Photosensitive radiation-curable or radiation-sensitive resin composition, photosensitive radiation-curable or radiation-sensitive film, pattern forming method, and method for manufacturing an electronic device

Abstract

The present invention provides a photosensitive radiation-curable or radiation-sensitive resin composition, a photosensitive radiation-curable or radiation-sensitive film using the above photosensitive radiation-curable or radiation-sensitive resin composition, a pattern forming method, and a method for manufacturing an electronic device. In the photosensitive radiation-curable or radiation-sensitive resin composition, there are contained (A) an acid-decomposable resin, (B) a compound represented by the general formula (b1), and (C) a compound represented by the general formula (c1), and the proportion of the content of the compound (C) relative to the content of the compound (B) is 0.01% by mass or more and 10% by mass or less. L represents a single bond or a divalent linking group. A represents a group that decomposes by the action of an acid. B represents a group that decomposes by the action of an acid, a hydroxyl group, or a carboxyl group. Among them, at least one B represents a hydroxyl group or a carboxyl group. n represents an integer of 1 to 5. X represents an (n + 1)-valent linking group. M + represents a sulfonium ion or an iodonium ion.

Description

Technical Field

[0001] The present invention relates to a photosensitive radiation-curable or radiation-sensitive resin composition, a photosensitive radiation-curable or radiation-sensitive film, a patterning method, and a method for manufacturing an electronic device. More specifically, the present invention relates to a photosensitive radiation-curable or radiation-sensitive resin composition, a photosensitive radiation-curable or radiation-sensitive film, a patterning method, and a method for manufacturing an electronic device, which are preferably used in ultramicro lithography processes and other photofabrication processes that can be applied to manufacturing processes for very large scale integration (LSI) and high-capacity microchips, manufacturing processes for nanoimprint molds, and manufacturing processes for high-density information recording media. Background Art

[0002] Conventionally, in the manufacturing processes of semiconductor devices such as IC (Integrated Circuit) and LSI, fine processing has been performed by lithography using a photoresist composition. In recent years, with the high integration of integrated circuits, there has been an increasing demand for forming ultra-fine patterns in the sub-micron region or the quarter-micron region. At the same time, the exposure wavelength has also shown a trend of shortening from g-ray to i-ray and then to KrF excimer laser, and now an exposure machine using an ArF excimer laser with a wavelength of 193 nm has been developed. And, as a technique for further improving the resolution, the so-called immersion method of filling a high refractive index liquid (hereinafter, also referred to as "immersion liquid") between the projection lens and the specimen has been developed.

[0003] And now, in addition to excimer lasers, lithography using an electron beam (EB), X-ray, extreme ultraviolet (EUV), etc. is also under development. At the same time, a resist composition that is effectively sensitive to various actinic rays or radiations is being developed.

[0004] For example, Patent Document 1 describes a resist composition containing: a resin having an acid-decomposable group; as an acid generator, a salt composed of a specific cation and a specific anion having an acid-decomposable group; and a salt composed of a specific cation and an anion different from the cation and anion in the above salt.

[0005] Prior Art Documents

[0006] Patent Documents

[0007] Patent Document 1: Japanese Patent Application Laid-Open No. 2013-41257 Summary of the Invention

[0008] Technical Problem to be Solved by the Invention

[0009] In recent years, due to further miniaturization of the formed patterns and the like, the performance required for resist compositions has become higher.

[0010] In view of the above circumstances, an object of the present invention is to provide a photosensitive or radiation-sensitive resin composition excellent in resolution and line width roughness (LWR) performance, and capable of reducing development defects and etching defects, a photosensitive or radiation-sensitive film using the above photosensitive or radiation-sensitive resin composition, a pattern forming method, and a method for manufacturing an electronic device.

[0011] Means for Solving the Technical Problem

[0012] The present inventors have found that the above object can be achieved by the following structure. [1]

[0014] A photosensitive or radiation-sensitive resin composition containing:

[0015] (A) A resin having a group that decomposes by the action of an acid and increases in polarity;

[0016] (B) A compound represented by the following general formula (b1) that generates an acid upon irradiation with actinic rays or radiation; and

[0017] (C) A compound represented by the following general formula (c1) that generates an acid upon irradiation with actinic rays or radiation, and the content ratio of the compound (C) to the content of the compound (B) is 0.01% by mass or more and 10% by mass or less.

[0018] [Chemical Formula 1]

[0019]

[0020] In the general formula (b1), L represents a single bond or a divalent linking group. When there are a plurality of Ls, the plurality of Ls may be the same or different. A represents a group that decomposes by the action of an acid. When there are a plurality of As, the plurality of As may be the same or different. n represents an integer of 1 to 5. X represents an (n + 1)-valent linking group. M + represents a sulfonium ion or an iodonium ion.

[0021] [Chemical Formula 2]

[0022]

[0023] In the general formula (c1), L represents a single bond or a divalent linking group. When there are a plurality of Ls, the plurality of Ls may be the same or different. n represents an integer of 1 to 5. X represents an (n + 1)-valent linking group. M +Represents a sulfonium ion or an iodonium ion. Among them, L, n, X, and M in the general formula (c1) + are the same as L, n, X, and M in the general formula (b1) respectively. + B represents a group that decomposes by the action of an acid, a hydroxyl group, or a carboxyl group. When there are multiple Bs, the multiple Bs can be the same or different. Among them, at least one B represents a hydroxyl group or a carboxyl group. [2]

[0025] The photosensitive radiation-curable or radiation-sensitive resin composition according to [1], wherein the compound (B) is represented by the following general formula (b2), and the compound (C) is represented by the following general formula (c2).

[0026] [Chemical formula 3]

[0027]

[0028] In the general formula (b2), L represents a single bond or a divalent linking group. When there are multiple Ls, the multiple Ls can be the same or different. A represents a group that decomposes by the action of an acid. When there are multiple As, the multiple As can be the same or different. n represents an integer from 1 to 5. M + represents a sulfonium ion or an iodonium ion.

[0029] [Chemical formula 4]

[0030]

[0031] In the general formula (c2), L represents a single bond or a divalent linking group. When there are multiple Ls, the multiple Ls can be the same or different. n represents an integer from 1 to 5. M + represents a sulfonium ion or an iodonium ion. Among them, L, n, and M in the general formula (c2) + are the same as L, n, and M in the general formula (b2) respectively. + B represents a group that decomposes by the action of an acid, a hydroxyl group, or a carboxyl group. When there are multiple Bs, the multiple Bs can be the same or different. Among them, at least one B represents a hydroxyl group or a carboxyl group. [3]

[0033] The photosensitive radiation-curable or radiation-sensitive resin composition according to [1], wherein the compound (B) is represented by the following general formula (b3), and the compound (C) is represented by the following general formula (c3).

[0034] [Chemical formula 5]

[0035]

[0036] In general formula (b3), L represents a single bond or a divalent linking group. When there are multiple Ls, the multiple Ls may be the same or different. A represents a group that decomposes by the action of an acid. When there are multiple As, the multiple As may be the same or different. o, p, and q each independently represent an integer from 0 to 5. Among them, the sum of o, p, and q is 1 or more and 5 or less. M + represents a sulfonium ion or an iodonium ion.

[0037] [Chemical formula 6]

[0038]

[0039] In general formula (c3), L represents a single bond or a divalent linking group. When there are multiple Ls, the multiple Ls may be the same or different. o, p, and q each independently represent an integer from 0 to 5. Among them, the sum of o, p, and q is 1 or more and 5 or less. M + represents a sulfonium ion or an iodonium ion. Among them, L, o, p, q, and M in general formula (c3) + are respectively the same as L, o, p, q, and M in general formula (b3). + B represents a group that decomposes by the action of an acid, a hydroxyl group, or a carboxyl group. When there are multiple Bs, the multiple Bs may be the same or different. Among them, at least one B represents a hydroxyl group or a carboxyl group. [4]

[0041] The photosensitive or radiation-sensitive resin composition according to any one of [1] to [3], wherein,

[0042] The group that decomposes by the action of an acid represented by A above is at least one group selected from the group consisting of the group represented by the following general formula (T-1) and the group represented by the following general formula (T-2).

[0043] [Chemical formula 7]

[0044]

[0045] In general formula (T-1),

[0046] R 11 represents a hydrogen atom or an alkyl group.

[0047] R 12 represents a hydrogen atom, an alkyl group, a cycloalkyl group, or an aryl group, and the above alkyl group and cycloalkyl group may also contain an ether bond or a carbonyl bond.

[0048] R 13 represents, an alkyl group, a cycloalkyl group, or an aryl group, and the above alkyl group and cycloalkyl group may also contain an ether bond or a carbonyl bond.

[0049] R 11 and R12 They can bond to each other to form a ring.

[0050] R 12 and R 13 They can bond to each other to form a ring.

[0051] * represents a connecting bond.

[0052] In general formula (T-2),

[0053] R 21 、R 22 and R 23 each independently represents an alkyl group.

[0054] R 21 ~R 23 Two of them can bond to each other to form a ring.

[0055] * represents a connecting bond. [5]

[0057] The photosensitive or radiation-sensitive resin composition according to [4], wherein

[0058] The group decomposed by the action of an acid represented by A above is the group represented by the above general formula (T-1). [6]

[0060] The photosensitive or radiation-sensitive resin composition according to any one of [1] to [5], wherein

[0061] The ratio of the content of the above compound (C) to the content of the above compound (B) is 0.01% by mass or more and 5% by mass or less. [7]

[0063] The photosensitive or radiation-sensitive resin composition according to any one of [1] to [6], wherein

[0064] The sulfonium ion or iodonium ion represented by the above M + does not have a nitrogen atom. [8]

[0066] The photosensitive or radiation-sensitive resin composition according to any one of [1] to [7], wherein

[0067] The above resin (A) contains a repeating unit represented by the following general formula (I).

[0068] [Chemical formula 8]

[0069]

[0070] In general formula (I),

[0071] 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 Can be used with Ar 4 bonded to form a ring, in which case R 42 represents a single bond or an alkylene group.

[0072] X 4 Represents a single bond, -COO- or -CONR 64 -, R 64 represents a hydrogen atom or an alkyl group.

[0073] L 4 represents a single bond or an alkylene group.

[0074] Ar 4 represents an (n+1)-valent aromatic ring group, when it is combined with R 42 When they are bonded to form a ring, they represent an (n+2)-valent aromatic ring group.

[0075] n represents an integer of 1-5. [9]

[0077] An actinic ray-sensitive or radiation-sensitive film formed using the actinic ray-sensitive or radiation-sensitive resin composition according to any one of [1] to [8].

[10]

[0079] A pattern forming method comprises the following steps:

[0080] a resist film forming step of forming a resist film using the actinic ray-sensitive or radiation-sensitive resin composition described in any one of [1] to [8];

[0081] An exposure step of exposing the resist film to light; and

[0082] In the development step, the exposed resist film is developed using a developer.

[11]

[0084] A method for manufacturing an electronic device, comprising the pattern forming method described in

[10] .

[0085] Effects of the Invention

[0086] According to the present invention, it is possible to provide a photosensitive actinic or radiation-sensitive resin composition having excellent resolution and line width roughness (LWR) performance and capable of reducing development defects and etching defects, a photosensitive actinic or radiation-sensitive film using the above photosensitive actinic or radiation-sensitive resin composition, a pattern forming method, and a method for manufacturing an electronic device. Detailed Embodiments

[0087] Hereinafter, the present invention will be described in detail.

[0088] The constituent elements described below can be illustrated based on representative embodiments of the present invention, but the present invention is not limited to such embodiments.

[0089] In this specification, "actinic ray" or "radiation" refers to, for example, the bright line spectrum of a mercury lamp, far ultraviolet rays typified by excimer lasers, extreme ultraviolet rays (EUV: Extreme Ultraviolet), X-rays, soft X-rays, and electron beams (EB: Electron Beam). "Light" in this specification refers to actinic rays or radiation. Unless otherwise specified, "exposure" in this specification includes not only exposure using the bright line spectrum of a mercury lamp, far ultraviolet rays typified by excimer lasers, extreme ultraviolet rays (EUV light), and X-rays, but also drawing using particle rays such as electron beams and ion beams.

[0090] In this specification, "~" is used to indicate that the numerical values described before and after it are included as the lower limit value and the upper limit value.

[0091] In this specification, "(meth)acrylate" means at least one of acrylate and methacrylate. And "(meth)acrylic acid" means at least one of acrylic acid and methacrylic acid.

[0092] In this specification, the weight average molecular weight (Mw), number average molecular weight (Mn), and dispersity (also referred to as molecular weight distribution) (Mw / Mn) of a resin are defined as polystyrene conversion values obtained by GPC (gel permeation chromatography) measurement using a GPC apparatus (HLC-8120GPC manufactured by TOSOH CORPORATION) (solvent: tetrahydrofuran, flow rate (sample injection volume): 10 μL, column: TSK gel Multipore HXL-M manufactured by TOSOH CORPORATION, column temperature: 40 °C, flow rate: 1.0 mL / minute, detector: refractive index detector).

[0093] In the notations of the groups (atomic groups) in this specification, unless otherwise stated, the notations of substituted and unsubstituted groups include not only groups without substituents but also groups with substituents. For example, "alkyl" includes not only alkyl groups without substituents (unsubstituted alkyl groups) but also alkyl groups with substituents (substituted alkyl groups). Further, in this specification, "organic group" means a group containing at least one carbon atom.

[0094] Moreover, in this specification, when it is described that "it may have a substituent", there are no particular limitations on the type, position, and number of the substituents. The number of substituents may be, for example, 1, 2, 3, or more. As an example of the substituent, a monovalent non-metallic atomic group other than a hydrogen atom can be cited. For example, it can be selected from the following substituents T.

[0095] (Substituent T)

[0096] As the substituent T, halogen atoms such as fluorine atom, chlorine atom, bromine atom, and iodine atom can be cited; alkoxy groups such as methoxy group, ethoxy group, and tert-butoxy group; aryloxy groups such as phenoxy group and p-tolyloxy group; alkoxycarbonyl groups such as methoxycarbonyl group, butoxycarbonyl group, and phenoxycarbonyl group; acyloxy groups such as acetoxy group, propionyloxy group, and benzoyloxy group; acyl groups such as acetyl group, benzoyl group, isobutyryl group, acryloyl group, methacryloyl group, and methoxyvaleryl group; alkylthio groups such as methylthio group and tert-butylthio group; arylthio groups such as phenylthio group and p-tolylthio group; alkyl (for example, having 1 to 10 carbon atoms); cycloalkyl (for example, having 3 to 20 carbon atoms); aryl (for example, having 6 to 20 carbon atoms); heteroaryl; hydroxyl group; carboxyl group; formyl group; sulfo group; cyano group; alkylaminocarbonyl; arylaminocarbonyl; sulfonamide group; silyl group; amino group; monoalkylamino; dialkylamino; arylamino, nitro; and combinations thereof.

[0097] The radiation-sensitive or actinic ray-sensitive resin composition according to the present invention (hereinafter, also referred to as "the composition of the present invention") is a radiation-sensitive or actinic ray-sensitive resin composition containing (A) a resin having a group that increases in polarity by the action of an acid; (B) a compound represented by the following general formula (b1) that generates an acid upon irradiation with actinic rays or radiation; and (C) a compound represented by the following general formula (c1) that generates an acid upon irradiation with actinic rays or radiation, and the content ratio of the compound (C) to the content of the compound (B) is 0.01% by mass or more and 10% by mass or less.

[0098] [Chemical formula 9]

[0099]

[0100] In general formula (b1), L represents a single bond or a divalent linking group. When there are a plurality of Ls, the plurality of Ls may be the same or different. A represents a group that decomposes by the action of an acid. When there are a plurality of As, the plurality of As may be the same or different. n represents an integer of 1 to 5. X represents an (n + 1)-valent linking group. M + represents a sulfonium ion or an iodonium ion.

[0101] [Chemical formula 10]

[0102]

[0103] In general formula (c1), L represents a single bond or a divalent linking group. When there are a plurality of Ls, the plurality of Ls may be the same or different. n represents an integer of 1 to 5. X represents an (n + 1)-valent linking group. M + represents a sulfonium ion or an iodonium ion. Among them, L, n, X, and M in general formula (c1) + are respectively the same as L, n, X, and M in general formula (b1) + . B represents a group that decomposes by the action of an acid, a hydroxyl group, or a carboxyl group. When there are a plurality of Bs, the plurality of Bs may be the same or different. Among them, at least one B represents a hydroxyl group or a carboxyl group.

[0104] The composition of the present invention is preferably a resist composition, and can be a positive resist composition or a negative resist composition. Further, it can be a resist composition for alkaline development or a resist composition for organic solvent development. Among them, a positive resist composition for alkaline development is preferred.

[0105] Further, the composition of the present invention is preferably a chemically amplified resist composition, and more preferably a chemically amplified positive resist composition.

[0106] Although the reason why the composition of the present invention has excellent resolution and LWR performance and can reduce development defects and etching defects is not yet fully understood, the present inventors presume as follows.

[0107] The composition of the present invention is a compound that generates an acid upon irradiation with actinic rays or radiation, contains a compound (B) having a group that decomposes by the action of an acid, has the same skeleton as the compound (B), and contains a compound (C) having a hydroxyl group or a carboxyl group in a specific ratio with respect to the compound (B).

[0108] It is considered that since the compound (C) has a hydroxyl group or a carboxyl group, it becomes a dissolution accelerator for the film formed using the composition of the present invention, and development defects caused by dissolution residues of the film are suppressed.

[0109] It is considered that since the addition amount of the compound (C) is within an appropriate range, the solubility of the film in the developer does not become too high and the resolution is excellent. Also, it is considered that for the hydroxyl group or carboxyl group of the compound (C), it is easy to coordinate with metal impurities that cause etching defects, but since the addition amount of the compound (C) is within an appropriate range, it is also difficult to generate etching defects.

[0110] Moreover, it is considered that since the compound (C) has the same skeleton as the compound (B), it is easy to be compatible with the compound (B), and by being uniformly distributed in the film, the LWR performance becomes good.

[0111] [Resin (A) having a group that decomposes by the action of an acid and increases in polarity]

[0112] The resin (A) having a group that decomposes by the action of an acid and increases in polarity (also referred to as "resin (A)") will be described.

[0113] The resin (A) is a resin having a group that decomposes by the action of an acid and increases in polarity (also referred to as "acid-decomposable group") (hereinafter, also referred to as "acid-decomposable resin").

[0114] The resin (A) is a resin that, due to having an acid-decomposable group, decomposes by the action of an acid and increases in solubility in an alkaline developer.

[0115] The resin (A) preferably contains a repeating unit having an acid-decomposable group.

[0116] As the resin (A), known resins can be appropriately used. For example, it is possible to preferably use the known compounds disclosed in paragraphs

[0055] to

[0191] of the specification of US Patent Application Publication No. 2016 / 0274458A1, paragraphs

[0035] to

[0085] of the specification of US Patent Application Publication No. 2015 / 0004544A1, and paragraphs

[0045] to

[0090] of the specification of US Patent Application Publication No. 2016 / 0147150A1 as photoacid generators.

[0117] The acid-decomposable group preferably has a structure in which a polar group is protected by a group (detachable group) that decomposes and detaches by the action of an acid.

[0118] As polar groups, for example, carboxyl group, phenolic hydroxyl group, fluorinated alcohol group, sulfonic acid group, sulfonamide group, sulfimide group, (alkylsulfonyl)(alkylcarbonyl)methylene, (alkylsulfonyl)(alkylcarbonyl)imide group, bis(alkylcarbonyl)methylene, bis(alkylcarbonyl)imide group, bis(alkylsulfonyl)methylene, bis(alkylsulfonyl)imide group, tris(alkylcarbonyl)methylene and tris(alkylsulfonyl)methylene and other acidic groups (typically groups that dissociate in a 2.38 mass% aqueous solution of tetramethylammonium hydroxide) and alcohol hydroxyl groups, etc. can be cited.

[0119] In addition, an alcohol hydroxyl group is a hydroxyl group bonded to a hydrocarbon group, and refers to a hydroxyl group other than a hydroxyl group directly bonded to an aromatic ring (phenolic hydroxyl group). As the hydroxyl group, an aliphatic alcohol group in which the α-position is substituted with an electron-withdrawing group such as a fluorine atom (for example, hexafluoroisopropanol group, etc.) is excluded. As the alcohol hydroxyl group, a hydroxyl group with a pKa (acid dissociation constant) of 12 or more and 20 or less is preferred.

[0120] Among them, as the polar group, carboxyl group, phenolic hydroxyl group, fluorinated alcohol group (preferably hexafluoroisopropanol group) or sulfonic acid group is preferred.

[0121] As a group that decomposes and detaches by the action of an acid (detaching group), for example, groups represented by the formulas (Y1) to (Y4) can be cited.

[0122] Formula (Y1): -C(Rx 1 )(Rx 2 )(Rx 3 )

[0123] Formula (Y2): -C(=O)OC(Rx 1 )(Rx 2 )(Rx 3 )

[0124] Formula (Y3): -C(R 36 )(R 37 )(OR 38 )

[0125] Formula (Y4): -C(Rn)(H)(Ar)

[0126] In formulas (Y1) and (Y2), Rx 1 ~Rx 3 each independently represents an alkyl group (linear or branched) or a cycloalkyl group (monocyclic or polycyclic). In addition, when all of Rx 1 ~Rx 3 are alkyl groups (linear or branched), it is preferred that at least 2 of Rx 1 ~Rx 3 are methyl groups.

[0127] Among them, Rx is preferably1 ~Rx 3 Each independently represents a linear or branched alkyl group, more preferably Rx 1 ~Rx 3 Each independently represents a linear alkyl group.

[0128] Rx 1 ~Rx 3 Two of ~Rx may be bonded to form a monocyclic or polycyclic ring.

[0129] As Rx 1 ~Rx 3 The alkyl group is preferably an alkyl group having 1 to 4 carbon atoms such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, and tert-butyl.

[0130] As Rx 1 ~Rx 3 The cycloalkyl group is preferably a monocyclic cycloalkyl group such as cyclopentyl and cyclohexyl, and a polycyclic cycloalkyl group such as norbornyl, tetracyclodecyl, tetracyclododecyl, and adamantyl.

[0131] As Rx 1 ~Rx 3 The cycloalkyl group formed by bonding two of ~Rx is preferably a monocyclic cycloalkyl group such as cyclopentyl and cyclohexyl, and a polycyclic cycloalkyl group such as norbornyl, tetracyclodecyl, tetracyclododecyl, and adamantyl, more preferably a monocyclic cycloalkyl group having 5 to 6 carbon atoms.

[0132] Rx 1 ~Rx 3 In the cycloalkyl group formed by bonding two of ~Rx, for example, one of the methylene groups constituting the ring may be substituted with a group having a heteroatom such as an oxygen atom or a heteroatom-containing group such as a carbonyl group.

[0133] The group represented by formula (Y1) or formula (Y2) is preferably, for example, Rx 1 is methyl or ethyl, and Rx 2 and Rx 3 are bonded to form the above cycloalkyl group.

[0134] In formula (Y3), R 36 ~R 38 Each independently represents a hydrogen atom or a monovalent organic group. R 37 and R 38 may be bonded to each other to form a ring. Examples of the monovalent organic group include an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, and an alkenyl group. R 36 is also preferably a hydrogen atom.

[0135] As formula (Y3), a group represented by the following formula (Y3-1) is preferred.

[0136] [Chemical Formula 11]

[0137]

[0138] Herein, L 1 and L 2 each independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, or a group formed by combining them (for example, a group formed by combining an alkyl group and an aryl group).

[0139] M represents a single bond or a divalent linking group.

[0140] Q represents an alkyl group that may contain a heteroatom, a cycloalkyl group that may contain a heteroatom, an aryl group that 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 them (for example, a group formed by combining an alkyl group and a cycloalkyl group).

[0141] In the alkyl group and the cycloalkyl group, for example, one of the methylene groups may be substituted with a group having a heteroatom such as an oxygen atom or a heteroatom-containing group such as a carbonyl group.

[0142] In addition, preferably, one of L 1 and L 2 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.

[0143] At least two of Q, M, and L 1 may be bonded to form a ring (preferably a 5-membered ring or a 6-membered ring).

[0144] From the viewpoint of miniaturization of the pattern, preferably, L 2 is a secondary alkyl group or a tertiary alkyl group, more preferably a tertiary alkyl group. Examples of the secondary alkyl group include isopropyl, cyclohexyl, or norbornyl, and examples of the tertiary alkyl group include tert-butyl or adamantyl. In these cases, since the Tg (glass transition temperature) and the activation energy increase, the film strength can be ensured and blurring can be suppressed.

[0145] 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.

[0146] The resin (A) preferably has an acetal structure.

[0147] The acid-decomposable group preferably has an acetal structure. The acetal structure is, for example, a structure in which a polar group such as a carboxyl group, a phenolic hydroxyl group, or a fluorinated alcohol group is protected by a group represented by the above formula (Y3).

[0148] As the repeating unit having an acid-decomposable group, the repeating unit represented by formula (A) is preferred.

[0149] [Chemical Formula 12]

[0150]

[0151] L 1 represents a divalent linking group, R 1 ~R 3 each independently represents a hydrogen atom or a monovalent substituent, and R 4 represents a group that decomposes and detaches by the action of an acid.

[0152] L 1 represents a divalent linking group. As the divalent linking group, examples include -CO-, -O-, -S-, -SO-, -SO 2 -, a hydrocarbon group (for example, an alkylene group, a cycloalkylene group, an alkenylene group, an arylene group, etc.) and a linking group formed by linking a plurality of them. Among them, as L 1 , -CO- and an arylene group are preferred.

[0153] As the arylene group, a phenylene group is preferred.

[0154] The alkylene group may be linear or branched. The number of carbon atoms of the alkylene group is not particularly limited, but is preferably 1 to 10, more preferably 1 to 3.

[0155] R 1 ~R 3 each independently represents a hydrogen atom or a monovalent substituent. As the monovalent substituent, examples include an alkyl group, a cycloalkyl group, or a halogen atom.

[0156] The alkyl group may be linear or branched. The number of carbon atoms of the alkyl group is not particularly limited, but is preferably 1 to 10, more preferably 1 to 3.

[0157] The cycloalkyl group may be monocyclic or polycyclic. The number of carbon atoms of the cycloalkyl group is preferably 3 to 8.

[0158] As the halogen atom, examples include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

[0159] R 4 represents a group that decomposes and detaches by the action of an acid (detaching group).

[0160] Among them, as the detaching group, examples include the groups represented by the above formulas (Y1) to (Y4), and the group represented by the above formula (Y3) is preferred.

[0161] When each of the above groups has a substituent, examples of the substituent include an alkyl group (having 1 to 4 carbon atoms), a halogen atom, a hydroxyl group, an alkoxy group (having 1 to 4 carbon atoms), a carboxyl group, and an alkoxycarbonyl group (having 2 to 6 carbon atoms). The number of carbon atoms in the substituent is preferably 8 or less.

[0162] As the repeating unit having an acid-decomposable group, a repeating unit represented by the general formula (AI) is also preferred.

