cation (ZaI) and cation (ZaII) described in the description of the specific compound, respectively.

[0635] Furthermore, in the general formula (ZIII), R 206 and R 207 and R in the general formula (ZII) 204 and R 205 That is, in the general formula (ZIII), R 206 and R 207 and R in the general formula (ZaII) 204 and R 205 Respectively the same.

[0636] In the general formula (ZI) and (ZII), Z - Represents an anion. Represents an anion (anion with significantly low ability to cause nucleophilic reaction).

[0637] Examples of the anion include sulfonic acid anions (aliphatic sulfonic acid anions, aromatic sulfonic acid anions, camphorsulfonic acid anions, etc.), carboxylic acid anions (aliphatic carboxylic acid anions, aromatic carboxylic acid anions, aralkyl carboxylic acid anions, etc.), sulfonylimide anions, bis(alkylsulfonyl)imide anions, and tris(alkylsulfonyl)methylated anions.

[0638] As Z in formula (ZI) - And Z in formula (ZII) - , preferably an anion represented by the following formula (3).

[0639] [Chemical formula 63]

[0640]

[0641] In formula (3),

[0642] o represents an integer of 1 to 3. p represents an integer of 0 to 10. q represents an integer of 0 to 10.

[0643] Xf represents a fluorine atom or an alkyl group substituted with at least one fluorine atom. The number of carbon atoms in the alkyl group is preferably 1 to 10, more preferably 1 to 4. The alkyl group substituted with at least one fluorine atom is preferably a perfluoroalkyl group.

[0644] Xf is preferably a fluorine atom or a perfluoroalkyl group having 1 to 4 carbon atoms, and more preferably a fluorine atom or CF 3. In particular, it is further preferred that both Xf are fluorine atoms.

[0645] R4 and R5 each independently represent a hydrogen atom, a fluorine atom, an alkyl group, or an alkyl group substituted with at least one fluorine atom. When there are a plurality of R4 and R5, R4 and R5 may be the same or different.

[0646] The alkyl group represented by R4 and R5 may have a substituent, and preferably has a carbon number of 1 to 4. R4 and R5 are preferably hydrogen atoms.

[0647] Specific examples and preferred embodiments of the alkyl group substituted with at least one fluorine atom are the same as the specific examples and preferred embodiments of Xf in formula (3).

[0648] L represents a divalent linking group. When there are a plurality of L, L may be the same or different.

[0649] Examples of divalent linking groups include -O-CO-O-, -COO-, -OCO-, -CONH-, -NHCO-, -CO-, -O-, -S-, -SO-, -SO2-, alkylene (preferably having 1 to 6 carbon atoms), cycloalkylene (preferably having 3 to 15 carbon atoms), alkenylene (preferably having 2 to 6 carbon atoms), and divalent linking groups formed by combining a plurality of these. Among them, preferred are -O-CO-O-, -COO-, -OCO-, -CONH-, -NHCO-, -CO-, -O-, -SO2-, -O-CO-O-alkylene-, -alkylene-O-CO-O-, -COO-alkylene-, -OCO-alkylene-, -CONH-alkylene- or -NHCO-alkylene-, and more preferred are -O-CO-O-, -O-CO-O-alkylene-, -alkylene-O-CO-O-, -COO-, -OCO-, -CONH-, -SO2-, -COO-alkylene- or -OCO-alkylene-.

[0650] W represents an organic group including a cyclic structure, among which a cyclic organic group is preferred.

[0651] Examples of the cyclic organic group include an alicyclic group, an aryl group, and a heterocyclic group.

[0652] The alicyclic group may be monocyclic or polycyclic. As the monocyclic alicyclic group, for example, monocyclic cycloalkyl groups such as cyclopentyl, cyclohexyl and cyclooctyl can be cited. As the polycyclic alicyclic group, for example, polycyclic cycloalkyl groups such as norbornyl, tricyclodecyl, tetracyclodecyl, tetracyclododecyl and adamantyl can be cited. Among them, the alicyclic group having a bulky structure with a carbon number of 7 or more, such as norbornyl, tricyclodecyl, tetracyclodecyl, tetracyclododecyl and adamantyl, is preferred.

[0653] The aryl group may be monocyclic or polycyclic. Examples of the aryl group include phenyl, naphthyl, phenanthrenyl and anthracenyl.

[0654] The heterocyclic group may be monocyclic or polycyclic. A polycyclic heterocyclic group can further inhibit the diffusion of acid. In addition, the heterocyclic group may or may not be aromatic. As heterocyclic rings with aromaticity, for example, furan rings, thiophene rings, benzofuran rings, benzothiophene rings, dibenzofuran rings, dibenzothiophene rings and pyridine rings may be mentioned. As heterocyclic rings without aromaticity, for example, tetrahydropyran rings, lactone rings, sultone rings and decahydroisoquinoline rings may be mentioned. As heterocyclic rings in heterocyclic groups, furan rings, thiophene rings, pyridine rings or decahydroisoquinoline rings are particularly preferred.

[0655] The above-mentioned cyclic organic group may have a substituent. As such a substituent, for example, an alkyl group (may be any of a linear or branched group, preferably having 1 to 12 carbon atoms), a cycloalkyl group (may be any of a monocyclic, polycyclic or spirocyclic group, preferably having 3 to 20 carbon atoms), an aryl group (preferably having 6 to 14 carbon atoms), a hydroxyl group, an alkoxy group, an ester group, an amide group, a carbamate group, a urea group, a thioether group, a sulfonamide group and a sulfonate group may be mentioned. In addition, the carbon constituting the cyclic organic group (the carbon contributing to the formation of the ring) may be a carbonyl carbon.

[0656] As the anion represented by formula (3), SO3 is preferred. - -CF2-CH2-OCO-(L)q'-W、SO3 - -CF2-CHF-CH2-OCO-(L)q'-W、SO3 - -CF2-COO-(L)q'-W、SO3 - -CF2-CF2-CH2-CH2-(L)qW or SO3 - -CF2-CH(CF3)-OCO-(L)q'-W. Here, L, q and W are the same as those in formula (3). q' represents an integer of 0 to 10.

[0657] As Z in formula (ZI) - And Z in formula (ZII) -, and an anion represented by the following formula (4) is also preferred.

[0658] [Chemical formula 64]

[0659]

[0660] In formula (4),

[0661] X B1 and X B2 Each independently represents a hydrogen atom or a monovalent organic group having no fluorine atom. B1 and X B2 Preferred is a hydrogen atom.

[0662] X B3 and X B4 Each independently represents a hydrogen atom or a monovalent organic group. B3 and X B4 At least one of X is a fluorine atom or a monovalent organic group having a fluorine atom, and more preferably X B3 and X B4 Both of them are fluorine atoms or monovalent organic groups having fluorine atoms. B3 and X B4 Both of these are alkyl groups substituted with fluorine.

[0663] L, q and W are the same as those in formula (3).

[0664] As Z in formula (ZI) - And Z in formula (ZII) - , preferably an anion represented by the following formula (5).

[0665] [Chemical formula 65]

[0666]

[0667] In formula (5), Xa each independently represents a fluorine atom or an alkyl group substituted with at least one fluorine atom. Xb each independently represents a hydrogen atom or an organic group without a fluorine atom. The definitions and preferred embodiments of o, p, q, R4, R5, L and W are the same as those of formula (3).

[0668] As Z in formula (ZI) - And Z in formula (ZII) - , and an anion represented by the following formula (6) is also preferred.

[0669] [Chemical formula 66]

[0670]

[0671] In formula (6), R 1 and R2 Each independently represents a substituent which is not an electron withdrawing group or a hydrogen atom.

[0672] Examples of the substituent that is not an 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.

[0673] 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.

[0674] Examples of the monovalent hydrocarbon group represented by the above R' include:

[0675] Alkyl groups such as methyl, ethyl, propanol, and butyl; alkenyl groups such as vinyl, propenyl, and butenyl; alkynyl groups such as ethynyl, propynyl, and butynyl; monovalent chain hydrocarbon groups;

[0676] Cycloalkyl groups such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, norbornyl and adamantyl; cycloalkenyl groups such as cyclopropenyl, cyclobutenyl, cyclopentenyl and norbornyl; monovalent alicyclic hydrocarbon groups;

[0677] Aryl groups such as phenyl, tolyl, xylyl, mesityl, naphthyl, methylnaphthyl, anthracenyl, and methylanthryl; aralkyl groups such as benzyl, phenethyl, phenylpropyl, naphthylmethyl, and anthracenyl; and monovalent aromatic hydrocarbon groups.

[0678] Among them, R 1 and R 2 Each independently is preferably a hydrocarbon group (preferably a cycloalkyl group) or a hydrogen atom.

[0679] In formula (6), L represents a divalent linking group consisting of a combination of one or more linking groups S and one or more alkylene groups which may have a substituent, or a divalent linking group consisting of one or more linking groups S.

[0680] The linking group 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-* BThe groups in the group.

[0681] When L is a form of "a divalent linking group consisting of a combination of one or more linking groups S and one or more alkylene groups which may have a substituent", "a divalent linking group consisting of a combination of one or more linking groups S and one or more alkylene groups which may not have a substituent", the linking group S is preferably 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 In other words, when the alkylene groups in the "divalent connecting group consisting of one or more connecting groups S and one or more alkylene groups which may have a substituent" are all unsubstituted alkylene groups, the connecting group S is preferably 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.

[0682] * A R in expression (6) 3 Bonding position on the side, * B In the expression (6), -SO3 - side bonding position.

[0683] In a divalent linking group consisting of a combination of one or more linking groups S and one or more alkylene groups that may have a substituent, there may be only one linking group S or two or more. Similarly, there may be only one alkylene group that may have a substituent or two or more. When there are multiple linking groups S, the multiple linking groups S may be the same or different. When there are multiple alkylene groups, the multiple alkylene groups may be the same or different.

[0684] 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 ”.

[0685] In the divalent linking group composed of one or more linking groups S, there may be only one linking group S, or there may be two or more linking groups S. When there are multiple linking groups S, the linking groups S when there are multiple linking groups S may be the same or different.

[0686] In this case, it is also preferred to select 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 ”.

[0687] However, in any case, in L, relative to -SO3 - , the atom at the β-position is not a carbon atom having a fluorine atom as a substituent.

