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 actinic ray- or radiation-sensitive resin composition, a photosensitive actinic ray- or radiation-sensitive film formed from the photosensitive actinic ray- or radiation-sensitive resin composition, a pattern forming method, and a method for manufacturing an electronic device. The photosensitive actinic ray- or radiation-sensitive resin composition contains (A) a resin whose polarity increases by the action of an acid and (B) a compound that generates an acid upon irradiation with actinic rays or radiation, and the compound is represented by a specific general formula. Among them, the resin (A) contains a repeating unit represented by a specific general formula.

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 pattern forming 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 pattern forming method, and a method for manufacturing an electronic device that are preferably used in an ultramicro lithography process applicable to a manufacturing process of a super LSI (Large Scale Integration) and a high-capacity microchip, a mold making process for nanoimprinting, a manufacturing process of a high-density information recording medium, and other photosensitive etching processes. Background Art

[0002] Conventionally, in a manufacturing process of semiconductor devices such as ICs (Integrated Circuits) and LSIs, fine processing based on lithography using a photoresist composition has been performed. In recent years, with the high integration of integrated circuits, formation of ultra-fine patterns in a sub-micron region or a quarter-micron region has been required. Along with this, the exposure wavelength has also tended to be shortened, such as from g-ray to i-ray and further to a KrF excimer laser. Currently, an exposure apparatus using an ArF excimer laser having a wavelength of 193 nm as a light source has been developed. Also, as a technique for further improving the resolution, development of a so-called immersion method in which a liquid having a high refractive index (hereinafter, also referred to as "immersion liquid") is filled between a projection lens and a specimen has been carried out.

[0003] And currently, in addition to excimer lasers, lithography using an electron beam (EB), X-rays, extreme ultraviolet rays (EUV), etc. is also under development. Along with this, a chemically amplified resist composition that effectively responds to various radiations and has excellent sensitivity and resolution has been developed.

[0004] For example, Patent Document 1 describes a photosensitive radiation-curable or radiation-sensitive resin composition containing at least one of a resin (A), a compound (C1), and a compound (C2), wherein the resin (A) has a group that is decomposed by the action of an acid to generate a polar group, the compound (C1) has a group that generates a first acidic functional group by irradiation with actinic rays or radiation and a group that generates a second acidic functional group different from the first acidic functional group by irradiation with actinic rays or radiation, and the compound (C2) has two or more groups that generate a specific structure by irradiation with actinic rays or radiation.

[0005] Further, Patent Document 2 describes a photosensitive or radiation-sensitive resin composition containing: a resin that decomposes by the action of an acid and increases its solubility in an alkaline developer; and a compound that generates an acid upon irradiation with actinic rays or radiation and is represented by a specific formula.

[0006] Prior Art Documents

[0007] Patent Documents

[0008] Patent Document 1: Japanese Unexamined Patent Application Publication No. 2014-149409

[0009] Patent Document 2: International Publication No. 2020 / 045534 Summary of the Invention

[0010] Technical Problem to be Solved by the Invention

[0011] However, in recent years, due to further miniaturization of the formed patterns, etc., in ultra-fine (especially, line width or space width of 30 nm or less) pattern formation methods, a photosensitive or radiation-sensitive resin composition capable of further improving LWR (line width roughness) and resolution is required.

[0012] An object of the present invention is to provide a photosensitive or radiation-sensitive resin composition capable of achieving both an improvement in roughness performance and an improvement in resolution in a high dimension in ultra-fine (especially, line width or space width of 30 nm or less) pattern formation. Further, another object of the present invention is to provide a photosensitive or radiation-sensitive film, a pattern formation method, and a method for manufacturing an electronic device using the above photosensitive or radiation-sensitive resin composition.

[0013] Means for Solving the Technical Problem

[0014] The present inventors have found that the above problems can be achieved by the following structure. [1]

[0016] A photosensitive or radiation-sensitive resin composition containing:

[0017] Resin (A) whose polarity increases by the action of an acid; and

[0018] Compound (B): which generates an acid upon irradiation with actinic rays or radiation and is represented by the following general formula (I),

[0019] The above resin (A) contains a repeating unit represented by the following general formula (AI).

[0020] [Chemical Formula 1]

[0021]

[0022] In general formula (AI),

[0023] R A , R B and R C each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, a cyano group or an alkoxycarbonyl group. Among them, R C may bond with Ar A to form a ring, and at this time R C represents a single bond or an alkylene group.

[0024] L A represents a single bond or a divalent linking group.

[0025] Ar A represents an (n + 1)-valent aromatic ring group. When Ar A bonds with R C to form a ring, it represents an (n + 2)-valent aromatic ring group.

[0026] n represents an integer from 1 to 5.

[0027] [Chemical formula 2]

[0028]

[0029] In general formula (I),

[0030] M 1 + and M 2 + each independently represent a cation.

[0031] X represents a single bond or an (m + 1)-valent linking group.

[0032] A 1 - and A 2 - each independently represent an anionic group. A 1 - represents a structure different from the acid anionic group represented by A 2 -

[0033] m represents 1 or 2. When m represents 2, multiple M 1 + may be the same or different. When m represents 2, multiple A 1 - may be the same or different.

[0034] Among them, M of the compound represented by general formula (I)​1 + and M 2 + The compound (PI) in which the hydrogen atoms are respectively substituted has an acid dissociation constant a1 of the group represented by HA 1 and an acid dissociation constant a2 of the group represented by A 2 H. The acid dissociation constant a1 is lower than the acid dissociation constant a2, and the acid dissociation constant a1 is -1.5 or more. [2]

[0036] The photosensitive or radiation-sensitive resin composition according to [1], wherein

[0037] In the above general formula (I), A 1 - and A 2 - are each independently a group selected from the groups represented by the following general formulas (B-1) to (B-27).

[0038] [Chemical formula 3]

[0039]

[0040] [Chemical formula 4]

[0041]

[0042] In the general formula (B-1),

[0043] Y F1 represents a fluorine atom or a perfluoroalkyl group.

[0044] Y 1 represents a hydrogen atom or a substituent having no fluorine atom.

[0045] In the general formula (B-2),

[0046] Y 2 each independently represents a hydrogen atom or a substituent having no fluorine atom.

[0047] In the general formula (B-3),

[0048] Y F2 represents a fluorine atom or a perfluoroalkyl group.

[0049] Y 3 represents a hydrogen atom or a substituent having no fluorine atom.

[0050] Ra represents an organic group.

[0051] In the general formula (B-4),

[0052] Y 4Each independently represents a hydrogen atom or a substituent having no fluorine atom.

[0053] Ra 1 represents an organic group.

[0054] In general formula (B-5),

[0055] Y F3 represents a fluorine atom or a perfluoroalkyl group.

[0056] Y 5 represents a hydrogen atom or a substituent having no fluorine atom.

[0057] Rb represents a hydrogen atom or an organic group.

[0058] In general formula (B-6),

[0059] Y 6 Each independently represents a hydrogen atom or a substituent having no fluorine atom.

[0060] Rb 1 represents a hydrogen atom or an organic group.

[0061] In general formula (B-7),

[0062] Y F4 represents a fluorine atom or a perfluoroalkyl group.

[0063] Y 7 represents a hydrogen atom or a substituent having no fluorine atom.

[0064] Rc represents an organic group.

[0065] In general formula (B-8),

[0066] Y 8 Each independently represents a hydrogen atom or a substituent having no fluorine atom.

[0067] Rc 1 represents an organic group.

[0068] In general formula (B-9),

[0069] Y F5 represents a fluorine atom or a perfluoroalkyl group.

[0070] Y 9 represents a hydrogen atom or a substituent having no fluorine atom.

[0071] Rd represents an organic group.

[0072] In general formula (B-10),

[0073] Y 10 Each independently represents a hydrogen atom or a substituent having no fluorine atom.

[0074] Rd 1 represents an organic group.

[0075] In general formula (B-12),

[0076] Re represents a hydrogen atom, an organic group, or a halogen atom.

[0077] o represents an integer from 1 to 4.

[0078] When o represents an integer of 2 or more, multiple Res may be the same or different.

[0079] In general formula (B-13),

[0080] Y F6 represents a fluorine atom or a perfluoroalkyl group.

[0081] Y 11 represents a hydrogen atom or a substituent having no fluorine atom.

[0082] In general formula (B-14),

[0083] Y 12 each independently represents a hydrogen atom or a substituent having no fluorine atom.

[0084] In general formula (B-15),

[0085] Y F7 represents a fluorine atom or a perfluoroalkyl group.

[0086] Y 13 represents a hydrogen atom or a substituent having no fluorine atom.

[0087] Rf represents an organic group.

[0088] In general formula (B-16),

[0089] Y 14 each independently represents a hydrogen atom or a substituent having no fluorine atom.

[0090] Rf 1 represents an organic group.

[0091] In general formula (B-17),

[0092] Y F8 represents a fluorine atom or a perfluoroalkyl group.

[0093] Y 15 represents a hydrogen atom or a substituent having no fluorine atom.

[0094] Rg represents an organic group.

[0095] Rh represents an organic group.

[0096] In general formula (B-18),

[0097] Y 16 each independently represents a hydrogen atom or a substituent having no fluorine atom.

[0098] Rg 1 represents an organic group.

[0099] Rh 1 represents an organic group.

[0100] In general formula (B-19),

[0101] Y F9 represents a fluorine atom or a perfluoroalkyl group.

[0102] Y 17 represents a hydrogen atom or a substituent having no fluorine atom.

[0103] In general formula (B-20),

[0104] Y 18 each independently represents a hydrogen atom or a substituent having no fluorine atom.

[0105] In general formula (B-21),

[0106] Y F10 represents a fluorine atom or a perfluoroalkyl group.

[0107] Y 19 represents a hydrogen atom or a substituent having no fluorine atom.

[0108] Ri represents an organic group.

[0109] Rj represents an organic group.

[0110] In general formula (B-22),

[0111] Y 20 each independently represents a hydrogen atom or a substituent having no fluorine atom.

[0112] Ri 1 represents an organic group.

[0113] Rj 1 represents an organic group.

[0114] In general formula (B-23),

[0115] Rk represents a hydrogen atom or a substituent having no fluorine atom.

[0116] p represents an integer from 1 to 4.

[0117] When p represents an integer of 2 or more, the plurality of Rk may be the same or different.

[0118] In general formula (B-24),

[0119] Rl represents a hydrogen atom, an organic group, or a halogen atom.

[0120] q represents an integer of 1 to 4.

[0121] When q represents an integer of 2 or more, the plurality of R1 may be the same or different.

[0122] Rc 2 represents an organic group.

[0123] In general formula (B-25),

[0124] Y F11 each independently represents a fluorine atom or a perfluoroalkyl group.

[0125] Rc 3 represents an organic group.

[0126] In general formula (B-26),

[0127] Y F12 each independently represents a fluorine atom or a perfluoroalkyl group.