[0163] [Chemical formula 13]

[0164]

[0165] In the general formula (AI),

[0166] Xa 1 represents a hydrogen atom or an alkyl group.

[0167] T represents a single bond or a divalent linking group.

[0168] Rx 1 ~Rx 3 each independently represents an alkyl group (linear or branched) or a cycloalkyl group (monocyclic or polycyclic). Among them, when Rx 1 ~Rx 3 are all alkyl groups (linear or branched), it is preferred that at least two of Rx 1 ~Rx 3 are methyl groups.

[0169] Rx 1 ~Rx 3 Two of them can also be bonded to form a cycloalkyl group (monocyclic or polycyclic).

[0170] Examples of the alkyl group represented by Xa 1 include a methyl group or a group represented by -CH 2 -R 11 . R 11 represents a halogen atom (such as a fluorine atom), a hydroxyl group, or a monovalent organic group. Examples include an alkyl group having 5 or fewer carbon atoms and an acyl group having 5 or fewer carbon atoms. An alkyl group having 3 or fewer carbon atoms is preferred, and a methyl group is more preferred. As Xa 1 , a hydrogen atom, a methyl group, a trifluoromethyl group, or a hydroxymethyl group is preferred.

[0171] Examples of the divalent linking group of T include an alkylene group, an aromatic ring group, a -COO-Rt- group, and an -O-Rt- group. In the formula, Rt represents an alkylene group or a cycloalkylene group.

[0172] 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 -CH 2 - group, -(CH 2 ) 2 - group or -(CH 2 ) 3 - group.

[0173] As Rx 1 ~Rx 3 alkyl groups, preferred are alkyl groups having 1 to 4 carbon atoms such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl and tert-butyl.

[0174] As Rx 1 ~Rx 3 cycloalkyl groups, preferred are monocyclic cycloalkyl groups such as cyclopentyl and cyclohexyl, or polycyclic cycloalkyl groups such as norbornyl, tetracyclodecyl, tetracyclododecyl and adamantyl.

[0175] As the cycloalkyl group formed by bonding two of Rx 1 ~Rx 3 , preferred are monocyclic cycloalkyl groups such as cyclopentyl and cyclohexyl. In addition, polycyclic cycloalkyl groups such as norbornyl, tetracyclodecyl, tetracyclododecyl and adamantyl are also preferred. Among them, monocyclic cycloalkyl groups having 5 to 6 carbon atoms are preferred.

[0176] Rx 1 ~Rx 3 In the cycloalkyl group formed by bonding two of them, for example, one of the methylene groups constituting the ring may be substituted with a group having a heteroatom such as an oxygen atom or a heteroatom-containing group such as a carbonyl group.

[0177] The repeating unit represented by the general formula (AI) is preferably such that, for example, Rx 1 is methyl or ethyl, and Rx 2 and Rx 3 bond to form the above cycloalkyl group.

[0178] When the above groups have substituents, examples of the substituents include alkyl groups (having 1 to 4 carbon atoms), halogen atoms, hydroxyl groups, alkoxy groups (having 1 to 4 carbon atoms), carboxyl groups and alkoxycarbonyl groups (having 2 to 6 carbon atoms). The number of carbon atoms in the substituents is preferably 8 or less.

[0179] As the repeating unit represented by the general formula (AI), an acid-decomposable (meth)acrylic acid tertiary alkyl ester-based repeating unit (where Xa 1 represents a hydrogen atom or a methyl group, and T represents a single bond repeating unit) is preferred.

[0180] Resin (A) may contain, alone, one kind of repeating unit having an acid-decomposable group, or may contain two or more kinds of such repeating units in combination.

[0181] With respect to all the repeating units in resin (A), the content of the repeating unit having an acid-decomposable group in resin (A) (when there are a plurality of repeating units having an acid-decomposable group, it is the total thereof) is preferably 10 to 90 mol%, more preferably 20 to 80 mol%, and still more preferably 30 to 70 mol%.

[0182] (Repeating unit having a lactone group or a sultone group)

[0183] Resin (A) may further contain a repeating unit having a lactone group or a sultone group.

[0184] As the lactone group or the sultone group, any group may be used as long as it has a lactone structure or a sultone structure. Preferably, it is a group having a 5- to 7-membered ring lactone structure or a 5- to 7-membered ring sultone structure. More preferably, it is a group in which another ring structure is fused to the 5- to 7-membered ring lactone structure in the form of forming a bicyclic structure or a spiro ring structure, or a group in which another ring structure is fused to the 5- to 7-membered ring sultone structure in the form of forming a bicyclic structure or a spiro ring structure. More preferably, it has a repeating unit containing a group having a lactone structure represented by any one of the following general formulas (LC1-1) to (LC1-21) or a group having a sultone structure represented by any one of the following general formulas (SL1-1) to (SL1-3). Further, the group having a lactone structure or a sultone structure may be directly bonded to the main chain. As a preferred structure, groups represented by general formula (LC1-1), general formula (LC1-4), general formula (LC1-5), general formula (LC1-6), general formula (LC1-13), and general formula (LC1-14) are preferred.

[0185] [Chemical formula 14]

[0186]

[0187] The lactone structure portion or the sultone structure portion may have a substituent (Rb 2 ). As the preferred substituent (Rb 2 ), examples thereof include an alkyl group having 1 to 8 carbon atoms, a cycloalkyl group having 4 to 7 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, an alkoxycarbonyl group having 1 to 8 carbon atoms, a carboxyl group, a halogen atom, a hydroxyl group, a cyano group, and an acid-decomposable group. n2 represents an integer of 0 to 4. When n2 is 2 or more, a plurality of Rb 2 may be different, and a plurality of Rb 2 may be bonded to each other to form a ring.

[0188] As a repeating unit containing a group having a lactone structure or a sultone structure, for example, a repeating unit represented by the following general formula (AII) can be cited.

[0189] [Chemical formula 15]

[0190]

[0191] In the general formula (AII), Rb 0 represents a hydrogen atom, a halogen atom or an alkyl group having 1 to 4 carbon atoms.

[0192] As Rb 0 The preferred substituents that the alkyl group can have include a hydroxyl group and a halogen atom.

[0193] As Rb 0 The halogen atom, examples thereof include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom. Rb 0 Is preferably a hydrogen atom or a methyl group.

[0194] 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 -Ab 1 -CO 2 - is preferred. Ab 1 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.

[0195] V represents a group having a lactone structure or a sultone structure.

[0196] As the group having a lactone structure or a sultone structure of V, a group represented by any one of the general formulas (LC1-1) to (LC1-21) and the general formulas (SL1-1) to (SL1-3) is preferred.

[0197] Repeating units containing a group having a lactone structure or a sultone structure usually have optical isomers, but any optical isomers can be used. Also, one kind of optical isomer can be used alone, or multiple optical isomers can be used in combination. When mainly using one kind of optical isomer, its optical purity (ee) is preferably 90 or more, more preferably 95 or more.

[0198] Furthermore, the resin (A) may also contain a repeating unit having a structure in which one or more methylene groups in the lactone structure or the sultone structure are replaced by an oxygen atom or a sulfur atom.

[0199] Specific examples of the repeating unit containing a group having a lactone structure or a sultone structure and the repeating unit having a structure in which one or more methylene groups in the lactone structure or the sultone structure are replaced by an oxygen atom or a sulfur atom are shown below, but the present invention is not limited thereto. In the formula, Rx represents H, CH 3 , CH 2 OH or CF3.

[0200] [Chemical Formula 16]

[0201]

[0202] [Chemical Formula 17]

[0203]

[0204] [Chemical Formula 18]

[0205]

[0206] [Chemical Formula 19]

[0207]

[0208] With respect to all the repeating units in the resin (A), the content of the repeating unit having a lactone group or a sultone group is preferably 1 to 60 mol%, more preferably 5 to 50 mol%, and still more preferably 10 to 40 mol%.

[0209] (Repeating unit having an acid group)

[0210] The resin (A) may also contain a repeating unit having an acid group.

[0211] As the acid group, an acid group having an acid dissociation constant (pKa) of 13 or less is preferred.

[0212] The pKa is the same as the pKa of the acid generated by irradiation of the compound (B) described later with actinic rays or radiation.

[0213] As the repeating unit having an acid group, a repeating unit represented by the formula (B) is preferred.

[0214] [Chemical Formula 20]

[0215]

[0216] R 3 represents a hydrogen atom or a monovalent organic group.

[0217] As the monovalent organic group, a group represented by -L 4 -R 8 is preferred. L 4 represents a single bond or an ester group. R8 Examples thereof include an alkyl group, a cycloalkyl group, an aryl group, or a group formed by combining them.

[0218] R 4 and R 5 each independently represent a hydrogen atom, a halogen atom, or an alkyl group.

[0219] Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom.

[0220] L 2 represents a single bond or an ester group.

[0221] L 3 represents an (n + m + 1)-valent aromatic hydrocarbon ring group or an (n + m + 1)-valent alicyclic hydrocarbon ring group. Examples of the aromatic hydrocarbon ring group include a phenyl ring group and a naphthalene ring group. The alicyclic hydrocarbon ring group may be a monocyclic or polycyclic group. For example, a cycloalkyl ring group can be cited.

[0222] R 6 represents a hydroxyl group or a fluorinated alcohol group (preferably a hexafluoroisopropanol group). Additionally, when R 6 is a hydroxyl group, L 3 is preferably an (n + m + 1)-valent aromatic hydrocarbon ring group.

[0223] R 7 represents a halogen atom. Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom.

[0224] m represents an integer of 1 or more. m is preferably an integer of 1 to 3, more preferably an integer of 1 to 2.

[0225] n represents 0 or an integer of 1 or more. n is preferably an integer of 1 to 4.

[0226] Additionally, (n + m + 1) is preferably an integer of 1 to 5.

[0227] As the repeating unit having an acid group, a repeating unit represented by the following general formula (I) is also preferred.

[0228] Including the repeating unit represented by the following general formula (I) is a preferred embodiment of the resin (A).

[0229] [Chemical formula 21]

[0230]

[0231] In the general formula (I),

[0232] R 41 、R 42 and R 43Each independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, a cyano group, or an alkoxycarbonyl group. Among them, R 42 may bond with Ar 4 to form a ring, and in this case, R 42 represents a single bond or an alkylene group.

[0233] X 4 represents a single bond, -COO-, or -CONR 64 -, and R 64 represents a hydrogen atom or an alkyl group.

[0234] L 4 represents a single bond or an alkylene group.

[0235] Ar 4 represents an (n + 1)-valent aromatic ring group, and when it bonds with R 42 to form a ring, it represents an (n + 2)-valent aromatic ring group.

[0236] n represents an integer from 1 to 5.

[0237] As the R 41 , R 42 , and R 43 alkyl groups in the general formula (I), they are preferably alkyl groups with 20 or fewer carbon atoms such as methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, hexyl, 2-ethylhexyl, octyl, and dodecyl, more preferably alkyl groups with 8 or fewer carbon atoms, and further preferably alkyl groups with 3 or fewer carbon atoms.

[0238] As the R 41 , R 42 , and R 43 cycloalkyl groups in the general formula (I), they can be monocyclic or polycyclic. Among them, they are preferably monocyclic cycloalkyl groups with 3 to 8 carbon atoms such as cyclopropyl, cyclopentyl, and cyclohexyl.

[0239] As the R 41 , R 42 , and R 43 halogen atoms in the general formula (I), examples include fluorine atom, chlorine atom, bromine atom, and iodine atom, and preferably fluorine atom.

[0240] As the alkyl groups contained in the alkoxycarbonyl groups of R 41 , R 42 , and R 43 in the general formula (I), they are preferably the same alkyl groups as those of the above R 41 , R 42 , and R 43 .

[0241] 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.

[0242] Ar 4 represents an (n+1)-valent aromatic ring group. The divalent aromatic ring group in the case where n is 1 may have a substituent, and is preferably an arylene group having 6 to 18 carbon atoms such as phenylene, tolylene, naphthylene and anthracene, or an 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.

[0243] 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.

[0244] The (n+1)-valent aromatic ring group may further have a substituent.

[0245] 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.

[0246] As X 4 -CONR 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.

[0247] As X 4 , preferably a single bond, -COO- or -CONH-, more preferably a single bond or -COO-.

[0248] As L 4 The alkylene group in is preferably an alkylene group having 1 to 8 carbon atoms, such as methylene, ethylene, propylene, butylene, hexylene, and octylene.

[0249] As Ar 4, preferably an aromatic ring group having 6 to 18 carbon atoms, more preferably a benzene ring group, a naphthalene ring group or a biphenylene ring group.

[0250] The repeating unit represented by the general formula (I) preferably has a hydroxystyrene structure. That is, Ar 4 is preferably a benzene ring group.

[0251] As the repeating unit represented by the general formula (I), the repeating unit represented by the following general formula (1) is preferred.

[0252] [Chemical formula 22]

[0253]

[0254] In the general formula (1),

[0255] A represents a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom or a cyano group.

[0256] 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. When there are a plurality of them, they may be the same or different. When there are a plurality of Rs, they may form a ring together with each other. As R, a hydrogen atom is preferred.

[0257] a represents an integer of 1 to 3.

[0258] b represents an integer of 0 to (3 - a).

[0259] Hereinafter, specific examples of the repeating unit represented by the general formula (I) are shown, but the present invention is not limited thereto. In the formula, a represents 1 or 2.

[0260] [Chemical formula 23]

[0261]

[0262] [Chemical formula 24]

[0263]

[0264] [Chemical formula 25]

[0265]

[0266] In addition, among the above repeating units, the repeating units specifically described below are preferred. In the formula, R represents a hydrogen atom or a methyl group, and a represents 1, 2 or 3.

[0267] [Chemical formula 26]

[0268]

[0269] [Chemical formula 27]

[0270]

[0271] Moreover, with respect to all the repeating units in the resin (A), the content of the repeating units having an acid group is preferably 10 to 90 mol%, more preferably 10 to 80 mol%, still more preferably 15 to 75 mol%, and particularly preferably 20 to 70 mol%.

[0272] In addition to the above repeating structural units, the resin (A) may also have various repeating units for purposes such as adjusting dry-etching resistance, adaptability to a standard developer, substrate adhesion, resist profile, resolution, heat resistance, sensitivity, etc.

[0273] The resin (A) can be synthesized according to a conventional method (e.g., radical polymerization). As a general synthesis method, for example, (1) a batch polymerization method in which a monomer species and an initiator are dissolved in a solvent and polymerized by heating, (2) a dropwise polymerization method in which a solution containing a monomer species and an initiator is added dropwise to a heated solvent over 1 to 10 hours, etc. can be cited.

[0274] The weight-average molecular weight of the resin (A) is preferably 1000 to 200000, more preferably 2000 to 30000, still more preferably 3000 to 25000. The dispersity (Mw / Mn) is generally 1.0 to 3.0, preferably 1.0 to 2.6, more preferably 1.0 to 2.0, and still more preferably 1.1 to 2.0.

[0275] The resin (A) can be used alone or in combination of two or more.

[0276] In the composition of the present invention, the content of the resin (A) is usually 20% by mass or more, preferably 40% by mass or more, more preferably 50% by mass or more, and still more preferably 60% by mass or more with respect to the total solid content. The upper limit is not particularly limited, and it is preferably 99.5% by mass or less, more preferably 99% by mass or less, and still more preferably 98% by mass or less.

[0277] In addition, the total solid content of the composition of the present invention refers to other components (components capable of forming a photosensitive or radiation-sensitive film) other than the solvent.

[0278] [(B) A compound represented by the general formula (b1) that generates an acid upon irradiation with actinic rays or radiation]

[0279] The photosensitive actinic ray- or radiation-sensitive resin composition of the present invention contains (B) a compound represented by the following general formula (b1) that generates an acid upon irradiation with actinic rays or radiation (also referred to as "compound (B)" or "acid generator (B)").

[0280] Compound (B) is a compound that generates an acid upon irradiation with actinic rays or radiation (photoacid generator).

[0281] [Chemical formula 28]

[0282]

[0283] In general formula (b1), L represents a single bond or a divalent linking group. When there are multiple Ls, the multiple Ls may be the same or different. A represents a group that decomposes by the action of an acid. When there are multiple As, the multiple As may be the same or different. n represents an integer from 1 to 5. X represents an (n + 1)-valent linking group. M + represents a sulfonium ion or an iodonium ion.

[0284] In general formula (b1), X represents an (n + 1)-valent linking group.

[0285] The linking group represented by X is not particularly limited, and examples thereof include an aliphatic group (which may be linear, branched, or cyclic), an aromatic group, -O-, -CO-, -COO-, -OCO-, and a group formed by combining two or more of these groups.

[0286] As the above aliphatic group, a group formed by removing n hydrogen atoms from an alkyl group (which may be linear or branched, preferably having 1 to 20 carbon atoms, more preferably 1 to 10 carbon atoms) and a group formed by removing n hydrogen atoms from a cycloalkyl group (which may be monocyclic or polycyclic, preferably having 3 to 20 carbon atoms, more preferably 5 to 10 carbon atoms) are preferred.

[0287] The above aliphatic group may also have a substituent, and examples of the substituent include the above substituent T.

[0288] The above aliphatic group may also have a heteroatom (e.g., a sulfur atom, an oxygen atom, a nitrogen atom, etc.) between carbon-carbon atoms.

[0289] As the above aromatic group, a group formed by removing n hydrogen atoms from an aryl group (preferably having 6 to 20 carbon atoms, more preferably 6 to 18 carbon atoms. And the above aryl group is further preferably an aryl group having 6 to 10 carbon atoms. Specific examples of the above aryl group include a phenyl group, a terphenyl group, etc.) is preferred.

[0290] The above aromatic group may also have a substituent, and as the substituent, for example, the above substituent T can be cited.

[0291] The above aromatic group may also have a heteroatom (for example, a sulfur atom, an oxygen atom, a nitrogen atom, etc.) between carbon-carbon atoms.

[0292] X is preferably an n + 1-valent aromatic group.

[0293] In the general formula (b1), n represents an integer of 1 to 5, preferably represents an integer of 1 to 3, more preferably represents 2 or 3, and still more preferably represents 3.

[0294] In the general formula (b1), L represents a single bond or a divalent linking group.

[0295] There is no particular limitation on the divalent linking group represented by L. For example, an aliphatic group (which may be linear, branched, or cyclic), an aromatic group, -O-, -CO-, -COO-, -OCO-, and a group formed by combining two or more of them can be cited.

[0296] As the above aliphatic group, an alkylene group (which may be linear or branched, preferably having 1 to 20 carbon atoms, more preferably having 1 to 10 carbon atoms) and a cycloalkylene group (which may be monocyclic or polycyclic, preferably having 3 to 20 carbon atoms, more preferably having 5 to 10 carbon atoms) are preferred.

[0297] The above aliphatic group may also have a substituent, and as the substituent, for example, the above substituent T can be cited.

[0298] The above aliphatic group may also have a heteroatom (for example, a sulfur atom, an oxygen atom, a nitrogen atom, etc.) between carbon-carbon atoms.

[0299] As the above aromatic group, an arylene group (preferably having 6 to 20 carbon atoms, more preferably having 6 to 10 carbon atoms) is preferred.

[0300] The above aromatic group may also have a substituent, and as the substituent, for example, the above substituent T can be cited.

[0301] The above aromatic group may also have a heteroatom (for example, a sulfur atom, an oxygen atom, a nitrogen atom, etc.) between carbon-carbon atoms.

[0302] L is preferably an arylene group.

[0303] In the general formula (b1), A represents a group that decomposes by the action of an acid.

[0304] The group decomposed by the action of an acid (acid-decomposable group) represented by A is not particularly limited, and examples thereof include the acid-decomposable groups described in the above resin (A).

[0305] The acid-decomposable group preferably has a structure in which a polar group is protected by a group (detachable group) decomposed and detached by the action of an acid.

[0306] As the polar group, a carboxyl group, a phenolic hydroxyl group, or an alcoholic hydroxyl group is preferable.

[0307] The group decomposed by the action of an acid represented by A is preferably at least one group selected from the group consisting of the group represented by the following general formula (T-1) and the group represented by the following general formula (T-2), and more preferably the group represented by the following general formula (T-1). It is considered that the group represented by the general formula (T-1) has high reactivity to an acid and the reaction easily proceeds uniformly, so that the LWR performance becomes particularly good.

[0308] [Chemical formula 29]

[0309]

[0310] In the general formula (T-1),

[0311] R 11 represents a hydrogen atom or an alkyl group.

[0312] R 12 represents a hydrogen atom, an alkyl group, a cycloalkyl group, or an aryl group, and the above alkyl group and cycloalkyl group may also contain an ether bond or a carbonyl bond.

[0313] R 13 represents an alkyl group, a cycloalkyl group, or an aryl group, and the above alkyl group and cycloalkyl group may also contain an ether bond or a carbonyl bond.

[0314] R 11 and R 12 may be bonded to each other to form a ring.

[0315] R 12 and R 13 may be bonded to each other to form a ring.

[0316] * represents a connecting bond.

[0317] In the general formula (T-2),

[0318] R 21 , R 22 and R 23 each independently represent an alkyl group.

[0319] R 21 to R 23 in two of them may be bonded to each other to form a ring.

[0320] * indicates a linking bond.

[0321] In general formula (T-1), R 11 represents a hydrogen atom or an alkyl group.

[0322] When R 11 represents an alkyl group, the alkyl group can be linear or branched, and is preferably an alkyl group having 1 to 10 carbon atoms, more preferably an alkyl group having 1 to 5 carbon atoms, and further preferably an alkyl group having 1 to 3 carbon atoms. Examples of the alkyl group include a methyl group, an ethyl group, a propyl group, a n-butyl group, a sec-butyl group, a hexyl group, an octyl group, etc.

[0323] The above alkyl group may also have a substituent, and examples of the substituent include the above substituent T.

[0324] R 11 is preferably a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and more preferably a hydrogen atom.

[0325] In general formula (T-1), R 12 represents a hydrogen atom, an alkyl group, a cycloalkyl group or an aryl group.

[0326] When R 12 represents an alkyl group, the alkyl group can be linear or branched, and is preferably an alkyl group having 1 to 10 carbon atoms, more preferably an alkyl group having 1 to 5 carbon atoms. Examples of the alkyl group include a methyl group, an ethyl group, a propyl group, a n-butyl group, a sec-butyl group, a tert-butyl group, a hexyl group, an octyl group, etc.

[0327] The above alkyl group may also have a substituent, and examples of the substituent include the above substituent T.

[0328] The above alkyl group may also contain an ether bond or a carbonyl bond.

[0329] When R 12 represents a cycloalkyl group, the cycloalkyl group can be monocyclic or polycyclic, and is preferably a cycloalkyl group having 3 to 20 carbon atoms, more preferably a cycloalkyl group having 5 to 15 carbon atoms, and further preferably a cycloalkyl group having 5 to 10 carbon atoms. Examples of the cycloalkyl group include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cyclooctyl group, an adamantyl group, a norbornyl group, an isobornyl group, a camphenyl group, a dicyclopentyl group, an α-pinene group, a tricyclodecyl group, a tetracyclododecyl group, an androstanyl group, etc.

[0330] The above cycloalkyl group may also have a substituent, and examples of the substituent include the above substituent T.

[0331] The above cycloalkyl group may also contain an ether bond or a carbonyl bond.

[0332] When R 12When representing an aryl group, as the aryl group, an aryl group having 6 to 20 carbon atoms, more preferably 6 to 15 carbon atoms, and still more preferably 6 to 10 carbon atoms is preferred. As the aryl group, for example, a phenyl group, a naphthyl group, etc. can be cited.

[0333] The above aryl group may also have a substituent. As the substituent, for example, the above substituent T can be cited.

[0334] R 12 Is preferably a hydrogen atom or an alkyl group having 1 to 5 carbon atoms.

[0335] In the general formula (T-1), R 13 Represents an alkyl group, a cycloalkyl group or an aryl group.

[0336] R 13 The alkyl group, cycloalkyl group or aryl group represented is the same as the alkyl group, cycloalkyl group or aryl group described as the above R 12 Represents.

[0337] R 13 Is preferably an alkyl group having 1 to 5 carbon atoms.

[0338] R 11 And R 12 Can be bonded to each other to form a ring.

[0339] As R 11 And R 12 The ring formed by bonding to each other is preferably an aliphatic ring.

[0340] As the above aliphatic ring, a cycloalkane having 3 to 20 carbon atoms is preferred, and a cycloalkane having 5 to 15 carbon atoms is more preferred. The above cycloalkane can be a monocyclic ring or a polycyclic ring.

[0341] The above aliphatic ring may also have a substituent. As the substituent, for example, the above substituent T can be cited.

[0342] The above aliphatic ring may also have a heteroatom (for example, a sulfur atom, an oxygen atom, a nitrogen atom, etc.) between carbon-carbon atoms.

[0343] R 12 And R 13 Can be bonded to each other to form a ring.

[0344] As R 12 And R 13 The ring formed by bonding to each other is preferably an aliphatic ring containing an oxygen atom on the ring.

[0345] As the above aliphatic ring, it preferably has 3 to 20 carbon atoms, more preferably 5 to 15 carbon atoms. The above aliphatic ring can be a monocyclic ring or a polycyclic ring.

[0346] The above-mentioned aliphatic ring may also have substituents, and as the substituents, for example, the above-mentioned substituent T can be cited.

[0347] The above-mentioned aliphatic ring may also have heteroatoms other than oxygen atoms (for example, sulfur atoms, nitrogen atoms, etc.) between carbon-carbon atoms.

[0348] In the general formula (T-1), R 11 and R 12 do not bond to each other and R 12 and R 13 bond to each other to form a ring is one of the preferred modes in the present invention.

[0349] In the general formula (T-2), R 21 , R 22 and R 23 each independently represent an alkyl group,

[0350] When R 21 , R 22 and R 23 represent an alkyl group, there is no particular limitation as the alkyl group, and it may be linear or branched. As the above-mentioned alkyl group, preferably an alkyl group having 1 to 4 carbon atoms such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, etc.

[0351] The above-mentioned alkyl group may have substituents. As the substituents, for example, aryl groups (for example, having 6 to 15 carbon atoms), halogen atoms, hydroxyl groups, alkoxy groups (for example, having 1 to 4 carbon atoms), carboxyl groups, alkoxycarbonyl groups (for example, having 2 to 6 carbon atoms), etc. can be cited. The number of carbon atoms in the substituents is preferably 8 or less.

[0352] Two of R 21 to R 23 may bond to each other to form a ring.

[0353] When two of R 21 to R 23 bond to each other to form a ring, preferably two of R 21 to R 23 bond to each other to form a cycloalkyl group. As the above-mentioned cycloalkyl group, it may be a monocyclic cycloalkyl group such as cyclopentyl or cyclohexyl, or a polycyclic cycloalkyl group such as norbornyl, tetracyclodecyl, tetracyclododecyl, or adamantyl. Among them, a monocyclic cycloalkyl group having 5 to 6 carbon atoms is preferred.

[0354] In the above-mentioned cycloalkyl group, for example, one of the methylene groups constituting the ring may be substituted with a group having a heteroatom such as an oxygen atom or a heteroatom group such as a carbonyl group.