[0688] When the atom at the β-position is a carbon atom, the carbon atom need not be directly substituted with a fluorine atom, but may have a substituent having a fluorine atom (for example, a fluoroalkyl group such as a trifluoromethyl group).

[0689] In other words, the atom at the β position is the atom that is identical to -C(R 1 )(R 2 )-directly bonded to an atom in L.

[0690] In this case, L preferably has only one linking group S.

[0691] That is, L preferably represents a divalent linking group consisting of a combination of one linking group S and one or more alkylene groups which may have a substituent, or a divalent linking group consisting of one linking group S.

[0692] For example, L is preferably a group represented by the following formula (6-2).

[0693] * a -(CR 2a 2) X -Q-(CR 2b 2) Y -* b (6-2)

[0694] In formula (6-2), * a It is expressed as R in formula (6) 3 bonding position.

[0695] * b It represents the same as -C(R 1 )(R 2 )-bonding position.

[0696] X and Y each independently represent an integer of 0-10, and preferably an integer of 0-3.

[0697] R 2a and R 2b Each independently represents a hydrogen atom or a substituent.

[0698] When R 2a and R 2b When there are multiple R 2a and R 2b They may be the same or different.

[0699] When Y is 1 or more, it is the same as -C(R 1 )(R 2 )- Direct Bonding CR 2b R in 2 2b It is an atom other than a fluorine atom.

[0700] 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 .

[0701] Wherein, when X+Y in formula (6-2) is 1 or more and R in formula (6-2) 2a and R 2b When all 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 .

[0702] * A R in expression (6) 3 Bonding position on the side, * B In the expression (6), -SO3 - side bonding position.

[0703] In formula (6), R 3 Represents an organic group.

[0704] The organic group is not limited as long as it has more than 1 carbon atom, and may be a linear group (e.g., a linear alkyl group), a branched group (e.g., a branched alkyl group such as 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 (e.g., an oxygen atom, a sulfur atom, and / or a nitrogen atom, etc.).

[0705] Among them, R 3 Preferably, it is an organic group having a cyclic structure. The cyclic structure may be monocyclic or polycyclic and may have a substituent. The ring in the organic group having a cyclic structure is preferably directly bonded to L in formula (6).

[0706] The organic group having a cyclic structure may or may not have a heteroatom (oxygen atom, sulfur atom and / or nitrogen atom, etc.), for example. The heteroatom may be substituted by one or more carbon atoms forming a cyclic structure.

[0707] The organic group having a 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 a cyclic structure is preferably a hydrocarbon group having a cyclic structure.

[0708] The hydrocarbon group having a cyclic structure is preferably a monocyclic or polycyclic cycloalkyl group. These groups may have a substituent.

[0709] The cycloalkyl group may be a monocyclic group (cyclohexyl group, etc.) or a polycyclic group (adamantyl group, etc.), and preferably has 5 to 12 carbon atoms.

[0710] As the above-mentioned lactone group and sultone group, for example, preferably, in any of the structures represented by the above-mentioned general formulas (LC1-1) to (LC1-21) and the structures represented by the general formulas (SL1-1) to (SL1-3), a group formed by removing one hydrogen atom from a ring atom constituting the lactone structure or the sultone structure.

[0711] As Z in formula (ZI) - And Z in formula (ZII) - , may be a benzenesulfonate anion, preferably a benzenesulfonate anion substituted by a branched alkyl group or a cycloalkyl group.

[0712] As Z in formula (ZI) - And Z in formula (ZII) - , and an aromatic sulfonic acid anion represented by the following formula (SA1) is also preferred.

[0713] [Chemical formula 67]

[0714]

[0715] In formula (SA1),

[0716] Ar represents an aryl group, and may have a substituent other than the sulfonic acid anion and the -(DB) group. Examples of the substituent that may be present include a fluorine atom and a hydroxyl group.

[0717] n represents an integer greater than or equal to 0. n is preferably 1 to 4, more preferably 2 to 3, and even more preferably 3.

[0718] D represents a single bond or a divalent linking group. Examples of the divalent linking group include an ether group, a thioether group, a carbonyl group, a sulfoxide group, a sulfone group, a sulfonate group, an ester group, and a group composed of two or more thereof in combination.

[0719] B represents a hydrocarbon group.

[0720] Preferably, D is a single bond, and B is an aliphatic hydrocarbon structure. More preferably, B is an isopropyl group or a cyclohexyl group.

[0721] Preferred examples of the sulfonium cation in the formula (ZI) and the iodonium cation in the formula (ZII) are shown below.

[0722] [Chemical formula 68]

[0723]

[0724] The anion Z in the formula (ZI) is shown below: - and the anion Z in formula (ZII) - A preferred example of .

[0725] [Chemical formula 69]

[0726]

[0727] [Chemical formula 70]

[0728]

[0729] Any combination of the above-mentioned cations and anions can be used as the photoacid generator.

[0730] Furthermore, the photoacid generator may have a cationic group (e.g., -I + -、>S + - etc.) and anionic groups (e.g., -SO3 - ), and the cationic group and the anionic group are linked by a covalent bond.

[0731] Examples of such betaine compounds include compound (ZbI) and compound (ZbII).

[0732] The compound (ZbI) is a compound represented by a newly defined general formula: In the general formula (ZaI), R 201 ~R 203 One of them is a group obtained by removing w from the above formula (3), a group obtained by removing w from the above formula (4), a group obtained by removing w from the above formula (5), and a group obtained by removing R from the above formula (6) 3 An aryl group in which any one of the groups formed is used as a substituent.

[0733] The above compound (ZbII) is a compound represented by a newly defined general formula: In the above general formula (ZaII), R 204 and R 205One of them is a group obtained by removing w from the above formula (3), a group obtained by removing w from the above formula (4), a group obtained by removing w from the above formula (5), and a group obtained by removing R from the above formula (6) 3 An aryl group in which any one of the groups formed is used as a substituent.

[0734] An example of the photoacid generator as a betaine compound and the compound represented by the formula (ZIII) are shown below.

[0735] [Chemical formula 71]

[0736]

[0737] The photoacid generator may be in the form of a low molecular weight compound or in the form of being embedded in a part of a polymer. Furthermore, the form of a low molecular weight compound and the form of being embedded in a part of a polymer may be used in combination.

[0738] The photoacid generator is preferably in the form of a low molecular weight compound.

[0739] 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 further preferably 1,000 or less.

[0740] When the photoacid generator is in a form of being embedded in a part of a polymer, the photoacid generator may be embedded in a part of the resin X described above, or may be embedded in a resin different from the resin X.

[0741] The photoacid generator may be used alone or in combination of two or more.

[0742] In the composition, the content of the photoacid generator (when multiple types are present, the total amount) is preferably 0.1 to 35.0 mass %, more preferably 0.3 to 25.0 mass %, and even more preferably 0.5 to 20.0 mass % based on the total solid content of the composition.

[0743] When a compound having a cation (ZaI-3b) or a cation (ZaI-4b) is included as the photoacid generator, the content of the photoacid generator contained in the composition (when there are multiple types, the total) is preferably 0.2 to 35.0 mass %, more preferably 0.5 to 30.0 mass %, based on the total solid content of the composition.

[0744] 〔Acid diffusion control agent〕

[0745] The composition of the present invention may contain an acid diffusion controller.

[0746] The acid diffusion controller captures the acid generated from the photoacid generator, etc. during exposure, and functions as a quencher that inhibits the reaction of the acid-decomposable resin in the unexposed portion due to the excessively generated acid. As the acid diffusion controller, for example, a basic compound (DA), a basic compound (DB) whose basicity is reduced or eliminated by irradiation with actinic rays or radiation, an onium salt (DC) that becomes a relatively weak acid relative to the acid generator, a low molecular compound (DD) having a nitrogen atom and a group that is separated by the action of an acid, and an onium salt compound (DE) having a nitrogen atom in the cationic portion can be used. In the composition of the present invention, a known acid diffusion controller can be appropriately used. For example, known compounds disclosed in paragraphs <0627> to <0664> in U.S. Patent Application Publication No. 2016 / 0070167A1, paragraphs <0095> to <0187> in U.S. Patent Application Publication No. 2015 / 0004544A1, paragraphs <0403> to <0423> in U.S. Patent Application Publication No. 2016 / 0237190A1, and paragraphs <0259> to <0328> in U.S. Patent Application Publication No. 2016 / 0274458A1 can be preferably used as acid diffusion controllers.

[0747] <Basic compounds (DA)>

[0748] As the basic compound (DA), compounds having structures represented by the following formulae (A) to (E) are preferred.

[0749] [Chemical formula 72]

[0750]

[0751] In the general formula (A) and the general formula (E),

[0752] R 200 , R 201 and R 202 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 (having 6 to 20 carbon atoms). 201 With R 202 They may be bonded to each other to form a ring.

[0753] R 203 , R 204 , R 205 and R 206 They may be the same or different and each independently represents an alkyl group having 1 to 20 carbon atoms.

[0754] The alkyl group in the general formula (A) and the general formula (E) may have a substituent or may be unsubstituted.

[0755] 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.

[0756] The alkyl group in the general formula (A) and the general formula (E) is more preferably unsubstituted.

[0757] The basic compound (DA) is preferably guanidine, aminopyrrolidine, pyrazole, pyrazoline, piperazine, aminomorpholine, aminoalkylmorpholine or piperidine, and more preferably an imidazole structure, a diazabicyclic structure, an onium hydroxide structure, an onium carboxylate structure, a trialkylamine structure, a compound having an aniline structure or a pyridine structure, an alkylamine derivative having a hydroxyl group and / or an ether bond, or an aniline derivative having a hydroxyl group and / or an ether bond.

[0758] <Basic compounds whose basicity is reduced or eliminated by irradiation with actinic rays or radiation (DB)>

[0759] A basic compound (DB) whose basicity is reduced or eliminated by irradiation with actinic rays or radiation (hereinafter also referred to as "compound (DB)") is a compound having a proton accepting functional group and which is decomposed by irradiation with actinic rays or radiation so that the proton accepting property is reduced, eliminated, or changes from proton accepting property to acidic property.

[0760] The proton accepting functional group is a functional group having a group or electron that can electrostatically interact with a proton, and for example, it refers to a functional group having a macrocyclic compound structure such as a cyclic polyether, or a functional group having a nitrogen atom having an unshared electron pair that does not contribute to π conjugation. The nitrogen atom having an unshared electron pair that does not contribute to π conjugation is, for example, a nitrogen atom having a partial structure represented by the following formula.