[0128] Rd 2 represents an organic group.

[0129] In general formula (B-27),

[0130] Y F13 each independently represents a fluorine atom or a perfluoroalkyl group.

[0131] In general formulas (B-1) to (B-27),

[0132] * represents a bonding position. [3]

[0134] The photosensitive radiation-sensitive or radiation-sensitive resin composition according to [1] or [2], wherein

[0135] in the above compound (PI), the difference between the acid dissociation constant a1 and the acid dissociation constant a2 is 2.0 or more. [4]

[0137] The photosensitive radiation-sensitive or radiation-sensitive resin composition according to any one of [1] to [3], wherein

[0138] in the above compound (PI), the acid dissociation constant a2 is 2.0 or more. [5]

[0140] The photosensitive actinic or radiation-sensitive resin composition according to any one of [2] to [4], wherein,

[0141] In the above general formula (I), A 1 - is a group represented by the above general formula (B-2) or (B-23). [6]

[0143] The photosensitive actinic or radiation-sensitive resin composition according to any one of [2] to [5], wherein,

[0144] In the above general formula (I), A 1 - is a group represented by the above general formula (B-2). [7]

[0146] The photosensitive actinic or radiation-sensitive resin composition according to any one of [1] to [6], wherein,

[0147] (A) The resin whose polarity is increased by the action of an acid contains a repeating unit having an acid-decomposable group, and the repeating unit having an acid-decomposable group is a repeating unit selected from a repeating unit having a group that decomposes by the action of an acid to generate a carboxyl group and a repeating unit having a group that decomposes by the action of an acid to generate a phenolic hydroxyl group. [8]

[0149] The photosensitive actinic or radiation-sensitive resin composition according to [7], wherein,

[0150] The repeating unit having an acid-decomposable group contains one or more selected from the repeating units represented by the following general formulas (3) to (7).

[0151] [Chemical formula 5]

[0152]

[0153] In general formula (3), R 5 , R 6 and R 7 each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, a cyano group or an alkoxycarbonyl group.

[0154] L 2 represents a single bond or a divalent linking group.

[0155] R 8 ~R 10 each independently represent an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group or an alkenyl group. Further, R 8 ~R 10Two of them can be bonded to each other to form a ring.

[0156] In general formula (4), R 11 ~R 14 each independently represents a hydrogen atom or an organic group. Among them, at least one of R 11 and R 12 represents an organic group.

[0157] X 1 represents -CO-, -SO- or -SO 2 -.

[0158] Y 1 represents -O-, -S-, -SO-, -SO 2 - or -NR 34 -. R 34 represents a hydrogen atom or an organic group.

[0159] L 3 represents a single bond or a divalent linking group.

[0160] R 15 ~R 17 each independently represents an alkyl group, a cycloalkyl group which may have a fluorine atom, an aryl group, an aralkyl group or an alkenyl group. Additionally, two of R 15 ~R 17 can be bonded to each other to form a ring.

[0161] In general formula (5), R 18 and R 19 each independently represents a hydrogen atom or an organic group. R 20 and R 21 each independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group or an alkenyl group. Additionally, R 20 and R 21 can be bonded to each other to form a ring.

[0162] In general formula (6), R 22 , R 23 and R 24 each independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, a cyano group or an alkoxycarbonyl group.

[0163] L 4 represents a single bond or a divalent linking group.

[0164] Ar 1 represents an aromatic ring group.

[0165] R 25 ~R 27 each independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group or an alkenyl group. Additionally, R 26 and R27 can bond to each other to form a ring. And, Ar 1 can bond with R 24 or R 25 to form a ring.

[0166] In general formula (7), R 28 , R 29 and R 30 each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, a cyano group or an alkoxycarbonyl group.

[0167] L 5 represents a single bond or a divalent linking group.

[0168] R 31 and R 32 each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group or an alkenyl group.

[0169] R 33 represents an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group or an alkenyl group. Additionally, R 32 and R 33 can bond to each other to form a ring. [9]

[0171] The photosensitive actinic ray or radiation-sensitive resin composition according to [8], wherein,

[0172] the repeating unit having an acid-decomposable group includes one or more selected from the repeating unit represented by the above general formula (6) and the repeating unit represented by the above general formula (7).

[10]

[0174] The photosensitive actinic ray or radiation-sensitive resin composition according to any one of [7] to [9], wherein,

[0175] the repeating unit having an acid-decomposable group does not contain a halogen atom.

[0176]

[11] A photosensitive actinic ray or radiation-sensitive resin composition, which contains:

[0177] Resin (A), the polarity of which increases by the action of an acid; and

[0178] Compound (B), which generates an acid upon irradiation with actinic rays or radiation and is represented by the following general formula (I),

[0179] The above resin (A) includes a repeating unit represented by the following general formula (AI).

[0180] [Chemical formula 6]

[0181]

[0182] In general formula (AI),

[0183] R A , R B and R C each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, a cyano group or an alkoxycarbonyl group. Among them, R C can bond with Ar A to form a ring, and at this time R C represents a single bond or an alkylene group.

[0184] L A represents a single bond or a divalent linking group.

[0185] Ar A represents an (n + 1)-valent aromatic ring group. When Ar A bonds with R C to form a ring, it represents an (n + 2)-valent aromatic ring group.

[0186] n represents an integer from 1 to 5.

[0187] [Chemical formula 7]

[0188]

[0189] In general formula (I),

[0190] M 1 + and M 2 + each independently represent a cation.

[0191] X represents an (m + 1)-valent linking group.

[0192] A 1 and A 2 each independently are groups selected from the groups represented by the following general formulas (B-1) to (B-27).

[0193] [Chemical formula 8]

[0194]

[0195] [Chemical formula 9]

[0196]

[0197] In general formula (B-1),

[0198] Y F1 represents a fluorine atom or a perfluoroalkyl group.

[0199] Y 1 represents a hydrogen atom or a substituent having no fluorine atom.

[0200] In general formula (B-2),

[0201] Y 2 each independently represents a hydrogen atom or a substituent having no fluorine atom.

[0202] In general formula (B-3),

[0203] Y F2 represents a fluorine atom or a perfluoroalkyl group.

[0204] Y 3 each independently represents a hydrogen atom or a substituent having no fluorine atom.

[0205] Ra represents an organic group.

[0206] In general formula (B-4),

[0207] Y 4 each independently represents a hydrogen atom or a substituent having no fluorine atom.

[0208] Ra 1 represents an organic group.

[0209] In general formula (B-5),

[0210] Y F3 represents a fluorine atom or a perfluoroalkyl group.

[0211] Y 5 each independently represents a hydrogen atom or a substituent having no fluorine atom.

[0212] Rb represents a hydrogen atom or an organic group.

[0213] In general formula (B-6),

[0214] Y 6 each independently represents a hydrogen atom or a substituent having no fluorine atom.

[0215] Rb 1 represents a hydrogen atom or an organic group.

[0216] In general formula (B-7),

[0217] Y F4 represents a fluorine atom or a perfluoroalkyl group.

[0218] Y 7 each independently represents a hydrogen atom or a substituent having no fluorine atom.

[0219] Rc represents an organic group.

[0220] In general formula (B-8),

[0221] Y 8Each independently represents a hydrogen atom or a substituent having no fluorine atom.

[0222] Rc 1 represents an organic group.

[0223] In general formula (B-9),

[0224] Y F5 represents a fluorine atom or a perfluoroalkyl group.

[0225] Y 9 represents a hydrogen atom or a substituent having no fluorine atom.

[0226] Rd represents an organic group.

[0227] In general formula (B-10),

[0228] Y 10 Each independently represents a hydrogen atom or a substituent having no fluorine atom.

[0229] Rd 1 represents an organic group.

[0230] In general formula (B-12),

[0231] Re represents a hydrogen atom, an organic group or a halogen atom.

[0232] o represents an integer from 1 to 4.

[0233] When o represents an integer of 2 or more, multiple Res may be the same or different.

[0234] In general formula (B-13),

[0235] Y F6 represents a fluorine atom or a perfluoroalkyl group.

[0236] Y 11 represents a hydrogen atom or a substituent having no fluorine atom.

[0237] In general formula (B-14),

[0238] Y 12 Each independently represents a hydrogen atom or a substituent having no fluorine atom.

[0239] In general formula (B-15),

[0240] Y F7 represents a fluorine atom or a perfluoroalkyl group.

[0241] Y 13 represents a hydrogen atom or a substituent having no fluorine atom.

[0242] Rf represents an organic group.

[0243] In general formula (B-16),

[0244] Y 14 each independently represents a hydrogen atom or a substituent having no fluorine atom.

[0245] Rf 1 represents an organic group.

[0246] In general formula (B-17),

[0247] Y F8 represents a fluorine atom or a perfluoroalkyl group.

[0248] Y 15 each independently represents a hydrogen atom or a substituent having no fluorine atom.

[0249] Rg represents an organic group.

[0250] Rh represents an organic group.

[0251] In general formula (B-18),

[0252] Y 16 each independently represents a hydrogen atom or a substituent having no fluorine atom.

[0253] Rg 1 represents an organic group.

[0254] Rh 1 represents an organic group.

[0255] In general formula (B-19),

[0256] Y F9 represents a fluorine atom or a perfluoroalkyl group.

[0257] Y 17 each independently represents a hydrogen atom or a substituent having no fluorine atom.

[0258] In general formula (B-20),

[0259] Y 18 each independently represents a hydrogen atom or a substituent having no fluorine atom.

[0260] In general formula (B-21),

[0261] Y F10 represents a fluorine atom or a perfluoroalkyl group.

[0262] Y 19 each independently represents a hydrogen atom or a substituent having no fluorine atom.

[0263] Ri represents an organic group.

[0264] Rj represents an organic group.

[0265] In general formula (B-22),

[0266] Y 20 each independently represents a hydrogen atom or a substituent having no fluorine atom.

[0267] Ri 1 represents an organic group.

[0268] Rj 1 represents an organic group.

[0269] In general formula (B-23),

[0270] Rk represents a hydrogen atom or a substituent having no fluorine atom.

[0271] p represents an integer from 1 to 4.

[0272] When p represents an integer of 2 or more, multiple Rk's may be the same or different.

[0273] In general formula (B-24),

[0274] Rl represents a hydrogen atom, an organic group, or a halogen atom.

[0275] q represents an integer from 1 to 4.

[0276] When q represents an integer of 2 or more, multiple R1's may be the same or different.

[0277] Rc 2 represents an organic group.

[0278] In general formula (B-25),

[0279] Y F11 each independently represents a fluorine atom or a perfluoroalkyl group.

[0280] Rc 3 represents an organic group.

[0281] In general formula (B-26),

[0282] Y F12 each independently represents a fluorine atom or a perfluoroalkyl group.

[0283] Rd 2 represents an organic group.