[0355] In the general formula (b1), M + represents a sulfonium ion or an iodonium ion,

[0356] M + The sulfonium ion or iodonium ion represented by + preferably does not have a nitrogen atom. It is considered that by not having a nitrogen atom, the acid generated will not be neutralized and the LWR performance becomes particularly good.

[0357] M + There is no particular limitation, but it is preferably a cation represented by the following general formula (ZIA) or general formula (ZIIA).

[0358] [Chemical formula 30]

[0359]

[0360] In the above general formula (ZIA),

[0361] R 201 、R 202 and R 203 each independently represents an organic group.

[0362] 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.

[0363] And, two of R 201 ~R 203 can be bonded to form a ring structure, and can also contain an oxygen atom, a sulfur atom, an ester bond, an amide bond or a carbonyl group in the ring. As the group formed by bonding two of R 201 ~R 203 , examples include alkylene groups (for example, butylene group, pentylene group) and -CH 2 -CH 2 -O-CH 2 -CH 2 -.

[0364] As a preferred form of the cation in the general formula (ZIA), examples include the following cations (ZI-11), cation (ZI-12), the cation represented by the general formula (ZI-13) (cation (ZI-13)) and the cation represented by the general formula (ZI-14) (cation (ZI-14)).

[0365] When n is 2 or more, the divalent or higher cation can also be a cation having a plurality of structures represented by the general formula (ZIA). As such a cation, for example, there can be mentioned at least one of R 201 ~R 203 in the cation represented by the general formula (ZIA) being bonded to R 201 ~R203 A divalent cation such as one formed by bonding at least one of the structures in

[0366] First, the cation (ZI-11) will be described.

[0367] The cation (ZI-11) is an arylsulfonium cation in which at least one of R 201 ~R 203 in the above general formula (ZIA) is an aryl group.

[0368] In the arylsulfonium cation, R 201 ~R 203 can all be aryl groups, or a part of R 201 ~R 203 can be aryl groups and the rest can be alkyl or cycloalkyl groups.

[0369] Examples of the arylsulfonium cation include triarylsulfonium cation, diarylalkylsulfonium cation, aryldialkylsulfonium cation, diarylcycloalkylsulfonium cation, and arylbicycloalkylsulfonium cation.

[0370] The aryl group contained in the arylsulfonium cation is preferably a phenyl group or a naphthyl group, more preferably a phenyl group. The aryl group can be an aryl group containing a heterocyclic structure having an oxygen atom, a nitrogen atom, a sulfur atom, etc. Examples of the heterocyclic structure include pyrrole residue, furan residue, thiophene residue, indole residue, benzofuran residue, and benzothiophene residue. When the arylsulfonium cation has two or more aryl groups, the two or more aryl groups can be the same or different.

[0371] The alkyl or cycloalkyl group that the arylsulfonium cation optionally has preferably has 1 to 15 carbon atoms in a straight-chain alkyl group, 3 to 15 carbon atoms in a branched-chain alkyl group, or 3 to 15 carbon atoms in a cycloalkyl group. Examples include methyl, ethyl, propyl, n-butyl, sec-butyl, tert-butyl, cyclopropyl, cyclobutyl, and cyclohexyl.

[0372] R 201 ~R 203 The aryl, alkyl, and cycloalkyl groups of can each independently have an alkyl group (e.g., having 1 to 15 carbon atoms), a cycloalkyl group (e.g., having 3 to 15 carbon atoms), an aryl group (e.g., having 6 to 14 carbon atoms), an alkoxy group (e.g., having 1 to 15 carbon atoms), an alkylsulfonyl group (e.g., having 1 to 15 carbon atoms), an alkylcarbonyloxy group (e.g., having 2 to 15 carbon atoms), a halogen atom, a hydroxyl group, a lactone ring group, or a phenylthio group as a substituent. These substituents can also have substituents.

[0373] Examples of the lactone ring group include a group obtained by removing a hydrogen atom from the structure represented by any one of the following (KA-1-1) to (KA-1-17).

[0374] Next, the cation (ZI-12) will be described.

[0375] The cation (ZI-12) is a compound in which R in formula (ZIA) 201 ~R 203 each independently represents an organic group without an aromatic ring. Here, the aromatic ring also includes an aromatic ring containing a heteroatom.

[0376] As R 201 ~R 203 The organic group without an aromatic ring usually has 1 to 30 carbon atoms, preferably 1 to 20 carbon atoms.

[0377] R 201 ~R 203 are each independently 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 still more preferably a linear or branched 2-oxoalkyl group.

[0378] As the alkyl group and cycloalkyl group of R 201 ~R 203 preferably mentioned are a linear alkyl group having 1 to 10 carbon atoms or a branched alkyl group having 3 to 10 carbon atoms (e.g., methyl, ethyl, propyl, butyl and pentyl), and a cycloalkyl group having 3 to 10 carbon atoms (e.g., cyclopentyl, cyclohexyl and norbornyl).

[0379] R 201 ~R 203 may be further substituted by a halogen atom, an alkoxy group (e.g., having 1 to 5 carbon atoms), a hydroxyl group, a cyano group or a nitro group.

[0380] Next, the cation (ZI-13) will be described.

[0381] [Chemical formula 31]

[0382]

[0383] In the general formula (ZI-13), Q 1 represents an alkyl group, a cycloalkyl group or an aryl group, and when having a ring structure, the above ring structure may also contain at least one of an oxygen atom, a sulfur atom, an ester bond, an amide bond and a carbon-carbon double bond. R 6c and R 7c each independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, a cyano group or an aryl group. R 6c and R 7c may be bonded to form a ring. R x and R yEach independently represents an alkyl group, a cycloalkyl group or an alkenyl group. R x and R y may bond to form a ring. Further, at least two selected from Q 1 , R 6c and R 7c bond to form a ring structure, and the ring structure may also contain a carbon-carbon double bond.

[0384] In the general formula (ZI-13), as the alkyl group and cycloalkyl group represented by Q 1 , a linear alkyl group having 1 to 15 carbon atoms (preferably 1 to 10 carbon atoms), a branched alkyl group having 3 to 15 carbon atoms (preferably 3 to 10 carbon atoms), or a cycloalkyl group having 3 to 15 carbon atoms (preferably 1 to 10 carbon atoms) is preferred. Specifically, methyl, ethyl, propyl, n-butyl, sec-butyl, tert-butyl, cyclopropyl, cyclobutyl, cyclohexyl, norbornyl, etc. can be mentioned.

[0385] As the aryl group represented by Q 1 , 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 sulfur atom, etc. As the heterocyclic structure, a furan ring, a thiophene ring, a benzofuran ring, a benzothiophene ring, etc. can be mentioned.

[0386] The above Q 1 may further have a substituent. As such a case, for example, benzyl etc. can be mentioned as Q 1 .

[0387] Further, when Q 1 has a ring structure, the ring structure may also contain at least one of an oxygen atom, a sulfur atom, an ester bond, an amide bond and a carbon-carbon double bond.

[0388] As the alkyl group, cycloalkyl group and aryl group represented by R 6c and R 7c , the same groups as the above Q 1 can be mentioned, and their preferred modes are also the same. And R 6c and R 7c may bond to form a ring.

[0389] As the halogen atom represented by R 6c and R 7c , for example, a fluorine atom, a chlorine atom, a bromine atom and an iodine atom can be mentioned.

[0390] As the alkyl group and cycloalkyl group represented by R x and R y , the same groups as the above Q 1 can be mentioned, and their preferred modes are also the same.

[0391] As the R represented byx and R y represents an alkenyl group, preferably an allyl group or a vinyl group.

[0392] The above R x and R y may also have substituents. As such a case, for example, 2-oxoalkyl or alkoxycarbonylalkyl can be cited as R x and R y .

[0393] As the 2-oxoalkyl represented by R x and R y for example, a group having 1 to 15 carbon atoms (preferably 1 to 10 carbon atoms) can be cited. Specifically, 2-oxopropyl and 2-oxobutyl can be cited.

[0394] As the alkoxycarbonylalkyl represented by R x and R y for example, a group having 1 to 15 carbon atoms (preferably 1 to 10 carbon atoms) can be cited. And, R x and R y may be bonded to form a ring.

[0395] R x and R y The ring structure formed by connecting to each other may also contain an oxygen atom, a sulfur atom, an ester bond, an amide bond or a carbon-carbon double bond.

[0396] In the general formula (ZI-13), Q 1 and R 6c may be bonded to form a ring structure, and the formed ring structure may also contain a carbon-carbon double bond.

[0397] Among them, the above cation (ZI-13) is preferably the cation (ZI-13A).

[0398] The cation (ZI-13A) is a phenacylsulfonium cation represented by the following general formula (ZI-13A).

[0399] [Chemical formula 32]

[0400]

[0401] In the general formula (ZI-13A),

[0402] R 1c to 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.

[0403] As R 6c and R 7c , which have the same meanings as R 6c and R 7c in the above general formula (ZI-13), and their preferred modes are also the same.

[0404] As R x and R y , which have the same meanings as R x and R y in the above general formula (ZI-13), and their preferred modes are also the same.

[0405] R 1c ~R 5c Any two or more of them, R x and R y can be bonded to each other to form a ring structure, and the ring structure can independently contain an oxygen atom, a sulfur atom, an ester bond, an amide bond or a carbon-carbon double bond. Moreover, R 5c and R 6c , R 5c and R x can be bonded to each other to form a ring structure, and the ring structure can also independently contain a carbon-carbon double bond. Moreover, R 6c and R 7c can be bonded to each other to form a ring structure.

[0406] As the above ring structure, an aromatic or non-aromatic hydrocarbon ring, an aromatic or non-aromatic heterocyclic ring, and a polycyclic fused ring formed by combining two or more of these rings can be cited. As the ring structure, a 3- to 10-membered ring can be cited, preferably a 4- to 8-membered ring, and more preferably a 5-membered ring or a 6-membered ring.

[0407] As R 1c ~R 5c Any two or more of them, R 6c and R 7c and R x and R y The groups formed by bonding can include a butylene group and a pentylene group, etc.

[0408] As the group formed by bonding R 5c and R 6c and R 5c and R x It is preferably a single bond or an alkylene group. As the alkylene group, a methylene group and an ethylene group, etc. can be cited.

[0409] Next, the cation (ZI-14) will be described.

[0410] The cation (ZI-14) is represented by the following general formula (ZI-14).

[0411] [Chemical Formula 33]

[0412]

[0413] In the general formula (ZI-14),

[0414] l represents an integer of 0 to 2.

[0415] r represents an integer of 0 to 8.

[0416] R 13 represents a hydrogen atom, a fluorine atom, a hydroxyl group, an alkyl group, a cycloalkyl group, an alkoxy group, an alkoxycarbonyl group, or a group having a monocyclic or polycyclic cycloalkyl skeleton. These groups may also have substituents.

[0417] R 14 When there are a plurality of them, they each independently represent an alkyl group, a cycloalkyl group, an alkoxy group, an alkylsulfonyl group, a cycloalkylsulfonyl group, an alkylcarbonyl group, an alkoxycarbonyl group, or an alkoxy group having a monocyclic or polycyclic cycloalkyl skeleton. These groups may also have substituents.

[0418] R 15 each independently represents an alkyl group, a cycloalkyl group or a naphthyl group. These groups may also have substituents. Two R 15 may be bonded to each other to form a ring. When two R 15 are bonded to each other to form a ring, a heteroatom such as an oxygen atom or a nitrogen atom may be contained in the ring skeleton. In one embodiment, two R 15 are alkylene groups, preferably bonded to each other to form a ring structure.

[0419] In the general formula (ZI-14), R 13 , R 14 and R 15 The alkyl groups of are linear or branched. The number of carbon atoms of the alkyl group is preferably 1 to 10. As the alkyl group, methyl, ethyl, n-butyl or tert-butyl is more preferable.

[0420] Next, the general formula (ZIIA) will be described.

[0421] In the general formula (ZIIA), R 204 and R 205 each independently represents an aryl group, an alkyl group or a cycloalkyl group.

[0422] As the aryl group of R 204 and R 205 , phenyl or naphthyl is preferable, and phenyl is more preferable. R 204 and R 205The aryl group may be an aryl group containing a heterocyclic structure having an oxygen atom, a nitrogen atom, a sulfur atom, etc. As the skeleton of the aryl group having a heterocyclic structure, for example, pyrrole, furan, thiophene, indole, benzofuran, benzothiophene, etc. can be cited.

[0423] As R 204 and R 205 The alkyl group and cycloalkyl group of may preferably be a linear alkyl group having 1 to 10 carbon atoms or a branched alkyl group having 3 to 10 carbon atoms (for example, methyl, ethyl, propyl, butyl, and pentyl), or a cycloalkyl group having 3 to 10 carbon atoms (for example, cyclopentyl, cyclohexyl, and norbornyl).

[0424] R 204 and R 205 The aryl group, alkyl group, and cycloalkyl group of may each independently have a substituent. As the substituent that the aryl group, alkyl group, and cycloalkyl group of R 204 and R 205 may have, for example, an alkyl group (for example, having 1 to 15 carbon atoms), a cycloalkyl group (for example, having 3 to 15 carbon atoms), an aryl group (for example, having 6 to 15 carbon atoms), an alkoxy group (for example, having 1 to 15 carbon atoms), a halogen atom, a hydroxyl group, a lactone ring group, and a phenylthio group, etc.

[0425] As the lactone ring group, for example, a group obtained by removing a hydrogen atom from a structure represented by any one of the following (KA-1-1) to (KA-1-17) can be cited.

[0426] [Chemical formula 34]

[0427]

[0428] The structure containing the above lactone ring structure may or may not have a substituent. As the substituent, for example, the above substituent T can be cited.

[0429] The following shows preferred examples of M + but the present invention is not limited to these. Me represents methyl, and Bu represents n-butyl.

[0430] [Chemical formula 35]

[0431]

[0432] [Chemical formula 36]

[0433]

[0434] [Chemical formula 37]

[0435]

[0436] [Chemical formula 38]

[0437]

[0438] Compound (B) is preferably represented by the following general formula (b2).

[0439] [Chemical formula 39]

[0440]

[0441] In the general formula (b2), L represents a single bond or a divalent linking group. When there are a plurality of Ls, the plurality of Ls may be the same or different. A represents a group that is decomposed by the action of an acid. When there are a plurality of As, the plurality of As may be the same or different. n represents an integer of 1 to 5. M + represents a sulfonium ion or an iodonium ion.

[0442] L, A, n and M in the general formula (b2) + are respectively the same as L, A, n and M in the above general formula (b1). + Same.

[0443] Compound (B) is particularly preferably represented by the following general formula (b3).

[0444] [Chemical formula 40]

[0445]

[0446] In the general formula (b3), L represents a single bond or a divalent linking group. When there are a plurality of Ls, the plurality of Ls may be the same or different. A represents a group that is decomposed by the action of an acid. When there are a plurality of As, the plurality of As may be the same or different. o, p and q each independently represent an integer of 0 to 5. Among them, the sum of o, p and q is 1 or more and 5 or less. M + represents a sulfonium ion or an iodonium ion.

[0447] L, A and M in the general formula (b3) + are respectively the same as L, A and M in the above general formula (b1). + Same.

[0448] o, p and q in the general formula (b3) preferably each independently represent an integer of 0 to 3, more preferably an integer of 0 to 2, and still more preferably 0 or 1.

[0449] The following shows preferred specific examples of the anionic part of compound (B), but the present invention is not limited to these. Et represents ethyl.

[0450] [Chemical formula 41]

[0451]

[0452] [Chemical Formula 42]

[0453]

[0454] [Chemical Formula 43]

[0455]

[0456] [Chemical Formula 44]

[0457]

[0458] The pKa of the acid produced by compound (B) is preferably -10 or more and 5 or less.

[0459] pKa (acid dissociation constant) represents the pKa in an aqueous solution and is defined in the Chemical Handbook (II) (Revised 4th Edition, 1993, edited by the Chemical Society of Japan, Maruzen Company, Limited). The lower the pKa value, the stronger the acid strength. The pKa in an aqueous solution can be actually measured by using an infinitely diluted aqueous solution and measuring the acid dissociation constant at 25°C. Alternatively, it can be obtained by using the following Package 1 and calculating the values based on the Hammett substituent constant and the values in the known literature database. All the pKa values described in this specification represent the values obtained by calculation using this package.

[0460] Package 1: Advanced Chemistry Development (ACD / Labs) Software V8.14 for Solaris (1994 - 2007 ACD / Labs).

[0461] As a preferred example of compound (B), compounds shown in the examples and compounds formed by combining the above anions and the above cations can be cited.

[0462] Compound (B) can be synthesized, for example, by using a coupling reaction method.

[0463] The coupling reaction can be applied, for example, to the Suzuki coupling, etc. The counter cation can be converted to the desired cation M by a known anion exchange method or a conversion method based on an ion exchange resin described in, for example, Japanese Patent Laid-Open No. 6-184170. + .

[0464] Compound (B) can be used alone in one kind or two or more kinds can be used in combination.

[0465] Based on the total solid content of the composition, in the composition of the present invention, the content of compound (B) (when there are multiple kinds, the total thereof) is preferably 0.1 to 35% by mass, more preferably 0.5 to 25% by mass, still more preferably 1 to 20% by mass, and particularly preferably 5 to 20% by mass.

[0466] [(C) A compound represented by the general formula (c1) that generates an acid upon irradiation with actinic rays or radiation]

[0467] The photosensitive actinic ray- or radiation-sensitive resin composition of the present invention contains (C) a compound represented by the following general formula (c1) that generates an acid upon irradiation with actinic rays or radiation (also referred to as "compound (C)" or "acid generator (C)").

[0468] Compound (C) is a compound that generates an acid upon irradiation with actinic rays or radiation (photoacid generator).

[0469] [Chemical formula 45]

[0470]

[0471] In the general formula (c1), L represents a single bond or a divalent linking group. When there are multiple Ls, the multiple Ls may be the same or different. n represents an integer from 1 to 5. X represents an (n + 1)-valent linking group. M + represents a sulfonium ion or an iodonium ion. Among them, L, n, X, and M in the general formula (c1) + are respectively the same as L, n, X, and M in the general formula (b1) + B represents a group that decomposes upon the action of an acid, a hydroxyl group, or a carboxyl group. When there are multiple Bs, the multiple Bs may be the same or different. Among them, at least one B represents a hydroxyl group or a carboxyl group.

[0472] In the general formula (c1), L, n, X, and M + are respectively the same as L, n, X, and M in the general formula (b1) + and are the same.

[0473] In the general formula (c1), B represents a group that decomposes upon the action of an acid, a hydroxyl group, or a carboxyl group.

[0474] When B in the general formula (c1) represents a group that decomposes upon the action of an acid, as the group that decomposes upon the action of an acid, it is the same as A in the general formula (b1).

[0475] At least one of Bs in the formula (c1) represents a hydroxyl group or a carboxyl group.

[0476] Compound (C) is preferably represented by the following general formula (c2).

[0477] [Chemical formula 46]

[0478]

[0479] In general formula (c2), L represents a single bond or a divalent linking group. When there are multiple Ls, the multiple Ls may be the same or different. n represents an integer from 1 to 5. M + represents a sulfonium ion or an iodonium ion. Among them, L, n, and M in general formula (c2) + are the same as L, n, and M in general formula (b2), respectively + respectively. B represents a group that decomposes by the action of an acid, a hydroxyl group, or a carboxyl group. When there are multiple Bs, the multiple Bs may be the same or different. Among them, at least one B represents a hydroxyl group or a carboxyl group.

[0480] B in general formula (c2) is the same as B in the above general formula (c1).

[0481] Compound (C) is particularly preferably represented by the following general formula (c3).

[0482] [Chemical formula 47]

[0483]

[0484] In general formula (c3), L represents a single bond or a divalent linking group. When there are multiple Ls, the multiple Ls may be the same or different. o, p, and q each independently represent an integer from 0 to 5. Among them, the sum of o, p, and q is 1 or more and 5 or less. M + represents a sulfonium ion or an iodonium ion. Among them, L, o, p, q, and M in general formula (c3) + are the same as L, o, p, q, and M in general formula (b3), respectively + respectively. B represents a group that decomposes by the action of an acid, a hydroxyl group, or a carboxyl group. When there are multiple Bs, the multiple Bs may be the same or different. Among them, at least one B represents a hydroxyl group or a carboxyl group.

[0485] B in general formula (c3) is the same as B in the above general formula (c1).

[0486] In the present invention, it is preferred that compound (B) is represented by the above general formula (b2), and compound (C) is represented by the above general formula (c2). More preferably, compound (B) is represented by the above general formula (b3), and compound (C) is represented by the above general formula (c3).

[0487] The following shows preferred specific examples of the anionic part of compound (C), but the present invention is not limited to these.

[0488] [Chemical formula 48]

[0489]

[0490] [Chemical Formula 49]

[0491]

[0492] [Chemical Formula 50]

[0493]

[0494] The pKa of the acid produced by compound (C) is the same as the pKa of the acid produced by compound (B).

[0495] As a preferred example of compound (C), compounds shown in the examples, and compounds formed by combining the above anions and the above cations (the cations cited in the description of compound (B)) can be mentioned.

[0496] Compound (C) can be synthesized, for example, by using a coupling reaction method.

[0497] For the coupling reaction, for example, Suzuki coupling can be applied. The counter cation can be converted to the desired cation M, for example, by a known anion exchange method or a conversion method based on an ion exchange resin described in Japanese Patent Laid-Open No. 6-184170 etc. + .

[0498] Compound (C) can be used alone or in combination of two or more.

[0499] In the composition of the present invention, the content of compound (C) (when there are a plurality of them, the total thereof) is 0.01% by mass or more and 10% by mass or less, preferably 0.01% by mass or more and 5% by mass or less, more preferably 0.01% by mass or more and 3% by mass or less, and further preferably 0.01% by mass or more and 1% by mass or less, relative to the content of compound (B) in the composition of the present invention.

[0500] In addition, within a range not impairing the effects of the present invention, the composition of the present invention may contain a compound that generates an acid upon irradiation with actinic rays or radiation, other than compound (B) and compound (C).

[0501] [Acid diffusion control agent]

[0502] The composition of the present invention preferably contains an acid diffusion control agent. The acid diffusion control agent captures the acid generated from a photoacid generator etc. during exposure and functions as a quencher that suppresses the reaction of the acid-decomposable resin in the unexposed portion due to the excessively generated acid.

[0503] As an acid diffusion control agent, for example, a basic compound (DA), a basic compound (DB) whose basicity is reduced or eliminated by irradiation with actinic rays or radioactive rays, an onium salt (DC) that is a relatively weak acid with respect to an acid generator, a low-molecular compound (DD) having a nitrogen atom and a group that is detached by the action of an acid, or an onium salt compound (DE) having a nitrogen atom in the cation moiety can be used as the acid diffusion control agent. In the composition of the present invention, a known acid diffusion control agent can be appropriately used. For example, paragraphs

[0627] to

[0664] in the specification of US Patent Application Publication No. 2016 / 0070167A1, paragraphs

[0095] to

[0187] in the specification of US Patent Application Publication No. 2015 / 0004544A1, paragraphs

[0403] to

[0423] in the specification of US Patent Application Publication No. 2016 / 0237190A1, and paragraphs

[0259] to

[0328] in the specification of US Patent Application Publication No. 2016 / 0274458A1 can be preferably used as the acid diffusion control agent.

[0504] As the basic compound (DA), a compound having a structure represented by the following general formulas (A) to (E) is preferably used.

[0505] [Chemical formula 51]

[0506]

[0507] In general formulas (A) and (E),

[0508] 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). R 201 and R 202 may be bonded to each other to form a ring.

[0509] R 203 、R 204 、R 205 and R 206 may be the same or different and each independently represents an alkyl group having 1 to 20 carbon atoms.

[0510] The alkyl groups in general formulas (A) and (E) may have substituents or may be unsubstituted.

[0511] Regarding the above alkyl groups, as the alkyl groups having substituents, aminoalkyl groups having 1 to 20 carbon atoms, hydroxyalkyl groups having 1 to 20 carbon atoms, or cyanoalkyl groups having 1 to 20 carbon atoms are preferred.

[0512] The alkyl group in general formula (A) and general formula (E) is more preferably unsubstituted.

[0513] As the basic compound (DA), thiazole, benzothiazole, oxazole, benzoxazole, guanidine, aminopyrrolidine, pyrazole, pyrazoline, piperazine, aminomorpholine, aminoalkylmorpholine, piperidine, or a compound having these structures is preferred, and a thiazole structure, benzothiazole structure, oxazole structure, benzoxazole structure, imidazole structure, diazabicyclic structure, hydroxonium structure, carboxonium structure, 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 is more preferred.

[0514] The basic compound (DB) (hereinafter, also referred to as "compound (DB)") whose basicity is reduced or eliminated by irradiation with actinic rays or radiation is a compound having a proton-accepting functional group, and which decomposes by irradiation with actinic rays or radiation, thereby reducing, eliminating the proton-accepting property, or changing from a proton-accepting property to an acidic property.

[0515] The proton-accepting functional group is a group or electron having a functional group capable of electrostatic interaction with a proton. For example, it represents a functional group having a macrocyclic compound structure such as a cyclic polyether, or a functional group having a nitrogen atom which has an unshared electron pair not contributing to π-conjugation. The nitrogen atom having an unshared electron pair not contributing to π-conjugation is, for example, a nitrogen atom having a partial structure represented by the following formula.

[0516] [Chemical formula 52]

[0517]

[0518] Preferred partial structures as 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.

[0519] Compound (DB) generates a compound whose proton-accepting property is reduced or eliminated or changed from a proton-accepting property to an acidic property by decomposition by irradiation with actinic rays or radiation. Here, the reduction or elimination of the proton-accepting property or the change from a proton-accepting property to an acidic property is a change in the proton-accepting property caused by the addition of a proton to the proton-accepting functional group. Specifically, it means that when a proton adduct is formed from compound (DB) having a proton-accepting functional group and a proton, the equilibrium constant in this chemical equilibrium decreases.

[0520] The proton-accepting property can be confirmed by measuring the pH.

[0521] The acid dissociation constant pKa of the compound produced by the decomposition of the compound (DB) upon irradiation with actinic rays or radiation preferably satisfies pKa < -1, more preferably -13 < pKa < -1, and still more preferably -13 < pKa < -3.

[0522] The acid dissociation constant pKa represents the acid dissociation constant pKa in an aqueous solution. For example, it is defined in "Kagaku Binran (II)" (Revised 4th Edition, 1993, edited by the Chemical Society of Japan, Maruzen Company, Limited). The lower the value of the acid dissociation constant pKa, the stronger the acid strength. The acid dissociation constant pKa in an aqueous solution can be actually measured by using an infinitely diluted aqueous solution and measuring the acid dissociation constant at 25°C. Alternatively, it can be obtained by using the following Package 1 and calculating the values based on the Hammett substituent constant and the values in the database of known literature values. All the pKa values described in this specification represent the values obtained by calculation using this package.

[0523] Package 1: Advanced Chemistry Development (ACD / Labs) Software V8.14 for Solaris (1994 - 2007 ACD / Labs).