[0761] [Chemical formula 73]

[0762]

[0763] Preferred partial structures of the proton accepting functional group include, for example, a crown ether structure, an azacrown ether structure, a primary amine structure, a secondary amine structure, a tertiary amine structure, a pyridine structure, an imidazole structure, and a pyrazine structure.

[0764] Compound (DB) generates a compound that is decomposed by irradiation with actinic rays or radiation, thereby reducing or eliminating proton accepting properties or changing from proton accepting properties to acidic properties. Here, the reduction or disappearance of proton accepting properties or the change from proton accepting properties to acidic properties is a change in proton accepting properties caused by the addition of protons to proton accepting functional groups, and specifically, it means that when a proton adduct is generated from a compound (DB) having a proton accepting functional group and a proton, the equilibrium constant in the chemical equilibrium decreases.

[0765] The proton acceptor property can be confirmed by performing pH measurement.

[0766] The acid dissociation constant pKa of the compound generated by decomposition of the compound (DB) by irradiation with actinic rays or radiation preferably satisfies pKa<-1, more preferably -13<pKa<-1, and further preferably -13<pKa<-3.

[0767] In addition, the acid dissociation constant pKa can be obtained by the above method.

[0768] <Onium salt (DC) that is a relatively weak acid relative to the photoacid generator>

[0769] In the composition of the present invention, an onium salt (DC) that is a relatively weak acid relative to the photoacid generator may be used as an acid diffusion controller.

[0770] When a photoacid generator is used in combination with an onium salt that generates an acid that is relatively weak relative to the acid generated from the photoacid generator, if the acid generated from the photoacid generator collides with the onium salt having unreacted weak acid anions by irradiation with actinic rays or radiation, the weak acid is released by salt exchange to generate an onium salt having strong acid anions. In this process, the strong acid is exchanged for a weak acid having a lower catalytic ability, so that the acid is apparently inactivated and the acid diffusion can be controlled.

[0771] As the onium salt that becomes a relatively weak acid with respect to the photoacid generator, compounds represented by the following general formulae (d1-1) to (d1-3) are preferred.

[0772] [Chemical formula 74]

[0773]

[0774] In the general formulas (d1-1) to (d1-3), R 51 is a hydrocarbon group which may have a substituent. 2c is a hydrocarbon group having 1 to 30 carbon atoms which may have a substituent (wherein the carbon adjacent to S does not have a fluorine atom and / or a fluoroalkyl group as a substituent). 2c -SO3 -" is preferably different from the anions represented by formulae (3) to (6) and formula (SA1) mentioned in the description of the photoacid generator. 52 is an organic group (alkyl, etc.), Y 3 is -SO2-, a linear, branched or cyclic alkylene or arylene group, Y 4 is -CO- or -SO2-, and Rf is a hydrocarbon group having a fluorine atom (such as a fluoroalkyl group). + are each independently an ammonium cation, a sulfonium cation or an iodonium cation.

[0775] As M + Preferred examples of the sulfonium cation or iodonium cation represented by the general formula (ZaI) and the iodonium cation represented by the general formula (ZaII) are mentioned.

[0776] The onium salt (DC) that is a relatively weak acid to the photoacid generator may be a compound having a cation site and an anion site in the same molecule and linked by a covalent bond (hereinafter also referred to as "compound (DCA)").

[0777] The compound (DCA) is preferably a compound represented by any one of the following general formulas (C-1) to (C-3).

[0778] [Chemical formula 75]

[0779]

[0780] In the general formulas (C-1) to (C-3),

[0781] R1, R2 and R3 each independently represent a substituent having 1 or more carbon atoms.

[0782] L1 represents a divalent linking group or a single bond that links the cationic part and the anionic part.

[0783] -X - Indicates selected from -COO - 、-SO3 - 、-SO2 - and -N - - Anionic site in R4: R4 represents a monovalent substituent having at least one of a carbonyl group (-C(=O)-), a sulfonyl group (-S(=O)2-) and a sulfinyl group (-S(=O)-) at the bonding site with the adjacent N atom.

[0784] R1, R2, R3, R4 and L1 may be bonded to each other to form a ring structure. In the general formula (C-3), two of R1 to R3 together represent a divalent substituent and may be bonded to the N atom via a double bond.

[0785] Examples of the substituent having 1 or more carbon atoms in R1 to R3 include alkyl, cycloalkyl, aryl, alkoxycarbonyl, cycloalkyloxycarbonyl, aryloxycarbonyl, alkylaminocarbonyl, cycloalkylaminocarbonyl and arylaminocarbonyl. Among them, alkyl, cycloalkyl or aryl is preferred.

[0786] As the divalent linking group L1, there can be mentioned a linear or branched alkylene group, a cycloalkylene group, an arylene group, 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 thereof. L1 is preferably an alkylene group, an arylene group, an ether bond, an ester bond, or a group formed by combining two or more thereof.

[0787] <Low molecular weight compound having a nitrogen atom and a group that is dissociated by the action of an acid (DD)>

[0788] The low molecular compound (DD) having a nitrogen atom and a group that is dissociated by the action of an acid (hereinafter, also referred to as "compound (DD)") is preferably an amine derivative having a group that is dissociated by the action of an acid on the nitrogen atom.

[0789] The group that is released by the action of an acid is preferably an acetal ester 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.

[0790] 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.

[0791] Compound (DD) may have a carbamate group having a protecting group on the nitrogen atom. The protecting group constituting the carbamate group is represented by the following general formula (d-1).

[0792] [Chemical formula 76]

[0793]

[0794] In the general formula (d-1),

[0795] 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 Can be connected to each other to form a ring.

[0796] R bThe alkyl, cycloalkyl, aryl and aralkyl groups represented by the above-mentioned groups may be independently substituted by a hydroxyl group, a cyano group, an amino group, a pyrrolidino group, a piperidino group, a morpholino group, an oxo group or the like, an alkoxy group or a halogen atom. b The same applies to the alkoxyalkyl groups represented.

[0797] 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.

[0798] As 2 R b Examples of the ring formed by mutually connecting hydrocarbons include alicyclic hydrocarbons, aromatic hydrocarbons, heterocyclic hydrocarbons, and derivatives thereof.

[0799] Examples of specific structures of the group represented by the general formula (d-1) include the structure disclosed in paragraph <0466> of US Patent Publication No. US2012 / 0135348A1, but the structure is not limited thereto.

[0800] The compound (DD) is preferably a compound represented by the following general formula (6).

[0801] [Chemical formula 77]

[0802]

[0803] In general formula (6),

[0804] l represents an integer of 0 to 2, m represents an integer of 1 to 3, and l+m=3 is satisfied.

[0805] R a represents 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.

[0806] R b The meaning of R in the above general formula (1) is b The same, preferred examples are also the same.

[0807] 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 as the following groups, which may be substituted as R b The alkyl, cycloalkyl, aryl and aralkyl groups are substituted.

[0808] As the above R aSpecific examples of the alkyl, cycloalkyl, aryl and aralkyl groups (these groups may be substituted by the above groups) include the same as for R b The same groups as the above specific examples.

[0809] Specific examples of particularly preferred compounds (DD) in the present invention include compounds disclosed in paragraph <0475> of US Patent Application Publication No. 2012 / 0135348A1, but are not limited thereto.

[0810] <Onium salt compound having a nitrogen atom in the cation part (DE)>

[0811] The onium salt compound (DE) having a nitrogen atom in the cation portion (hereinafter also referred to as "compound (DE)") is preferably a compound having a basic site containing a nitrogen atom in the cation portion. The basic site is preferably an amino group, more preferably an aliphatic amino group. It is further preferred that all atoms adjacent to the nitrogen atom in the basic site are hydrogen atoms or carbon atoms. Furthermore, from the viewpoint of improving basicity, it is preferred that the electron-withdrawing functional group (carbonyl, sulfonyl, cyano, halogen atom, etc.) is not directly connected to the nitrogen atom.

[0812] Preferred specific examples of compound (DE) include compounds disclosed in paragraph <0203> in the specification of US Patent Application Publication No. 2015 / 0309408A1, but are not limited thereto.

[0813] Preferred examples of the acid diffusion controller are shown below.

[0814] [Chemical formula 78]

[0815]

[0816] [Chemical formula 79]

[0817]

[0818] When the composition of the present invention contains an acid diffusion controller, the content of the acid diffusion controller (when there are two or more, the total amount) is preferably 0.1 to 11.0 mass %, more preferably 0.1 to 10.0 mass %, further preferably 0.1 to 8.0 mass %, and particularly preferably 0.1 to 5.0 mass % relative to the total solid content of the composition.

[0819] In the composition of the present invention, the acid diffusion controller may be used alone or in combination of two or more.

[0820] 〔Hydrophobic resin〕

[0821] The composition of the present invention may contain a hydrophobic resin other than the resin (A) in addition to the above-mentioned resin (A).

[0822] The hydrophobic resin is preferably designed to be localized on the surface of the resist film, but unlike the surfactant, it is not necessarily required to have a hydrophilic group in the molecule and may not contribute to uniform mixing of polar substances and non-polar substances.

[0823] Examples of the effects of adding a hydrophobic resin include control of static and dynamic contact angles of the resist film surface with respect to water and suppression of outgassing.

[0824] From the viewpoint of partial localization to the film surface, the hydrophobic resin preferably has any one or more of "fluorine atom", "silicon atom" and "CH3 partial structure contained in the side chain of the resin", and more preferably has two or more. In addition, the hydrophobic resin preferably has a hydrocarbon group with a carbon number of 5 or more. These groups may be present in the main chain of the resin or substituted in the side chain.

[0825] When the hydrophobic resin contains fluorine atoms and / or silicon atoms, the 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.

[0826] When the hydrophobic resin contains a fluorine atom, the partial structure having a fluorine atom is preferably an alkyl group having a fluorine atom, a cycloalkyl group having a fluorine atom, or an aryl group having a fluorine atom.

[0827] The alkyl group having a fluorine atom (preferably having 1 to 10 carbon atoms, more preferably having 1 to 4 carbon atoms) is a linear or branched alkyl group in which at least one hydrogen atom is substituted with a fluorine atom, and may have a substituent other than a fluorine atom.