[0284] In general formula (B-27),

[0285] Y F13 each independently represents a fluorine atom or a perfluoroalkyl group.

[0286] In general formulas (B-1) to (B-27),

[0287] * indicates the bonding position.

[0288] A 1 - represents a structure different from the group represented by A 2 - represents a structure different from the group represented by A

[0289] m represents 1 or 2. When m represents 2, multiple Ms 1 + may be the same or different. When m represents 2, multiple As 1 - may be the same or different.

[12]

[0291] A photosensitive radiation-sensitive or radiation-sensitive film formed from the photosensitive radiation-sensitive or radiation-sensitive resin composition according to any one of [1] to

[11] .

[13]

[0293] A pattern forming method, comprising:

[0294] A resist film forming step of forming a resist film using the photosensitive radiation-sensitive or radiation-sensitive resin composition according to any one of [1] to

[11] ;

[0295] An exposure step of exposing the resist film; and

[0296] A developing step of developing the exposed resist film using a developer.

[14]

[0298] A method for manufacturing an electronic device, comprising the pattern forming method according to

[13] .

[0299] Advantages of the Invention

[0300] According to the present invention, it is possible to provide a photosensitive radiation-sensitive or radiation-sensitive resin composition that can achieve both an improvement in roughness performance and an improvement in resolution in high dimensions in the formation of ultra-fine patterns (especially, line width or space width of 30 nm or less). According to the present invention, it is possible to provide a photosensitive radiation-sensitive or radiation-sensitive film, a pattern forming method, and a method for manufacturing an electronic device using the above photosensitive radiation-sensitive or radiation-sensitive resin composition. Detailed Description

[0301] Hereinafter, the present invention will be described in detail.

[0302] The constituent elements described below will be described based on representative embodiments of the present invention, but the present invention is not limited to such embodiments.

[0303] The "actinic ray" or "radiation ray" in this specification refers to, for example, the bright line spectrum of a mercury lamp, far ultraviolet rays represented by excimer lasers, extreme ultraviolet rays (EUV: Extreme Ultraviolet), X-rays, soft X-rays, and electron beams (EB: Electron Beam), etc. The "light" in this specification refers to actinic rays or radiation rays. Unless otherwise specified, the "exposure" in this specification includes not only exposure using the bright line spectrum of a mercury lamp, far ultraviolet rays represented by excimer lasers, extreme ultraviolet rays, X-rays, and EUV, etc., but also drawing using particle rays such as electron beams and ion beams.

[0304] In this specification, "~" is used to indicate the meaning of including the numerical values described before and after it as the lower limit value and the upper limit value.

[0305] Unless otherwise specified, the bonding direction of the divalent group marked in this specification is not restricted. For example, when Y in the compound represented by the general formula "X - Y - Z" is -COO-, Y can be -CO - O - or -O - CO -. And the above compound can be "X - CO - O - Z" or "X - O - CO - Z".

[0306] In this specification, (meth)acrylate represents at least one of acrylate and methacrylate. And (meth)acrylic acid represents at least one of acrylic acid and methacrylic acid.

[0307] In this specification, the weight average molecular weight (Mw), number average molecular weight (Mn), and dispersity (also called molecular weight distribution) (Mw / Mn) of the resin are defined as the polystyrene conversion values obtained by GPC (Gel Permeation Chromatography) measurement using a GPC device (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).

[0308] In the notations of 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) but also alkyl groups with substituents (substituted alkyl). In addition, the "organic group" in this specification refers to a group containing at least one carbon atom.

[0309] In addition, in this specification, the type, position, and number of substituents when "may have substituents" are not particularly limited. The number of substituents can be, for example, 1, 2, 3, or more. Examples of substituents include monovalent non-metal atomic groups other than hydrogen atoms, and they can be selected from the following substituents T.

[0310] (Substituent T)

[0311] Examples of substituent T include halogen atoms such as fluorine atom, chlorine atom, bromine atom, and iodine atom; 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 oxalyl 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 group; arylaminocarbonyl group; sulfonamide group; silyl group; amino group; monoalkylamino group; dialkylamino group; arylamino group, nitro group; formyl group; and combinations thereof.

[0312] In this specification, the acid dissociation constant (pKa) represents the pKa in an aqueous solution. Specifically, it is calculated using the following software package 1 to obtain the value based on the Hammett substituent constant and the database of known literature values. All the pKa values described in this specification represent the values calculated using this software package.

[0313] Software package 1: Advanced Chemistry Development (ACD / Labs) Software V8.14 for Solaris (1994 - 2007 ACD / Labs).

[0314] On the other hand, pKa can also be obtained by the molecular orbital algorithm. As a specific method, it can be mentioned that by calculating H in the solvent based on the thermodynamic cycle +A method for calculating the dissociation free energy. (In addition, in this specification, water is usually used as the above solvent, and DMSO (dimethyl sulfoxide) is used when pKa cannot be obtained with water.)

[0315] Regarding H + As for the method for calculating the dissociation free energy, for example, it can be calculated by DFT (density functional method), but various other methods have been reported in the literature and the like, and it is not limited thereto. In addition, there are multiple software that can implement DFT, for example, Gaussian16 can be cited.

[0316] As described above, the pKa in this specification refers to the value obtained by calculating the values in the database of Hammett-based substituent constants and known literature values using software package 1. However, when pKa cannot be calculated by this method, the value obtained by Gaussian16 based on DFT (density functional method) is adopted.

[0317] [Photosensitive or radiation-sensitive resin composition]

[0318] The photosensitive or radiation-sensitive resin composition (hereinafter, also referred to as "the composition of the present invention") according to the present invention contains: resin (A), the polarity of which increases by the action of an acid; and compound (B), which generates an acid upon irradiation with actinic rays or radiation and is represented by the following general formula (I), wherein the above resin (A) contains a repeating unit represented by the following general formula (AI).

[0319] [Chemical formula 10]

[0320]

[0321] In the general formula (AI),

[0322] R A , R B and R C each independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, a cyano group or an alkoxycarbonyl group. Among them, R C may bond with Ar A to form a ring, and in this case, R C represents a single bond or an alkylene group.

[0323] L A represents a single bond or a divalent linking group.

[0324] Ar A represents an (n + 1)-valent aromatic ring group. When Ar A bonds with R C to form a ring, it represents an (n + 2)-valent aromatic ring group.

[0325] n represents an integer from 1 to 5.

[0326] [Chemical Formula 11]

[0327]

[0328] In general formula (I),

[0329] M 1 + and M 2 + each independently represents a cation.

[0330] X represents a single bond or a (m + 1)-valent linking group.

[0331] A 1 - and A 2 - each independently represents an anionic group. A 1 - represents a structure different from the acid anionic group represented by A 2 - represents.

[0332] m represents 1 or 2. When m represents 2, multiple Ms 1 + can be the same or different. When m represents 2, multiple As 1 - can be the same or different.

[0333] Among them, the compound of formula (I) where M 1 + and M 2 + are each replaced by a hydrogen atom (PI) has an acid dissociation constant a1 of the group represented by HA 1 and an acid dissociation constant a2 of the group represented by A 2 H, the acid dissociation constant a1 is lower than the acid dissociation constant a2, and the acid dissociation constant a1 is -1.5 or more.

[0334] The composition of the present invention is preferably a resist composition, and can also be a positive resist composition or a negative resist composition. Moreover, it can be a resist composition for alkaline development or a resist composition for organic solvent development. Among them, a positive resist composition and a resist composition for alkaline development are preferred.

[0335] Furthermore, the composition of the present invention is preferably a chemically amplified resist composition, and more preferably a chemically amplified positive resist composition.

[0336] In the formation of ultra-fine patterns (especially, those with a line width or space width of 30 nm or less), the reason why the composition of the present invention can achieve both an improvement in roughness performance and an improvement in resolution in a high dimension has not been fully elucidated, but the present inventors presume as follows.

[0337] First of all, heretofore, a resist composition containing a photoacid generator and an acid diffusion controller as separate compounds has been widely known. In the resist film formed from such a resist composition, the acid diffusion controller in the unexposed portion can capture the acid generated by the photoacid generator in the exposed portion, thereby suppressing the excessive diffusion of the acid into the unexposed portion. As the acid diffusion controller, a salt of an acid having an acid strength weaker than that of the acid generated by the photoacid generator (so-called weak acid salt) is known.

[0338] Thus, in the resist composition, by including a photoacid generator and an acid diffusion controller such as the above-mentioned weak acid salt, it is considered that a pattern with excellent resolution can be formed. However, in recent requirements for ultra-fine pattern formation, it has become difficult to obtain the required performance using the conventional resist composition. For example, in addition to excellent resolution, it is also difficult to achieve both excellent roughness performance and other properties in a high dimension.

[0339] As a result of in-depth research by the present inventors, it is considered that in the resist film formed from the above-mentioned conventional resist composition, the photoacid generator and the acid diffusion controller contained as separate compounds are liable to aggregate strictly between the photoacid generators and between the acid diffusion controllers. In other words, in the formed resist film, there are liable to be portions with a high (or low) concentration of the photoacid generator and portions with a high (or low) concentration of the acid diffusion controller. As a result, the concentration distribution of the photoacid generator and the acid diffusion controller becomes non-uniform. It is considered that this non-uniformity is the cause of a decrease in roughness performance, etc., especially in the formation of ultra-fine patterns when the resist film is exposed.

[0340] On the other hand, the photosensitive actinic ray or radiation-sensitive composition of the present invention contains (B) a compound represented by the above general formula (I) that generates an acid upon irradiation with actinic rays or radiation.

[0341] Since the compound represented by the above general formula (I) contains, in one molecule, a structural moiety (A 1 - M 1 + ) having a function equivalent to that of a photoacid generator and a structural moiety (A 2 - M 2 + (capturing the acid generated by the above A 1 - M 1 +The structural part of the acid generated))both, so that the compound that functions both as a photoacid generator and an acid diffusion control agent can be more uniformly present in the resist film.

[0342] Therefore, excellent resolution can be obtained, and the width of the pattern obtained after development is easily stabilized. That is, it is considered that the roughness performance of the formed pattern is further improved.

[0343] The resin (A) in the composition of the present invention has a repeating unit represented by the following general formula (AI). It is considered that the above compound (B) can further inhibit the aggregation of the compound (B) by interacting with the hydroxyl group at the end of the above repeating unit, and can further improve the roughness performance of the formed pattern.

[0344] Moreover, when the strength of the acid generated by the photoacid generator is too strong, the acid generated in the exposed area tends to diffuse excessively not only in the exposed area but also into the unexposed area.

[0345] However, the M of the compound represented by the above general formula (I) 1 + and M 2 + The acid dissociation constant a1 of the compound (PI) in which the hydrogen atoms are respectively substituted is -1.5 or more. In other words, it can be speculated that in the above compound (B), from the structural part (A 1 M 1 + ) having the function equivalent to that of a photoacid generator, the strength of the generated acid becomes an acid with appropriately suppressed strength, which can inhibit the excessive diffusion into the above unexposed area. Especially in the formation of ultra-fine patterns, the roughness performance of the formed pattern is further improved.