[0524] In the composition of the present invention, an onium salt (DC) that is a relatively weak acid with respect to the photoacid generator can be used as an acid diffusion control agent.

[0525] When a photoacid generator and an onium salt that generates an acid that is a relatively weak acid with respect to the acid generated by the photoacid generator are mixed and used, if the acid generated by the photoacid generator upon irradiation with actinic rays or radiation collides with the onium salt having an unreacted weak acid anion, a weak acid is released by salt exchange to generate an onium salt having a strong acid anion. In this process, the strong acid is exchanged for a weak acid with lower catalytic ability, so that the acid can be inactivated on the surface to control acid diffusion.

[0526] As the onium salt that is a relatively weak acid with respect to the photoacid generator, a compound represented by the following general formulas (d1-1) to (d1-3) is preferred.

[0527] [Chemical formula 53]

[0528]

[0529] In the formula, R 51 is a hydrocarbon group that may have a substituent, and Z 2c is a hydrocarbon group having 1 to 30 carbon atoms that may have a substituent (wherein it is assumed that the carbon adjacent to S is not substituted by a fluorine atom), and R 52 is an organic group, and Y 3is a linear, branched or cyclic alkylene or arylene group, Rf is a hydrocarbon group containing fluorine atoms, and M + are each independently an ammonium cation, a sulfonium cation or an iodonium cation.

[0530] As a preferred example of the sulfonium cation or iodonium cation represented by M + the sulfonium cation exemplified by the general formula (ZIA) and the iodonium cation exemplified by the general formula (ZIIA) can be mentioned.

[0531] The onium salt (DC) that is a relatively weak acid with respect to the photoacid generator may also be a compound having a cationic moiety and an anionic moiety in the same molecule and the cationic moiety and the anionic moiety are connected by a covalent bond (hereinafter, also referred to as "compound (DCA)").

[0532] As the compound (DCA), a compound represented by any one of the following general formulas (C-1) to (C-3) is preferred.

[0533] [Chemical formula 54]

[0534]

[0535] In general formulas (C-1) to (C-3),

[0536] R 1 、R 2 and R 3 each independently represent a substituent having 1 or more carbon atoms.

[0537] L 1 represents a divalent linking group or a single bond that connects the cationic moiety and the anionic moiety.

[0538] -X - represents an anionic moiety selected from -COO - 、-SO 3 - 、-SO 2 - and -N - -R 4 in. R 4 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 connecting site with the adjacent N atom.

[0539] R 1 、R 2 、R 3 、R 4 and L 1can be bonded to each other to form a ring structure. Further, in the general formula (C-3), R 1 ~R 3 two of them together represent a divalent substituent, and can be bonded to the N atom through a double bond.

[0540] As the substituent having 1 or more carbon atoms in R 1 ~R 3 , examples thereof include an alkyl group, a cycloalkyl group, an aryl group, an alkoxycarbonyl group, a cycloalkoxycarbonyl group, an aryloxycarbonyl group, an alkylaminocarbonyl group, a cycloalkylaminocarbonyl group, and an arylaminocarbonyl group. An alkyl group, a cycloalkyl group, or an aryl group is preferred.

[0541] As L 1 which is a divalent linking group, examples thereof include 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 urethane bond, a urea bond, and a group formed by combining two or more of them. L 1 is preferably an alkylene group, an arylene group, an ether bond, an ester bond, or a group formed by combining two or more of them.

[0542] The low molecular weight compound (DD) having a nitrogen atom and a group that is cleaved by the action of an acid (hereinafter, also referred to as "compound (DD)") is preferably an amine derivative having a group that is cleaved by the action of an acid on the nitrogen atom.

[0543] As the group that is cleaved by the action of an acid, an acetal group, a carbonate group, a urethane group, a tertiary ester group, a tertiary hydroxyl group, or a hemiacetal amine ether group is preferred, and a urethane group or a hemiacetal amine ether group is more preferred.

[0544] The molecular weight of the compound (DD) is preferably 100 to 1000, more preferably 100 to 700, and still more preferably 100 to 500.

[0545] The compound (DD) may also have a urethane group having a protecting group on the nitrogen atom. As the protecting group constituting the urethane group, it is represented by the following general formula (d-1).

[0546] [Chemical formula 55]

[0547]

[0548] In the general formula (d-1),

[0549] 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). R bThey can be bonded to each other to form a ring.

[0550] R b The alkyl, cycloalkyl, aryl and aralkyl groups represented by can be independently substituted by functional groups such as hydroxyl, cyano, amino, pyrrolidine group, piperidino group, morpholino group, oxo group, etc., alkoxy groups or halogen atoms. For R b The same applies to the alkoxyalkyl group represented.

[0551] As R b , it is preferably a linear or branched alkyl, cycloalkyl or aryl group, more preferably a linear or branched alkyl or cycloalkyl group.

[0552] As the ring formed by the two Rs b connected to each other, alicyclic hydrocarbons, aromatic hydrocarbons, heterocyclic hydrocarbons and their derivatives, etc. can be cited.

[0553] As the specific structure of the group represented by the general formula (d-1), the structure disclosed in paragraph

[0466] of the specification of US Patent Publication No. US2012 / 0135348A1 can be cited, but it is not limited thereto.

[0554] Compound (DD) preferably has a structure represented by the following general formula (6).

[0555] [Chemical formula 56]

[0556]

[0557] In the general formula (6),

[0558] l represents an integer from 0 to 2, m represents an integer from 1 to 3, and l + m = 3 is satisfied.

[0559] R a represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group or an aralkyl group. When l is 2, the two Rs a can be the same or different, and the two Rs a can also be connected to each other to form a heterocycle together with the nitrogen atom in the formula. This heterocycle may also contain heteroatoms other than the nitrogen atom in the formula.

[0560] R b has the same meaning as R in the above general formula (d-1) b , and the preferred examples are also the same.

[0561] In the general formula (6), as R aThe alkyl group, cycloalkyl group, aryl group, and aralkyl group may each independently be substituted with the same groups as the above-mentioned groups, and the groups are represented by R b The alkyl group, cycloalkyl group, aryl group, and aralkyl group represented by may be substituted groups.

[0562] As the above-mentioned R a Specific examples of the alkyl group, cycloalkyl group, aryl group, and aralkyl group (these groups may be substituted with the above-mentioned groups) may include the same groups as the above-mentioned specific examples for R b

[0563] Specific examples of the particularly preferred compound (DD) in the present invention may include the compounds disclosed in paragraph

[0475] of the specification of US Patent Application Publication No. 2012 / 0135348A1, but are not limited thereto.

[0564] The onium salt compound (DE) having a nitrogen atom in the cationic moiety (hereinafter, also referred to as "compound (DE)") is preferably a compound having a basic moiety containing a nitrogen atom in the cationic moiety. The basic moiety is preferably an amino group, more preferably an aliphatic amino group. Further preferably, all atoms adjacent to the nitrogen atom in the basic moiety are hydrogen atoms or carbon atoms. And, from the viewpoint of enhancing basicity, it is preferred that an electron-withdrawing functional group (such as a carbonyl group, a sulfonyl group, a cyano group, and a halogen atom) is not directly connected to the nitrogen atom.

[0565] Specific examples of the compound (DE) may include the compounds disclosed in paragraph

[0203] of the specification of US Patent Application Publication No. 2015 / 0309408A1, but are not limited thereto.

[0566] Preferred examples of the acid diffusion control agent are shown below, but the present invention is not limited to these. Me represents a methyl group.

[0567] [Chemical formula 57]

[0568]

[0569] [Chemical formula 58]

[0570]

[0571] [Chemical formula 59]

[0572]

[0573] [Chemical formula 60]

[0574]

[0575] [Chemical formula 61]

[0576] ​

[0577] [Chemical Formula 62]

[0578]

[0579] [Chemical Formula 63]

[0580]

[0581] [Chemical Formula 64]

[0582]

[0583] In the composition of the present invention, the acid diffusion control agent may be used alone in one kind, or two or more kinds may be used in combination.

[0584] Relative to the total solid content of the composition, the content of the acid diffusion control agent in the composition of the present invention (when there are multiple kinds, it is the total thereof) is preferably 0.001 to 20% by mass, more preferably 0.01 to 10% by mass.

[0585] [(E) Fluorine-containing compound having a group that decomposes by the action of an alkaline developer and has an increased solubility in the alkaline developer]

[0586] The composition of the present invention may also contain (E) a fluorine-containing compound having a group that decomposes by the action of an alkaline developer and has an increased solubility in the alkaline developer (also referred to as "fluorine-containing compound (E)").

[0587] By containing fluorine, the fluorine-containing compound (E) can be concentrated on the surface of the photosensitive radiation-sensitive or radiation-sensitive film of the present invention and can exhibit the desired performance.

[0588] A group that decomposes by the action of an alkaline developer and has an increased solubility in the alkaline developer is called a "polarity-converting group". As specific examples, a lactone group, a carboxylic acid ester group (-COO-), an acid anhydride group (-C(O)OC(O)-), an acid imide group (-NHCONH-), a carboxylic acid thioester group (-COS-), a carbonate group (-OC(O)O-), a sulfate ester group (-OSO 2 O-), a sulfonate group (-SO 2 O-), etc. can be cited.

[0589] In addition, an ester group directly connected to the main chain of the repeating unit in, for example, an acrylate ester, etc. is not included in the polarity-converting group of the present invention because of its poor function of decomposing by the action of an alkaline developer and having an increased solubility in the alkaline developer.

[0590] From the viewpoint of uneven surface distribution, the fluorine-containing compound (E) preferably has a fluoroalkyl group.

[0591] The fluorine-containing compound (E) is more preferably a resin (also referred to as "resin (E)").

[0592] The fluorine-containing compound (E) is more preferably a resin containing a repeating unit having a polarity-converting group (also referred to as "repeating unit (e)").

[0593] As the repeating unit (e), for example, a repeating unit represented by the general formula (K0) can be cited.

[0594] [Chemical formula 65]

[0595]

[0596] In the general formula (K0), R k1 represents a hydrogen atom, a halogen atom, a hydroxyl group, an alkyl group, a cycloalkyl group, an aryl group, or a group containing a polarity-converting group.

[0597] R k2 represents an alkyl group, a cycloalkyl group, an aryl group, or a group containing a polarity-converting group.

[0598] Among them, at least one of R k1 and R k2 has a polarity-converting group.

[0599] In addition, as described above, the ester group directly connected to the main chain of the repeating unit represented by the general formula (K0) is not included in the polarity-converting group in the present invention.

[0600] As the polarity-converting group, a group represented by X in the partial structure represented by the general formula (KA-1) or the general formula (KB-1) is preferably used.

[0601] That is, the repeating unit (e) preferably has at least one of the partial structures represented by the general formula (KA-1) and the general formula (KB-1), and the polarity-converting group is represented by X in the partial structure represented by the general formula (KA-1) or the general formula (KB-1).

[0602] [Chemical formula 66]

[0603]

[0604] X in the general formula (KA-1) or the general formula (KB-1) represents a carboxylic acid ester group: -COO-, an acid anhydride group: -C(O)OC(O)-, an acid imide group: -NHCONH-, a carboxylic acid thioester group: -COS-, a carbonate group: -OC(O)O-, a sulfate group: -OSO 2 O-, a sulfonate group: -SO 2 O-.

[0605] Y1 and Y 2 may be the same or different, and represent an electron-withdrawing group.

[0606] In addition, the repeating unit (e) preferably has a polarity conversion group by including a group having a partial structure represented by the general formula (KA-1) or the general formula (KB-1). However, as in the case of the partial structure represented by the general formula (KA-1), Y 1 and Y 2 when it is monovalent, in the case of the partial structure represented by the general formula (KB-1), when the above partial structure does not have a linking bond, the group having the above partial structure means a group having a group of valence 1 or more obtained by removing at least one of any hydrogen atoms in the above partial structure.

[0607] The partial structure represented by the general formula (KA-1) or the general formula (KB-1) is connected to the main chain of the resin (E) via a substituent at an arbitrary position.

[0608] The partial structure represented by the general formula (KA-1) is a structure that forms a ring structure together with the group as X.

[0609] As X in the general formula (KA-1), a carboxylic acid ester group (i.e., in the case where KA-1 forms a lactone ring structure), an acid anhydride group, and a carbonate group are preferred. A carboxylic acid ester group is more preferred.

[0610] The ring structure represented by the general formula (KA-1) may have a substituent. For example, it may have nka substituents Z ka1 .

[0611] When Z ka1 is plural, they each independently represent an alkyl group, a cycloalkyl group, an ether group, a hydroxyl group, an amide group, an aryl group, a lactone ring group, or an electron-withdrawing group.

[0612] Z ka1 may be connected to each other to form a ring. As the ring formed by Z ka1 connected to each other, for example, a cycloalkyl ring, a heterocycle (a cyclic ether ring, a lactone ring, etc.) can be cited.

[0613] nka represents an integer of 0 to 10. An integer of 0 to 8 is preferred, an integer of 0 to 5 is more preferred, an integer of 1 to 4 is further preferred, and an integer of 1 to 3 is most preferred.

[0614] As the electron-withdrawing group of Z ka1 is the same as the electron-withdrawing group of Y 1 and Y 2 described later, represented by a halogen atom.

[0615] In addition, the above electron-withdrawing group may be substituted by another electron-withdrawing group.

[0616] Z ka1 is preferably an alkyl group, a cycloalkyl group, an ether group, a hydroxyl group or an electron-withdrawing group, more preferably an alkyl group, a cycloalkyl group or an electron-withdrawing group. In addition, as the ether group, an ether group substituted with an alkyl group or a cycloalkyl group, etc., that is, an alkyl ether group, etc., is preferred. Preferred examples of the electron-withdrawing group are the same as the electron-withdrawing group for Y 1 and Y 2 described later.

[0617] As Z ka1 the halogen atom may be a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, etc., and is preferably a fluorine atom.

[0618] As Z ka1 the alkyl group may have a substituent and may be either straight-chain or branched-chain. As the straight-chain alkyl group, the number of carbon atoms is preferably 1 to 30, more preferably 1 to 20. For example, it may be a methyl group, an ethyl group, a n-propyl group, a n-butyl group, a sec-butyl group, a tert-butyl group, a n-pentyl group, a n-hexyl group, a n-heptyl group, a n-octyl group, a n-nonyl group, a n-decyl group, etc. As the branched-chain alkyl group, the number of carbon atoms is preferably 3 to 30, more preferably 3 to 20. For example, it may be an isopropyl group, an isobutyl group, a tert-butyl group, an isopentyl group, a tert-pentyl group, an isohexyl group, a tert-hexyl group, an isooctyl group, a tert-octyl group, an isononyl group, a tert-decanoyl group, etc. Groups having 1 to 4 carbon atoms such as a methyl group, an ethyl group, a n-propyl group, an isopropyl group, a n-butyl group, an isobutyl group, and a tert-butyl group are preferred.

[0619] As Z ka1 the cycloalkyl group may have a substituent, may be monocyclic, polycyclic, or bridged. For example, the cycloalkyl group may have a bridged structure. As the monocyclic type, a cycloalkyl group having 3 to 8 carbon atoms is preferred. For example, it may be a cyclopropyl group, a cyclopentyl group, a cyclohexyl group, a cyclobutyl group, a cyclooctyl group, etc. As the polycyclic type, groups having a bicyclic, tricyclic, tetracyclic structure, etc., with 5 or more carbon atoms can be cited. A cycloalkyl group having 6 to 20 carbon atoms is preferred. For example, it may be an adamantyl group, a norbornyl group, an isobornyl group, a camphenyl group, a dicyclopentyl group, an α-pinene group, a tricyclodecyl group, a tetracyclododecyl group, an androstanyl group, etc. The following structure is also preferred as the cycloalkyl group. In addition, a part of the carbon atoms in the cycloalkyl group may be substituted with a heteroatom such as an oxygen atom.

[0620] [Chemical formula 67]

[0621]

[0622] As the preferred groups of the above alicyclic moiety, adamantyl, noradamantyl, decahydronaphthyl, tricyclodecyl, tetracyclododecyl, norbornyl, cedrol, cyclohexyl, cycloheptyl, cyclooctyl, cyclodecyl, cyclododecyl can be mentioned. More preferably, adamantyl, decahydronaphthyl, norbornyl, cedrol, cyclohexyl, cycloheptyl, cyclooctyl, cyclodecyl, cyclododecyl, tricyclodecyl.

[0623] As the substituents of these alicyclic structures, alkyl, halogen atom, hydroxyl group, alkoxy group, carboxyl group, alkoxycarbonyl group can be mentioned. As the alkyl, lower alkyls such as methyl, ethyl, propyl, isopropyl, butyl are preferred, and methyl, ethyl, propyl, isopropyl are further preferred. As the above alkoxy group, alkoxy groups having 1 to 4 carbon atoms such as methoxy, ethoxy, propoxy, butoxy are preferred. As the substituents that the alkyl and alkoxy group can have, hydroxyl group, halogen atom, alkoxy group (preferably having 1 to 4 carbon atoms), etc. can be mentioned.

[0624] As the lactone ring group of Z ka1 a group obtained by removing a hydrogen atom from the structure represented by any one of the following (KA-1-1) to (KA-1-17) can be mentioned.

[0625] As the aryl group of Z ka1 for example, phenyl and naphthyl can be mentioned.

[0626] As the substituents that the alkyl, cycloalkyl and aryl group of Z ka1 can further have, hydroxyl group, halogen atom (fluorine, chlorine, bromine, iodine), nitro group, cyano group, the above alkyl, methoxy, ethoxy, hydroxyethoxy, propoxy, hydroxypropoxy, n-butoxy, isobutoxy, sec-butoxy, tert-butoxy and other alkoxy groups, methoxycarbonyl, ethoxycarbonyl and other alkoxycarbonyl groups, benzyl, phenethyl, cumyl and other aralkyl groups, aralkyloxy groups, formyl, acetyl, butyryl, benzoyl, cyanamide, valeryl and other acyl groups, butyryloxy and other acyloxy groups, the above alkenyl, vinyloxy, allyloxy, propenyloxy, butenyloxy and other alkenyloxy groups, the above aryl, phenoxy and other aryloxy groups, benzoyloxy and other aryloxycarbonyl groups, etc. can be mentioned.

[0627] X in the general formula (KA-1) is a carboxylic acid ester group, preferably the partial structure represented by the general formula (KA-1) is a lactone ring, preferably a 5- to 7-membered lactone ring.

[0628] In addition, as shown in the following (KA-1-1) to (KA-1-17), it is preferred that another ring structure is fused to the 5- to 7-membered lactone ring which is the partial structure represented by the general formula (KA-1) in the form of forming a bicyclic structure or a spiro ring structure.

[0629] Regarding the surrounding ring structures to which the ring structure represented by the general formula (KA-1) can be bonded, for example, the structures in the following (KA-1-1) to (KA-1-17) or structures based thereon can be cited.

[0630] As a structure containing the lactone ring structure represented by the general formula (KA-1), a structure represented by any one of the following (KA-1-1) to (KA-1-17) is more preferable. In addition, the lactone structure can be directly bonded to the main chain. Preferred structures are (KA-1-1), (KA-1-4), (KA-1-5), (KA-1-6), (KA-1-13), (KA-1-14), (KA-1-17).

[0631] [Chemical formula 68]

[0632]

[0633] The structure containing the above lactone ring structure may or may not have a substituent. As a preferred substituent, the same group as the substituent that the ring structure represented by the above general formula (KA-1) can have can be cited.

[0634] Although there are also structures with optically active forms for the lactone structure, any optically active form can be used. And, one kind of optically active form can be used alone, or multiple optically active forms can be used in combination. When mainly using one kind of optically active form, its optical purity (ee) is preferably 90% or more, more preferably 95% or more, and most preferably 98% or more.

[0635] As X in the general formula (KB-1), a carboxylic acid ester group (-COO-) is preferably cited.

[0636] Y in the general formula (KB-1) 1 and Y 2 each independently represents an electron-withdrawing group.

[0637] The electron-withdrawing group is preferably a partial structure represented by the following formula (EW). The * in the formula (EW) represents a linking bond directly connected to (KA-1) or a linking bond directly connected to X in (KB-1).

[0638] [Chemical formula 69]

[0639]

[0640] In the formula (EW),

[0641] n ew is the repetition number of the linking group represented by -C(R ew1 )(R ew2 )-, and represents an integer of 0 or 1. When n ewWhen it is 0, it represents a single bond, indicating a direct bond with Y ew1 .

[0642] Y ew1 Examples include halogen atoms, cyano groups, nitrile groups, nitro groups, halo(cyclo)alkyl groups, haloaryl groups, oxy groups, carbonyl groups, sulfonyl groups, sulfinyl groups, and combinations thereof represented by -C(R f1 )(R f2 )-R f3 . The electron-withdrawing group can be, for example, the following structure. In addition, "halo(cyclo)alkyl" means an alkyl group and a cycloalkyl group at least partially halogenated. R ew3 and R ew4 each independently represent any structure. R ew3 , R ew4 . In any structure, the partial structure represented by formula (EW) has electron-withdrawing properties and can be connected to the main chain of the resin, for example, but is preferably an alkyl group, a cycloalkyl group, or a fluorinated alkyl group.

[0643] [Chemical formula 70]

[0644]

[0645] When Y ew1 is a group with a valence of 2 or more, the remaining bonding sites form bonds with any atom or substituent. Y ew1 , R ew1 and R ew2 . At least one of the groups among them can be connected to the main chain of the resin (E) via another substituent.

[0646] Y ew1 is preferably a halogen atom, or a halo(cyclo)alkyl group or a haloaryl group represented by -C(R f1 )(R f2 )-R f3 .

[0647] R ew1 and R ew2 each independently represent any substituent, for example, a hydrogen atom, an alkyl group, a cycloalkyl group, or an aryl group.

[0648] R ew1 , R ew2 and Y ew1 . At least two of them can be connected to each other to form a ring.

[0649] Here, R f1 represents a halogen atom, a perhaloalkyl group, a perhalocycloalkyl group, or a perhaloaryl group, more preferably a fluorine atom, a perfluoroalkyl group, or a perfluorocycloalkyl group, and even more preferably a fluorine atom or a trifluoromethyl group.

[0650] R f2 and Rf3 Each independently represents a hydrogen atom, a halogen atom or an organic group, R f2 and R f3 may be connected to form a ring. As the organic group, for example, it represents an alkyl group, a cycloalkyl group, an alkoxy group, which may be substituted by a halogen atom (preferably a fluorine atom), and more preferably R f2 , R f3 is a (halo)alkyl group. More preferably, R f2 represents the same group as R f1 or is connected to R f3 to form a ring.

[0651] R f1 and R f3 may be connected to form a ring. As the formed ring, a (halo)cycloalkyl ring, a (halo)aryl ring, etc. can be cited.

[0652] As the (halo)alkyl group in R f1 ~R f3 , for example, the alkyl group in the above Z ka1 and its halogenated structure can be cited.

[0653] As the (per)halocycloalkyl group and (per)haloaryl group in R f1 ~R f3 , or in the ring formed by connecting R f2 and R f3 , for example, the structure obtained by halogenating the cycloalkyl group in the above Z ka1 is more preferably a fluorocycloalkyl group represented by -C (n) F (2n-2) H and a perfluoroaryl group represented by -C (n) F (n-1) . Here, the number of carbon atoms n is not particularly limited, preferably 5 to 13, more preferably 6.

[0654] As the ring that at least two of R ew1 , R ew2 and Y ew1 can be connected to each other to form, a cycloalkyl group or a heterocyclic group is preferably cited. As the heterocyclic group, a lactone ring group is preferred. As the lactone ring, for example, the structures represented by the above (KA-1-1) to (KA-1-17) can be cited.

[0655] In addition, the repeating unit (e) may have a plurality of partial structures represented by the general formula (KA-1), a plurality of partial structures represented by the general formula (KB-1), or both the partial structure of the general formula (KA-1) and the general formula (KB-1).

[0656] In addition, a part or all of the partial structure of the general formula (KA-1) may also serve as Y in the general formula (KB-1)1 or Y 2 An electron-withdrawing group. For example, when X in the general formula (KA-1) is a carboxylic acid ester group, the carboxylic acid ester group can also function as Y in the general formula (KB-1). 1 or Y 2 An electron-withdrawing group.

[0657] The repeating unit (e) can be a repeating unit (e') having a fluorine atom and a polarity-converting group on one side chain, a repeating unit (e*) having a polarity-converting group and no fluorine atom, or a repeating unit (e") having a polarity-converting group on one side chain and a fluorine atom on a side chain different from the above side chain within the same repeating unit. However, the resin (E) more preferably has the repeating unit (e') as the repeating unit (e). That is, the repeating unit (e) having at least one polarity-converting group more preferably has a fluorine atom.

[0658] In addition, when the resin (E) has the repeating unit (e*), a copolymer with a repeating unit having a fluorine atom (the repeating unit (e1) described later) is preferred. And in the repeating unit (e"), the side chain having a polarity-converting group and the side chain having a fluorine atom are preferably bonded to the same carbon atom in the main chain, that is, in the positional relationship as shown in the following formula (K1).

[0659] In the formula, B1 represents a partial structure having a polarity-converting group, and B2 represents a partial structure having a fluorine atom.

[0660] [Chemical formula 71]

[0661]

[0662] And in the repeating unit (e*) and the repeating unit (e"), the polarity-converting group is more preferably a partial structure represented by -COO- in the structure represented by the general formula (KA-1).

[0663] The hydrolysis rate of the resin (E) to the alkaline developer is preferably 0.001 nm / sec or more, more preferably 0.01 nm / sec or more, further preferably 0.1 nm / sec or more, and most preferably 1 nm / sec or more.

[0664] Here, the hydrolysis rate of the resin (E) to the alkaline developer is the rate of film thickness reduction when only the resin (E) forms a resin film with respect to TMAH (aqueous solution of tetramethylammonium hydroxide) (2.38% by mass) at 23°C.

[0665] The resin (E) of the present invention is preferably a resin (E1) containing a repeating unit (e) having at least 2 or more polarity-converting groups and having a fluorine atom.

[0666] When the repeating unit (e) has at least two polarity-converting groups, the repeating unit (e) preferably has a partial structure having two polarity-converting groups represented by the following general formula (KY-1). In addition, when the structure represented by the general formula (KY-1) does not have a linking bond, it is a group having a valence of 1 or more obtained by removing at least one of any hydrogen atoms in the above structure.

[0667] [Chemical formula 72]

[0668]

[0669] In the general formula (KY-1),

[0670] R ky1 and R ky4 each independently represent a hydrogen atom, a halogen atom, an alkyl group, a cycloalkyl group, a carbonyl group, a carbonyloxy group, an oxycarbonyl group, an ether group, a hydroxyl group, a cyano group, an amide group or an aryl group. Alternatively, R ky1 and R ky4 may also bond to the same atom to form a double bond. For example, R ky1 and R ky4 may bond to the same oxygen atom to form a part of a carbonyl group (=O).