[0828] The cycloalkyl group having a fluorine atom is a monocyclic or polycyclic cycloalkyl group in which at least one hydrogen atom is substituted with a fluorine atom, and may further have a substituent other than a fluorine atom.

[0829] Examples of the aryl group having a fluorine atom include a group in which at least one hydrogen atom in an aryl group such as a phenyl group and a naphthyl group is substituted with a fluorine atom, and the aryl group may further have a substituent other than a fluorine atom.

[0830] Examples of the repeating unit having a fluorine atom or a silicon atom include the repeating units exemplified in paragraph <0519> of US 2012 / 0251948A1.

[0831] Furthermore, as described above, it is also preferred that the hydrophobic resin contains a CH3 partial structure in the side chain portion.

[0832] Here, the CH3 partial structure of the side chain part in the hydrophobic resin includes the CH3 partial structure of an ethyl group, a propyl group, or the like.

[0833] On the other hand, the methyl group directly bonded to the main chain of the hydrophobic resin (for example, the α-methyl group of the repeating unit having a methacrylic acid structure) contributes little to the surface localization of the hydrophobic resin due to the influence of the main chain, and is therefore set as a CH3 partial structure not included in the present invention.

[0834] Regarding the hydrophobic resin, reference may be made to the description in paragraphs <0348> to <0415> in JP-A-2014-010245, and these contents are incorporated into the specification of the present application.

[0835] Moreover, as a hydrophobic resin, resins described in Japanese Unexamined Patent Publication No. 2011-248019, Japanese Unexamined Patent Publication No. 2010-175859, and Japanese Unexamined Patent Publication No. 2012-032544 can also be preferably used besides these.

[0836] Preferred examples of monomers corresponding to the repeating units constituting the hydrophobic resin are shown below.

[0837] [Chemical formula 80]

[0838]

[0839] [Chemical formula 81]

[0840]

[0841] When the composition of the present invention contains a hydrophobic resin, the content of the hydrophobic resin is preferably 0.01 to 20% by mass, more preferably 0.1 to 15% by mass, further preferably 0.1 to 10% by mass, and particularly preferably 0.1 to 6% by mass, based on the total solid content of the composition.

[0842] 〔Surfactant〕

[0843] The composition of the present invention may contain a surfactant. By containing a surfactant, a pattern with more excellent adhesion and fewer development defects can be formed.

[0844] As the surfactant, a fluorine-based and / or silicon-based surfactant is preferable.

[0845] 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. In addition, Eftop EF301 or EF303 (manufactured by Shin-Akita Kasei Co., Ltd.); Fluorad FC430, 431 or 4430 (manufactured by Sumitomo 3M Limited); Megaface F-171, F-173, F-176, F-189, F-113, F-110, F-177, F-120 or R08 (manufactured by DIC CORPORATION); Surflon S-382, SC101, 102, 103, 104, 105 or 106 (manufactured by ASAHI GLASS CO., LTD.); TroySol S-366 (manufactured by Troy Chemical Industries Inc.); GF-300 or GF-150 (manufactured by Toagosei Chemical Co., Ltd.), Surflon S-393 (manufactured by SEIMI CHEMICAL CO., LTD. manufacturing); Eftop EF121, EF122A, EF122B, RF122C, EF125M, EF135M, EF351, EF352, EF801, EF802 or EF601 (manufactured by Gemco Co., Ltd.); PF636, PF656, PF6320 or PF6520 (manufactured by OMNOVA Solutions Inc.); KH-20 (manufactured by Asahi Kasei Corporation); FTX-204G, 208G, 218G, 230G, 204D, 208D, 212D, 218D or 222D (manufactured by Neos Corporation). In addition, as a silicon-based surfactant, polysiloxane polymer KP-341 (manufactured by Shin-Etsu Chemical Co., Ltd.) can also be used.

[0846] In addition, the surfactant can be synthesized by using a fluoroaliphatic compound manufactured by a telomerization method (also called a short-chain polymer (telomer) method) or an oligomerization method (also called an oligomer method) in addition to the known surfactants shown above. Specifically, a polymer having a fluoroaliphatic group derived from the fluoroaliphatic compound can be used as a surfactant. The fluoroaliphatic compound can be synthesized by the method described in, for example, Japanese Patent Application Laid-Open No. 2002-90991.

[0847] As the polymer having a fluoroaliphatic group, a copolymer of a monomer having a fluoroaliphatic group and (poly(oxyalkylene))acrylate and / or (poly(oxyalkylene))methacrylate is preferred, which may be irregularly distributed or block copolymerized. Furthermore, as the poly(oxyalkylene) group, there may be mentioned a poly(oxyethylene) group, a poly(oxypropylene) group and a poly(oxybutylene) group, and it may also be a unit having alkylene groups of different chain lengths within the same chain length, such as poly(oxyethylene, a block conjugate of oxypropylene and oxyethylene) or a block conjugate of poly(oxyethylene and oxypropylene). In addition, the copolymer of a monomer having a fluoroaliphatic group and (poly(oxyalkylene))acrylate (or methacrylate) is not only a binary copolymer, but may also be a ternary or higher copolymer formed by simultaneously copolymerizing two or more different monomers having a fluoroaliphatic group and two or more different (poly(oxyalkylene))acrylates (or methacrylates).

[0848] For example, commercially available surfactants include Megaface F-178, F-470, F-473, F-475, F-476, and F-472 (manufactured by DIC CORPORATION), C6F 13 Copolymers of acrylate (or methacrylate) having a C3F7 group and (poly(oxyethylene)) acrylate (or methacrylate) and (poly(oxypropylene)) acrylate (or methacrylate).

[0849] Furthermore, surfactants other than the fluorine-based and / or silicon-based surfactants described in paragraph <0280> of US Patent Application Publication No. 2008 / 0248425 may also be used.

[0850] These surfactants may be used alone or in combination of two or more.

[0851] 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 of the present invention.

[0852] 〔Solvent〕

[0853] The composition of the present invention may also contain a solvent.

[0854] The solvent preferably contains at least one of (M1) propylene glycol monoalkyl ether carboxylate and (M2), wherein (M2) is at least one selected from the group consisting of propylene glycol monoalkyl ether, lactate, acetate, alkoxypropionate, linear ketone, cyclic ketone, lactone and alkylene carbonate. In addition, the solvent may contain components other than components (M1) and (M2).

[0855] The present inventors have found that by using such a solvent in combination with the resin (A), the coating property of the composition is improved and a pattern with a small number of development defects can be formed. Although the reason is not clear, the present inventors believe that the reason is that since the solubility, boiling point and viscosity of these solvents in the resin (A) are well balanced, the uneven film thickness of the composition film and the generation of precipitates during spin coating can be suppressed.

[0856] The component (M1) is preferably at least one selected from the group consisting of propylene glycol monomethyl ether acetate (PGMEA), propylene glycol monomethyl ether propionate and propylene glycol monoethyl ether acetate, and more preferably propylene glycol monomethyl ether acetate (PGMEA).

[0857] As component (M2), the following components are preferred.

[0858] As the propylene glycol monoalkyl ether, propylene glycol monomethyl ether (PGME: propylene glycol monomethylether) or propylene glycol monoethyl ether (PGEE) is preferred.

[0859] As the lactic acid ester, ethyl lactate, butyl lactate or propyl lactate is preferred.

[0860] As the acetate, methyl acetate, ethyl acetate, butyl acetate, isobutyl acetate, propyl acetate, isoamyl acetate, methyl formate, ethyl formate, butyl formate, propyl formate or 3-methoxybutyl acetate is preferred.

[0861] Furthermore, butyl butyrate is also preferred.

[0862] As the alkoxypropionate, methyl 3-methoxypropionate (MMP: methyl 3-Methoxypropionate) or ethyl 3-ethoxypropionate (EEP: ethyl 3-ethoxypropionate) is preferred.

[0863] As the chain ketone, 1-octanone, 2-octanone, 1-nonanone, 2-nonanone, acetone, 2-heptanone, 4-heptanone, 1-hexanone, 2-hexanone, diisobutyl ketone, phenylacetone, methyl ethyl ketone, methyl isobutyl ketone, acetylacetone, acetonylacetone, ionone, diacetone alcohol, acetyl carbinol, acetophenone, methyl naphthyl ketone or methyl amyl ketone is preferred.

[0864] The cyclic ketone is preferably methylcyclohexanone, isophorone or cyclohexanone.

[0865] As the lactone, γ-butyrolactone is preferred.

[0866] As the alkylene carbonate, propylene carbonate is preferred.

[0867] As the component (M2), propylene glycol monomethyl ether (PGME), ethyl lactate, ethyl 3-ethoxypropionate, methyl amyl ketone, cyclohexanone, butyl acetate, amyl acetate, γ-butyrolactone or propylene carbonate is more preferred.

[0868] In addition to the above components, it is preferable to use an ester solvent having 7 or more carbon atoms (preferably 7 to 14, more preferably 7 to 12, and even more preferably 7 to 10) and 2 or less heteroatoms.

[0869] As the ester solvent having 7 or more carbon atoms and 2 or less heteroatoms, preferred are pentyl acetate, 2-methylbutyl acetate, 1-methylbutyl acetate, hexyl acetate, pentyl propionate, hexyl propionate, butyl propionate, isobutyl isobutyrate, heptyl propionate and butyl butyrate, and more preferred is isoamyl acetate.

[0870] As the component (M2), a component having a flash point (hereinafter also referred to as fp) of 37°C or higher is preferred. As such a component (M2), propylene glycol monomethyl ether (fp: 47°C), ethyl lactate (fp: 53°C), ethyl 3-ethoxypropionate (fp: 49°C), methyl amyl ketone (fp: 42°C), cyclohexanone (fp: 44°C), amyl acetate (fp: 45°C), methyl 2-hydroxyisobutyrate (fp: 45°C), γ-butyrolactone (fp: 101°C) or propylene carbonate (fp: 132°C) is preferred. Among them, propylene glycol monoethyl ether, ethyl lactate, amyl acetate or cyclohexanone is more preferred, and propylene glycol monoethyl ether or ethyl lactate is further preferred.

[0871] In addition, the "flash point" herein refers to the value described in the reagent product catalog of Tokyo Chemical Industry Co., Ltd. or Sigma-Aldrich.

[0872] The mixing mass ratio (M1 / M2) of the component (M1) and the component (M2) in the mixed solvent is preferably in the range of "100 / 0" to "15 / 85", and more preferably in the range of "100 / 0" to "40 / 60". With this configuration, the number of development defects can be further reduced.