[0346] [(B) A compound that generates an acid upon irradiation with actinic rays or radiation and is represented by the following general formula (1)]

[0347] As described above, the photosensitive actinic ray or radiation-sensitive resin composition of the present invention contains (B) a compound that generates an acid upon irradiation with actinic rays or radiation and is represented by the following general formula (I) (also referred to as "compound (B)", "photoacid generator (B)").

[0348] Compound (B) is a compound (photoacid generator) that generates an acid upon irradiation with actinic rays or radiation.

[0349] <Compound represented by general formula (I)>

[0350] [Chemical formula 12]

[0351]

[0352] In general formula (I),

[0353] M 1 + and M 2 + each independently represents a cation.

[0354] X represents a single bond or a (m + 1)-valent linking group.

[0355] A 1 - and A 2 - each independently represents an anionic group. A 1 - represents a structure different from the acid anionic group represented by A 2 - represents.

[0356] m represents 1 or 2. When m represents 2, multiple M 1 + can be the same or different. When m represents 2, multiple A 1 - can be the same or different.

[0357] Among them, for the M of the compound represented by general formula (I) 1 + and M 2 + the compound (PI) in which each is replaced by a hydrogen atom has an acid dissociation constant a1 of the group represented by HA 1 and an acid dissociation constant a2 of the group represented by A 2 H. The acid dissociation constant a1 is lower than the acid dissociation constant a2, and the acid dissociation constant a1 is -1.5 or more.

[0358] In general formula (I), for the cations represented by M 1 + and M 2 + as described later.

[0359] In general formula (I), when m is 1, the divalent linking group represented by X is not particularly limited, and examples thereof include -NR-, -CO-, -O-, alkylene (preferably having 1 to 8 carbon atoms, which may be linear or branched), cycloalkylene (preferably having 3 to 15 carbon atoms), alkenylene (preferably having 2 to 6 carbon atoms), divalent aliphatic heterocyclic group (preferably a 5- to 10-membered ring having at least one N atom, O atom, S atom or Se atom in the ring structure, more preferably a 5- to 7-membered ring, and still more preferably a 5- to 6-membered ring), divalent aromatic heterocyclic group (preferably a 5- to 10-membered ring having at least one N atom, O atom, S atom or Se atom in the ring structure, more preferably a 5- to 7-membered ring, and still more preferably a 5- to 6-membered ring), divalent aromatic hydrocarbon ring group (preferably a 6- to 10-membered ring, and still more preferably a 6-membered ring), and a group formed by combining a plurality of them. The above R can be a hydrogen atom or a monovalent organic group. The monovalent organic group is not particularly limited, and for example, it is preferably an alkyl group (preferably having 1 to 6 carbon atoms).

[0360] These divalent linking groups may also contain a group selected from the group consisting of -S-, -SO- and -SO 2 -.

[0361] Moreover, the above alkylene, cycloalkylene, alkenylene, divalent aliphatic heterocyclic group, divalent aromatic heterocyclic group, and divalent aromatic hydrocarbon ring group may have a substituent. The substituent is not particularly limited, and for example, the above substituent T can be cited.

[0362] As a specific example of the trivalent linking group when m is 2, a group formed by removing any one hydrogen atom from the above specific examples of the divalent linking group can be preferably cited.

[0363] As the anionic group represented by A 1 - and A 2 - The acid dissociation constant a1 is lower than the acid dissociation constant a2. As long as the acid dissociation constant a1 is -1.5 or more, there is no particular limitation. For example, a group independently selected from the groups represented by the following general formulas (B-1) to (B-27) can be cited.

[0364] [Chemical formula 13]

[0365]

[0366] [Chemical formula 14]

[0367]

[0368] In general formula (B-1),

[0369] Y F1 represents a fluorine atom or a perfluoroalkyl group.

[0370] Y 1 represents a hydrogen atom or a substituent having no fluorine atom.

[0371] In general formula (B-2),

[0372] Y 2 each independently represents a hydrogen atom or a substituent having no fluorine atom.

[0373] In general formula (B-3),

[0374] Y F2 represents a fluorine atom or a perfluoroalkyl group.

[0375] Y 3 represents a hydrogen atom or a substituent having no fluorine atom.

[0376] Ra represents an organic group.

[0377] In general formula (B-4),

[0378] Y 4 each independently represents a hydrogen atom or a substituent having no fluorine atom.

[0379] Ra 1 represents an organic group.

[0380] In general formula (B-5),

[0381] Y F3 represents a fluorine atom or a perfluoroalkyl group.

[0382] Y 5 represents a hydrogen atom or a substituent having no fluorine atom.

[0383] Rb represents a hydrogen atom or an organic group.

[0384] In general formula (B-6),

[0385] Y 6 each independently represents a hydrogen atom or a substituent having no fluorine atom.

[0386] Rb 1 represents a hydrogen atom or an organic group.

[0387] In general formula (B-7),

[0388] Y F4 represents a fluorine atom or a perfluoroalkyl group.

[0389] Y 7 represents a hydrogen atom or a substituent having no fluorine atom.

[0390] Rc represents an organic group.

[0391] In general formula (B-8),

[0392] Y 8 each independently represents a hydrogen atom or a substituent having no fluorine atom.

[0393] Rc 1 represents an organic group.

[0394] In general formula (B-9),

[0395] Y F5 represents a fluorine atom or a perfluoroalkyl group.

[0396] Y 9 represents a hydrogen atom or a substituent having no fluorine atom.

[0397] Rd represents an organic group.

[0398] In general formula (B-10),

[0399] Y 10 each independently represents a hydrogen atom or a substituent having no fluorine atom.

[0400] Rd 1 represents an organic group.

[0401] In general formula (B-12),

[0402] Re represents a hydrogen atom, an organic group or a halogen atom.

[0403] o represents an integer of 1 to 4.

[0404] When o represents an integer of 2 or more, a plurality of Res may be the same or different.

[0405] In general formula (B-13),

[0406] Y F6 represents a fluorine atom or a perfluoroalkyl group.

[0407] Y 11 represents a hydrogen atom or a substituent having no fluorine atom.

[0408] In general formula (B-14),

[0409] Y 12 each independently represents a hydrogen atom or a substituent having no fluorine atom.

[0410] In general formula (B-15),

[0411] Y F7 represents a fluorine atom or a perfluoroalkyl group.

[0412] Y 13 represents a hydrogen atom or a substituent having no fluorine atom.

[0413] Rf represents an organic group.

[0414] In general formula (B-16),

[0415] Y 14 each independently represents a hydrogen atom or a substituent having no fluorine atom.

[0416] Rf 1 represents an organic group.

[0417] In general formula (B-17),

[0418] Y F8 represents a fluorine atom or a perfluoroalkyl group.

[0419] Y 15 represents a hydrogen atom or a substituent having no fluorine atom.

[0420] Rg represents an organic group.

[0421] Rh represents an organic group.

[0422] In general formula (B-18),

[0423] Y 16 each independently represents a hydrogen atom or a substituent having no fluorine atom.

[0424] Rg 1 represents an organic group.

[0425] Rh 1 represents an organic group.

[0426] In general formula (B-19),

[0427] Y F9 represents a fluorine atom or a perfluoroalkyl group.

[0428] Y 17 represents a hydrogen atom or a substituent having no fluorine atom.

[0429] In general formula (B-20),

[0430] Y 18 each independently represents a hydrogen atom or a substituent having no fluorine atom.

[0431] In general formula (B-21),

[0432] Y F10 represents a fluorine atom or a perfluoroalkyl group.

[0433] Y19 represents a hydrogen atom or a substituent having no fluorine atom.

[0434] Ri represents an organic group.

[0435] Rj represents an organic group.

[0436] In general formula (B-22),

[0437] Y 20 each independently represents a hydrogen atom or a substituent having no fluorine atom.

[0438] Ri 1 represents an organic group.

[0439] Rj 1 represents an organic group.

[0440] In general formula (B-23),

[0441] Rk represents a hydrogen atom or a substituent having no fluorine atom.

[0442] p represents an integer from 1 to 4.

[0443] When p represents an integer of 2 or more, multiple Rk's may be the same or different.

[0444] In general formula (B-24),

[0445] R1 represents a hydrogen atom, an organic group or a halogen atom.

[0446] q represents an integer from 1 to 4.

[0447] When q represents an integer of 2 or more, multiple R1's may be the same or different.

[0448] Rc 2 represents an organic group.

[0449] In general formula (B-25),

[0450] Y F11 each independently represents a fluorine atom or a perfluoroalkyl group.

[0451] Rc 3 represents an organic group.

[0452] In general formula (B-26),

[0453] Y F12 each independently represents a fluorine atom or a perfluoroalkyl group.

[0454] Rd 2 represents an organic group.

[0455] In general formula (B-27),

[0456] Y F13 Each independently represents a fluorine atom or a perfluoroalkyl group.

[0457] In the general formulas (B-1) to (B-27),

[0458] *Indicates bonding position.

[0459] In the general formula (B-1), Y F1 The perfluoroalkyl group represented by is preferably 1-15, more preferably 1-10, and even more preferably 1-6.

[0460] As not having 1 The substituent of the fluorine atom represented by is not particularly limited as long as it is a substituent not having a fluorine atom, and is preferably an organic group not having a fluorine atom, for example, an organic group other than a fluorine atom and a perfluoroalkyl group, preferably an alkyl group other than a perfluoroalkyl group (which may be either linear or branched) and a cycloalkyl group.

[0461] The alkyl group is not particularly limited and may be linear or branched. An alkyl group having 1 to 15 carbon atoms is preferred, and an alkyl group having 1 to 10 carbon atoms is more preferred.

[0462] The cycloalkyl group may be a monocyclic or polycyclic group and is not particularly limited, but is preferably a cycloalkyl group having 3 to 15 carbon atoms, and more preferably a cycloalkyl group having 3 to 10 carbon atoms.

[0463] The above-mentioned alkyl group and cycloalkyl group may have a substituent other than a fluorine atom. The substituent is not particularly limited, and examples thereof include the above-mentioned substituent T (excluding a fluorine atom).

[0464] In the general formula (B-2), as the compound not having Y 2 The substituent of the fluorine atom represented by Y is different from the substituent of the fluorine atom represented by Y in the general formula (B-1) above. 1 The substituents of the fluorine atoms represented by have the same meanings and preferred aspects are also the same.

[0465] In the general formula (B-3), as Y F2 The perfluoroalkyl group represented by F1 The perfluoroalkyl groups represented have the same meanings and preferred aspects are also the same.