[0671] R ky2 and R ky3 are each independently an electron-withdrawing group, or R ky1 and R ky2 are connected to form a lactone ring and R ky3 is an electron-withdrawing group. As the formed lactone ring, the structures of the above (KA-1-1) to (KA-1-17) are preferred. As the electron-withdrawing group, the same groups as Y 1 and Y 2 in the above formula (KB-1) can be mentioned. Preferably, it is a halogen atom or a halo(cyclo)alkyl group or a haloaryl group represented by the above -C(R f1 )(R f2 )-R f3 . Preferably, R ky3 is a halogen atom or a halo(cyclo)alkyl group or a haloaryl group represented by the above -C(R f1 )(R f2 )-R f3 , R ky2 and R ky1 are connected to form a lactone ring, or it is an electron-withdrawing group without a halogen atom.

[0672] R ky1 , R ky2 and R ky4 may also be connected to each other to form a monocyclic or polycyclic structure.

[0673] R ky1 and R ky4 Specific examples may include the same groups as Z in formula ((KA-1)). ka1 Same groups.

[0674] As R ky1 and R ky2 The lactone ring formed by connection, preferably having the structures of the above (KA-1-1) to (KA-1-17). As the electron-withdrawing group, specific examples may include the same groups as Y in the above formula (KB-1). 1 and Y 2 Same groups.

[0675] As the structure represented by the general formula (KY-1), the structure represented by the following general formula (KY-2) is more preferred. In addition, the structure represented by the general formula (KY-2) is a monovalent or higher-valent group obtained by removing at least one of any hydrogen atoms in the above structure.

[0676] [Chemical formula 73]

[0677]

[0678] In formula (KY-2),

[0679] R ky6 to R ky10 Each independently represents a hydrogen atom, a halogen atom, an alkyl group, a cycloalkyl group, a carbonyl group, a carbonyloxy group, an oxycarbonyl group, an ether group, a hydroxyl group, a cyano group, an amide group, or an aryl group.

[0680] R ky6 to R ky10 Two or more of them may also be connected to each other to form a monocyclic or polycyclic structure.

[0681] R ky5 represents an electron-withdrawing group. Specific examples of the electron-withdrawing group may include the same groups as the above Y 1 and Y 2 , preferably a halogen atom, or a halo(cyclo)alkyl group or a haloaryl group represented by the above -C(R f1 )(R f2 )-R f3 .

[0682] R ky5 to R ky10 Specific examples may include the same groups as Z in formula (KA-1). ka1 Same groups.

[0683] The structure represented by formula (KY-2) is more preferably a partial structure represented by the following general formula (KY-3).

[0684] [Chemical formula 74]

[0685]

[0686] In formula (KY-3),

[0687] Z ka1 and nka are respectively synonymous with the above general formula (KA-1). R ky5 is synonymous with the above formula (KY-2).

[0688] L ky represents an alkylene group, an oxygen atom or a sulfur atom. As L ky 's alkylene group, methylene, ethylene, etc. can be cited. L ky is preferably an oxygen atom or a methylene group, more preferably a methylene group.

[0689] The repeating unit (e) is not limited as long as it is a repeating unit obtained by addition polymerization, condensation polymerization, addition-condensation polymerization, etc., but is preferably a repeating unit obtained by addition polymerization of a carbon-carbon double bond. As an example, acrylate-based repeating units (including those with substituents at the α-position and β-position), styrene-based repeating units (including those with substituents at the α-position and β-position), vinyl ether-based repeating units, norbornene-based repeating units, repeating units of maleic acid derivatives (maleic anhydride and its derivatives, maleimide, etc.) can be cited, etc. Acrylate-based repeating units, styrene-based repeating units, vinyl ether-based repeating units, norbornene-based repeating units are preferred, acrylate-based repeating units, vinyl ether-based repeating units, norbornene-based repeating units are more preferred, and acrylate-based repeating units are most preferred.

[0690] As a more specific structure of the repeating unit (e), a repeating unit having the partial structure shown below is preferred.

[0691] The repeating unit (e) can be a repeating unit having the partial structure shown below.

[0692] [Chemical formula 75]

[0693]

[0694] In the general formula (ee),

[0695] When there are multiple Z 1 s, they each independently represent a single bond, an ether bond, an ester bond, an amide bond, a urethane bond or a urea bond, preferably an ester bond.

[0696] When there are multiple Z 2 s, they each independently represent a linear or cyclic alkylene group, preferably an alkylene group with 1 or 2 carbon atoms or a cycloalkylene group with 5 to 10 carbon atoms.

[0697] Ta each independently represents an alkyl group, a cycloalkyl group, an alkoxy group, a nitrile group, a hydroxyl group, an amide group, an aryl group, or an electron-withdrawing group (synonymous with the electron-withdrawing group as Y in the above general formula (KB-1)), preferably represents an alkyl group, a cycloalkyl group, an electron-withdrawing group, and more preferably represents an electron-withdrawing group. When there are multiple Ta, Ta can bond to each other to form a ring. 1 and Y 2 of the electron-withdrawing group), and preferably represents an alkyl group, a cycloalkyl group, an electron-withdrawing group, and more preferably represents an electron-withdrawing group. When there are multiple Ta, Ta can bond to each other to form a ring.

[0698] L 0 represents a single bond or an m + 1-valent hydrocarbon group (preferably having 20 or fewer carbon atoms), and preferably represents a single bond. The single bond as L 0 is the case where m is 1. The m + 1-valent hydrocarbon group as L 0 represents, for example, an alkylene group, a cycloalkylene group, a phenylene group, or an m + 1-valent hydrocarbon group obtained by removing m - 1 arbitrary hydrogen atoms from a combination thereof.

[0699] L each independently represents a carbonyl group, a carbonyloxy group, or an ether group.

[0700] Tc represents a hydrogen atom, an alkyl group, a cycloalkyl group, a nitrile group, a hydroxyl group, an amide group, an aryl group, or an electron-withdrawing group (synonymous with the electron-withdrawing group as Y 1 and Y 2 of the electron-withdrawing group).

[0701] * represents a bonding bond to the resin main chain or side chain. That is, the partial structure represented by formula (ee) can be directly connected to the main chain, or the partial structure represented by formula (ee) can be bonded to the side chain of the resin. In addition, the bonding bond to the main chain refers to the bonding bond to the atom existing in the bonding that constitutes the main chain, and the bonding bond to the side chain refers to the bonding bond to the atom existing other than the bonding that constitutes the main chain.

[0702] m represents an integer from 1 to 28, preferably an integer from 1 to 3, and more preferably 1.

[0703] k represents an integer from 0 to 2, and preferably 1.

[0704] q represents the repetition number of the group (Z 2 -Z 1 ), represents an integer from 0 to 5, and preferably from 0 to 2.

[0705] r represents an integer from 0 to 5.

[0706] In addition, it is also possible to substitute - (L)r - Tc with the above - L 0 - (Ta)m.

[0707] When a fluorine atom is present at the end of the sugar lactone, it is also preferred that a fluorine atom is present on a side chain different from the side chain of the sugar lactone in the same repeating unit (repeating unit (e”)).

[0708] As Z 2 In the case of a linear alkylene group as the chain-like alkylene group for Z, the number of carbon atoms is preferably 1 to 30, more preferably 1 to 20. In the case of a branched alkylene group, the number of carbon atoms is preferably 3 to 30, more preferably 3 to 20. As R 2 Specific examples of the chain-like alkylene group for R can be groups obtained by removing any one hydrogen atom from the specific examples of the alkyl group as Z ka1 above.

[0709] As Z 2 The cyclic alkylene group for Z preferably has 3 to 8 carbon atoms. Specific examples thereof can be groups obtained by removing any one hydrogen atom from the cycloalkyl group as Z ka1 above.

[0710] The preferred number of carbon atoms and specific examples of the alkyl and cycloalkyl groups for Ta and Tc are the same as those described for the alkyl and cycloalkyl groups as Z ka1 above.

[0711] As the alkoxy group for Ta, the number of carbon atoms is preferably 1 to 8, and examples thereof include methoxy, ethoxy, propoxy, butoxy and the like.

[0712] As the aryl group for Ta and Tc, an aryl group having 6 to 12 carbon atoms is preferred, and examples thereof include phenyl and naphthyl.

[0713] As L 0 The preferred number of carbon atoms and specific examples of the alkylene group and cycloalkylene group are the same as those described for the chain-like alkylene group and cyclic alkylene group as Z 2 above.

[0714] As a more specific structure of the repeating unit (e), a repeating unit having the partial structure shown below is preferred.

[0715] [Chemical formula 76]

[0716]

[0717] In the general formulas (ea-2) and (eb-2),

[0718] n represents an integer of 0 to 11, preferably represents an integer of 0 to 5, and more preferably represents 1 or 2.

[0719] p represents an integer of 0 to 5, preferably represents an integer of 0 to 3, and more preferably represents 1 or 2.

[0720] Tb independently represents an alkyl group, a cycloalkyl group, an alkoxy group, a nitrile group, a hydroxyl group, an amide group, an aryl group or an electron-withdrawing group (as Y in the above general formula (KB-1) 1 and Y2 (synonymous with an electron-withdrawing group), preferably represents an alkyl group, a cycloalkyl group, or an electron-withdrawing group. When there are multiple Tb's, they can bond to each other to form a ring.

[0721] * represents a bonding site to the main chain or side chain of the resin. That is, the partial structure represented by formula (ea-2) or (eb-2) can be directly connected to the main chain, or the partial structure represented by formula (ea-2) or (eb-2) can be bonded to the side chain of the resin.

[0722] Z 1 and Z 2 Ta, Tc, L, *, m, q, r have the same meanings as in the general formula (ee), and are preferably the same.

[0723] As a more specific structure of the repeating unit (e), a repeating unit having the following partial structure can also be cited.

[0724] [Chemical formula 77]

[0725]

[0726] In the general formula (KY-4),

[0727] R 2 represents a linear or cyclic alkylene group. If there are multiple, they can be the same or different.

[0728] R 3 represents a linear, branched, or cyclic hydrocarbon group in which part or all of the hydrogen atoms on the structural carbon are replaced by fluorine atoms.

[0729] R 4 represents a halogen atom, a cyano group, a hydroxyl group, an amide group, an alkyl group, a cycloalkyl group, an alkoxy group, a phenyl group, an acyl group, an alkoxycarbonyl group, or a group represented by R-C(=O)- or R-C(=O)O- (R represents an alkyl group or a cycloalkyl group). When there are multiple R 4 's, they can be the same or different, and two or more R 4 's can bond to form a ring.

[0730] X represents an alkylene group, an oxygen atom, or a sulfur atom.

[0731] When there are multiple Z and Za, they each independently represent a single bond, an ether bond, an ester bond, an amide bond, a urethane bond, or a urea bond. If there are multiple, they can be the same or different.

[0732] * represents a bonding site to the main chain or side chain of the resin.

[0733] o is the number of substituents, representing an integer from 1 to 7.

[0734] m represents the number of substituents, which is an integer from 0 to 7.

[0735] n represents the number of repetitions, which is an integer from 0 to 5.

[0736] As -R 2 -Z-, preferably has a structure represented by -(CH 2 ) l -COO- (where l represents an integer from 1 to 5).

[0737] As R 2 The preferred carbon atom number range and specific examples of the linear or cyclic alkylene group of R 2 are the same as those described for the linear alkylene group and cyclic alkylene group in Z of the general formula (ee).

[0738] As R 3 For the straight-chain, branched-chain or cyclic hydrocarbon group of R, in the case of a straight chain, the number of carbon atoms is preferably 1 to 30, more preferably 1 to 20; in the case of a branched chain, the number of carbon atoms is preferably 3 to 30, more preferably 3 to 20; in the case of a cyclic structure, the number of carbon atoms is 6 to 20. As specific examples of R 3 can be cited the specific examples of the alkyl group and cycloalkyl group described above as Z ka1 The preferred number of carbon atoms and specific examples of the alkyl group and cycloalkyl group of R 4 are the same as those described for the alkyl group and cycloalkyl group of Z ka1 above.

[0739] As R 4 The acyl group is preferably an acyl group having 1 to 6 carbon atoms, and examples thereof include formyl, acetyl, propionyl, butyryl, isobutyryl, valeryl, pivaloyl, etc.

[0740] As R 4 For the alkyl moiety in the alkoxy group and alkoxycarbonyl group of R, a straight-chain, branched-chain or cyclic alkyl moiety can be cited, and the preferred number of carbon atoms and specific examples of the alkyl moiety are the same as those described for the alkyl group and cycloalkyl group of Z ka1 above.

[0741] The alkylene group as X can be a linear or cyclic alkylene group, and the preferred number of carbon atoms and specific examples thereof are the same as those described for the linear alkylene group and cyclic alkylene group of R 2 above.

[0742] More preferably, it has a repeating unit having a partial structure represented by the general formula (KY-5).

[0743] [Chemical formula 78]

[0744]

[0745] In the general formula (KY-5),

[0746] R 2 represents a chain or cyclic alkylene group, and if there are a plurality of them, they may be the same or different.

[0747] R 3 represents a linear, branched or cyclic hydrocarbon group in which part or all of the hydrogen atoms on the structural carbon are substituted by fluorine atoms.

[0748] R 4 represents a halogen atom, a cyano group, a hydroxyl group, an amide group, an alkyl group, a cycloalkyl group, an alkoxy group, a phenyl group, an acyl group, an alkoxycarbonyl group, or a group represented by R-C(=O)- or R-C(=O)O- (R represents an alkyl group or a cycloalkyl group). When there are a plurality of R 4 s, they may be the same or different, and two or more R 4 s may be bonded to form a ring.

[0749] X represents an alkylene group, an oxygen atom or a sulfur atom.

[0750] Z represents a single bond, an ether bond, an ester bond, an amide bond, a urethane bond or a urea bond, and if there are a plurality of them, they may be the same or different.

[0751] * represents a bonding bond to the resin main chain or side chain.

[0752] n represents the number of repetitions and represents an integer from 0 to 5.

[0753] m is the number of substituents and represents an integer from 0 to 7.

[0754] R 2 ~R 4 and the preferred ranges and specific examples of the number of carbon atoms in X are the same as those described in the general formula (KY-4).

[0755] As the structure of -R 2 -Z-, a structure represented by -(CH 2 ) l -COO- (l represents an integer from 1 to 5) is preferred.

[0756] As a more specific structure of the repeating unit (e), a repeating unit having the following partial structure can also be cited.

[0757] [Chemical formula 79]

[0758]

[0759] In the general formulas (rf-1) and (rf-2),

[0760] X' represents an electron-withdrawing substituent, preferably a carbonyloxy group, an oxycarbonyl group, an alkylene group substituted by a fluorine atom, or a cycloalkylene group substituted by a fluorine atom.

[0761] A represents a single bond or a divalent linking group represented by -C(Rx)(Ry)-. Here, Rx and Ry each independently represent a hydrogen atom, a fluorine atom, an alkyl group (preferably having 1 to 6 carbon atoms and may be substituted by a fluorine atom or the like), or a cycloalkyl group (preferably having 5 to 12 carbon atoms and may be substituted by a fluorine atom or the like). As Rx and Ry, a hydrogen atom, an alkyl group, or an alkyl group substituted by a fluorine atom is preferred.

[0762] X represents an electron-withdrawing group, preferably a fluorinated alkyl group, a fluorinated cycloalkyl group, an aryl group substituted by fluorine or a fluorinated alkyl group, or an aralkyl group substituted by fluorine or a fluorinated alkyl group.

[0763] * represents a bonding site to the main chain or side chain of the resin. That is, it represents a single bond or a bonding site bonded to the main chain of the resin through a linking group.

[0764] In addition, when X' is a carbonyloxy group or an oxycarbonyl group, A is not a single bond.

[0765] As the alkylene group in the alkylene group substituted by a fluorine atom of X', in the case of a linear alkylene group, the number of carbon atoms is preferably 1 to 30, more preferably 1 to 20, and in the case of a branched alkylene group, the number of carbon atoms is preferably 3 to 30, more preferably 3 to 20. As a specific example of the above alkylene group, a group obtained by removing any one hydrogen atom from the specific examples of the alkyl group as Z ka1 can be cited. As the alkylene group substituted by a fluorine atom, a perfluoroalkylene group is preferred.

[0766] As the cycloalkylene group in the cycloalkylene group substituted by a fluorine atom of X', the number of carbon atoms is preferably 3 to 8. As a specific example thereof, a group obtained by removing any one hydrogen atom from the specific examples of the cycloalkyl group as Z ka1 can be cited. As the cycloalkylene group substituted by a fluorine atom, a perfluorocycloalkylene group is preferred.

[0767] As the alkyl group in the fluorinated alkyl group of X, in the case of a linear alkyl group, the number of carbon atoms is preferably 1 to 30, more preferably 1 to 20, and in the case of a branched alkyl group, the number of carbon atoms is preferably 3 to 30, more preferably 3 to 20. As a specific example of the above alkyl group, the specific examples of the alkyl group as Z ka1 can be cited. As the fluorinated alkyl group, a perfluoroalkyl group is preferred.

[0768] As the cycloalkyl group in the fluorinated cycloalkyl group of X, the number of carbon atoms is preferably 3 to 8. As a specific example thereof, the specific examples of the cycloalkyl group as Z ka1 can be cited. As the fluorinated cycloalkyl group, a perfluorocycloalkyl group is preferred.

[0769] As the aryl group in the aryl group substituted with fluorine or a fluoroalkyl group for X, preferably an aryl group having 6 to 12 carbon atoms can be mentioned, such as a phenyl group and a naphthyl group. And, as specific examples of the fluoroalkyl group in the aryl group substituted with a fluoroalkyl group, they are the same as those described for the fluoroalkyl group for X.

[0770] As the aralkyl group in the aralkyl group substituted with fluorine or a fluoroalkyl group for X, preferably an aralkyl group having 6 to 12 carbon atoms can be mentioned, such as a benzyl group, a phenethyl group, a naphthylmethyl group, a naphthylethyl group, a naphthylbutyl group, etc. And, as specific examples of the fluoroalkyl group in the aralkyl group substituted with a fluoroalkyl group, they are the same as those described for the fluoroalkyl group for X.

[0771] The resin (E) preferably has a repeating unit represented by the following general formula (2) as the repeating unit (e).

[0772] [Chemical formula 80]

[0773]

[0774] In the general formula (2), R 21 represents a hydrogen atom or a monovalent organic group. X 2 represents a divalent linking group. R 22 and R 23 each independently represent a fluoroalkyl group. R 24 represents a hydrogen atom, a fluorine atom or a monovalent organic group.

[0775] As the divalent linking group represented by X 2 in the general formula (2), preferably a divalent linking group having the above-mentioned polarity-converting group, and particularly preferably having a lactone structure.

[0776] In the general formula (2), R 21 preferably represents a hydrogen atom or an alkyl group, more preferably a hydrogen atom or an alkyl group having 1 to 5 carbon atoms.

[0777] In the general formula (2), R 22 and R 23 each independently represent a fluoroalkyl group, preferably a fluoroalkyl group having 1 to 10 carbon atoms, more preferably a fluoroalkyl group having 1 to 5 carbon atoms.

[0778] In the general formula (2), R 24 preferably represents a hydrogen atom, a fluorine atom or a fluoroalkyl group having 1 to 10 carbon atoms, more preferably a hydrogen atom, a fluorine atom or a fluoroalkyl group having 1 to 5 carbon atoms.

[0779] The following shows specific examples of the repeating unit (e) having a polarity-converting group, but is not limited thereto.

[0780] Ra represents a hydrogen atom, a fluorine atom, a methyl group, or a trifluoromethyl group.

[0781] [Chemical Formula 81]

[0782]

[0783] [Chemical Formula 82]

[0784]

[0785] The content rate of the repeating unit (e) in the resin (E) is preferably 10 to 100 mol%, more preferably 20 to 100 mol%, still more preferably 30 to 100 mol%, and most preferably 40 to 100 mol% with respect to all the repeating units in the resin (E).

[0786] The content rate of the repeating unit (e') in the resin (E) is preferably 10 to 100 mol%, more preferably 20 to 100 mol%, still more preferably 30 to 100 mol%, and most preferably 40 to 100 mol% with respect to all the repeating units in the resin (E).

[0787] The content rate of the repeating unit (e*) in the resin (E) is preferably 5 to 70 mol%, more preferably 5 to 60 mol%, still more preferably 10 to 50 mol%, and most preferably 10 to 40 mol% with respect to all the repeating units in the resin (E). The content rate of the repeating unit having a fluorine atom used together with the repeating unit (e*) is preferably 10 to 95 mol%, more preferably 15 to 85 mol%, still more preferably 20 to 80 mol%, and most preferably 25 to 75 mol% with respect to all the repeating units in the resin (E).

[0788] The content rate of the repeating unit (e'') in the resin (E) is preferably 10 to 100 mol%, more preferably 20 to 100 mol%, still more preferably 30 to 100 mol%, and most preferably 40 to 100 mol% with respect to all the repeating units in the resin (E).

[0789] The fluorine atoms in the resin (E) may be present in the main chain of the resin or may be substituted on the side chain.

[0790] The resin (E) may also have other repeating units. Preferred examples of the other repeating units are as follows.

[0791] (ey1) A repeating unit having a fluorine atom, being stable to acids, and being hardly soluble or insoluble in an alkaline developer.

[0792] (ey2) A repeating unit not having a fluorine atom, being stable to acids, and being hardly soluble or insoluble in an alkaline developer.

[0793] (ey3) has a fluorine atom and a repeating unit having a polar group other than the above (x) and (z).

[0794] (ey4) does not have a fluorine atom and has a repeating unit having a polar group other than the above (x) and (z).

[0795] (ey1) and (ey2) being insoluble or poorly soluble in an alkaline developer in the repeating unit means that (ey1) and (ey2) do not contain a group that generates an alkali-soluble group by the action of an alkali-soluble group, an acid, or an alkaline developer (for example, an acid-decomposable group or a polarity-converting group).

[0796] The repeating units (ey1) and (ey2) preferably have an alicyclic hydrocarbon structure that does not have a polar group.

[0797] Preferred embodiments of the repeating units (ey1) to (ey4) are shown below.

[0798] As the repeating units (ey1) and (ey2), repeating units represented by the following general formula (CIII) are preferred.

[0799] [Chemical formula 83]

[0800]

[0801] In the general formula (CIII),

[0802] R c31 represents a hydrogen atom, an alkyl group that may be substituted with a fluorine atom, a cyano group, or a -CH 2 -O-Rac 2 group. In the formula, Rac 2 represents a hydrogen atom, an alkyl group, or an acyl group. R c31 is preferably a hydrogen atom, a methyl group, a hydroxymethyl group, a trifluoromethyl group, and particularly preferably a hydrogen atom or a methyl group.

[0803] R c32 represents a group having an alkyl group, a cycloalkyl group, an alkenyl group, a cycloalkenyl group, or an aryl group. These groups may be substituted with a group containing a silicon atom, a fluorine atom, etc.

[0804] L c3 represents a single bond or a divalent linking group.

[0805] In the general formula (CIII), the alkyl group of R c32 preferably has 3 to 20 carbon atoms and is a straight-chain or branched-chain alkyl group.

[0806] The cycloalkyl group preferably has 3 to 20 carbon atoms.

[0807] The alkenyl group preferably has 3 to 20 carbon atoms.

[0808] The cycloalkenyl group is preferably a cycloalkenyl group having 3 to 20 carbon atoms.

[0809] The aryl group is preferably a phenyl group or a naphthyl group having 6 to 20 carbon atoms, and they may have substituents.

[0810] R c32 is preferably an unsubstituted alkyl group or an alkyl group substituted with a fluorine atom. L c3 The divalent linking group is preferably an alkylene group (preferably having 1 to 5 carbon atoms), an oxy group, a phenylene group, or an ester bond (a group represented by -COO-).

[0811] As the repeating units (ey1) and (ey2), repeating units represented by the following general formula (C4) or general formula (C5) are preferred.

[0812] [Chemical formula 84]

[0813]

[0814] In general formula (C4) and general formula (C5),

[0815] R c5 represents a hydrocarbon group having at least one ring structure and having neither a hydroxyl group nor a cyano group.

[0816] Rac represents a hydrogen atom, an alkyl group that may be substituted with a fluorine atom, a cyano group, or -CH 2 -O-Rac 2 group. In the formula, Rac 2 represents a hydrogen atom, an alkyl group, or an acyl group. Rac is preferably a hydrogen atom, a methyl group, a hydroxymethyl group, a trifluoromethyl group, and particularly preferably a hydrogen atom or a methyl group.

[0817] R c5 The ring structure contained in has a monocyclic hydrocarbon group and a polycyclic hydrocarbon group. As the monocyclic hydrocarbon group, for example, a cycloalkyl group having 3 to 12 carbon atoms and a cycloalkenyl group having 3 to 12 carbon atoms can be mentioned. As the preferred monocyclic hydrocarbon group, a monocyclic hydrocarbon group having 3 to 7 carbon atoms.

[0818] The polycyclic hydrocarbon group includes a ring-aggregated hydrocarbon group and a crosslinked cyclic hydrocarbon group. As the crosslinked cyclic hydrocarbon ring, a bicyclic hydrocarbon ring, a tricyclic hydrocarbon ring, a tetracyclic hydrocarbon ring, etc. can be mentioned. And the crosslinked cyclic hydrocarbon ring also includes a fused-ring hydrocarbon ring (a fused ring having a plurality of 5- to 8-membered cycloalkane rings). As the preferred crosslinked cyclic hydrocarbon ring, a norbornyl group and an adamantyl group can be mentioned.

[0819] These alicyclic hydrocarbon groups may have substituents. Preferred substituents include a halogen atom, an alkyl group, a hydroxyl group protected by a protecting group, an amino group protected by a protecting group, etc. Preferred halogen atoms include bromine, chlorine, and fluorine atoms. Preferred alkyl groups include methyl, ethyl, butyl, and tert-butyl groups. The above-mentioned alkyl groups may further have substituents. Substituents that may further be present include a halogen atom, an alkyl group, a hydroxyl group protected by a protecting group, and an amino group protected by a protecting group.

[0820] 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. Preferred alkyl groups include alkyl groups having 1 to 4 carbon atoms. Preferred substituted methyl groups include methoxymethyl, methoxythiomethyl, benzyloxymethyl, tert-butoxymethyl, and 2-methoxyethoxymethyl. Preferred substituted ethyl groups include 1-ethoxyethyl and 1-methyl-1-methoxyethyl. Preferred acyl groups include aliphatic acyl groups having 1 to 6 carbon atoms such as formyl, acetyl, propionyl, butyryl, isobutyryl, valeryl, and pivaloyl. Examples of the alkoxycarbonyl group include alkoxycarbonyl groups having 2 to 4 carbon atoms.

[0821] R c6 represents an alkyl group, a cycloalkyl group, an alkenyl group, a cycloalkenyl group, an alkoxycarbonyl group, or an alkylcarbonyloxy group. These groups may be substituted with a fluorine atom or a silicon atom.

[0822] R c6 The alkyl group is preferably a straight-chain or branched-chain alkyl group having 1 to 20 carbon atoms. The cycloalkyl group is preferably a cycloalkyl group having 3 to 20 carbon atoms.