[0873] As described above, the solvent may contain components other than components (M1) and (M2). In this case, the content of components other than components (M1) and (M2) is preferably within a range of 30% by mass or less, more preferably within a range of 5 to 30% by mass, relative to the total amount of the solvent.

[0874] The content of the solvent in the composition of the present invention is preferably set to a solid content concentration of 0.5 to 30% by mass, more preferably 1 to 20% by mass. This allows the composition of the present invention to have a more excellent coating property.

[0875] <Other additives>

[0876] The composition of the present invention may further contain resins other than those mentioned above, crosslinking agents, acid growth agents, dyes, plasticizers, photosensitizers, light absorbers, alkali-soluble resins, dissolution inhibitors or dissolution accelerators, and the like.

[0877] [Resist film, pattern forming method]

[0878] Using the above composition, a resist film can be formed and a pattern can be formed.

[0879] The procedure of the pattern forming method using the above-mentioned composition is not particularly limited, but preferably includes the following steps.

[0880] Step 1: A step of forming a resist film on a carrier (on a substrate) using a composition Step 2: A step of exposing the resist film Step 3: A step of developing the exposed resist film using a developer to form a pattern

[0881] Hereinafter, the steps of each of the above processes will be described in detail.

[0882] [Step 1: Resist film forming step]

[0883] Step 1 is a step of forming a resist film on a carrier (on a substrate) using a composition.

[0884] The composition is defined as above.

[0885] A specific example of the method for preparing the composition is shown below.

[0886] In the composition used in the pattern forming method of the present invention, the content of metal atoms is preferably reduced.

[0887] Hereinafter, first, a specific example of a method for reducing the metal atom content in a composition is described, and then a specific example of a method for preparing the composition is described.

[0888] As a method for reducing the content of metal atoms in the composition, for example, a regulation method by filtering using a filter can be cited. As the filter pore size, the pore size is preferably less than 100nm, more preferably less than 10nm, and further preferably less than 5nm. As the filter, a filter made of polytetrafluoroethylene, polyethylene or nylon is preferred. The filter can be composed of a composite material combining the above-mentioned filter raw materials and an ion exchange medium. The filter can use a filter that has been 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.

[0889] In addition, methods for reducing the metal atom content in the composition include a method of selecting raw materials with a low metal content as raw materials for various materials constituting the composition, a method of filtering the raw materials for various materials constituting the composition, and a method of performing distillation under conditions that minimize contamination by lining the inside of the apparatus with Teflon (registered trademark).

[0890] Furthermore, as a method for reducing the metal atom content in the composition, in addition to the above-mentioned filtration, it can also be removed by an adsorbent, or a combination of filtration and adsorbent can be used. As the adsorbent, a known adsorbent can be used, for example, an inorganic adsorbent such as silica gel and zeolite and an organic adsorbent such as activated carbon can be used.

[0891] Furthermore, in order to reduce the metal atom content in the composition, it is necessary to prevent the mixing of metal impurities during the manufacturing process. Whether the metal impurities are sufficiently removed from the manufacturing equipment can be confirmed by measuring the content of the metal component contained in the cleaning liquid used when cleaning the manufacturing equipment.

[0892] Next, a specific example of the method for preparing the composition will be described.

[0893] In the manufacture of the composition, for example, it is preferred to dissolve various components such as the above-mentioned resin and photoacid generator in a solvent, and then use multiple filters with different raw materials to filter (it can also be a circulation filtration). For example, it is preferred to connect a polyethylene filter with a pore size of 50nm, a nylon filter with a pore size of 10nm, and a polyethylene filter with a pore size of 3 to 5nm in sequence for filtration. The filtration is also preferably carried out by a circulation filtration method more than 2 times. In addition, the above-mentioned filtration process also has the effect of reducing the metal atom content in the composition. The pressure difference between the filters is as small as possible, usually below 0.1MPa, preferably below 0.05MPa, and more preferably below 0.01MPa. The pressure difference between the filter and the filling nozzle is also as small as possible, usually below 0.5MPa, preferably below 0.2MPa, and more preferably below 0.1MPa.

[0894] In addition, as a method of performing circulation filtration using a filter in the production of the composition, a method of performing circulation filtration two or more times using a polytetrafluoroethylene filter having a pore size of 50 nm is also preferred.

[0895] It is preferred to replace the gas inside the composition production apparatus with an inert gas such as nitrogen, thereby preventing active gases such as oxygen from dissolving in the composition.

[0896] After filtering through the filter, the composition is filled in a clean container. The composition filled in the container is preferably stored in a refrigerator. Thus, performance degradation caused by the passage of time is suppressed. The shorter the time from the completion of filling in the composition container to the start of refrigerated storage, the better, usually within 24 hours, preferably within 16 hours, more preferably within 12 hours, and more preferably within 10 hours. The storage temperature is preferably 0 to 15°C, more preferably 0 to 10°C, and more preferably 0 to 5°C.

[0897] Next, a method for forming a resist film on a substrate using the composition will be described.

[0898] As a method of forming a resist film on a substrate using the composition, there is a method of applying the composition on the substrate.

[0899] The composition can be applied to a substrate (e.g., silicon, silicon dioxide coating) used in the manufacture of integrated circuit elements by an appropriate coating method such as a spin coater or a coating machine. As a coating method, spin coating using a spin coater is preferred. The rotation speed when spin coating using a spin coater is preferably 1000 to 3000 rpm.

[0900] After the composition is applied, the substrate may be dried to form a resist film. In addition, various base films (inorganic film, organic film, anti-reflection film) may be formed under the resist film as needed.

[0901] As a drying method, a method of drying by heating can be cited. Heating can be performed using a device provided in a general exposure machine and / or a developer, or using a hot plate or the like. The heating temperature is preferably 80 to 150° C., more preferably 80 to 140° C., and further preferably 80 to 130° C. The heating time is preferably 30 to 1000 seconds, more preferably 60 to 800 seconds, and further preferably 60 to 600 seconds.

[0902] The film thickness of the resist film is not particularly limited, but is preferably 10 to 150 nm, more preferably 15 to 100 nm, from the viewpoint of being able to form a finer pattern with higher precision.

[0903] Alternatively, a top coat layer may be formed on the resist film using a top coat composition.

[0904] It is preferred that the top coating composition can be further uniformly applied to the upper layer of the resist film without being mixed with the resist film.

[0905] Furthermore, it is preferred that the resist film be dried before forming the top coat layer. Next, a top coat layer composition is applied on the obtained resist film by the same method as the above-mentioned method for forming the resist film, and further dried, thereby forming the top coat layer.

[0906] The thickness of the top coat layer is preferably 10 to 200 nm, more preferably 20 to 100 nm.

[0907] The top coating composition includes, for example, a resin, an additive, and a solvent.

[0908] As the resin, the same resin as the hydrophobic resin can be used. The content of the resin is preferably 50 to 99.9% by mass, more preferably 60 to 99.7% by mass, based on the total solid content of the top coating composition.

[0909] As the above-mentioned additive, the above-mentioned acid diffusion controller can be used. In addition, a compound having a radical-trapping group such as a compound containing an N-oxyl radical can also be used. As such a compound, for example, [4-(benzoyloxy)-2,2,6,6-tetramethylpiperidinyloxy] radical can be cited. The content of the additive is preferably 0.01 to 20% by mass, more preferably 0.1 to 15% by mass, relative to the total solid content of the top coating composition.

[0910] The solvent preferably does not dissolve the resist film, and examples thereof include alcohol solvents (such as 4-methyl-2-pentanol), ether solvents (such as diisoamyl ether), ester solvents, fluorine solvents, and hydrocarbon solvents (such as n-decane).

[0911] The content of the solvent in the top coating composition is preferably set to a solid content concentration of 0.5 to 30% by mass, more preferably 1 to 20% by mass.

[0912] In addition to the above-mentioned additives, the top coating composition may further contain a surfactant, and as the above-mentioned surfactant, a surfactant that can be contained in the composition of the present invention can be used. The content of the surfactant is preferably 0.0001 to 2% by mass, more preferably 0.0005 to 1% by mass relative to the total solid content of the top coating composition.

[0913] The top coat layer is not particularly limited and can be formed by a conventionally known method. For example, the top coat layer can be formed based on the contents described in paragraphs <0072> to <0082> in Japanese Patent Application Laid-Open No. 2014-059543.

[0914] For example, it is preferable to form a top coat layer containing a basic compound as described in Japanese Patent Application Laid-Open No. 2013-061648 on the resist film. Specific examples of the basic compound that can be contained in the top coat layer include the basic compounds that can be contained in the composition of the present invention.

[0915] Also, the top coating layer preferably includes a compound including at least one group or bond selected from the group consisting of an ether bond, a thioether bond, a hydroxyl group, a thiol group, a carbonyl bond, and an ester bond.

[0916] [Process 2: Exposure process]

[0917] Step 2 is a step of exposing the resist film to light.

[0918] As the exposure method, there can be mentioned a method of irradiating the formed resist film with actinic rays or radiation through a predetermined mask.

[0919] As actinic rays or radiation, there can be mentioned infrared light, visible light, ultraviolet light, far ultraviolet light, extreme ultraviolet light, X-rays and electron beams. Preferably, the wavelength is below 250nm, more preferably below 220nm, and far ultraviolet light of 1 to 200nm is particularly preferred. Specifically, there can be mentioned KrF excimer laser (248nm), ArF excimer laser (193nm), F2 excimer laser (157nm), EUV (13nm), X-rays and electron beams.

[0920] It is preferable to perform baking (heating) after exposure and before development. Baking promotes the reaction of the exposed part, and the sensitivity and pattern shape are further improved.

[0921] The heating temperature is preferably 80 to 150°C, more preferably 80 to 140°C, and even more preferably 80 to 130°C.

[0922] The heating time is preferably 10 to 1000 seconds, more preferably 10 to 180 seconds, and even more preferably 30 to 120 seconds.

[0923] Heating can be performed using a device included in a general exposure machine and / or a developing machine, or heating can be performed using a hot plate or the like.

[0924] This process is also called post-exposure bake.

[0925] [Process 3: Development process]

[0926] Step 3 is a step of developing the exposed resist film using a developer to form a pattern.