[0466] As not having 3 The substituent of the fluorine atom represented by Y is different from the substituent of the fluorine atom represented by Y in the general formula (B-1) above. 1 The substituents of the fluorine atoms represented by have the same meanings and preferred aspects are also the same.

[0467] The organic group represented by Ra is not particularly limited, and examples thereof include organic groups having 1 to 30 carbon atoms. The organic group is not particularly limited, and alkyl, cycloalkyl or aryl is preferably selected.

[0468] The above alkyl group is not particularly limited and may be linear or branched, preferably an alkyl group having 1 to 15 carbon atoms, more preferably an alkyl group having 1 to 10 carbon atoms.

[0469] The cycloalkyl group may be monocyclic or polycyclic and is not particularly limited, preferably a cycloalkyl group having 3 to 15 carbon atoms, more preferably a cycloalkyl group having 3 to 10 carbon atoms.

[0470] The aryl group is not particularly limited, preferably an aryl group having 6 to 20 carbon atoms, more preferably an aryl group having 6 to 10 carbon atoms.

[0471] The above alkyl, cycloalkyl and aryl groups may have substituents. The substituent is not particularly limited, and the above substituent T can be cited.

[0472] In the general formula (B-4), as the substituent that does not have a fluorine atom represented by Y 4 it has the same meaning as the substituent that does not have a fluorine atom represented by Y in the above general formula (B-1), and the preferred mode is also the same. 1 In the general formula (B-4), as the substituent that does not have a fluorine atom represented by Y

[0473] The organic group represented by Ra 1 has the same meaning as the organic group represented by Ra in the above general formula (B-3), and the preferred mode is also the same.

[0474] In the general formula (B-5), as the perfluoroalkyl group represented by Y F3 it has the same meaning as the perfluoroalkyl group represented by Y in the above general formula (B-1), and the preferred mode is also the same. F1 In the general formula (B-5), as the perfluoroalkyl group represented by Y

[0475] As the substituent that does not have a fluorine atom represented by Y 5 it has the same meaning as the substituent that does not have a fluorine atom represented by Y in the above general formula (B-1), and the preferred mode is also the same. 1 In the general formula (B-5), as the substituent that does not have a fluorine atom represented by Y

[0476] The organic group represented by Rb has the same meaning as the organic group represented by Ra in the above general formula (B-3), and the preferred mode is also the same.

[0477] In the general formula (B-6), as the substituent that does not have a fluorine atom represented by Y 6 it has the same meaning as the substituent that does not have a fluorine atom represented by Y in the above general formula (B-1), and the preferred mode is also the same. 1 In the general formula (B-6), as the substituent that does not have a fluorine atom represented by Y

[0478] As the organic group represented by Rb 1 has the same meaning as the organic group represented by Ra in the above general formula (B-3), and the preferred modes are also the same.

[0479] In the general formula (B-7), as the perfluoroalkyl group represented by Y F4 has the same meaning as the perfluoroalkyl group represented by Y in the above general formula (B-1), and the preferred modes are also the same. F1 has the same meaning as the perfluoroalkyl group represented by Y in the above general formula (B-1), and the preferred modes are also the same.

[0480] As the substituent that does not have a fluorine atom represented by Y 7 has the same meaning as the substituent that does not have a fluorine atom represented by Y in the above general formula (B-1), and the preferred modes are also the same. 1 has the same meaning as the substituent that does not have a fluorine atom represented by Y in the above general formula (B-1), and the preferred modes are also the same.

[0481] As the organic group represented by Rc

[0482] In the general formula (B-8), as the substituent that does not have a fluorine atom represented by Y 8 has the same meaning as the substituent that does not have a fluorine atom represented by Y in the above general formula (B-1), and the preferred modes are also the same. 1 has the same meaning as the substituent that does not have a fluorine atom represented by Y in the above general formula (B-1), and the preferred modes are also the same.

[0483] As the organic group represented by Rc 1 has the same meaning as the organic group represented by Ra in the above general formula (B-3), and the preferred modes are also the same.

[0484] In the general formula (B-9), as the perfluoroalkyl group represented by Y F5 has the same meaning as the perfluoroalkyl group represented by Y in the above general formula (B-1), and the preferred modes are also the same. F1 has the same meaning as the perfluoroalkyl group represented by Y in the above general formula (B-1), and the preferred modes are also the same.

[0485] As the substituent that does not have a fluorine atom represented by Y 9 has the same meaning as the substituent that does not have a fluorine atom represented by Y in the above general formula (B-1), and the preferred modes are also the same. 1 has the same meaning as the substituent that does not have a fluorine atom represented by Y in the above general formula (B-1), and the preferred modes are also the same.

[0486] As the organic group represented by Rd

[0487] In the general formula (B-10), as the substituent that does not have a fluorine atom represented by Y 10 has the same meaning as the substituent that does not have a fluorine atom represented by Y in the above general formula (B-1), and the preferred modes are also the same. 1 has the same meaning as the substituent that does not have a fluorine atom represented by Y in the above general formula (B-1), and the preferred modes are also the same.

[0488] As the organic group represented by Rd 1 It has the same meaning as the organic group represented by Ra in the above general formula (B-3), and the preferred modes are also the same.

[0489] In the general formula (B-12), as the organic group represented by Re, it has the same meaning as the organic group represented by Ra in the above general formula (B-3), and the preferred modes are also the same.

[0490] As the halogen atom represented by Re, fluorine atom, chlorine atom, bromine atom or iodine atom can be cited.

[0491] In the general formula (B-13), as the perfluoroalkyl group represented by Y F6 It has the same meaning as the perfluoroalkyl group represented by Y in the above general formula (B-1), and the preferred modes are also the same. F1 In the general formula (B-13), as the perfluoroalkyl group represented by Y, it has the same meaning as the perfluoroalkyl group represented by Y in the above general formula (B-1), and the preferred modes are also the same.

[0492] As the substituent that does not have the fluorine atom represented by Y 11 It has the same meaning as the substituent that does not have the fluorine atom represented by Y in the above general formula (B-1), and the preferred modes are also the same. 1 In the general formula (B-13), as the substituent that does not have the fluorine atom represented by Y, it has the same meaning as the substituent that does not have the fluorine atom represented by Y in the above general formula (B-1), and the preferred modes are also the same.

[0493] In the general formula (B-14), as the substituent that does not have the fluorine atom represented by Y 12 It has the same meaning as the substituent that does not have the fluorine atom represented by Y in the above general formula (B-1), and the preferred modes are also the same. 1 In the general formula (B-14), as the substituent that does not have the fluorine atom represented by Y, it has the same meaning as the substituent that does not have the fluorine atom represented by Y in the above general formula (B-1), and the preferred modes are also the same.

[0494] In the general formula (B-15), as the perfluoroalkyl group represented by Y F7 It has the same meaning as the perfluoroalkyl group represented by Y in the above general formula (B-1), and the preferred modes are also the same. F1 In the general formula (B-15), as the perfluoroalkyl group represented by Y, it has the same meaning as the perfluoroalkyl group represented by Y in the above general formula (B-1), and the preferred modes are also the same.

[0495] As the substituent that does not have the fluorine atom represented by Y 13 It has the same meaning as the substituent that does not have the fluorine atom represented by Y in the above general formula (B-1), and the preferred modes are also the same. 1 In the general formula (B-15), as the substituent that does not have the fluorine atom represented by Y, it has the same meaning as the substituent that does not have the fluorine atom represented by Y in the above general formula (B-1), and the preferred modes are also the same.

[0496] As the organic group represented by Rf, it has the same meaning as the organic group represented by Ra in the above general formula (B-3), and the preferred modes are also the same.

[0497] In the general formula (B-16), as the substituent that does not have the fluorine atom represented by Y 14 It has the same meaning as the substituent that does not have the fluorine atom represented by Y in the above general formula (B-1), and the preferred modes are also the same. 1 In the general formula (B-16), as the substituent that does not have the fluorine atom represented by Y, it has the same meaning as the substituent that does not have the fluorine atom represented by Y in the above general formula (B-1), and the preferred modes are also the same.

[0498] As the Rf1 The organic group represented has the same meaning as the organic group represented by Ra in the above general formula (B-3), and the preferred modes are also the same.

[0499] In general formula (B-17), as the perfluoroalkyl group represented by Y F8 has the same meaning as the perfluoroalkyl group represented by Y in the above general formula (B-1), and the preferred modes are also the same. F1 The perfluoroalkyl group represented has the same meaning as the perfluoroalkyl group represented by Y in the above general formula (B-1), and the preferred modes are also the same.

[0500] As the substituent that does not have a fluorine atom represented by Y 15 has the same meaning as the substituent that does not have a fluorine atom represented by Y in the above general formula (B-1), and the preferred modes are also the same. 1 The substituent that does not have a fluorine atom represented has the same meaning as the substituent that does not have a fluorine atom represented by Y in the above general formula (B-1), and the preferred modes are also the same.

[0501] The organic groups represented by Rg and Rf respectively have the same meaning as the organic group represented by Ra in the above general formula (B-3), and the preferred modes are also the same.

[0502] In general formula (B-18), as the substituent that does not have a fluorine atom represented by Y 16 has the same meaning as the substituent that does not have a fluorine atom represented by Y in the above general formula (B-1), and the preferred modes are also the same. 1 The substituent that does not have a fluorine atom represented has the same meaning as the substituent that does not have a fluorine atom represented by Y in the above general formula (B-1), and the preferred modes are also the same.

[0503] As the organic group represented by Rg 1 、Rf 1 The organic groups represented respectively have the same meaning as the organic group represented by Ra in the above general formula (B-3), and the preferred modes are also the same.

[0504] In general formula (B-19), as the perfluoroalkyl group represented by Y F9 has the same meaning as the perfluoroalkyl group represented by Y in the above general formula (B-1), and the preferred modes are also the same. F1 The perfluoroalkyl group represented has the same meaning as the perfluoroalkyl group represented by Y in the above general formula (B-1), and the preferred modes are also the same.

[0505] As the substituent that does not have a fluorine atom represented by Y 17 has the same meaning as the substituent that does not have a fluorine atom represented by Y in the above general formula (B-1), and the preferred modes are also the same. 1 The substituent that does not have a fluorine atom represented has the same meaning as the substituent that does not have a fluorine atom represented by Y in the above general formula (B-1), and the preferred modes are also the same.

[0506] In general formula (B-20), as the substituent that does not have a fluorine atom represented by Y 18 has the same meaning as the substituent that does not have a fluorine atom represented by Y in the above general formula (B-1), and the preferred modes are also the same. 1 The substituent that does not have a fluorine atom represented has the same meaning as the substituent that does not have a fluorine atom represented by Y in the above general formula (B-1), and the preferred modes are also the same.

[0507] In general formula (B-21), as the perfluoroalkyl group represented by Y F10 has the same meaning as the perfluoroalkyl group represented by Y in the above general formula (B-1), and the preferred modes are also the same. F1The perfluoroalkyl groups represented have the same meaning and the same preferred embodiments.