[0823] The alkenyl group is preferably an alkenyl group having 3 to 20 carbon atoms.

[0824] The cycloalkenyl group is preferably a cycloalkenyl group having 3 to 20 carbon atoms.

[0825] The alkoxycarbonyl group is preferably an alkoxycarbonyl group having 2 to 20 carbon atoms.

[0826] The alkylcarbonyloxy group is preferably an alkylcarbonyloxy group having 2 to 20 carbon atoms.

[0827] n represents an integer of 0 to 5. When n is 2 or more, multiple R c6 may be the same or different.

[0828] R c6 is preferably an unsubstituted alkyl group or an alkyl group substituted with a fluorine atom, and particularly preferably trifluoromethyl or tert-butyl.

[0829] As (ey1) and (ey2), repeating units represented by the following general formula (CI I-AB) are also preferred.

[0830] [Chemical Formula 85]

[0831]

[0832] In formula (CII-AB),

[0833] R c11 ’ and R c12 ’ each independently represent a hydrogen atom, a cyano group, a halogen atom or an alkyl group.

[0834] Zc’ contains 2 carbon atoms (C-C) to which it is bonded, and represents a group of atoms for forming an alicyclic structure.

[0835] Furthermore, the above general formula (CII-AB) is further preferably the following general formula (CII-AB1) or general formula (CII-AB2).

[0836] [Chemical Formula 86]

[0837]

[0838] In formula (CII-AB1) and formula (CII-AB2),

[0839] Rc 13 ’ to Rc 16 ’ each independently represent a hydrogen atom, a halogen atom, an alkyl group or a cycloalkyl group.

[0840] Furthermore, at least two of Rc 13 ’ to Rc 16 ’ can be bonded to form a ring.

[0841] n represents 0 or 1.

[0842] Specific examples of (ey1) and (ey2) are given below, but the present invention is not limited to these. In the formula, Ra represents H, CH 3 , CH 2 OH, CF 3 or CN.

[0843] [Chemical Formula 87]

[0844]

[0845] As (ey3) and (ey4), a repeating unit having a hydroxyl group or a cyano group is preferably used as a polar group. Thereby, the affinity for the developer is improved. 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. In the alicyclic hydrocarbon structure substituted with a hydroxyl group or a cyano group, as the alicyclic hydrocarbon structure, an adamantyl group, a diadamantyl group, or a norbornyl group is preferable. As a preferable alicyclic hydrocarbon structure substituted with a hydroxyl group or a cyano group, a mono-hydroxyadamantyl group, a di-hydroxyadamantyl group, a mono-hydroxy diadamantyl group, a di-hydroxyadamantyl group, a norbornyl group substituted with a cyano group, etc. can be mentioned.

[0846] As the repeating unit having the above atomic group, the repeating units represented by the following general formula (CAIIa) to general formula (CAIId) can be mentioned.

[0847] [Chemical formula 88]

[0848]

[0849] In general formula (CAIIa) to general formula (CAIId),

[0850] R 1 c represents a hydrogen atom, a methyl group, a trifluoromethyl group, or a hydroxymethyl group.

[0851] R 2 c to R 4 c each independently represents a hydrogen atom, a hydroxyl group, or a cyano group. Among them, R 2 c to R 4 c at least one of which represents a hydroxyl group or a cyano group. Preferably, 1 or 2 of R 2 c to R 4 c are hydroxyl groups, and the rest are hydrogen atoms. In general formula (CAIIa), it is further preferable that 2 of R 2 c to R 4 c are hydroxyl groups, and the rest are hydrogen atoms.

[0852] The following shows specific examples of the repeating units represented by (ey3) and (ey4), but the present invention is not limited to these.

[0853] [Chemical formula 89]

[0854]

[0855] The content ratio of the repeating units represented by (ey1) to (ey4) is preferably 5 to 40 mol%, more preferably 5 to 30 mol%, and further preferably 10 to 25 mol% with respect to all the repeating units in the resin (E).

[0856] The resin (E) may have a plurality of repeating units represented by (ey1) to (ey4).

[0857] The content rate of fluorine atoms in the resin (E) is preferably 5 to 80% by mass, more preferably 10 to 80% by mass, relative to the molecular weight of the resin (E). Further, the repeating unit containing fluorine atoms is preferably 10 to 100% by mass, more preferably 30 to 100% by mass, relative to all the repeating units in the resin (E).

[0858] From the viewpoint of improving non-uniform distribution, the molecular weight of the fluorine-containing compound (E) is preferably 1,000 to 100,000.

[0859] The weight average molecular weight of the resin (E) is preferably 1,000 to 100,000, more preferably 1,000 to 50,000, and still more preferably 2,000 to 15,000.

[0860] The molecular weight distribution (Mw / Mn, also referred to as dispersity) of the resin (E) is preferably in the range of 1 to 3, more preferably in the range of 1 to 2, still more preferably in the range of 1 to 1.8, and most preferably in the range of 1 to 1.5.

[0861] As the resin (E), various commercially available products can be used, or it can be synthesized in the same manner as the resin (A) by a conventional method (for example, radical polymerization).

[0862] The fluorine-containing compound (E) can be used alone or in combination of two or more.

[0863] From the viewpoint of resolution, based on the total solid content of the composition of the present invention, the content rate of the fluorine-containing compound (E) in the composition of the present invention is preferably 0.01 to 10% by mass, more preferably 0.1 to 10% by mass, and still more preferably 0.1 to 5% by mass.

[0864] [Solvent]

[0865] The composition of the present invention preferably contains a solvent.

[0866] In the composition of the present invention, a known resist solvent can be appropriately used. For example, it is preferable to use the known compounds disclosed in paragraphs

[0665] to

[0670] of the specification of U.S. Patent Application Publication No. 2016 / 0070167A1, paragraphs

[0210] to

[0235] of the specification of U.S. Patent Application Publication No. 2015 / 0004544A1, paragraphs

[0424] to

[0426] of the specification of U.S. Patent Application Publication No. 2016 / 0237190A1, and paragraphs

[0357] to

[0366] of the specification of U.S. Patent Application Publication No. 2016 / 0274458A1 as an acid diffusion control agent.

[0867] As solvents that can be used when preparing the composition, for example, there can be cited organic solvents such as alkylene glycol monoalkyl ether carboxylates, alkylene glycol monoalkyl ethers, alkyl lactates, alkyl alkoxypropionates, cyclic lactones (preferably having 4 to 10 carbon atoms), monoketone compounds that can have a ring (preferably having 4 to 10 carbon atoms), alkylene carbonates, alkyl alkoxyacetates, and alkyl pyruvates.

[0868] As the organic solvent, a mixed solvent obtained by mixing a solvent having a hydroxyl group in its structure and a solvent not having a hydroxyl group can be used.

[0869] As the solvent having a hydroxyl group and the solvent not having a hydroxyl group, the above-exemplified compounds can be appropriately selected. As the solvent containing a hydroxyl group, alkylene glycol monoalkyl ethers or alkyl lactates are preferred, and propylene glycol monomethyl ether (PGME), propylene glycol monoethyl ether (PGEE), methyl 2-hydroxyisobutyrate, or ethyl lactate are more preferred. And as the solvent not having a hydroxyl group, alkylene glycol monoalkyl ether acetates, alkyl alkoxypropionates, monoketone compounds that can have a ring, cyclic lactones, or alkyl acetates are preferred. Among them, propylene glycol monomethyl ether acetate (PGMEA), ethyl ethoxypropionate, 2-heptanone, γ-butyrolactone, cyclohexanone, cyclopentanone, or butyl acetate are more preferred, and propylene glycol monomethyl ether acetate, γ-butyrolactone, ethyl ethoxypropionate, cyclohexanone, cyclopentanone, or 2-heptanone are further preferred. As the solvent not having a hydroxyl group, propylene carbonate is also preferred.

[0870] The mixing ratio (mass ratio) of the solvent having a hydroxyl group and the solvent not having a hydroxyl group is 1 / 99 to 99 / 1, preferably 10 / 90 to 90 / 10, and more preferably 20 / 80 to 60 / 40. From the viewpoint of coating uniformity, a mixed solvent containing 50% by mass or more of the solvent not having a hydroxyl group is preferred.

[0871] Preferably, the solvent contains propylene glycol monomethyl ether acetate, which can be a single solvent of propylene glycol monomethyl ether acetate or a mixed solvent of two or more kinds containing propylene glycol monomethyl ether acetate.

[0872] [Surfactant]

[0873] The composition of the present invention can further contain a surfactant. By containing a surfactant, in the case of using an exposure light source having a wavelength of 250 nm or less, particularly a wavelength of 220 nm or less, a pattern having excellent adhesion and fewer development defects can be formed with good sensitivity and resolution.

[0874] As the surfactant, fluorine-based and / or silicon-based surfactants are particularly preferably used.

[0875] As the fluorine-based and / or silicon-based surfactant, for example, the surfactant described in paragraph

[0276] of the specification of US Patent Application Publication No. 2008 / 0248425 can be cited. Also, Eftop EF301 or EF303 (manufactured by Shin-Akita Kasei Co., Ltd.); Fluorad FC430, 431 or 4430 (manufactured by Sumitomo 3M Limited); Megaface F171, F173, F176, F189, F113, F110, F177, F120 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.); 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.); or FTX-204G, 208G, 218G, 230G, 204D, 208D, 212D, 218D or 222D (manufactured by Neos Corporation) can be used. Further, as the silicon-based surfactant, polysiloxane polymer KP-341 (manufactured by Shin-Etsu Chemical Co., Ltd.) can also be used.

[0876] Moreover, in addition to the well-known surfactants as shown above, fluorinated aliphatic compounds produced by adjusting the telomerization method (also called the telomer method) or the oligomerization method (also called the oligomer method) can be used to synthesize surfactants. Specifically, a polymer having a fluorinated aliphatic group derived from the fluorinated aliphatic compound can be used as the surfactant. The fluorinated aliphatic compound can be synthesized by, for example, the method described in Japanese Patent Application Laid-Open No. 2002-90991.

[0877] Further, surfactants other than those of the fluorine-based and / or silicon-based types described in paragraph

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

[0878] These surfactants may be used alone or in combination of two or more.

[0879] When the composition of the present invention contains a surfactant, its content is preferably 0 to 2% by mass, more preferably 0.0001 to 2% by mass, and still more preferably 0.0005 to 1% by mass based on the total solid content of the composition.

[0880] [Other Additives]

[0881] In addition to the components described above, the composition of the present invention may appropriately contain carboxylic acids, carboxylic acid onium salts, dissolution inhibiting compounds having a molecular weight of 3000 or less described in Proceedings of SPIE, 2724, 355 (1996), dyes, plasticizers, photosensitizers, light absorbers, antioxidants, and the like.

[0882] In particular, carboxylic acids can also be appropriately used to improve performance. As the carboxylic acid, aromatic carboxylic acids such as benzoic acid and naphthoic acid are preferred.

[0883] When the composition of the present invention contains a carboxylic acid, the content of the carboxylic acid is preferably 0.01 to 10% by mass, more preferably 0.01 to 5% by mass, and still more preferably 0.01 to 3% by mass relative to the total solid content of the composition.

[0884] From the viewpoint of improving resolution, the photosensitive radiation-curable or radiation-sensitive resin composition in the present invention is preferably used with a film thickness of 10 to 250 nm, more preferably 20 to 200 nm, and still more preferably 30 to 100 nm. By setting the solid content concentration in the composition within an appropriate range to make it have an appropriate viscosity and improve coatability and film-forming properties, such a film thickness can be achieved.

[0885] The solid content concentration of the photosensitive radiation-curable or radiation-sensitive resin composition in the present invention is generally 1.0 to 10% by mass, preferably 2.0 to 5.7% by mass, and still more preferably 2.0 to 5.3% by mass. By setting the solid content concentration within the above range, the resist solution can be uniformly coated on the substrate, and further, a resist pattern excellent in line width roughness can be formed.

[0886] The solid content concentration refers to the mass percentage of the mass of components other than the solvent relative to the total mass of the photosensitive radiation-curable or radiation-sensitive resin composition.

[0887] [Use]

[0888] The composition of the present invention relates to a photosensitizing or radiation-sensitive resin composition that reacts upon irradiation with actinic rays or radiation, thereby changing its properties. More specifically, the composition of the present invention relates to a photosensitizing or radiation-sensitive resin composition used in semiconductor manufacturing processes such as IC (Integrated Circuit) manufacturing, the manufacturing of circuit boards such as liquid crystals or thermal heads, the production of mold structures for imprinting, other photosensitive etching processes, or the manufacturing of lithographic printing plates or acid-curable compositions. The pattern formed in the present invention can be used in etching processes, ion implantation processes, bump electrode formation processes, redistribution formation processes, and MEMS (Micro Electro Mechanical Systems), etc.

[0889] [Photosensitizing or radiation-sensitive film]

[0890] The present invention also relates to a photosensitizing or radiation-sensitive film (preferably a resist film) formed from the photosensitizing or radiation-sensitive composition of the present invention. Such a film is formed, for example, by coating the composition of the present invention on a support such as a substrate. The thickness of the photosensitizing or radiation-sensitive film of the present invention is preferably 0.02 to 0.1 μm. As a method of coating on the substrate, it can be coated on the substrate by an appropriate coating method such as spin coating, roll coating, flow coating, dip coating, spray coating, or blade coating, but spin coating is preferred, and the rotation speed is preferably 1000 to 3000 rpm (rotations per minute). The coated film is pre-baked at 60 to 150 °C for 1 to 20 minutes, preferably pre-baked at 80 to 120 °C for 1 to 10 minutes to form a thin film.

[0891] The materials constituting the substrate to be processed and its outermost layer, for example, in the case of a semiconductor wafer, a silicon wafer can be used. As an example of the material that becomes the outermost layer, Si, SiO 2 , SiN, SiON, TiN, WSi, BPSG, SOG, organic antireflection films, etc. can be cited.

[0892] An antireflection film can also be pre-coated on the substrate before forming the resist film.

[0893] As the antireflection film, any of inorganic film types such as titanium, titanium dioxide, titanium nitride, chromium oxide, carbon, amorphous silicon, etc., and organic film types composed of light absorbents and polymer materials can be used. And, as the organic antireflection film, commercially available organic antireflection films such as the DUV30 series and DUV-40 series manufactured by Brewer Science and AR-2, AR-3, AR-5, etc. manufactured by Shipley can also be used.

[0894] In addition, in the pattern forming method of the present invention, a top coat layer may also be formed on the upper layer of the resist film. It is preferable that the top coat layer can be further uniformly coated on the upper layer of the resist film without mixing with the resist film.

[0895] There is no particular limitation on the top coat layer, and a conventionally known top coat layer can be formed by a conventionally known method. For example, a top coat layer can be formed based on the content described in paragraphs 0072 to 0082 of Japanese Patent Application Laid-Open No. 2014-059543.

[0896] For example, it is preferable to form a top coat layer containing a basic compound as described in Japanese Patent Application Laid-Open No. 2013-61648 on the resist film. Specific examples of the basic compound that the top coat layer may contain are the same as those of the above acid diffusion control agent.

[0897] Moreover, the top coat layer preferably contains a compound that contains 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.

[0898] In addition, the top coat layer preferably contains a resin. There is no particular limitation on the resin that the top coat layer may contain, and the same resin as the hydrophobic resin that may be contained in the photosensitive or radiation-sensitive composition can be used.

[0899] Regarding the hydrophobic resin, reference can be made to the descriptions in

[0017] to

[0023] of Japanese Patent Application Laid-Open No. 2013-61647 (corresponding to

[0017] to

[0023] of US Patent Publication No. 2013 / 244438) and

[0016] to

[0165] of Japanese Patent Application Laid-Open No. 2014-56194, and these contents are incorporated into the specification of the present application.

[0900] The top coat layer preferably contains a resin that contains a repeating unit having an aromatic ring. By containing a repeating unit having an aromatic ring, particularly in the case of electron beam or EUV exposure, the generation efficiency of secondary electrons and the acid generation efficiency of the compound that generates an acid by actinic rays or radiation are improved, and high sensitivity and high resolution effects can be expected during pattern formation.

[0901] When the top coat layer contains a plurality of resins, it preferably contains at least one resin (XA) having a fluorine atom and / or a silicon atom. More preferably, the top coat layer composition contains at least one resin (XA) having a fluorine atom and / or a silicon atom and a resin (XB) having a lower content of fluorine atoms and / or silicon atoms than the resin (XA). Thereby, when forming the top coat layer film, the resin (XA) is biased toward the surface of the top coat layer film, and thus properties such as development characteristics and immersion liquid followability can be improved.

[0902] Further, the topcoat layer may also contain an acid generator and a crosslinking agent.

[0903] Typically, the topcoat layer is formed from a composition for forming the topcoat layer.

[0904] The composition for forming the topcoat layer preferably dissolves each component in a solvent and performs filtration through a filter. As the filter, a polytetrafluoroethylene, polyethylene, or nylon filter with a pore size of 0.1 μm or less is preferred, more preferably 0.05 μm or less, and further preferably 0.03 μm or less. Further, when the solid component concentration of the composition is high (e.g., 25 mass% or more), the pore size of the filter used in the filtration through the filter is preferably 3 μm or less, more preferably 0.5 μm or less, and further preferably 0.3 μm or less. This filter is preferably a polytetrafluoroethylene, polyethylene, or nylon filter. In the filtration through the filter, for example, as disclosed in Japanese Patent Application Laid-Open No. 2002-62667 (JP 2002-62667 A), circulation filtration can be performed, or multiple filters can be connected in series or in parallel for filtration. Further, the composition can be filtered multiple times. Moreover, degassing treatment or the like can be performed on the composition before and after the filtration through the filter.

[0905] The composition for forming the topcoat layer preferably does not contain impurities such as metals. As the content of the metal component contained in these materials, it is preferably 10 ppm or less, more preferably 5 ppm or less, further preferably 1 ppm or less, and particularly preferably substantially free (below the detection limit of the measuring device).

[0906] In order to reduce the content of metal impurities in the resist composition (e.g., on the order of mass ppm), it is also preferred to perform glass lining treatment on a part or all of the interior of the apparatus used in the manufacturing process (such as the process of synthesizing raw materials) of the raw materials (resin, photoacid generator, etc.) of the resist composition. This method is described, for example, in the Chemical Industry Daily on December 21, 2017.

[0907] When the exposure described later is liquid immersion exposure, the topcoat layer is disposed between the resist film and the immersion liquid and also functions as a layer that prevents the resist film from directly contacting the immersion liquid. In this case, as the preferred properties of the topcoat layer (composition for forming the topcoat layer), the coating adaptability to the resist film, transparency to radiation, particularly to 193 nm, and low solubility in the immersion liquid (preferably water) are preferred. Further, it is preferred that the topcoat layer can be coated on the surface of the resist film more uniformly without mixing with the resist film.

[0908] In addition, in order to uniformly coat the composition for forming a top coat without dissolving the resist film on the surface of the resist film, the composition for forming a top coat preferably contains a solvent that does not dissolve the resist film. As the solvent that does not dissolve the resist film, it is further preferable to use a solvent having a different composition from the developer (organic developer) containing the organic solvent described later.

[0909] The coating method of the composition for forming a top coat is not particularly limited, and spin coating, spraying, roll coating, dipping, or the like, which are conventionally known, can be used.

[0910] The film thickness of the top coat is not particularly limited. From the viewpoint of transparency to the exposure light source, it is usually 5 nm to 300 nm, preferably 10 nm to 300 nm, more preferably 20 nm to 200 nm, and further preferably 30 nm to 100 nm.

[0911] After forming the top coat, the substrate is heated (PB) as needed.

[0912] From the viewpoint of resolution, the refractive index of the top coat is preferably close to that of the resist film.

[0913] The top coat is preferably insoluble in the immersion liquid, and more preferably insoluble in water.

[0914] From the viewpoint of immersion liquid followability, the receding contact angle of the top coat with respect to the immersion liquid of the top coat (23 °C) is preferably 50 to 100 degrees, and more preferably 80 to 100 degrees.

[0915] In immersion exposure, as the exposure head scans the wafer at high speed to form an exposure pattern, the immersion liquid needs to move on the wafer. Therefore, the contact angle of the immersion liquid with respect to the top coat in the dynamic state becomes important. In order to obtain better resist performance, it is preferable to have a receding contact angle within the above range.

[0916] When stripping the top coat, an organic developer can be used, or a stripper can be used additionally. As the stripper, a solvent with little penetration into the resist film is preferred. From the viewpoint that the stripping of the top coat can be carried out simultaneously with the development of the resist film, the top coat is preferably strippable using an organic developer. As the organic developer used for stripping, as long as it can dissolve and remove the low-exposure portion of the resist film, there is no particular limitation.

[0917] From the viewpoint of stripping with an organic developer, the dissolution rate of the top coat in the organic developer is preferably 1 to 300 nm / sec, and more preferably 10 to 100 nm / sec.

[0918] Here, the dissolution rate of the top coating with respect to the organic developer refers to the film thickness reduction rate when the top coating film is exposed to the developer after film formation, and in the present invention, it refers to the rate when immersed in butyl acetate at 23°C.

[0919] By setting the dissolution rate of the top coating with respect to the organic developer to 1 nm / sec or more, preferably 10 nm / sec or more, there is an effect of reducing the generation of development defects after development of the resist film. Also, by setting it to 300 nm / sec or less, preferably 100 nm / sec, it is possible to reduce the influence of exposure non-uniformity during liquid immersion exposure, and there is an effect of making the line edge roughness of the pattern after development of the resist film better.

[0920] The top coating can also be removed using other known developers, such as an alkaline aqueous solution. As the alkaline aqueous solution that can be used, specifically, an aqueous solution of tetramethylammonium hydroxide can be cited.

[0921] [Pattern Forming Method]

[0922] The present invention also relates to a pattern forming method, which includes the following steps: a resist film forming step of forming a resist film using the photosensitive or radiation-sensitive resin composition of the present invention; an exposure step of exposing the resist film; and a development step of developing the exposed resist film using a developer.

[0923] In the present invention, the above exposure is preferably performed using an electron beam, an ArF excimer laser, or extreme ultraviolet rays, and more preferably using an electron beam or extreme ultraviolet rays.

[0924] In the manufacture of precision integrated circuit elements, etc., for the exposure (pattern forming step) on the resist film, first, it is preferable to irradiate the resist film of the present invention with an ArF excimer laser, an electron beam, or extreme ultraviolet rays (EUV) in a pattern shape. The exposure dose is about 1 to 100 mJ / cm 2 in the case of an ArF excimer laser, preferably about 20 to 60 mJ / cm 2 in the case of an electron beam, the exposure is about 0.1 to 20 μC / cm 2 preferably about 3 to 10 μC / cm 2 in the case of extreme ultraviolet rays, the exposure is about 0.1 to 20 mJ / cm 2 preferably about 3 to 15 mJ / cm 2 about.

[0925] Next, on a hot plate, it is preferably heated at 60 to 150 °C for 5 seconds to 20 minutes, more preferably heated at 80 to 120 °C for 15 seconds to 10 minutes, and further preferably heated at 80 to 120 °C for 1 to 10 minutes for post-exposure heating (post-exposure bake), and then a pattern is formed by developing, rinsing, and drying. Here, the post-exposure heating can be appropriately adjusted according to the acid decomposability of the repeating unit having an acid-decomposable group in the resin (A). When the acid decomposability is low, the temperature of the post-exposure heating is preferably 110 °C or higher, and the heating time is also preferably 45 seconds or longer.

[0926] The developer can be appropriately selected, but an alkaline developer (typically an aqueous alkali solution) or a developer containing an organic solvent (also referred to as an organic-based developer) is preferably used. When the developer is an aqueous alkali solution, a 0.1 to 5 mass%, preferably 2 to 3 mass% aqueous alkali solution of tetramethylammonium hydroxide (TMAH), tetrabutylammonium hydroxide (TBAH), etc. is used, and development is carried out for 0.1 to 3 minutes, preferably 0.5 to 2 minutes, by a conventional method such as the dip method, the puddle method, or the spray method. An appropriate amount of alcohols and / or surfactants can be added to the alkaline developer. Thus, in the formation of a negative pattern, the film of the unexposed portion dissolves, and the exposed portion is difficult to dissolve in the developer, and in the formation of a positive pattern, the film of the exposed portion dissolves, and the film of the unexposed portion is difficult to dissolve in the developer, thereby forming a target pattern on the substrate.

[0927] Electron beam lithography can be roughly divided into a direct writing method and a mask projection method. The initial electron beam lithography method was the point beam method, but in order to improve the exposure efficiency, it evolved into a variable shaped beam method (Variable Shaped Beam, VSB), a partial batch method (cell projection), and further, as an extension thereof, developed into a mask projection method having all patterns like optical lithography.

[0928] On the other hand, there is a multi-beam method (hereinafter, also referred to as "electron beam multi-beam lithography", etc.) that improves the efficiency by simultaneously irradiating multiple electron beams. (For example, refer to Non-Patent Documents 1 and 2).

[0929] Non-Patent Document 1: Elmar Platzgummer, Stefan Cernusca, Christof Klein, Jan Klikovits, Samuel Kvasnica, Hans Loeschner, "eMET-50keV Electron Mask Exposure Tool Development based on proven multi-beam projection technology", Proc. SPIE Vol. 7823, 782308 (2010).

[0930] Non-Patent Document 2: Christof Klein, Hans Loeschner, Elmar Platzgummer, "Performance of the Proof-of-Concept Multi-Beam Mask Writer", Proc. SPIE Vol. 8880, 88801E (2013).

[0931] Exposure can be carried out by irradiating a photosensitive radiation-sensitive or radiation-sensitive film with multiple electron beams simultaneously. This can be performed using a multi-beam type mask drawing device (MBMW). According to the multi-beam type mask drawing device, since multiple portions can be drawn (exposed) at once, the throughput can be increased.

[0932] When the pattern forming method of the present invention has a step of developing using an alkaline developer, as the alkaline developer, for example, inorganic alkalis such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, and ammonia water can be used; primary amines such as ethylamine and n-propylamine; secondary amines such as diethylamine and di-n-butylamine; tertiary amines such as triethylamine and methyldiethylamine; alkanolamines such as dimethylethanolamine and triethanolamine; tetraalkylammonium hydroxides such as tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, tetraamylammonium hydroxide, tetrahexylammonium hydroxide, tetraoctylammonium hydroxide, ethyltrimethylammonium hydroxide, butyltrimethylammonium hydroxide, methyltripentylammonium hydroxide, and dibutyldipentylammonium hydroxide; quaternary ammonium salts such as trimethylphenylammonium hydroxide, trimethylbenzylammonium hydroxide, triethylbenzylammonium hydroxide, and dimethylbis(2-hydroxyethyl)ammonium hydroxide; and cyclic amines such as pyrrole and piperidine can be used as the alkaline aqueous solution.

[0933] Furthermore, an appropriate amount of alcohol and surfactant can also be added to the above alkaline aqueous solution for use.

[0934] The alkali concentration of the alkaline developer is usually 0.1 to 20% by mass.

[0935] The pH of the alkaline developer is usually 10.0 to 15.0.

[0936] Particularly preferred is an aqueous solution of 2.38% by mass of tetramethylammonium hydroxide.