[0927] As developing methods, there can be cited: a method of immersing a substrate in a tank filled with a developer for a certain period of time (dip method); a method of developing by causing the developer to bulge on the surface of the substrate due to surface tension and allowing the developer to stand for a certain period of time (puddle method); a method of spraying the developer onto the surface of the substrate (spray method); and a method of continuously spraying the developer on a substrate rotating at a certain speed while scanning a developer spray nozzle at a certain speed (dynamic dispense method).

[0928] Furthermore, after the step of developing, a step of stopping the development while replacing the solvent with another solvent may be performed.

[0929] The development time is not particularly limited as long as it is a time for the resin in the unexposed portion to fully dissolve, but is preferably 10 to 300 seconds, more preferably 20 to 120 seconds.

[0930] The temperature of the developer is preferably 0 to 50°C, more preferably 15 to 35°C.

[0931] Examples of the developer include an alkaline developer and an organic solvent developer.

[0932] The alkaline developer preferably uses an alkaline aqueous solution containing an alkali. The type of the alkaline aqueous solution is not particularly limited, and examples thereof include alkaline aqueous solutions containing quaternary ammonium salts represented by tetramethylammonium hydroxide, inorganic bases, primary amines, secondary amines, tertiary amines, alcoholamines or cyclic amines. Among them, the alkaline developer is preferably an aqueous solution of a quaternary ammonium salt represented by tetramethylammonium hydroxide (TMAH). An appropriate amount of alcohols, surfactants, etc. may be added to the alkaline developer. The alkali concentration of the alkaline developer is generally 0.1 to 20% by mass. Furthermore, the pH of the alkaline developer is generally 10.0 to 15.0.

[0933] The organic solvent developer refers to a developer containing an organic solvent.

[0934] At 20° C., the vapor pressure of the organic solvent contained in the organic solvent developer (when it is a mixed solvent, it is the vapor pressure as a whole) is preferably 5 kPa or less, more preferably 3 kPa or less, and further preferably 2 kPa or less. By setting the vapor pressure of the organic solvent to 5 kPa or less, evaporation of the developer on the substrate or in the developer cup is suppressed, and the temperature uniformity within the wafer surface is improved, resulting in improved dimensional uniformity within the wafer surface.

[0935] As the organic solvent used in the organic solvent developer, known organic solvents may be mentioned, and examples thereof include ester solvents, ketone solvents, alcohol solvents, amide solvents, ether solvents, and hydrocarbon solvents.

[0936] When EUV and electron beams are used in the above-mentioned exposure process, from the viewpoint of being able to suppress the swelling of the resist film, the organic solvent contained in the organic solvent developer preferably uses an ester solvent having 7 or more carbon atoms (preferably 7 to 14, more preferably 7 to 12, and further preferably 7 to 10) and 2 or less heteroatoms.

[0937] The heteroatom of the ester solvent is an atom other than a carbon atom and a hydrogen atom, and examples thereof include an oxygen atom, a nitrogen atom, and a sulfur atom. The number of heteroatoms is preferably 2 or less.

[0938] As the ester solvent having 7 or more carbon atoms and 2 or less heteroatoms, preferred are pentylacetate, isoamyl acetate, 2-methylbutyl acetate, 1-methylbutyl acetate, hexyl acetate, pentylacetate, hexyl propionate, butyl propionate, isobutyl isobutyrate, heptyl propionate or butyl butyrate, and more preferred is isoamyl acetate.

[0939] When EUV and electron beams are used in the exposure process, the organic solvent contained in the organic solvent developer may use a mixed solvent of the ester solvent and the hydrocarbon solvent or a mixed solvent of the ketone solvent and the hydrocarbon solvent instead of the ester solvent having 7 or more carbon atoms and 2 or less heteroatoms. In this case, it is also effective to suppress the swelling of the resist film.

[0940] When an ester solvent is used in combination with a hydrocarbon solvent, isoamyl acetate is preferably used as the ester solvent. In addition, as the hydrocarbon solvent, from the viewpoint of adjusting the solubility of the resist film, a saturated hydrocarbon solvent (e.g., octane, nonane, decane, dodecane, undecane, hexadecane, etc.) is preferably used.

[0941] When a ketone solvent and a hydrocarbon solvent are used in combination, 2-heptanone is preferably used as the ketone solvent. In addition, as the hydrocarbon solvent, from the viewpoint of adjusting the solubility of the resist film, a saturated hydrocarbon solvent (e.g., octane, nonane, decane, dodecane, undecane, hexadecane, etc.) is preferably used.

[0942] When the above-mentioned mixed solvent is used, the content of the hydrocarbon solvent is not particularly limited because it depends on the solvent solubility of the resist film, and a required amount may be determined by appropriate preparation.

[0943] A plurality of the above-mentioned organic solvents may be mixed, or may be mixed with solvents other than the above or water. However, in order to fully exert the effect of the present invention, the water content of the developer as a whole is preferably less than 10% by mass, and more preferably substantially free of water. The concentration of the organic solvent in the developer (when a plurality of organic solvents are mixed, the total) is preferably 50% by mass or more, more preferably 50 to 100% by mass, further preferably 85 to 100% by mass, particularly preferably 90 to 100% by mass, and most preferably 95 to 100% by mass.

[0944] 〔Other processes〕

[0945] The above-mentioned pattern forming method preferably includes a step of cleaning with a rinse liquid after step 3.

[0946] As a rinse liquid used in the rinse step after the step of developing with a developer, pure water can be mentioned, for example. In addition, an appropriate amount of a surfactant can be added to the pure water.

[0947] An appropriate amount of surfactant may be added to the flushing solution.

[0948] The method of the rinsing step is not particularly limited. Examples include a method of continuously spraying a rinsing liquid onto a substrate rotating at a certain speed (spin coating method), a method of immersing a substrate in a tank filled with a rinsing liquid for a certain period of time (immersion method), and a method of spraying the rinsing liquid onto the surface of the substrate (spray coating method).

[0949] Furthermore, the pattern forming method of the present invention may include a heating process (Post Bake) after the rinsing process. This process can remove the developer and rinse solution remaining between and inside the patterns due to baking. Furthermore, this process also has the effect of smoothing the resist pattern and improving the surface roughness of the pattern. The heating process after the rinsing process is usually performed at 40 to 250° C. (preferably 90 to 200° C.) for 10 seconds to 3 minutes (preferably 30 to 120 seconds).

[0950] Then, the formed pattern can be used as a mask to perform etching processing on the substrate.

[0951] That is, a pattern may be formed on the substrate by processing the substrate (or the underlying film and the substrate) using the pattern formed in step 3 as a mask.

[0952] The processing method of the substrate (or the underlying film and the substrate) is not particularly limited, but is preferably a method of forming a pattern on the substrate by dry etching the substrate (or the underlying film and the substrate) using the pattern formed in step 3 as a mask.

[0953] The dry etching may be a single-stage etching or a plurality of-stage etching. When the etching is a plurality of-stage etching, the etching in each stage may be the same process or different processes.

[0954] Any known method can be used for etching, and various conditions are appropriately determined according to the type or purpose of the substrate. For example, etching can be performed according to the Proceedings of SPIE Vol. 6924, 692420 (2008), Japanese Patent Publication No. 2009-267112, etc. In addition, etching can be performed according to the method described in "Chapter 4 Etching" of "Semiconductor Process Textbook Fourth Edition 2007 Issued by SEMI Japan".

[0955] Among them, oxygen plasma etching is preferable as dry etching.

[0956] In various materials other than the composition used in the pattern forming method of the present invention (e.g., developer, rinse solution, antireflection film forming composition, top coat forming composition, etc.), the less impurities such as metals (e.g., Na, K, Ca, Fe, Cu, Mg, Al, Li, Cr, Ni, Sn, Ag, As, Au, Ba, Cd, Co, Pb, Ti, V, W, and Zn, etc.), the better. The content of impurities contained in these materials is, for example, preferably 1 mass ppm or less.

[0957] As a method for reducing impurities such as metals in various materials other than the composition, for example, filtration using a filter can be cited. As the filter pore size, the pore size is preferably less than 100nm, more preferably less than 10nm, and further preferably less than 5nm. As the filter, a filter made of polytetrafluoroethylene, polyethylene or nylon is preferred. The filter can be composed of a composite material combining the above-mentioned filter raw materials and an ion exchange medium. The filter can use a filter that has been pre-cleaned with an organic solvent. In the filter filtering process, multiple filters can be connected in series or in parallel for use. When using multiple 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 multiple filtering can be a circulation filtering process.

[0958] Furthermore, methods for reducing impurities such as metals in various materials other than the composition include a method of selecting raw materials with a low metal content as raw materials constituting various materials, a method of filtering the raw materials constituting various materials, and a method of performing distillation under conditions that minimize contamination by lining the inside of an apparatus with Teflon (registered trademark), etc.

[0959] In addition, as a method for reducing impurities such as metals in various materials other than the composition, in addition to the above-mentioned filter filtration, impurities can also be removed by an adsorbent, or filter filtration and adsorbent can be used in combination. As the adsorbent, known adsorbents can be used, for example, inorganic adsorbents such as silica gel and zeolite and organic adsorbents such as activated carbon can be used. In order to reduce impurities such as metals contained in various materials other than the above-mentioned composition, it is necessary to prevent the mixing of metal impurities in the manufacturing process. Whether the metal impurities are fully removed from the manufacturing device can be confirmed by measuring the content of the metal component contained in the cleaning liquid used when cleaning the manufacturing device.

[0960] In order to prevent the failure of the liquid piping and various components (filters, O-rings, hoses, etc.) caused by static electricity charging and subsequent static electricity discharge, a conductive compound can be added to the organic treatment liquid such as the rinse liquid. The conductive compound is not particularly limited, and methanol can be cited as an example. The amount added is not particularly limited, and from the viewpoint of maintaining the preferred development characteristics or rinse characteristics, it is preferably 10% by mass or less, and more preferably 5% by mass or less.

[0961] As the liquid medicine piping, SUS (stainless steel) or various pipings coated with polyethylene, polypropylene or fluororesin (polytetrafluoroethylene or perfluoroalkoxy resin, etc.) subjected to antistatic treatment can be used. Similarly, polyethylene, polypropylene or fluororesin (polytetrafluoroethylene or perfluoroalkoxy resin, etc.) subjected to antistatic treatment can be used for the filter and O-ring.