[0508] As a substituent that does not have a fluorine atom represented by Y 19 it has the same meaning and the same preferred embodiments as the substituent that does not have a fluorine atom represented by Y in the above general formula (B-1). 1 The perfluoroalkyl groups represented have the same meaning and the same preferred embodiments.

[0509] As the organic groups represented by Ri and Rj, they have the same meaning and the same preferred embodiments as the organic group represented by Ra in the above general formula (B-3), respectively.

[0510] In the general formula (B-22), as a substituent that does not have a fluorine atom represented by Y 20 it has the same meaning and the same preferred embodiments as the substituent that does not have a fluorine atom represented by Y in the above general formula (B-1). 1 The perfluoroalkyl groups represented have the same meaning and the same preferred embodiments.

[0511] As the organic group represented by Ri 1 and Rj 1 they have the same meaning and the same preferred embodiments as the organic group represented by Ra in the above general formula (B-3), respectively.

[0512] In the general formula (B-23), as a substituent that does not have a fluorine atom represented by Rk, it has the same meaning and the same preferred embodiments as the substituent that does not have a fluorine atom represented by Y in the above general formula (B-1). 1 The perfluoroalkyl groups represented have the same meaning and the same preferred embodiments.

[0513] In the general formula (B-24), as the organic group represented by R1, it has the same meaning and the same preferred embodiments as the organic group represented by Ra in the above general formula (B-3), respectively.

[0514] And, as a preferred embodiment, the organic group represented by R1 is preferably an organic group that does not have a fluorine atom.

[0515] As the halogen atom represented by R1, a fluorine atom, a chlorine atom, a bromine atom or an iodine atom can be cited.

[0516] As the organic group represented by Rc 2 it has the same meaning and the same preferred embodiments as the organic group represented by Ra in the above general formula (B-3).

[0517] In the general formula (B-25), as the perfluoroalkyl group represented by Y F11 it has the same meaning and the same preferred embodiments as the perfluoroalkyl group represented by Y in the above general formula (B-1). F1 The perfluoroalkyl groups represented have the same meaning and the same preferred embodiments.

[0518] As the organic group represented by Rc 3The organic group represented is the same as the organic group represented by Ra in the above general formula (B-3), and the preferred embodiments are also the same.

[0519] In the general formula (B-26), as the perfluoroalkyl group represented by Y F12 is the same as the perfluoroalkyl group represented by Y in the above general formula (B-1), and the preferred embodiments are also the same. F1 The perfluoroalkyl group represented by Y

[0520] As the organic group represented by Rd 2 is the same as the organic group represented by Ra in the above general formula (B-3), and the preferred embodiments are also the same.

[0521] In the general formula (B-27), as the perfluoroalkyl group represented by Y F13 is the same as the perfluoroalkyl group represented by Y in the above general formula (B-1), and the preferred embodiments are also the same. F1 The perfluoroalkyl group represented by Y

[0522] In the above general formula (I), A 1 - is preferably a group represented by the above general formula (B-1), (B-2), (B-3), (B-4) or (B-23), more preferably a group represented by the above (B-2) or (B-23), and further preferably a group represented by the above (B-2).

[0523] In the above general formula (I), A 2 - is preferably a group represented by the above general formula (B-6), (B-8), (B-10), (B-11), (B-12) or (B-24), more preferably a group represented by the above (B-10), (B-11), (B-12) or (B-24), and further preferably a group represented by the above (B-11) or (B-24).

[0524] In the above general formula (I), A 1 - The combination with A 2 - is more preferably a combination in which A 1 - and A 2 - are each a preferred group.

[0525] In addition, the acid dissociation constant a1 and the acid dissociation constant a2 are obtained by the above method.

[0526] Hereinafter, the acid dissociation constant a1 and the acid dissociation constant a2 of the compound PI will be specifically described.

[0527] In general formula (I), when m represents 1, when determining the acid dissociation constant of compound PI, compound PI is equivalent to "a compound having HA 1 and HA 2 ." The pKa when it becomes "a compound having A 1 - and HA 2 " is the acid dissociation constant a1. The pKa when the above-mentioned "compound having A 1 - and HA 2 " becomes "a compound having A 1 - and A 2 - " is the acid dissociation constant a2.

[0528] In general formula (I), when m represents 2, when determining the acid dissociation constant of compound PI, compound PI is equivalent to "a compound having two HAs 1 and HA 2 ." When determining the acid dissociation constant of this compound PI, the pKa when compound PI becomes "a compound having one A 1 - , and one HA 1 and HA 2 " is the acid dissociation constant a1, and the pKa when "a compound having two As 1 - and HA 2 " becomes "a compound having two As 1 - and A 2 - " is the acid dissociation constant a2. That is, when compound PI has two acid dissociation constants derived from the acidic sites represented by HA 1 , the minimum value thereof is regarded as the acid dissociation constant a1.

[0529] Moreover, the above compound PI is equivalent to an acid generated by irradiating the compound represented by general formula (I) with actinic rays or radiation.

[0530] From the viewpoint of more excellent roughness performance of the formed pattern, in the above compound PI, the difference between the acid dissociation constant a1 and the above acid dissociation constant a2 is preferably 2.0 or more, more preferably 3.0 or more. In addition, the upper limit value of the difference between the acid dissociation constant a1 and the above acid dissociation constant a2 is not particularly limited, for example, it is 15.0 or less.

[0531] Furthermore, from the viewpoint of more effectively suppressing the excessive diffusion of acid to the unexposed area, in the above-mentioned compound PI, the acid dissociation constant a2 is preferably 2.0 or more, more preferably 3.0 or more, and still more preferably 4.0 or more.

[0532] Furthermore, the upper limit value of the acid dissociation constant a2 is not particularly limited, and is, for example, 10.0 or less, preferably 7.0 or less, and more preferably 6.0 or less.

[0533] Furthermore, in the above-mentioned compound PI, the acid dissociation constant a1 is -1.5 or more, more preferably -1.2 or more, and still more preferably -1.0 or more. In addition, the upper limit value of the acid dissociation constant a1 is not particularly limited, and is, for example, 2.0 or less, preferably 1.5 or less.

[0534] In general formula (I), the preferred forms of the cations represented by M 1 + and M 2 + are described in detail.

[0535] When m represents 1, M 1 + and M 2 + can be bonded via a single bond or a linking group to form a divalent cation.

[0536] Furthermore, when m represents 2, at least two of the two Ms 1 + and M 2 + can be bonded via a single bond or a linking group to form a divalent or trivalent cation.

[0537] The cations represented by M 1 + and M 2 + are not particularly limited, and are each independently preferably an onium cation, and preferably a cation represented by the following general formula (ZIA) or general formula (ZIIA).

[0538] [Chemical formula 15]

[0539]

[0540] In the above general formula (ZIA),

[0541] R 201 , R 202 and R 203 each independently represent a hydrogen atom or a substituent.

[0542] As R 201 , R 202and R 203 The substituents of 203 are preferably organic groups, and the number of carbon atoms of the organic group is usually 1 to 30, preferably 1 to 20.

[0543] Moreover, two of R 201 ~R 203 can be bonded to each other to form a ring (also referred to as a ring structure), and may contain an oxygen atom, a sulfur atom, an ester bond, an amide bond, or a carbonyl group within the ring. As the group formed by bonding two of R 201 ~R 203 to each other, an alkylene group (for example, butylene group, pentylene group, etc.) and -CH 2 -CH 2 -O-CH 2 -CH 2 - can be mentioned.

[0544] As a preferred mode of the cation of the general formula (ZIA), the following cations can be mentioned: cation (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)).

[0545] The cation can be a cation having a plurality of structures represented by the general formula (ZIA). As such a cation, for example, one in which at least one of R 201 ~R 203 of the cation represented by the general formula (ZIA) is bonded to at least one of R 201 ~R 203 of another cation represented by the general formula (ZIA) via a single bond or a linking group, such as a divalent cation having such a structure, can be mentioned.

[0546] First, the cation (ZI-11) will be described.

[0547] The cation (ZI-11) is a cation in which at least one of R 201 ~R 203 of the above general formula (ZIA) is an aryl group, that is, an arylsulfonium cation.

[0548] In the arylsulfonium cation, all of R 201 ~R 203 can be aryl groups, or a part of R 201 ~R 203 can be aryl groups and the rest can be alkyl groups or cycloalkyl groups.

[0549] As the arylsulfonium cation, for example, a triarylsulfonium cation, a diarylalkylsulfonium cation, an aryldialkylsulfonium cation, a diarylcycloalkylsulfonium cation, and an arylbicycloalkylsulfonium cation can be mentioned.

[0550] As the aryl group contained in the arylsulfonium cation, a phenyl group or a naphthyl group is preferred, and a phenyl group is more preferred. The aryl group may be an aryl group containing a heterocyclic structure having an oxygen atom, a nitrogen atom, a sulfur atom or the like. Examples of the heterocyclic structure include a pyrrole residue, a furan residue, a thiophene residue, an indole residue, a benzofuran residue, and a benzothiophene residue. When the arylsulfonium cation has two or more aryl groups, the two or more aryl groups may be the same or different.

[0551] The alkyl group or cycloalkyl group that the arylsulfonium cation optionally has is preferably a linear alkyl group having 1 to 15 carbon atoms, a branched alkyl group having 3 to 15 carbon atoms, or a cycloalkyl group having 3 to 15 carbon atoms. Examples thereof include a methyl group, an ethyl group, a propyl group, a n-butyl group, a sec-butyl group, a tert-butyl group, a cyclopropyl group, a cyclobutyl group, and a cyclohexyl group.

[0552] R 201 ~R 203 The aryl group, alkyl group, and cycloalkyl group of ~R may each independently have 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 14 carbon atoms), an alkoxy group (for example, having 1 to 15 carbon atoms), a halogen atom, a hydroxyl group, a lactone ring group, or a phenylthio group as a substituent.

[0553] 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 (LC1-1) to (LC1-21) can be cited.

[0554] Next, the cation (ZI-12) will be described.

[0555] The cation (ZI-12) is a compound in which R 201 ~R 203 in the formula (ZA) each independently represents an organic group having no aromatic ring. Here, the aromatic ring also includes an aromatic ring containing a heteroatom.

[0556] As R 201 ~R 203 The organic group having no aromatic ring usually has 1 to 30 carbon atoms, preferably 1 to 20 carbon atoms.

[0557] 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.

[0558] As R 201 ~R 203The alkyl and cycloalkyl groups therein preferably include linear alkyl groups having 1 to 10 carbon atoms or branched alkyl groups having 3 to 10 carbon atoms (e.g., methyl, ethyl, propyl, butyl, and pentyl), and cycloalkyl groups having 3 to 10 carbon atoms (e.g., cyclopentyl, cyclohexyl, and norbornyl).