[0937] As the rinsing liquid in the rinsing treatment performed after the alkaline development, pure water can be used, or an appropriate amount of a surfactant can be added and used.

[0938] Moreover, after the development treatment or the rinsing treatment, a treatment using a supercritical fluid to remove the developer or the rinsing liquid adhering to the pattern can be performed.

[0939] When the pattern forming method of the present invention has a step of developing using a developer containing an organic solvent, as the developer (hereinafter, also referred to as an organic developer) in the above step, polar solvents such as ketone solvents, ester solvents, alcohol solvents, amide group solvents, ether solvents, and hydrocarbon solvents can be used.

[0940] In the present invention, an ester solvent means a solvent having an ester group in the molecule, a ketone solvent means a solvent having a ketone group in the molecule, an alcohol solvent means a solvent having an alcohol hydroxyl group in the molecule, an amide group solvent means a solvent having an amide group in the molecule, and an ether solvent means a solvent having an ether bond in the molecule. Among them, there are also solvents having a plurality of the above functional groups in one molecule, but in this case, it is assumed to be applicable to any solvent type including the functional groups possessed by the solvent. For example, diethylene glycol monomethyl ether is assumed to be applicable to both the alcohol solvent and the ether solvent in the above classification. And a hydrocarbon solvent means a hydrocarbon solvent having no substituent.

[0941] Particularly preferred is a developer containing at least one solvent selected from ketone solvents, ester solvents, alcohol solvents, and ether solvents.

[0942] From the viewpoint of suppressing swelling of the resist film, the 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.

[0943] The heteroatoms of the above ester solvent are atoms other than carbon atoms and hydrogen atoms, and examples thereof include oxygen atoms, nitrogen atoms, sulfur atoms, etc. The number of heteroatoms is preferably 2 or less.

[0944] As preferred examples of ester solvents having 7 or more carbon atoms and 2 or less heteroatoms, amyl acetate, isoamyl acetate, 2-methylbutyl acetate, 1-methylbutyl acetate, hexyl acetate, pentyl propionate, hexyl propionate, heptyl propionate, butyl butyrate, isobutyl isobutyrate, etc. can be cited, and isoamyl acetate or isobutyl isobutyrate is particularly preferably used.

[0945] As the developer, a mixed solvent of the above ester solvent and the above hydrocarbon solvent or a mixed solvent of the above ketone solvent and the above hydrocarbon solvent can be used instead of the above ester solvent having 7 or more carbon atoms and 2 or less heteroatoms. In this case, it is also effective in suppressing the swelling of the resist film.

[0946] When an ester solvent is used in combination with a hydrocarbon solvent, isoamyl acetate is preferably used as the ester solvent. And, from the viewpoint of adjusting the solubility of the resist film, a saturated hydrocarbon solvent (for example, octane, nonane, decane, dodecane, undecane, hexadecane, etc.) is preferably used as the hydrocarbon solvent.

[0947] As the ketone solvent, for example, 1-octanone, 2-octanone, 1-nonanone, 2-nonanone, acetone, 2-heptanone (methyl pentyl ketone), 4-heptanone, 1-hexanone, 2-hexanone, diisobutyl ketone, 2,5-dimethyl-4-hexanone, cyclohexanone, methylcyclohexanone, phenylacetone, methyl ethyl ketone, methyl isobutyl ketone, acetylacetone, acetonylacetone, ionone, diacetonyl alcohol, acetylmethanol, acetophenone, methyl naphthyl ketone, isophorone, propylene carbonate, etc. can be cited, and diisobutyl ketone and 2,5-dimethyl-4-hexanone are particularly preferably used.

[0948] As the ester solvent, for example, methyl acetate, butyl acetate, ethyl acetate, isopropyl acetate, pentyl acetate, isoamyl acetate, propylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, diethylene glycol monoethyl ether acetate, ethyl 3-ethoxypropionate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, methyl formate, ethyl formate, butyl formate, propyl formate, ethyl lactate, butyl lactate, propyl lactate, butyl butyrate, methyl 2-hydroxyisobutyrate, etc. can be cited.

[0949] As alcohol solvents, for example, alcohols such as methanol, ethanol, n-propanol, isopropanol, n-butanol, sec-butanol, 4-methyl-2-pentanol, tert-butanol, isobutanol, n-hexanol, n-heptanol, n-octanol, n-decanol, etc.; glycol solvents such as ethylene glycol, diethylene glycol, triethylene glycol, etc.; glycol ether solvents such as ethylene glycol monomethyl ether, propylene glycol monomethyl ether, ethylene glycol monoethyl ether, propylene glycol monoethyl ether, diethylene glycol monomethyl ether, triethylene glycol monoethyl ether, methoxymethyl butanol, etc.

[0950] As ether solvents, for example, in addition to the above glycol ether solvents, anisole, dioxane, tetrahydrofuran, etc. can also be cited.

[0951] As amide solvents, for example, N-methyl-2-pyrrolidone, N,N-dimethylacetamide, N,N-dimethylformamide, hexamethylphosphoric triamide, 1,3-dimethyl-2-imidazolidinone, etc. can be used.

[0952] As hydrocarbon solvents, for example, aromatic hydrocarbon solvents such as toluene, xylene, etc.; aliphatic hydrocarbon solvents such as pentane, hexane, octane, decane, undecane, etc.

[0953] In addition, among the aliphatic hydrocarbon solvents as hydrocarbon solvents, it can also be a mixture of compounds with the same number of carbon atoms and different structures. For example, when using decane as the aliphatic hydrocarbon solvent, the aliphatic hydrocarbon solvent can also contain compounds with the same number of carbon atoms and different structures, namely 2-methylnonane, 2,2-dimethyloctane, 4-ethyloctane, isooctane, etc.

[0954] And, the above compounds with the same number of carbon atoms and different structures can contain only one kind, or can contain multiple kinds as described above.

[0955] A variety of the above solvents can be mixed, or can be mixed and used with solvents other than the above or water. However, in order to fully exert the effects of the present invention, the water content of the developing solution as a whole is preferably less than 10% by mass, and more preferably substantially free of water.

[0956] The concentration of the organic solvent (when mixing multiple kinds, it is the total) in the organic developing solution is preferably 50% by mass or more, more preferably 50 - 100% by mass, further preferably 85 - 100% by mass, still further preferably 90 - 100% by mass, and particularly preferably 95 - 100% by mass. The case where it is substantially composed only of organic solvents is most preferred. In addition, the case where it is substantially composed only of organic solvents means including the case of containing trace amounts of surfactants, antioxidants, stabilizers, defoamers, etc.

[0957] In particular, the organic developing solution is preferably a developing solution containing at least one organic solvent selected from the group consisting of ketone solvents, ester solvents, alcohol solvents, amide solvents, and ether solvents.

[0958] The vapor pressure of the organic developer is preferably 5 kPa or less, more preferably 3 kPa or less, and particularly preferably 2 kPa or less at 20°C. By setting the vapor pressure of the organic developer to 5 kPa or less, the evaporation of the developer on the substrate or in the developing cup is suppressed, the temperature uniformity within the wafer plane is improved, and as a result, the size uniformity within the wafer plane is improved.

[0959] Specific examples of solvents having a vapor pressure of 5 kPa or less include ketone solvents such as 1-octanone, 2-octanone, 1-nonanone, 2-nonanone, 2-heptanone (methyl pentyl ketone), 4-heptanone, 2-hexanone, diisobutyl ketone, cyclohexanone, methylcyclohexanone, phenylacetone, and methyl isobutyl ketone; ester solvents such as butyl acetate, amyl acetate, isoamyl acetate, pentyl acetate, propylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, diethylene glycol monoethyl ether acetate, ethyl 3-ethoxypropionate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, butyl formate, propyl formate, ethyl lactate, butyl lactate, and propyl lactate; alcohol solvents such as n-propanol, isopropanol, n-butanol, sec-butanol, tert-butanol, isobutanol, n-hexanol, n-heptanol, n-octanol, and n-decanol; glycol solvents such as ethylene glycol, diethylene glycol, and triethylene glycol; glycol ether solvents such as ethylene glycol monomethyl ether, propylene glycol monomethyl ether, ethylene glycol monoethyl ether, propylene glycol monoethyl ether, diethylene glycol monomethyl ether, triethylene glycol monoethyl ether, and methoxymethyl butanol; ether solvents such as tetrahydrofuran; amide solvents such as N-methyl-2-pyrrolidone, N,N-dimethylacetamide, and N,N-dimethylformamide; aromatic hydrocarbon solvents such as toluene and xylene; and aliphatic hydrocarbon solvents such as octane and decane.

[0960] Specific examples of solvents having a vapor pressure of 2 kPa or less, which is a particularly preferred range, include ketone solvents such as 1-octanone, 2-octanone, 1-nonanone, 2-nonanone, 2-heptanone, 4-heptanone, 2-hexanone, diisobutyl ketone, cyclohexanone, methylcyclohexanone, and propiophenone; ester solvents such as butyl acetate, amyl acetate, propylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, diethylene glycol monoethyl ether acetate, ethyl 3-ethoxypropionate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, ethyl lactate, butyl lactate, and propyl lactate; alcohol solvents such as n-butanol, sec-butanol, tert-butanol, isobutanol, n-hexanol, n-heptanol, n-octanol, and n-decanol; glycol solvents such as ethylene glycol, diethylene glycol, and triethylene glycol; glycol ether solvents such as ethylene glycol monomethyl ether, propylene glycol monomethyl ether, ethylene glycol monoethyl ether, propylene glycol monoethyl ether, diethylene glycol monomethyl ether, triethylene glycol monoethyl ether, and methoxymethylbutanol; amide solvents such as N-methyl-2-pyrrolidone, N,N-dimethylacetamide, and N,N-dimethylformamide; aromatic hydrocarbon solvents such as xylene; and aliphatic hydrocarbon solvents such as octane, decane, and undecane.

[0961] The organic developing solution may also contain a basic compound. Specific examples and preferred examples of the basic compound that the developing solution used in the present invention may contain are the same as those of the basic compound that the photosensitive radiation-sensitive or radiation-sensitive composition may contain.

[0962] An appropriate amount of a surfactant may be added to the organic developing solution as needed.

[0963] There is no particular limitation on the surfactant. For example, ionic or non-ionic fluorine-based and / or silicon-based surfactants may be used. Examples of these fluorine and / or silicon-based surfactants include those described in Japanese Patent Application Laid-Open No. 62-36663, Japanese Patent Application Laid-Open No. 61-226746, Japanese Patent Application Laid-Open No. 61-226745, Japanese Patent Application Laid-Open No. 62-170950, Japanese Patent Application Laid-Open No. 63-34540, Japanese Patent Application Laid-Open No. 7-230165, Japanese Patent Application Laid-Open No. 8-62834, Japanese Patent Application Laid-Open No. 9-54432, Japanese Patent Application Laid-Open No. 9-5988, U.S. Patent No. 5405720, U.S. Patent No. 5360692, U.S. Patent No. 5529881, U.S. Patent No. 5296330, U.S. Patent No. 5436098, U.S. Patent No. 5576143, U.S. Patent No. 5294511, and U.S. Patent No. 5824451. A non-ionic surfactant is preferably used. There is no particular limitation on the non-ionic surfactant, and a fluorine-based surfactant or a silicon-based surfactant is more preferably used.

[0964] The amount of the surfactant used is preferably 0.0001 to 2% by mass, more preferably 0.0001 to 1% by mass, and particularly preferably 0.0001 to 0.1% by mass, relative to the total amount of the developer.

[0965] As a developing method, for example, a method of immersing a substrate in a tank filled with a developer for a certain period of time (dip method), a method of causing the developer to bulge on the surface of the substrate by surface tension and allowing it to stand for a certain period of time for development (puddle method), a method of spraying the developer onto the surface of the substrate (spray method), a method of continuously spraying the developer while scanning a nozzle for spraying the developer at a certain speed on a substrate rotating at a certain speed (dynamic dispense method), etc. can be applied.

[0966] When the above various developing methods include a step of spraying the developer from a developing nozzle of a developing apparatus onto the resist film, the ejection pressure (the flow rate per unit area of the ejected developer) of the ejected developer is preferably 2 mL / sec / mm 2 More preferably, it is 1.5 mL / sec / mm or less below. 2 Further preferably, it is 1 mL / sec / mm or less below. 2 Although there is no particular lower limit for the flow rate, considering the throughput, it is preferably 0.2 mL / sec / mm or more. 2 Above.

[0967] By setting the ejection pressure of the ejected developer within the above range, pattern defects from the resist residues after development can be significantly reduced.

[0968] The details of this mechanism are not yet certain, but it may be because by setting the ejection pressure within the above range, the pressure of the developer on the resist film becomes smaller, suppressing accidental scratching or damage of the resist film / pattern.

[0969] In addition, the ejection pressure (mL / sec / mm 2 ) of the developer is the value at the outlet of the developing nozzle in the developing apparatus.

[0970] As a method of adjusting the ejection pressure of the developer, for example, a method of adjusting the ejection pressure with a pump or the like, a method of changing the pressure by supplying from a pressurized tank for adjustment, etc. can be cited.

[0971] Moreover, after the step of developing using a developer containing an organic solvent, a step of stopping the development while replacing it with another solvent can also be implemented.

[0972] After the step of developing using a developer containing an organic solvent, a step of cleaning using a rinsing liquid may be included, but from the viewpoints of throughput (productivity), amount of rinsing liquid used, etc., a step of cleaning using a rinsing liquid may not be included.

[0973] As the rinsing liquid used in the rinsing step after the step of developing using a developer containing an organic solvent, there is no particular limitation as long as it does not dissolve the resist pattern, and a usual solution containing an organic solvent can be used. As the above-mentioned rinsing liquid, a rinsing liquid containing at least one organic solvent selected from the group consisting of hydrocarbon solvents, ketone solvents, ester solvents, alcohol solvents, amide solvents, and ether solvents is preferably used.

[0974] As specific examples of the hydrocarbon solvent, ketone solvent, ester solvent, alcohol solvent, amide solvent, and ether solvent, the same solvents as those described in the developer containing an organic solvent can be cited. In particular, butyl acetate and methyl isobutyl carbinol can be preferably selected.

[0975] After the step of developing using a developer containing an organic solvent, a step of cleaning using a rinsing liquid containing at least one organic solvent selected from the group consisting of ester solvents, alcohol solvents, and hydrocarbon solvents is more preferably performed, and a step of cleaning using a rinsing liquid containing an alcohol solvent or a hydrocarbon solvent is further preferably performed.

[0976] As the organic solvent contained in the rinsing liquid, a hydrocarbon solvent is also preferably used in the organic solvent, and an aliphatic hydrocarbon solvent is more preferably used. As the aliphatic hydrocarbon solvent used in the rinsing liquid, from the viewpoint of further improving its effect, an aliphatic hydrocarbon solvent having 5 or more carbon atoms (for example, pentane, hexane, octane, decane, undecane, dodecane, hexadecane, etc.) is preferably used, an aliphatic hydrocarbon solvent having 8 or more carbon atoms is more preferably used, and an aliphatic hydrocarbon solvent having 10 or more carbon atoms is further preferably used.

[0977] In addition, there is no particular limitation on the upper limit value of the number of carbon atoms of the above-mentioned aliphatic hydrocarbon solvent. For example, it can be 16 or less, preferably 14 or less, and more preferably 12 or less.

[0978] Among the above-mentioned aliphatic hydrocarbon solvents, decane, undecane, and dodecane are particularly preferred, and undecane is most preferred.

[0979] Thus, by using a hydrocarbon solvent (especially an aliphatic hydrocarbon solvent) as the organic solvent contained in the rinsing liquid, the developer slightly infiltrated into the resist film after development is rinsed, and the effects of suppressing swelling and suppressing pattern collapse are further exerted.

[0980] The above-mentioned components can be mixed in multiple types, or can be used in combination with organic solvents other than the above.

[0981] The water content in the rinse liquid is preferably 10% by mass or less, more preferably 5% by mass or less, and particularly preferably 3% by mass or less. By setting the water content to 10% by mass or less, good development characteristics can be obtained.

[0982] The vapor pressure of the rinse liquid used after the development step using a developer containing an organic solvent is preferably 0.05 kPa or more and 5 kPa or less, more preferably 0.1 kPa or more and 5 kPa or less, and most preferably 0.12 kPa or more and 3 kPa or less at 20°C. By setting the vapor pressure of the rinse liquid to 0.05 kPa or more and 5 kPa or less, the temperature uniformity within the wafer surface can be improved, and swelling caused by the penetration of the rinse liquid can be suppressed, improving the dimensional uniformity within the wafer surface.

[0983] An appropriate amount of surfactant may also be added to the rinse liquid for use.

[0984] In the rinse step, the wafer developed using a developer containing the above-mentioned organic solvent is cleaned using a rinse liquid containing the organic solvent. The cleaning method is not particularly limited. For example, a method of continuously spraying the rinse liquid onto a substrate rotating at a certain speed (spin coating method), a method of immersing the substrate in a tank filled with the rinse liquid for a certain time (immersion method), a method of spraying the rinse liquid onto the substrate surface (spray coating method), etc. can be applied. Among them, it is preferably cleaned by the spin coating method, and after cleaning, the substrate is rotated at a speed of 2000 rpm to 4000 rpm to remove the rinse liquid from the substrate. Furthermore, it is also preferably followed by a heating step (Post Bake) after the rinse step. The developer and the rinse liquid remaining between and inside the patterns are removed by baking. The heating step after the rinse step is usually carried out at 40 to 160°C, preferably at 70 to 95°C, and usually for 10 seconds to 3 minutes, preferably for 30 seconds to 90 seconds.

[0985] When there is no step of cleaning using a rinse liquid, for example, the development method described in paragraphs

[0014] to

[0086] of JP-A-2015-216403 can be adopted.

[0986] Moreover, the pattern forming method of the present invention may also have a development step using an organic developer and a development step using an alkaline developer. By developing with the organic developer, the portion with weak exposure intensity is removed, and by developing with the alkaline developer, the portion with strong exposure intensity is also removed. Thus, through the multiple development process of performing multiple developments, a pattern is formed by dissolving only the region with intermediate exposure intensity, and therefore, a finer pattern than usual can be formed (the same mechanism as in paragraph

[0077] of JP-A-2008-292975).

[0987] The photosensitive radiation-sensitive or radiation-sensitive composition of the present invention and various materials used in the pattern forming method of the present invention (for example, resist solvents, developers, rinsing liquids, compositions for forming anti-reflection films, compositions for forming top coatings, etc.) preferably do not contain impurities such as metals, halogen-containing metal salts, acids, bases, components containing sulfur atoms or phosphorus atoms. Here, as impurities containing metal atoms, Na, K, Ca, Fe, Cu, Mn, Mg, Al, Cr, Ni, Zn, Ag, Sn, Pb, Li, or their salts, etc. can be cited.

[0988] As the content of impurities contained in these materials, it is preferably 1 ppm or less, more preferably 1 ppb or less, further preferably 100 ppt (parts per trillion) or less, particularly preferably 10 ppt or less, and most preferably substantially free of (below the detection limit of the measuring device).

[0989] As a method for removing impurities such as metals from various materials, for example, filtration using a filter can be cited. As the filter pore size, the pore size dimension is preferably 10 nm or less, more preferably 5 nm or less, and further preferably 3 nm or less. As the material of the filter, a filter made of polytetrafluoroethylene, polyethylene, or nylon is preferred. The filter can be a composite material combining these materials with an ion exchange medium. A filter that has been pre-cleaned with an organic solvent can be used. In the filter filtration 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 combined and used. Also, various materials can be filtered multiple times, and the process of performing multiple filtrations can be a circulating filtration process.

[0990] Also, as a method for reducing impurities such as metals contained in various materials, a method of selecting raw materials with a low metal content as raw materials constituting various materials can be cited; a method of performing filter filtration on the raw materials constituting various materials; a method of performing distillation under conditions of suppressing contamination as much as possible by lining the inside of the device with Teflon (registered trademark), etc. The preferred conditions for the filter filtration of the raw materials constituting various materials are the same as the above conditions.

[0991] In addition to filter filtration, impurities can also be removed using an adsorbent material, and filter filtration and an adsorbent material can be combined and used. As the adsorbent material, known adsorbent materials can be used. For example, inorganic adsorbent materials such as silica gel and zeolite; organic adsorbent materials such as activated carbon can be used.

[0992] In addition, as methods for reducing impurities such as metals contained in the organic treatment liquid of the present invention, there can be cited 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; a method of performing distillation under conditions that minimize contamination by lining the inside of the device with Teflon (registered trademark), etc. The preferred conditions for filtering the raw materials constituting various materials are the same as the above conditions.

[0993] In addition to filtering, impurities can also be removed by using adsorbents, or by using a combination of filtering and adsorbents. As adsorbents, known adsorbents can be used, for example, inorganic adsorbents such as silica gel and zeolite; and organic adsorbents such as activated carbon.

[0994] [Storage container]

[0995] As an organic solvent (also referred to as "organic treatment liquid") that can be used in a developer and a rinse liquid, it is preferred to use a solvent that has a storage portion and is stored in a storage container for an organic treatment liquid for pattern formation of a chemically amplified or non-chemically amplified resist film. As the storage container, it is preferred to use a storage container for an organic treatment liquid for pattern formation of a resist film, wherein the inner wall of the storage portion in contact with the organic treatment liquid is formed of a resin different from polyethylene resin, polypropylene resin, and polyethylene-polypropylene resin, or a metal subjected to rust prevention / metal dissolution prevention treatment. In the above-mentioned storage portion of the storage container, a predetermined organic solvent used as an organic treatment liquid for pattern formation of a resist film can be stored, and when the pattern of the resist film is formed, the organic solvent discharged from the above-mentioned storage portion is used.

[0996] When the storage container further comprises a sealing portion for sealing the storage portion, the sealing portion is preferably formed of a resin different from the following resins or a metal subjected to rustproofing / metal dissolution prevention treatment, wherein the resins are selected from one or more of the group consisting of polyethylene resins, polypropylene resins, and polyethylene-polypropylene resins.

[0997] Here, the sealing portion refers to a member that can block the housing portion from the outside air, and preferably includes a seal, an O-ring, and the like.

[0998] The resin different from one or more resins selected from the group consisting of polyethylene resins, polypropylene resins, and polyethylene-polypropylene resins is preferably a perfluororesin.

[0999] Examples of perfluororesins include tetrafluoroethylene resin (PTFE), tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer (PFA), tetrafluoroethylene-hexafluoropropylene copolymer resin (FEP), tetrafluoroethylene-ethylene copolymer resin (ETFE), chlorotrifluoroethylene-ethylene copolymer resin (ECTFE), polyvinylidene fluoride resin (PVDF), chlorotrifluoroethylene copolymer resin (PCTFE), polyvinyl fluoride resin (PVF), etc.

[1000] Examples of particularly preferred perfluororesins include tetrafluoroethylene resin, tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer, and tetrafluoroethylene-hexafluoropropylene copolymer resin.

[1001] Examples of metals in metals that have undergone rust prevention / metal dissolution prevention treatment include carbon steel, alloy steel, nickel-chromium steel, nickel-chromium-molybdenum steel, chromium steel, chromium-molybdenum steel, manganese steel, etc.

[1002] As the rust prevention / metal dissolution prevention treatment, it is preferable to apply a film coating technology.

[1003] The film coating technology is roughly divided into three types: metal coating (various electroplating), inorganic coating (various chemical conversion treatments, glass, concrete, ceramics, etc.), and organic coating (rust preventive oil, paint, rubber, plastic).

[1004] Examples of preferred film coating technologies include surface treatments with rust preventive oil, rust inhibitor, corrosion inhibitor, chelate, removable plastic, and lining agent.

[1005] Among them, various chromates, nitrites, silicates, phosphates, oleic acid, dimer acid, naphthenic acid and other carboxylic acids; carboxylic acid metal soaps, sulfonates, amine salts, esters (higher fatty acid glycerol esters or phosphate esters) and other corrosion inhibitors; ethylenediaminetetraacetic acid, gluconic acid, nitrilotriacetic acid, hydroxyethyl ethylenediamine triacetic acid, diethylenetriamine pentaacetic acid and other chelates and fluororesin lining are preferred. Particularly preferred are phosphate treatment and fluororesin lining.

[1006] Moreover, compared with direct coating treatment, it does not directly prevent rust, but as a treatment method for extending the rust prevention period through coating treatment, "pretreatment" in the stage before rust prevention treatment is also preferred.

[1007] As a specific example of such pretreatment, a treatment for removing various corrosion factors such as chlorides and sulfates present on the metal surface by cleaning and polishing can be preferably cited.

[1008] Examples of the containment vessel are as follows.

[1009] · FluoroPure PFA composite drum (liquid contact inner surface; PFA resin lining) manufactured by Entegris

[1010] · Steel drums and cans manufactured by JFE Corporation (liquid contact inner surface; zinc phosphate coating)

[1011] In addition, as the storage containers that can be used in the present invention, the containers described in Japanese Patent Laid-Open No. 11-021393

[0013] to

[0030] and Japanese Patent Laid-Open No. 10-45961

[0012] to

[0024] can also be cited.

[1012] In order to prevent failures of the chemical liquid piping and various components (filters, O-rings, hoses, etc.) caused by charging accompanied by static electricity and subsequent electrostatic discharge, a conductive compound can be added to the organic treatment liquid of the present invention. There is no particular limitation on the conductive compound. For example, methanol can be cited. The addition amount is not particularly limited. From the viewpoint of maintaining preferable development characteristics, it is preferably 10% by mass or less, and more preferably 5% by mass or less. Regarding the components of the chemical liquid piping, SUS (stainless steel) or various pipes coated with polyethylene, polypropylene, or fluororesin (polytetrafluoroethylene or perfluoroalkoxy resin, etc.) subjected to antistatic treatment can be used. Similarly, regarding the filters and O-rings, polyethylene, polypropylene, or fluororesin (polytetrafluoroethylene, perfluoroalkoxy resin, etc.) subjected to antistatic treatment can be used.

[1013] In addition, generally, after use, the developer and the rinse liquid are stored in a waste liquid tank through piping. At this time, if a hydrocarbon-based solvent is used as the rinse liquid, in order to prevent the resist dissolved in the developer from precipitating and adhering to the back surface of the wafer or the side surface of the piping, etc., there is a method of passing the solvent in which the resist is dissolved through the piping again. As the method of passing through the piping, a method of cleaning the back surface and side surface of the substrate with the solvent in which the resist is dissolved and flowing it through after cleaning with the rinse liquid, and a method of flowing the solvent in which the resist is dissolved through the piping without contacting the resist can be cited.

[1014] As the solvent passing through the piping, as long as it can dissolve the resist, there is no particular limitation. For example, the above-mentioned organic solvents can be used, and propylene glycol monomethyl ether acetate (PGMEA), propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, propylene glycol monobutyl ether acetate, propylene glycol monomethyl ether propionate, propylene glycol monoethyl ether propionate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether (PGME), propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, 2-heptanone, ethyl lactate, 1-propanol, acetone, etc. can be used. Among them, PGMEA, PGME, and cyclohexanone are preferably used.