[0962] The method of improving the surface roughness of the pattern formed by the method of the present invention can also be applied. As a method for improving the surface roughness of the pattern, for example, the method disclosed in International Publication No. 2014 / 002808, in which the pattern is treated by a plasma containing a hydrogen gas, can be cited. In addition, the known methods described in Japanese Patent Publication No. 2004-235468, U.S. Patent Application Publication No. 2010 / 0020297, Japanese Patent Publication No. 2008-083384, and Proc. of SPIE Vol. 8328 83280N-1 "EUV Resist Curing Technique for LWR Reduction And Etch Selectivity Enhancement" can also be cited.

[0963] When the formed pattern is linear, the aspect ratio obtained by dividing the pattern height by the line width is preferably 2.5 or less, more preferably 2.1 or less, and further preferably 1.7 or less.

[0964] When the formed pattern is a groove (slot) pattern or a contact hole pattern, the aspect ratio obtained by dividing the pattern height by the groove width or hole diameter is preferably 4.0 or less, more preferably 3.5 or less, and further preferably 3.0 or less.

[0965] The pattern forming method of the present invention can also be used for guided pattern formation in DSA (Directed Self-Assembly) (for example, refer to ACS Nano Vol. 4 No. 8 pp. 4815-4823).

[0966] Furthermore, the pattern formed by the above method can be used as a core material (core) of a spacer process disclosed in, for example, Japanese Patent Application Laid-Open No. 3-270227 and Japanese Patent Application Laid-Open No. 2013-164509.

[0967] [Method for manufacturing electronic device]

[0968] Furthermore, the present invention relates to a method for manufacturing an electronic device including the above-mentioned pattern forming method and an electronic device manufactured by the manufacturing method.

[0969] The electronic device of the present invention is an electronic device that is suitably mounted on electrical and electronic equipment (home appliances, OA (Office Automation), media-related equipment, optical equipment, communication equipment, etc.).

[0970] Example

[0971] Below, the present invention is further described in detail according to the embodiments. As long as it does not depart from the purpose of the present invention, the material, usage, ratio, processing content and processing steps shown in the following embodiments can be appropriately changed. Therefore, the scope of the present invention should not be interpreted as being limited by the following embodiments.

[0972] [Manufacturing of composition]

[0973] Components contained in the actinic ray-sensitive or radiation-sensitive resin composition (hereinafter, also referred to as “composition”) used in Examples and Comparative Examples and a production process are shown below.

[0974] <Specified compounds and comparative compounds>

[0975] (Synthesis of specific compound (I)-35)

[0976] Specific compound (I)-35 was synthesized according to the following scheme.

[0977] [Chemical formula 82]

[0978]

[0979] Butylamide (15.0 g, 172.2 mmol) and tetrahydrofuran (300 mL) were added to a 500 mL three-necked flask, and the resulting solution was cooled to 0°C. Then, butyllithium (1.6 M hexane solution, 107.5 mL, 172.2 mmol) was added dropwise to the above solution. After the above solution was further stirred at 0°C for 30 minutes, the above solution was slowly added dropwise to a THF solution (300 mL) of (I)-35A (54.45 g, 172.2 mmol) cooled to 0°C to obtain a mixed solution. After the obtained mixed solution was stirred at room temperature (23°C) for 2 hours, 1N hydrochloric acid was added to the above mixed solution until pH = 3, and 300 mL of ethyl acetate was further added to the above mixed solution. After the organic phase of the mixed solution was washed 3 times with water (100 mL), the solvent was distilled off from the above organic phase under reduced pressure. Hexane (300 mL) was added to the obtained residue to obtain (I)-35B (33.0 g, yield: 50%) as a white solid.

[0980] (I)-35B (22.0 g, 57.40 mmol), tetrahydrofuran (300 mL) and 5 mass% sodium bicarbonate aqueous solution (300 mL) were added to a 1L eggplant flask, and the resulting solution was stirred at 60°C for 6 hours. After distilling tetrahydrofuran from the above solution under reduced pressure, dichloromethane (300 mL) and triphenylphosphine bromide (39.41 g, 114.80 mmol) were added to the above solution, and stirred at room temperature for 30 minutes. The above solution was transferred to a separatory funnel, and the organic phase was washed three times with water (150 mL). The solvent was distilled off from the above organic phase under reduced pressure, and tert-butyl methyl ether was added to the resulting residue to obtain a white solid (I)-35 (41.6 g) (yield: 80%).

[0981] The obtained white solid ((I)-35) was analyzed by NMR (Nuclear Magnetic Resonance) method. The results are as follows. 1 H NMR (400MHz, MeOD)a 0.91 (t, J = 7.44Hz, 3H), 1.55-1.64 (m, 2H), 2.19 (t, J = 10.08Hz, 3H), 7.77-7.92 (m, 30H).

[0982] Referring to the above-mentioned synthesis method, the specific compounds shown below were synthesized.

[0983] Here, (Z)-1 is a comparative compound that does not correspond to the specific compound.

[0984] In the compound in which the cation in (z)-1 is replaced by a hydrogen atom, the pKa of the group represented by -SO3H in the above compound is -3.29, and the pKa of the group represented by -COOH is 0.37.

[0985] [Chemical formula 83]

[0986]

[0987] [Chemical formula 84]

[0988]

[0989] <Acid-decomposable resin (resin (A))>

[0990] The acid-decomposable resin (resin (A)) used for producing the composition is shown below.

[0991] [Chemical formula 85]

[0992]

[0993] [Chemical formula 86]

[0994]

[0995] [Chemical formula 87]

[0996]

[0997] The molar ratio of the repeating units constituting each of the above-described resins (corresponding sequentially from left to right), the weight average molecular weight (Mw) and the degree of dispersion (Mw / Mn) of each resin are shown in the following table.

[0998] [Table 1]

[0999]

[1000] <Photoacid generator>

[1001] When the composition contained a photoacid generator, the following photoacid generators were used.

[1002] [Chemical formula 88]

[1003]

[1004] [Chemical formula 89]

[1005]

[1006] <Acid diffusion control agent>

[1007] When the composition contained an acid diffusion controller, the following acid diffusion controller was used.

[1008] [Chemical formula 90]

[1009]

[1010] 〔Hydrophobic resin〕

[1011] When the composition contains a hydrophobic resin, a hydrophobic resin having a repeating unit based on the following monomer is used.

[1012] [Chemical formula 91]

[1013]

[1014] The molar ratio of the repeating unit based on each monomer in the hydrophobic resin used in the composition, the weight average molecular weight (Mw) and the degree of dispersion (Mw / Mn) of each resin are shown in the following table.

[1015] [Table 2]

[1016]

[1017] <Surfactant>

[1018] When the composition contained a surfactant, the following surfactants were used.

[1019] E-1: Megaface F176 (manufactured by DIC CORPORATION, fluorine-based surfactant)

[1020] E-2: Megaface R08 (manufactured by DIC CORPORATION, fluorine and silicon surfactants)

[1021] E-3: PF656 (manufactured by OMNOVA Solutions Inc., fluorine-based surfactant)

[1022] <Solvent>

[1023] The solvents contained in the composition are shown below.

[1024] F-1: Propylene glycol monomethyl ether acetate (PGMEA)

[1025] F-2: Propylene glycol monomethyl ether (PGME)

[1026] F-3: Propylene glycol monoethyl ether (PGEE)

[1027] F-4: Cyclohexanone

[1028] F-5: Cyclopentanone

[1029] F-6: 2-Heptanone

[1030] F-7: Ethyl lactate

[1031] F-8: γ-Butyrolactone

[1032] F-9: Propylene carbonate

[1033] <Preparation of Composition>

[1034] (Preparation of Compositions for ArF Exposure Test (Re-1 to Re-24, Re-35, Re-36, Re-39 to Re-51, Re-68)

[1035] The components shown in the following table were mixed so that the solid content concentration was 4% by mass. Then, the obtained mixed solution was first filtered through a polyethylene filter having a pore size of 50 nm, then filtered through a nylon filter having a pore size of 10 nm, and finally filtered through a polyethylene filter having a pore size of 5 nm, thereby preparing a composition (actinic ray-sensitive or radiation-sensitive linear resin composition) used in a test by ArF exposure.

[1036] In addition, in a composition, solid content means all components except a solvent. The obtained composition was used in an Example and a comparative example.

[1037] In the following tables, the content (mass %) of each component means the content relative to the total solid content.

[1038] (Preparation of Compositions for EUV Exposure Test (Re-25 to Re-34, Re-37, Re-38, Re-52 to Re-67, Re-69))

[1039] The components shown in the following table were mixed so that the solid content concentration was 2% by mass. Then, the obtained mixed solution was first filtered through a polyethylene filter having a pore size of 50 nm, then filtered through a nylon filter having a pore size of 10 nm, and finally filtered through a polyethylene filter having a pore size of 5 nm, thereby preparing a composition (actinic ray-sensitive or radiation-sensitive linear resin composition) used in a test by EUV exposure.

[1040] The mixing ratio of each composition is shown below.

[1041] Re-35 to Re-38 are compositions used as comparative examples, and the others are compositions used as examples.

[1042] In the table, the column "B group" indicates when the specific compound used is applied to the general formula (I), - Whether the group represented by is equivalent to the group represented by any of the general formulae (B-1) to (B-4).

[1043] [Table 3]

[1044]

[1045] [Table 4]

[1046]

[1047] [Table 5]

[1048]

[1049] [Table 6]

[1050]

[1051] [Manufacturing of top coating composition]

[1052] In this example, when a resist film was produced using the above-mentioned composition, a top coat layer was further produced on the resist film as needed.

[1053] The components and production steps used in the top coating composition for forming the top coating layer are shown below.

[1054] <Resin>

[1055] The mole fraction of the repeating unit based on each monomer in the resin used in the top coating composition, the weight average molecular weight (Mw) and the degree of dispersion (Mw / Mn) of each resin are shown in the following table.

[1056] In addition, the structures of the monomers corresponding to the repeating units shown in the table can refer to the monomers shown in the description of the above <Hydrophobic resin>.

[1057] [Table 7]

[1058]

[1059] <Additives>

[1060] The additives contained in the top coating composition are shown below.