[0559] R 201 ~R 203 may be further substituted with a halogen atom, an alkoxy group (e.g., having 1 to 5 carbon atoms), a hydroxyl group, a cyano group, or a nitro group.

[0560] Next, the cation (ZI-13) will be described.

[0561] [Chemical Formula 16]

[0562]

[0563] In the general formula (ZI-13), M represents an alkyl group, a cycloalkyl group, or an aryl group. When having a ring structure, the above ring structure may include at least one of an oxygen atom, a sulfur atom, an ester bond, an amide bond, and a carbon-carbon double bond. R 1c and R 2c each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, a cyano group, or an aryl group. R 1c and R 2c may be bonded to form a ring. R x and R y each independently represent an alkyl group, a cycloalkyl group, or an alkenyl group. R x and R y may be bonded to form a ring. And, at least two selected from M, R 1c and R 2c may be bonded to form a ring structure, and the above ring structure may include a carbon-carbon double bond.

[0564] In the general formula (ZI-13), as the alkyl and cycloalkyl groups represented by M, preferred are linear alkyl groups having 1 to 15 carbon atoms (preferably having 1 to 10 carbon atoms), branched alkyl groups having 3 to 15 carbon atoms (preferably having 3 to 10 carbon atoms), or cycloalkyl groups having 3 to 15 carbon atoms (preferably having 1 to 10 carbon atoms). Specifically, examples include methyl, ethyl, propyl, n-butyl, sec-butyl, tert-butyl, cyclopropyl, cyclobutyl, cyclohexyl, and norbornyl, etc.

[0565] As the aryl group represented by M, preferred is a phenyl group or a naphthyl group, and more preferably a phenyl group. The aryl group may be an aryl group containing a heterocyclic structure having an oxygen atom or a sulfur atom, etc. As the heterocyclic structure, examples include a furan ring, a thiophene ring, a benzofuran ring, and a benzothiophene ring, etc.

[0566] The above M may further have a substituent. As such a case, for example, benzyl, etc. may be cited as M.

[0567] In addition, when M has a ring structure, the above ring structure may contain at least one of an oxygen atom, a sulfur atom, an ester bond, an amide bond, and a carbon-carbon double bond.

[0568] As the alkyl group, cycloalkyl group, and aryl group represented by R 1c and R 2c the same groups as those of M described above may be mentioned, and their preferred modes are also the same. Moreover, R 1c and R 2c may be bonded to form a ring.

[0569] As the halogen atom represented by R 1c and R 2c for example, a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom may be mentioned.

[0570] As the alkyl group and cycloalkyl group represented by R x and R y the same groups as those of M described above may be mentioned, and their preferred modes are also the same.

[0571] As the alkenyl group represented by R x and R y allyl or vinyl is preferred.

[0572] The above R x and R y may further have substituents. As such a mode, for example, as R x and R y 2-oxoalkyl or alkoxycarbonylalkyl may be mentioned.

[0573] 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) may be mentioned. Specifically, 2-oxopropyl and 2-oxobutyl may be mentioned.

[0574] 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) may be mentioned. Moreover, R x and R y may be bonded to form a ring.

[0575] R x and R y The ring structure formed by connecting each other may contain an oxygen atom, a sulfur atom, an ester bond, an amide bond, or a carbon-carbon double bond.

[0576] In the general formula (ZI-13), M and R 15can be bonded to form a ring structure, and the formed ring structure may contain a carbon-carbon double bond.

[0577] Among them, the above-mentioned cation (ZI-13) is preferably the cation (ZI-13A).

[0578] The cation (ZI-13A) is a benzoylmethylsulfonium cation represented by the following general formula (ZI-13A).

[0579] [Chemical formula 17]

[0580]

[0581] In the general formula (ZI-13A),

[0582] R 1c ~R 5c each independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an alkoxy group, an aryloxy group, an alkoxycarbonyl group, an alkylcarbonyloxy group, a cycloalkylcarbonyloxy group, a halogen atom, a hydroxyl group, a nitro group, an alkylthio group or an arylthio group.

[0583] As R 6c and R 7c , it has the same meaning as R 1c and R 2c in the above general formula (ZI-13), and their preferred modes are also the same.

[0584] As R x and R y , it has the same meaning as R x and R y in the above general formula (ZI-13), and their preferred modes are also the same.

[0585] R 1c ~R 5c any two or more of them, R x and R y can each be bonded to form a ring structure, and the ring structure may independently contain an oxygen atom, a sulfur atom, an ester bond, an amide bond or a carbon-carbon double bond. And, R 5c and R 6c , R 5c and R x can each be bonded to form a ring structure, and the ring structure may independently contain a carbon-carbon double bond. And, R 6c and R 7c can each be bonded to form a ring structure.

[0586] As the above-mentioned ring structure, an aromatic or non-aromatic hydrocarbon ring, an aromatic or non-aromatic heterocyclic ring, and a polycyclic condensed 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, more preferably a 5-membered ring or a 6-membered ring.

[0587] As R 1c ~R 5c Among any two or more of, R 6c and R 7c and R x and R y The groups formed by bonding can include a butylene group, a pentylene group, etc.

[0588] As R 5c and R 6c and R 5c and R x The groups formed by bonding are preferably a single bond or an alkylene group. As the alkylene group, a methylene group, an ethylene group, etc. can be cited.

[0589] Next, the cation (ZI-14) will be described.

[0590] The cation (ZI-14) is represented by the following general formula (ZI-14).

[0591] [Chemical formula 18]

[0592]

[0593] In the general formula (ZI-14),

[0594] l represents an integer of 0 to 2.

[0595] r represents an integer of 0 to 8.

[0596] 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.

[0597] When there are a plurality of R 14 s, 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.

[0598] R 15 each independently represents an alkyl group, a cycloalkyl group, or a naphthyl group. These groups may also have substituents. Two R 15 s may bond to each other to form a ring. When two R 15When forming a ring by bonding to each other, heteroatoms such as oxygen atoms or nitrogen atoms may be contained within the ring skeleton. In one embodiment, it is preferred that two Rs 15 are alkylene groups and bond to each other to form a ring structure.

[0599] In the general formula (ZI-14), R 13 , R 14 and R 15 are linear or branched alkyl groups. 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 preferred.

[0600] Next, the general formula (ZIIA) will be described.

[0601] In the general formula (ZIIA), R 204 and R 205 each independently represent an aryl group, an alkyl group or a cycloalkyl group.

[0602] As the aryl groups of R 204 and R 205 , phenyl or naphthyl is preferred, and phenyl is more preferred. The aryl groups of R 204 and R 205 may be aryl groups containing a heterocyclic structure having an oxygen atom, a nitrogen atom or a sulfur atom. As the skeleton of the aryl group having a heterocyclic structure, for example, pyrrole, furan, thiophene, indole, benzofuran and benzothiophene can be mentioned.

[0603] As the alkyl groups and cycloalkyl groups of R 204 and R 205 , linear alkyl groups having 1 to 10 carbon atoms or branched alkyl groups having 3 to 10 carbon atoms (for example, methyl, ethyl, propyl, butyl and pentyl) or cycloalkyl groups having 3 to 10 carbon atoms (for example, cyclopentyl, cyclohexyl and norbornyl) are preferred.

[0604] The aryl groups, alkyl groups and cycloalkyl groups of R 204 and R 205 may each independently have a substituent. As the substituents that the aryl groups, alkyl groups and cycloalkyl groups of R 204 to R 207 may have, for example, alkyl groups (for example, having 1 to 15 carbon atoms), cycloalkyl groups (for example, having 3 to 15 carbon atoms), aryl groups (for example, having 6 to 15 carbon atoms), alkoxy groups (for example, having 1 to 15 carbon atoms), halogen atoms, hydroxy lactone groups and phenylthio groups.

[0605] As the lactone group, for example, a group obtained by removing a hydrogen atom from the structure represented by any one of the following (LC1-1) to (LC1-21) can be mentioned.

[0606] The following shows M as1 + , M 2 + Preferred examples of the cations of, but the present invention is not limited to these. Me represents methyl.

[0607] [Chemical Formula 19]

[0608]

[0609] [Chemical Formula 20]

[0610]

[0611] [Chemical Formula 21]

[0612]

[0613] [Chemical Formula 22]

[0614]

[0615] Preferred examples of the anion moiety in the compound represented by the general formula (1) are shown below, but the present invention is not limited to these. Me represents methyl.

[0616] [Chemical Formula 23]

[0617]

[0618] [Chemical Formula 24]

[0619]

[0620] [Chemical Formula 25]

[0621]

[0622] Preferred examples of the compound (B) are shown below, but the present invention is not limited to these. Me represents methyl. Also, as a preferred example of the compound (B), a compound formed by combining the above anion and the above cation can also be cited.

[0623] [Chemical Formula 26]

[0624]

[0625] [Chemical Formula 27]

[0626]

[0627] [Chemical Formula 28]

[0628]

[0629] [Chemical Formula 29]

[0630]

[0631] [Chemical Formula 30]

[0632]

[0633] The molecular weight of the above compound (B) is preferably from 300 to 3000, more preferably from 300 to 2000, and still more preferably from 300 to 1500.

[0634] Compound (B) can be used alone as one kind, or two or more kinds can be used in combination.

[0635] In the composition of the present invention, the content of compound (B) (the total when there are a plurality of them) 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 based on the total solid content of the composition.

[0636] [(B’) A compound that generates an acid upon irradiation with actinic rays or radiation other than the above compound (B)]

[0637] The composition of the present invention can contain a compound that generates an acid upon irradiation with actinic rays or radiation other than compound (B) within the range that does not impair the effects of the present invention.

[0638] [(A) A resin whose polarity increases by the action of an acid]

[0639] A resin (A) whose polarity increases by the action of an acid (hereinafter, also referred to as "acid-decomposable resin" or "resin (A)") will be described.

[0640] In addition, as described later, resin (A) can contain a repeating unit having a photoacid generator group.

[0641] In the pattern formation using a resist composition containing resin (A), typically, when an alkaline developer is used as the developer, a positive pattern is preferably formed, and when an organic developer is used as the developer, a negative pattern is preferably formed.

[0642] Resin (A) usually contains a group whose polarity increases by decomposition by the action of an acid (hereinafter, also referred to as "acid-decomposable group"), and preferably contains a repeating unit having an acid-decomposable group.

[0643] Hereinafter, the repeating units that resin (A) can contain will be described.

[0644] The above resin (A) contains a repeating unit represented by the following general formula (AI).

[0645] [Chemical Formula 31]

[0646]

[0647] In general formula (AI),

[0648] R A 、R B and R C each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, a cyano group or an alkoxycarbonyl group. Among them, R C can bond with Ar A to form a ring, and at this time R C represents a single bond or an alkylene group.

[0649] L A represents a single bond or a divalent linking group.

[0650] Ar A represents an (n + 1)-valent aromatic ring group. When bonding with R C to form a ring, it represents an (n + 2)-valent aromatic ring group.