[1015] [Method for manufacturing electronic device]

[1016] Further, the present invention also relates to a method for manufacturing an electronic device including the above-described pattern forming method. The electronic device manufactured by the method for manufacturing an electronic device of the present invention is preferably mounted on electrical and electronic equipment (for example, home appliances, OA (Office Automation) related equipment, media related equipment, optical equipment, communication equipment, etc.).

[1017] Examples

[1018] Hereinafter, the present invention will be further described in detail based on examples. As long as the gist of the present invention is not deviated from, materials, amounts used, ratios, processing contents, processing steps, etc. shown in the following examples can be appropriately changed. Therefore, the scope of the present invention should not be construed as being limited by the examples shown below.

[1019] <Resin (A)>

[1020] [Synthesis Example 1: Synthesis of Resin (A-3)]

[1021] (Synthesis of Chlorinated Ether Compound)

[1022] 25.0 g of 1-adamantanecarbaldehyde, 24.2 g of trimethyl orthoformate, 353 mg of camphorsulfonic acid, and 125 mL of hexane were added to a 500 mL eggplant-shaped flask, and the mixture was stirred at 25 °C for 1 hour. 1.5 g of triethylamine was added and stirred, and the organic phase was washed 3 times with 200 mL of distilled water. By removing hexane under reduced pressure, 33.0 g of the following compound 1 was obtained as an acetal compound.

[1023] Next, 28.6 g of acetyl chloride (AcCl) was added to 31.8 g of the obtained compound 1, and the mixture was stirred in a 40 °C water bath for 5 hours. After returning to 25 °C, unreacted acetyl chloride was removed under reduced pressure, and 36.2 g of the following compound 2 was obtained as a chlorinated ether compound.

[1024] [Chemical Formula 90]

[1025]

[1026] (Synthesis of Resin (A-3))

[1027] 18.0 g of poly(p-hydroxystyrene) (VP-2500, manufactured by Nippon Soda Co., Ltd.) was dissolved in 120 g of tetrahydrofuran (THF), 3.46 g of triethylamine was added, and the mixture was stirred in an ice-water bath. The compound 2 (6.12 g) obtained above was added dropwise to the reaction solution and stirred for 4 hours. A small amount of the reaction solution was collected and measured 1 1H-NMR, and the protection rate was 18.2%. Then, a small amount of compound 2 was added and stirred for 4 hours, and the measurement was repeated 1For the operation of \(^1H\)-NMR, distilled water was added to stop the reaction at the moment when the protection rate exceeded the target value of 20.0%. THF was distilled under reduced pressure, and the reactants were dissolved in ethyl acetate. The obtained organic phase was washed 5 times with distilled water, and then the organic phase was dropped into 1.5 L of hexane. The obtained precipitate was filtered and washed with a small amount of hexane. 10 g of the obtained powder was dissolved in 20 g of propylene glycol monomethyl ether acetate (PGMEA), and 300 g of ethyl acetate was added. The solution was transferred to a separatory funnel and washed with 300 g of acidic aqueous solution. After repeating this washing operation 3 times, it was washed 4 times with 300 g of distilled water. At this time, as the acidic aqueous solution, 0.1 mol / L hydrochloric acid aqueous solution or 0.5 mol / L oxalic acid aqueous solution was used. After distilling the solvent under reduced pressure, it was dissolved in 30 g of PGMEA. The low-boiling solvent was removed from the obtained solution using an evaporator, thereby obtaining a PGMEA solution (30.1 mass%) of 26.3 g of resin (A-3).

[1028] Regarding the obtained resin (A-3), 13 \(^{13}C\)-NMR (nuclear magnetic resonance) or 1 \(^1H\)-NMR was used to determine the content of the repeating unit. Also, the weight-average molecular weight (Mw) and dispersity (Mw / Mn) (in terms of polystyrene equivalent) of the resin were determined by GPC (eluent: tetrahydrofuran (THF)).

[1029] For the other resin (A) used, the same operations as those for resin (A-3) were also carried out for synthesis.

[1030] The structure and its content (molar ratio), weight-average molecular weight (Mw), and dispersity (Mw / Mn) of the repeating unit of the resin (A) used are shown below. In addition, the content (molar ratio) of the repeating unit is described on the right or left side of ().

[1031] [Chemical formula 91]

[1032]

[1033] [Chemical formula 92]

[1034]

[1035] [Chemical formula 93]

[1036]

[1037] [Chemical formula 94]

[1038]

[1039] [Chemical formula 95]

[1040]

[1041] [Chemical formula 96]

[1042]

[1043] [Chemical formula 97]

[1044]

[1045] [Chemical formula 98]

[1046]

[1047] <Acid generator (B) (Compound (B))>

[1048] [Synthesis Example 2: Synthesis of Acid Generator (B-7)]

[1049] (1) (Synthesis of B-7-1)

[1050] 50.0 g of 2,6-dichlorobenzenesulfonyl chloride was dissolved in 296 g of chloroform. After cooling to 0 °C, 22.6 g of isobutanol and 27.4 g of pyridine were added, and the mixture was stirred at room temperature for 3 hours. 1N hydrochloric acid was added to the reaction mixture and liquid separation was performed. The organic layer was washed with 1N hydrochloric acid, saturated sodium bicarbonate solution, and saturated brine, and then anhydrous magnesium sulfate was added and dried. After filtration, the solvent in the filtrate was distilled off under reduced pressure, and after vacuum drying, 51.4 g of Compound (B-7-1) was obtained.

[1051] (2) (Synthesis of B-7-2)

[1052] 10.00 g of Compound (B-7-1), 23.5 g of 4-(tetrahydro-2H-pyran-2-yloxy)phenylboronic acid, 30.0 g of tripotassium phosphate, 1.45 mg of Sphos (2-dicyclohexylphosphino-2’,6’-dimethoxybiphenyl), and 176 g of tetrahydrofuran were added and degassed. Then, 396 mg of palladium acetate was added, and the mixture was stirred at 80 °C for 4 hours. Ethyl acetate was added to the reaction mixture and liquid separation was performed. The organic layer was washed with saturated brine, and then anhydrous magnesium sulfate was added and dried. After filtration, the filtrate was passed through silica gel and washed with ethyl acetate. After distilling off the solvent under reduced pressure, the crude product was purified by silica gel chromatography to obtain 12.3 g of Compound (B-7-2).

[1053] (3) (Synthesis of B-7-3)

[1054] 6.00 g of Compound (B-7-2), 200 g of acetonitrile, and 4.76 g of sodium iodide were added, and the mixture was stirred at 80 °C for 10 hours. The solid was filtered and washed with acetonitrile. After vacuum drying, 4.84 g of Compound (B-7-3) was obtained.

[1055] (4) (Synthesis of (B-7))

[1056] 3.00 g of compound (B-7-3), 1.93 g of triphenylsulfonium bromide, 30 g of dichloromethane, and 30 g of pure water were added, and the mixture was stirred at room temperature for 3 hours. After washing the organic phase with pure water, the solvent was distilled off under reduced pressure and azeotroped with isopropyl ether. After vacuum drying, compound (B-7) (3.10 g) was obtained.

[1057] In addition, for compound (B-7), 1 1H-NMR spectrum (400 MHz, DMSO-d6) was δ = 7.99 - 7.72 (m, 15H), 7.44 - 7.36 (d, 4H), 7.30 - 7.22 (m, 1H), 7.07 - 7.00 (d, 2H), 6.95 - 6.85 (d, 4H), 5.49 - 5.40 (m, 2H), 3.93 - 3.74 (m, 2H), 3.68 - 3.51 (m, 2H), 1.97 - 1.46 (m, 12H).

[1058] Hereinafter, compounds (B-1) to (B-6), (B-8) to (B-32) were synthesized in the same manner.

[1059] Compounds (B-1) to (B-32) are composed of the cations described in Table 1 and the anions described in Table 1.

[1060]

[1061] The structures of the cations described in Table 1 are shown below. Me represents methyl and Bu represents n-butyl.

[1062] [Chemical formula 99]

[1063]

[1064] The structures of the anions described in Table 1 are shown below. Me represents methyl and Bu represents n-butyl.

[1065] [Chemical formula 100]

[1066]

[1067] <Acid generator (C) (Compound (C))>

[1068] [Synthesis Example 3: Synthesis of Compound (C-3)]

[1069] In the synthesis of the above compound (B-7-2), 4-hydroxyphenylboronic acid was used instead of 4-(tetrahydro-2H-pyran-2-yloxy)phenylboronic acid, and the synthesis was carried out in the same manner otherwise.

[1070] Hereinafter, compounds (C-1) to (C-2), (C-4) to (C-32) were synthesized using the same method.

[1071] Compounds (C-1) to (C-32) are composed of the cations described in Table 2 and the anions described in Table 2.

[1072]

[1073] The structures of the cations described in Table 2 are shown below. Me represents methyl and Bu represents n-butyl.

[1074] [Chemical formula 101]

[1075]

[1076] The structures of the anions described in Table 2 are shown below. Me represents methyl and Bu represents n-butyl.

[1077] [Chemical formula 102]

[1078]

[1079] <Acid diffusion control agent>

[1080] The structures of the acid diffusion control agents used are shown below.

[1081] [Chemical formula 103]

[1082]

[1083] [Chemical formula 104]

[1084]

[1085] <Resin (E)>

[1086] Regarding the resin (E) used, the structure of the repeating unit, its content (molar ratio), weight average molecular weight (Mw), and dispersity (Mw / Mn) are shown.

[1087] In addition, the weight average molecular weight (Mw) and dispersity (Mw / Mn) of the resin were measured in the same manner as for resin (A).

[1088] [Chemical formula 105]

[1089]

[1090] <Surfactant>

[1091] As the surfactant, the following W-1 to W-4 were used.

[1092] W-1: Megafac R08 (manufactured by DIC CORPORATION, fluorine-based and silicon-based)

[1093] W-2: Polysiloxane polymer KP-341 (manufactured by Shin-Etsu Chemical Co., Ltd., silicon-based)

[1094] W-3: TroySol S-366 (manufactured by Troy Chemical Industries Inc., fluorine-based)

[1095] W-4: PF6320 (manufactured by OMNOVA Solutions Inc., fluorine-based)

[1096] <Solvent>

[1097] The solvents used are shown below.

[1098] S-1: Propylene glycol monomethyl ether acetate (PGMEA)

[1099] S-2: Propylene glycol monomethyl ether (PGME)

[1100] S-3: Ethyl lactate (EL)

[1101] S-4: Ethyl 3-ethoxypropionate (EEP)

[1102] S-5: 2-Heptanone (MAK)

[1103] S-6: Methyl 3-methoxypropionate (MMP)

[1104] S-7: 3-Methoxybutyl acetate

[1105] [Preparation and Coating of Resist Composition Coating Liquid]

[1106] (1) Prepare a support

[1107] An 8-inch wafer with Cr oxynitride evaporated (a substance subjected to the shielding film treatment used in a normal photomask blank) was prepared.

[1108] (2) Preparation of resist composition

[1109] The components shown in Tables 3 to 5 were dissolved in the solvents shown in Tables 3 to 5 to prepare a solution, which was filtered through a polyethylene filter with a pore size of 0.03 μm to prepare a resist composition.

[1110] In addition, in Tables 3 to 5, the contents (mass %) of the resin (A), the acid diffusion control agent, the resin (E), and the surfactant refer to the content ratios relative to the total solid components of the resist composition. When a surfactant is used, its content is 0.01 mass % relative to the total solid components in all cases.

[1111] The total content (mass %) of the compound (B) and the compound (C) relative to the total solid components of the resist composition is described in the column of "(B)+(C) content (mass %)" of the acid generator (B) (compound (B)).

[1112] The ratio of the content of the compound (C) to the content of the compound (B) is described in the column of "content (mass % relative to B)" of the compound (C).

[1113] Moreover, the types of the solvents used and the content ratios (mass %) of the respective solvents relative to all the solvents are described in Tables 3 to 5.

[1114] The solid component concentration (solid component content) of the resist composition is also described in Tables 3 to 5.

[1115] In the resist composition R-53, the mass ratio of (B-1) to (B-4), {(B-1) / (B-4)}, is set to 1 / 1.

[1116] In the resist composition R-53, the mass ratio of (C-1) to (C-4), {(C-1) / (C-4)}, is set to 1 / 1.

[1117] In the resist composition R-54, the mass ratio of (B-10) to (B-12), {(B-10) / (B-12)}, is set to 2 / 3.

[1118] In the resist composition R-54, the mass ratio of (C-10) to (C-12), {(C-10) / (C-12)}, is set to 2 / 3.

[1119]

[1120]

[1121]

[1122] (3) Fabrication of the resist film

[1123] The resist composition was coated on the above-mentioned 8-inch wafer using a spin coater Mark8 manufactured by Tokyo Electron Limited, and dried on a hot plate at 120 °C for 600 seconds, thereby obtaining a resist film with a film thickness of 100 nm. That is, a wafer coated with the resist was obtained.

[1124] [EB Exposure and Development]

[1125] (4) Fabrication of Resist Pattern

[1126] The resist film obtained in the above (3) was pattern-irradiated using an electron beam lithography apparatus (manufactured by Advantest Corporation, F7000S, acceleration voltage 50 keV). After irradiation, it was heated on a hot plate at 100 °C for 600 seconds, immersed in a 2.38 mass% aqueous solution of tetramethylammonium hydroxide (TMAH) for 60 seconds, rinsed with water for 30 seconds, and then dried.

[1127] In addition, the exposure of the above electron beam irradiation apparatus (F7000S) is a single-beam method. However, it is estimated that the evaluation results will be the same even when multiple single beams are scanned simultaneously and exposure is performed in a multi-beam method.

[1128] [Etching]

[1129] An 8-inch wafer with a resist pattern formed thereon was dry-etched to form a hard mask pattern. In the dry etching, a fluorine-based gas (SF 6 ) was used as the etching gas, and the etching time was set to 20 seconds.

[1130] [Evaluation]

[1131] (5) Evaluation of Resist Pattern

[1132] The obtained pattern was evaluated for resolution and development defects by the following method. The results are shown in Tables 6 and 7 described later.

[1133] <Sensitivity>

[1134] The irradiation energy when analyzing a 1:1 line and space pattern with a resolution line width of 50 nm was defined as the sensitivity (Eop).

[1135] <L / S Resolution>

[1136] The ultimate resolution (the minimum line width at which a line and space (line:space = 1:1) can be separated and resolved) of the exposure dose representing the above sensitivity (Eop) was defined as the L / S resolution (nm).

[1137] <Line Width Roughness (LWR) Performance>

[1138] Regarding the line width roughness, at the above Eop, the line widths were measured at 50 arbitrary points in the length direction of 0.5 μm of a line and space pattern (line:space = 1:1) with a line width of 50 nm, and the standard deviation was calculated to obtain 3σ (nm). The smaller the value, the better the performance.

[1139] <Developing Defects>

[1140] For a 1:1 line and space pattern with a line width of 50 nm formed by the above sensitivity (Eop), using a defect inspection device KLA2360 (trade name) manufactured by KLA-Tenchore Corporation, the pixel size of the defect inspection device was set to 0.16 μm, and the threshold was set to 20. Defects (number / cm 2 ) were detected by extracting the differences caused by the overlap of the comparison image and pixel units, and then the number of defects per unit area (number / cm 2 ) was calculated. Then, through defect review, developing defects were classified and extracted from all defects, and the number of developing defects per unit area (number / cm 2 ) was calculated. Values less than 0.5 were set as A, those 0.5 or more and less than 1.0 were set as B, those 1.0 or more and less than 5.0 were set as C, and those 5.0 or more were set as D. The smaller the value, the better the performance.

[1141] <Etching Defects>

[1142] Regarding the formed hard mask pattern, the number of defects caused by pattern residue was counted. A mask blank defect inspection device (MAGICS series M2351) manufactured by Lasertec Corporation was used for counting the number of defects. Values less than 1 were set as A, those 1 or more and less than 10 were set as B, those 10 or more and less than 50 were set as C, and those 50 or more were set as D. The smaller the value, the better the performance.

[1143] [Table 6]

[1144]

[1145] [Table 7]

[1146]

[1147] From the results of Table 6 and Table 7, it can be seen that the resist composition of the examples has excellent resolution and LWR performance, and reduces developing defects and etching defects.

[1148] [Extreme Ultraviolet (EUV) Exposure]

[1149] (4) Fabrication of Resist Pattern

[1150] Using an EUV exposure apparatus (Micro Exposure Tool manufactured by Exitech Corporation, NA (numerical aperture) 0.3, Quadrupole, outer sigma 0.68, inner sigma 0.36), and an exposure mask (line / space = 1 / 1), pattern exposure was performed on the wafer coated with a resist film obtained in the above (3). After exposure, on a hot plate, it was heated at 100 °C for 90 seconds, then immersed in a 2.38 mass% aqueous solution of tetramethylammonium hydroxide (TMAH) for 60 seconds, and then rinsed with water for 30 seconds. Then, the wafer was rotated at 4000 rpm for 30 seconds, baked at 95 °C for 60 seconds, and dried.

[1151] [Etching]

[1152] Dry etching was performed on an 8-inch wafer on which a resist pattern was formed to form a hard mask pattern. In the dry etching, a fluorine-based gas (SF 6 ) was used as the etching gas, and the etching time was set to 20 seconds.

[1153] [Evaluation]

[1154] (5) Evaluation of the resist pattern

[1155] The obtained pattern was evaluated for resolution and development defects by the following method. The results are shown in Tables 8 and 9 described later.

[1156] <Sensitivity>

[1157] The exposure energy when analyzing a 1:1 line and space pattern with a resolved line width of 50 nm was defined as the sensitivity (Eop).

[1158] <L / S Resolution>

[1159] The ultimate resolution (the minimum line width at which lines and spaces (line:space = 1:1) are separated and resolved) of the exposure dose representing the above sensitivity (Eop) was defined as the resolution (nm).

[1160] <Line Width Roughness (LWR) Performance>

[1161] Regarding the line width roughness, at the above Eop, the line width was measured at 50 arbitrary points in the length direction of 0.5 μm of a line and space pattern (line:space = 1:1) with a line width of 50 nm, and its standard deviation was obtained, and 3σ (nm) was calculated. The smaller the value, the better the performance.

[1162] <Development Defects>

[1163] For a 1:1 line and space pattern with a line width of 50 nm formed from the above sensitivity (Eop), using a defect inspection device KLA2360 (trade name) manufactured by KLA-Tenchore, the pixel size of the defect inspection device was set to 0.16 μm, and the threshold was set to 20, and defects (number / cm 2 ) were detected by extracting from the differences caused by the overlap of the comparison image and pixel units, thereby calculating the number of defects per unit area (number / cm 2 ). Then, by performing defect review, development defects were classified and extracted from all the defects, thereby calculating the number of development defects per unit area (number / cm 2 ). Values less than 0.5 were set as A, those equal to or greater than 0.5 and less than 1.0 were set as B, those equal to or greater than 1.0 and less than 5.0 were set as C, and those equal to or greater than 5.0 were set as D. The smaller the value, the better the performance.

[1164] <Etching Defects>

[1165] Regarding the formed hard mask pattern, the number of defects caused by pattern residue was counted. The number of defects was counted using a mask blank defect inspection device (MAGICS series M2351) manufactured by Lasertec Corporation. Values less than 1 were set as A, those equal to or greater than 1 and less than 10 were set as B, those equal to or greater than 10 and less than 50 were set as C, and those equal to or greater than 50 were set as D. The smaller the value, the better the performance.

[1166] [Table 8]

[1167]

[1168] [Table 9]

[1169]

[1170] From the results of Table 8 and Table 9, it can be seen that the resist composition of the examples has excellent resolution and LWR performance, and reduces development defects and etching defects.

[1171] Industrial Applicability

[1172] According to the present invention, it is possible to provide a photosensitive radiation-curable or radiation-sensitive resin composition excellent in resolution and line width roughness (LWR) performance, and capable of reducing development defects and etching defects, a photosensitive radiation-curable or radiation-sensitive film using the above photosensitive radiation-curable or radiation-sensitive resin composition, a pattern forming method, and a method for manufacturing an electronic device.

[1173] Although the present invention has been described in detail with reference to specific embodiments, it will be apparent to those skilled in the art that various changes and modifications can be made without departing from the spirit and scope of the present invention.

[1174] This application claims priority based on a Japanese patent application filed on September 30, 2019 (Japanese Patent Application 2019-179944), and a Japanese patent application filed on May 29, 2020 (Japanese Patent Application 2020-094650), the contents of which are incorporated herein by reference.

Claims

1. A photosensitive actinic ray- or radiation-sensitive resin composition, comprising: (A) a resin having a group that decomposes by the action of an acid to increase polarity; (B) a compound represented by the following general formula (b1) that generates an acid upon irradiation with actinic rays or radiation; and (C) a compound represented by the following general formula (c1) that generates an acid upon irradiation with actinic rays or radiation, wherein the content ratio of the compound (C) to the content of the compound (B) is 0.01% by mass or more and 10% by mass or less. In general formula (b1), L represents a single bond or a divalent linking group. When there are multiple Ls, the multiple Ls may be the same or different. A represents a group that decomposes by the action of an acid. When there are multiple As, the multiple As may be the same or different. n represents an integer from 1 to 5. X represents an (n + 1)-valent linking group, and M + represents a sulfonium ion or an iodonium ion, In general formula (c1), L represents a single bond or a divalent linking group. When there are multiple Ls, the multiple Ls are the same or different. n represents an integer from 1 to 5. X represents an (n + 1)-valent linking group, and M + represents a sulfonium ion or an iodonium ion. Herein, L, n, X and M in general formula (c1) + are the same as L, n, X and M in general formula (b1), respectively, B represents a group that decomposes by the action of an acid, a hydroxyl group or a carboxyl group, when there is one B, it represents a hydroxyl group or a carboxyl group; when there are multiple Bs, the multiple Bs are the same or different, and at least one B represents a hydroxyl group or a carboxyl group. + ​ 2. The photosensitive actinic ray- or radiation-sensitive resin composition according to claim 1, wherein, the compound (B) is represented by the following general formula (b2), and the compound (C) is represented by the following general formula (c2). In general formula (b2), L represents a single bond or a divalent linking group, and when there are multiple Ls, the multiple Ls are the same or different; A represents a group that decomposes by the action of an acid, and when there are multiple As, the multiple As are the same or different; n represents an integer from 1 to 5; M + represents a sulfonium ion or an iodonium ion, In general formula (c2), L represents a single bond or a divalent linking group. When there are multiple Ls, the multiple Ls are the same or different. n represents an integer from 1 to 5, and M + represents a sulfonium ion or an iodonium ion. Among them, L, n, and M in general formula (c2) + are the same as L, n, and M in general formula (b2) respectively + respectively. B represents a group that decomposes by the action of an acid, a hydroxyl group, or a carboxyl group. When there is one B, it represents a hydroxyl group or a carboxyl group; when there are multiple Bs, the multiple Bs are the same or different. Among them, at least one B represents a hydroxyl group or a carboxyl group.

3. The photosensitive actinic ray- or radiation-sensitive resin composition according to claim 1, wherein, the compound (B) is represented by the following general formula (b3), and the compound (C) is represented by the following general formula (c3). In general formula (b3), L represents a single bond or a divalent linking group, and when there are a plurality of Ls, the plurality of Ls are the same or different; A represents a group that is decomposed by the action of an acid, and when there are a plurality of As, the plurality of As are the same or different; o, p and q each independently represent an integer of 0 to 5, where the sum of o, p and q is 1 or more and 5 or less; M + represents a sulfonium ion or an iodonium ion, In general formula (c3), L represents a single bond or a divalent linking group. When there are multiple Ls, the multiple Ls are the same or different. o, p, and q each independently represent an integer from 0 to 5, where the sum of o, p, and q is 1 or more and 5 or less. M + represents a sulfonium ion or an iodonium ion, where L, o, p, q, and M in general formula (c3) + are the same as L, o, p, q, and M in general formula (b3), respectively + B represents a group that decomposes by the action of an acid, a hydroxyl group, or a carboxyl group. When there is one B, it represents a hydroxyl group or a carboxyl group; when there are multiple Bs, the multiple Bs are the same or different, and at least one B represents a hydroxyl group or a carboxyl group.

4. The photosensitive actinic ray- or radiation-sensitive resin composition according to any one of claims 1 to 3, wherein, the group that decomposes by the action of an acid represented by A is at least one group selected from the group represented by the following general formula (T-1) and the group represented by the following general formula (T-2). In general formula (T-1), R 11 represents a hydrogen atom or an alkyl group, R 12 represents a hydrogen atom, an alkyl group, a cycloalkyl group or an aryl group, and the alkyl group and the cycloalkyl group optionally contain an ether bond or a carbonyl bond R 13 represents an alkyl group, a cycloalkyl group or an aryl group, and the alkyl group and the cycloalkyl group optionally contain an ether bond or a carbonyl bond R 11 and R 12 optionally bonded to each other to form a ring, R 12 and R 13 optionally bonded to each other to form a ring, * represents a linking bond. In general formula (T-2), R 21 、R 22 and R 23 each independently represent an alkyl group R 21 ~R 23 Two of them are optionally bonded to each other to form a ring, * represents a linking bond.

5. The photosensitive actinic ray- or radiation-sensitive resin composition according to claim 4, wherein, the group that decomposes by the action of an acid represented by A is the group represented by the general formula (T-1).

6. The photosensitive actinic ray- or radiation-sensitive resin composition according to any one of claims 1 to 3, wherein, the content ratio of the compound (C) to the content of the compound (B) is 0.01% by mass or more and 5% by mass or less.

7. The photosensitive actinic ray- or radiation-sensitive resin composition according to any one of claims 1 to 3, wherein, The M + represented sulfonium ion or iodonium ion does not have a nitrogen atom.

8. The photosensitive actinic ray- or radiation-sensitive resin composition according to any one of claims 1 to 3, wherein, the resin (A) contains a repeating unit represented by the following general formula (I). In general formula (I), R 41 、R 42 and R 43 each independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, a cyano group or an alkoxycarbonyl group, wherein R 42 optionally bonds with Ar 4 to form a ring, and when R 42 bonds with Ar 4 to form a ring, R 42 represents a single bond or an alkylene group. X 4 represents a single bond, -COO- or -CONR 64 -, R 64 represents a hydrogen atom or an alkyl group, L 4 represents a single bond or an alkylene group Ar 4 represents an aromatic ring group of (n + 1) valence, and when it forms a ring by bonding with R 42 it represents an aromatic ring group of (n + 2) valence. n represents an integer of 1 to 5.

9. A photosensitive actinic ray- or radiation-sensitive film formed using the photosensitive actinic ray- or radiation-sensitive resin composition according to any one of claims 1 to 8.

10. A pattern forming method, comprising the following steps: A resist film forming step of forming a resist film using the photosensitive actinic ray- or radiation-sensitive resin composition according to any one of claims 1 to 8; An exposure step of exposing the resist film; and A development step of developing the exposed resist film using a developer.

11. A method for manufacturing an electronic device, comprising the pattern forming method according to claim 10.

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