[1061] [Chemical formula 92]

[1062]

[1063] <Surfactant>

[1064] When the top coating composition contains a surfactant, the following surfactant was used. E-3: PF656 (manufactured by OMNOVA Solutions Inc., fluorine-based surfactant)

[1065] <Solvent>

[1066] The solvents contained in the top coating composition are shown below. FT-1: 4-methyl-2-pentanol (MIBC) FT-2: n-decane FT-3: diisoamyl ether

[1067] <Preparation of top coating composition>

[1068] Each component was dissolved in a solvent so as to satisfy the formulation described in the following table and to have a solid content concentration of 3.8% by mass, thereby preparing a solution.

[1069] Next, the resulting solution was filtered using a polyethylene filter having a pore size of 0.1 μm, thereby preparing a top coating composition.

[1070] [Table 8]

[1071]

[1072] 〔test〕

[1073] Using the composition prepared above, the LWR of the pattern developed under the conditions shown below was evaluated.

[1074] In all the tests, the composition used for pattern formation (actinic ray-sensitive or radiation-sensitive resin composition) was left to stand in an environment of 4° C. for 3 months after production.

[1075] <ArF immersion exposure, organic solvent development>

[1076] (Pattern Formation)

[1077] An organic antireflection film-forming composition ARC29SR (manufactured by Brewer Science) was applied to a silicon wafer and baked at 205° C. for 60 seconds to form an antireflection film having a thickness of 98 nm. A composition shown in Table 6 was applied thereon and baked at 100° C. for 60 seconds to form a resist film (actinic ray-sensitive or radiation-sensitive linear film) having a thickness of 90 nm.

[1078] In Examples 1-22, 1-23, and 1-24, a top coat film was formed on the upper layer of the resist film (the types of the top coat compositions used are shown in Table 6). The film thickness of the top coat film was 100 nm in each case.

[1079] The resist film was exposed using an ArF excimer laser immersion scanner (manufactured by ASML; XT1700i, NA1.20, Dipole, outer sigma 0.950, inner sigma 0.850, Y deflection) through a 6% halftone mask of a 1:1 line and space pattern with a line width of 45 nm. Ultrapure water was used as the immersion liquid.

[1080] The exposed resist film was baked at 90° C. for 60 seconds, developed with n-butyl acetate for 30 seconds, and then rinsed with 4-methyl-2-pentanol for 30 seconds and then spin-dried to obtain a negative pattern.

[1081] (evaluate)

[1082] A 45nm (1:1) line and space pattern analyzed with the optimal exposure when analyzing a line pattern with an average line width of 45nm was observed from the top of the pattern using a length-measuring scanning electron microscope (SEM, S-9380II manufactured by Hitachi, Ltd.). The line width of the pattern was observed at any point (100 points), and its measurement deviation was evaluated by 3σ and set as LWR. The smaller the value of LWR, the better the LWR performance. LWR (nm) is preferably less than 3.1nm, more preferably less than 2.9nm, and further preferably less than 2.6nm.

[1083] The results are shown in the following table.

[1084] In the table, the column "B group" indicates when the specific compound contained in the composition is applied to the general formula (I), - Whether the group represented by is equivalent to the group represented by any of the general formulae (B-1) to (B-4).

[1085] [Table 9]

[1086]

[1087] The results shown in the table confirmed that, from the viewpoint of the superior LWR performance of the pattern when the composition is stored for a long time, the specific compound is composed of B - The group represented is preferably a group represented by the general formulae (B-1) to (B-3), and more preferably a group represented by the general formula (B-1) or (B-2).

[1088] <ArF immersion exposure, alkali development>

[1089] (Pattern Formation)

[1090] An organic anti-reflection film-forming composition ARC29SR (manufactured by Brewer Science) was applied to a silicon wafer and baked at 205°C for 60 seconds to form an anti-reflection film having a thickness of 98 nm. A composition shown in Table 7 was applied thereon and baked at 100°C for 60 seconds to form a resist film having a thickness of 90 nm. For Examples 2-22, 2-23, and 2-24, a top coating film was formed on the upper layer of the resist film (the type of top coating composition used is shown in Table 7). The thickness of the top coating film was set to 100 nm in each case.

[1091] The resist film was exposed using an ArF excimer laser immersion scanner (manufactured by ASML; XT1700i, NA1.20, Dipole, outer sigma 0.950, inner sigma 0.890, Y deflection) through a 6% halftone mask of a 1:1 line and space pattern with a line width of 45 nm. Ultrapure water was used as the immersion liquid.

[1092] The exposed resist film was baked at 90° C. for 60 seconds, developed with a tetramethylammonium hydroxide aqueous solution (2.38 mass %) for 30 seconds, and then rinsed with pure water for 30 seconds and spin-dried to obtain a positive pattern.

[1093] (evaluate)

[1094] The obtained pattern was evaluated by the same method as the method for evaluating the LWR of the pattern in <ArF liquid immersion exposure, organic solvent development>.

[1095] The results are shown in the following table.

[1096] [Table 10]

[1097]

[1098] From the results shown in the table, the same tendency as the test results conducted by <ArF liquid immersion exposure, organic solvent development> was confirmed.

[1099] <EUV exposure, organic solvent development>

[1100] (Pattern Formation)

[1101] The lower film-forming composition AL412 (manufactured by Brewer Science) was applied on the silicon wafer and baked at 205°C for 60 seconds to form a base film with a thickness of 20 nm. The composition shown in Table 8 was applied thereon and baked at 100°C for 60 seconds to form a resist film with a thickness of 30 nm.

[1102] The silicon wafer with the obtained resist film was pattern irradiated using an EUV exposure device (manufactured by Exitech Corporation, Micro Exposure Tool, NA0.3, Quadrupol, outer sigma 0.68, inner sigma 0.36). In addition, as a reticle, a mask with a line size of 20 nm and a line: space of 1:1 was used.

[1103] The exposed resist film was baked at 90° C. for 60 seconds, developed with n-butyl acetate for 30 seconds, and spin-dried to obtain a negative pattern.

[1104] (evaluate)

[1105] A 20nm (1:1) line and space pattern analyzed with the optimal exposure when analyzing a line pattern with an average line width of 20nm was observed from the top of the pattern using a length-measuring scanning electron microscope (SEM, S-9380II manufactured by Hitachi, Ltd.). The line width of the pattern was observed at any point (100 points), and its measurement deviation was evaluated by 3σ and set as LWR. The smaller the value of LWR, the better the LWR performance. LWR (nm) is preferably less than 4.3nm, more preferably less than 3.9nm, and further preferably less than 3.5nm.

[1106] The results are shown in the following table.

[1107] In the table, the column "B group" indicates when the specific compound contained in the composition is applied to the general formula (I), - Whether the group represented by is equivalent to the group represented by any of the general formulae (B-1) to (B-4).

[1108] [Table 11]

[1109]

[1110] From the results shown in the table, the same tendency as the test results conducted by <ArF liquid immersion exposure, organic solvent development> was confirmed.

[1111] <EUV exposure, alkali development>

[1112] (Pattern Formation)

[1113] The lower film-forming composition AL412 (manufactured by Brewer Science) was applied on the silicon wafer and baked at 205°C for 60 seconds to form a base film with a thickness of 20 nm. The resin composition shown in Table 9 was applied thereon and baked at 100°C for 60 seconds to form a resist film with a thickness of 30 nm.

[1114] The silicon wafer with the obtained resist film was pattern irradiated using an EUV exposure device (manufactured by Exitech Corporation, Micro Exposure Tool, NA0.3, Quadrupol, outer sigma 0.68, inner sigma 0.36). In addition, as a reticle, a mask with a line size of 20 nm and a line: space of 1:1 was used.

[1115] The exposed resist film was baked at 90° C. for 60 seconds, developed with a tetramethylammonium hydroxide aqueous solution (2.38 mass %) for 30 seconds, and then rinsed with pure water for 30 seconds and spin-dried to obtain a positive pattern.

[1116] (evaluate)

[1117] The obtained pattern was evaluated by the same method as the method for evaluating the LWR of the pattern in <EUV exposure, organic solvent development>.

[1118] The results are shown in the following table.

[1119] [Table 12]

[1120]

[1121] From the results shown in the table, the same tendency as the test results conducted by <ArF liquid immersion exposure, organic solvent development> was confirmed.

Claims

1. An actinic ray-sensitive or radiation-sensitive resin composition comprising a compound represented by the general formula (I) and an acid-decomposable resin, M 1 + A - -L-B - M 2 + (I) In the general formula (I), M 1 + and M 2 + Each independently represents an organic cation, L represents a divalent organic group, A - represents an acidic anionic group, in ,exist The compound represented by the general formula (I) is 1 + and M 2 + In the compound represented by HA-L-BH, each of which is substituted with a hydrogen atom, the pKa of the group represented by HA is lower than the pKa of the group represented by BH, B - represents a group represented by any one of the general formulae (B-1), (B-2) and (B-4), In the general formulae (B-1), (B-2) and (B-4), * represents a bonding position, R B represents a cycloalkyl group or an aromatic ring group.

2. An actinic ray-sensitive or radiation-sensitive resin composition comprising a compound represented by the general formula (I) and an acid-decomposable resin, M 1 + A - -L-B - M 2 + (I) In the general formula (I), M 1 + and M 2 + Each independently represents an organic cation, L represents a divalent organic group, A - represents a group represented by the general formula (A-2), in, In the compound represented by the general formula (I), M 1 + and M 2 + In the compound represented by HA-L-BH, each of which is substituted with a hydrogen atom, the pKa of the group represented by HA is lower than the pKa of the group represented by BH, B - represents a group represented by any one of the general formulae (B-1), (B-2) and (B-4), In the general formulae (B-1), (B-2) and (B-4), * represents a bonding position, R B represents an organic group, In the general formula (A-2), * represents the bonding position, R A Represents an organic group.

3. The actinic ray-sensitive or radiation-sensitive resin composition according to claim 1 or 2, in, B - It represents a group represented by any one of the general formulae (B-1) to (B-2).

4. The actinic ray-sensitive or radiation-sensitive resin composition according to claim 1, in, A - represents a group represented by any one of the general formulae (A-1) to (A-2), In the general formulas (A-1) to (A-2), * represents a bonding position, R A represents an organic group, Among them, in the compound represented by the general formula (I), M 1 + and M 2 + In the compound represented by HA-L-BH respectively substituted with hydrogen atoms, the pKa of the group represented by HA is lower than the pKa of the group represented by BH. 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 process for 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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