[0651] n represents an integer from 1 to 5.

[0652] As the alkyl groups of R A 、R B and R C in general formula (AI), 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.

[0653] As the cycloalkyl groups of R A 、R B and R C in general formula (AI), it can be monocyclic or polycyclic. Among them, preferably monocyclic cycloalkyl groups with 3 to 8 carbon atoms such as cyclopropyl, cyclopentyl and cyclohexyl.

[0654] As the halogen atoms of R A 、R B and R C in general formula (AI), fluorine atom, chlorine atom, bromine atom and iodine atom can be cited, and preferably fluorine atom.

[0655] As the alkyl group contained in the alkoxycarbonyl group of R A 、R B and R C in general formula (AI), preferably the same as the above R A 、R Band R C an alkyl group identical to the alkyl group in

[0656] Each of the above groups may have a substituent. There is no particular limitation on preferred substituents in each of the above groups. For example, alkyl, cycloalkyl, aryl, amino, amide, urea, carbamate, hydroxy, carboxy, halogen atom, alkoxy, thioether, acyl, acyloxy, alkoxycarbonyl, cyano and nitro can be mentioned. The number of carbon atoms of the substituent is preferably 8 or less.

[0657] Ar A represents an (n + 1)-valent aromatic ring group. The divalent aromatic ring group when n is 1 is preferably an arylene group having 6 to 18 carbon atoms such as phenylene, tolylene group, naphthylene and anthrylene, or a divalent aromatic ring group containing a heterocycle such as a thiophene ring, furan ring, pyrrole ring, benzothiophene ring, benzofuran ring, benzopyrrole ring, triazine ring, imidazole ring, benzimidazole ring, triazole ring, thiadiazole ring and thiazole ring. In addition, the above aromatic ring group may have a substituent.

[0658] As a specific example of the (n + 1)-valent aromatic ring group when n is an integer of 2 or more, a group formed by removing (n - 1) arbitrary hydrogen atoms from the above specific examples of the divalent aromatic ring group can be mentioned.

[0659] The (n + 1)-valent aromatic ring group may also have a substituent.

[0660] There is no particular limitation on the substituent that the above alkyl, cycloalkyl, alkoxycarbonyl, alkylene and (n + 1)-valent aromatic ring group may have. For example, alkyl, methoxy, ethoxy, hydroxyethoxy, propoxy, hydroxypropoxy and butoxy and other alkoxy groups as well as aryl groups such as phenyl mentioned in R A 、R B and R C in the general formula (I) can be mentioned.

[0661] As the divalent linking group of L A there is no particular limitation, and -COO-, -CONR 64 -, alkylene or a group formed by combining two or more of these groups can be mentioned. R 64 represents a hydrogen atom or an alkyl group.

[0662] There is no particular limitation on the alkylene, and alkylene groups having 1 to 8 carbon atoms such as methylene, ethylene, propylene, butylene, hexylene and octylene are preferred.

[0663] As R 64Examples of the alkyl group having 20 or less carbon atoms include methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, hexyl, 2-ethylhexyl, octyl, and dodecyl. An alkyl group having 8 or less carbon atoms is preferred.

[0664] As Ar A , an aromatic ring group having 6 to 18 carbon atoms is preferred, and a benzene ring group, a naphthalene ring group, and a biphenylene ring group are more preferred.

[0665] The repeating unit represented by the general formula (AI) preferably has a hydroxystyrene structure. That is, Ar A is preferably a benzene ring group.

[0666] n is preferably an integer of 1 to 3, and more preferably 1 or 2.

[0667] The repeating unit represented by the general formula (AI) is exemplified below. In the formula, a represents 1, 2, or 3.

[0668] [Chemical formula 32]

[0669]

[0670] [Chemical formula 33]

[0671]

[0672]

[0673] [Chemical formula 34]

[0674]

[0675] In addition, the repeating unit represented by the general formula (AI) is preferably the repeating unit specifically described below. In the formula, R represents a hydrogen atom or a methyl group, and a represents 1, 2, or 3.

[0676] [Chemical formula 35]

[0677]

[0678] The content of the repeating unit represented by the general formula (AI) is preferably 30 mol% or more, more preferably 40 mol% or more, relative to all the repeating units in the resin (A). As the upper limit value, 90 mol% or less is preferred, 85 mol% or less is more preferred, and 80 mol% or less is further preferred.

[0679] (Repeating unit having an acid-decomposable group)

[0680] An acid-decomposable group refers to a group that decomposes by the action of an acid to generate a polar group. The acid-decomposable group preferably has a structure in which the polar group is protected by a leaving group that is detached by the action of an acid. That is, the resin (A) contains a repeating unit having a group that decomposes by the action of an acid to generate a polar group. The resin having this repeating unit increases in polarity by the action of an acid, so that its solubility in an alkaline developer increases while its solubility in an organic solvent decreases.

[0681] As the polar group, a base-soluble group is preferred. For example, carboxyl group, phenolic hydroxyl group, fluorinated alcohol group, sulfonic acid group, phosphoric 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, tris(alkylsulfonyl)methylene and other acidic groups, as well as alcoholic hydroxyl group, etc. can be cited.

[0682] Among them, as the polar group, carboxyl group, phenolic hydroxyl group, fluorinated alcohol group (preferably hexafluoroisopropanol group) or sulfonic acid group is preferred. In particular, as the polar group, carboxyl group or phenolic hydroxyl group is more preferred. That is, as the acid-decomposable group, a group that decomposes by the action of an acid to generate a carboxyl group or a group that decomposes by the action of an acid to generate a phenolic hydroxyl group is preferred.

[0683] The above resin (A) contains a repeating unit having an acid-decomposable group, and the repeating unit having an acid-decomposable group is preferably a repeating unit selected from a repeating unit having a group that decomposes by the action of an acid to generate a carboxyl group and a repeating unit having a group that decomposes by the action of an acid to generate a phenolic hydroxyl group.

[0684] As the leaving group that is detached by the action of an acid, for example, groups represented by the formulas (Y1) to (Y4) can be cited.

[0685] Formula (Y1): -C(Rx 1 )(Rx 2 )(Rx 3 )

[0686] Formula (Y2): -C(=O)OC(Rx 1 )(Rx 2 )(Rx 3 )

[0687] Formula (Y3): -C(R 36 )(R 37 )(OR 38 )

[0688] Formula (Y4): -C(Rn)(H)(Ar)

[0689] In formula (Y1) and formula (Y2), Rx 1 ~Rx 3 each independently represents an alkyl group (linear or branched), a cycloalkyl group (monocyclic or polycyclic), an aryl group (monocyclic or polycyclic), an aralkyl group (linear or branched), or an alkenyl group (linear or branched). Additionally, when all of Rx 1 ~Rx 3 are alkyl groups (linear or branched), it is preferred that at least two of Rx 1 ~Rx 3 are methyl groups.

[0690] Among them, it is preferred that Rx 1 ~Rx 3 each independently represents a linear or branched alkyl group, and more preferably Rx 1 ~Rx 3 each independently represents a linear alkyl group.

[0691] Two of Rx 1 ~Rx 3 can be bonded to each other to form a ring (which can be either a monocyclic or polycyclic ring).

[0692] As the alkyl group of Rx 1 ~Rx 3 , preferred are alkyl groups having 1 to 5 carbon atoms such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, and tert-butyl.

[0693] As the cycloalkyl group of Rx 1 ~Rx 3 , preferred are monocyclic cycloalkyl groups such as cyclopentyl and cyclohexyl, and polycyclic cycloalkyl groups such as norbornyl, tetracyclodecyl, tetracyclododecyl, and adamantyl.

[0694] As the aryl group of Rx 1 ~Rx 3 , preferred are aryl groups having 6 to 10 carbon atoms, such as phenyl, naphthyl, and anthracenyl.

[0695] As the aralkyl group of Rx 1 ~Rx 3 , preferred is a group formed by substituting one hydrogen atom of the above-mentioned alkyl group of Rx 1 ~Rx 3 with an aryl group having 6 to 10 carbon atoms (preferably phenyl), such as benzyl.

[0696] As the alkenyl group of Rx 1 ~Rx 3 , preferred is vinyl.

[0697] As Rx 1~Rx 3 A ring formed by bonding two of them in 3 , preferably a cycloalkyl group. As Rx 1 ~Rx 3 A cycloalkyl group formed by bonding two of them in 3 is preferably a monocyclic cycloalkyl group such as cyclopentyl or cyclohexyl, or a polycyclic cycloalkyl group such as norbornyl, tetracyclodecyl, tetracyclododecyl or adamantyl, and more preferably a monocyclic cycloalkyl group having 5 to 6 carbon atoms.

[0698] Rx 1 ~Rx 3 In the cycloalkyl group formed by bonding two of them in 3 , for example, one of the methylene groups constituting the ring may be substituted with a heteroatom group having a heteroatom such as an oxygen atom, a carbonyl group or the like, or a vinylidene group. And in these cycloalkyl groups, one or more of the ethylene groups constituting the cycloalkane ring may be substituted with vinylene.

[0699] 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 bond to form the above cycloalkyl group in the following manner.

[0700] In formula (Y3), R 36 ~R 38 each independently represents a hydrogen atom or a monovalent organic group. R 37 and R 38 may bond 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.

[0701] And the above alkyl group, cycloalkyl group, aryl group and aralkyl group may also contain a heteroatom group having a heteroatom such as an oxygen atom and / or a carbonyl group. For example, in the above alkyl group, cycloalkyl group, aryl group and aralkyl group, for example, one or more of the methylene groups may be substituted with a heteroatom group having a heteroatom such as an oxygen atom and / or a carbonyl group.

[0702] And R 38 may bond to another substituent on the main chain of the repeating unit to form a ring. The group formed by bonding R 38 and another substituent on the main chain of the repeating unit to each other is preferably an alkylene group such as a methylene group.

[0703] As formula (Y3), a group represented by the following formula (Y3-1) is preferred.

[0704] [Chemical formula 36]

[0705]

[0706] 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).

[0707] M represents a single bond or a divalent linking group.

[0708] 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).

[0709] 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.

[0710] 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.

[0711] 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).

[0712] 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.

[0713] 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.

[0714] From the viewpoint of excellent acid decomposability of the repeating unit, it is also preferable that when a non-aromatic ring is directly bonded to a polar group (or its residue) in a leaving group that protects a polar group, a ring member atom adjacent to the ring member atom directly bonded to the polar group (or its residue) in the non-aromatic ring does not have a halogen atom such as a fluorine atom as a substituent.

[0715] In addition, the leaving group that is removed by the action of an acid may also be 2-cyclopentenyl having a substituent (such as an alkyl group) such as 3-methyl-2-cyclopentenyl, and cyclohexyl having a substituent (such as an alkyl group) such as 1,1,4,4-tetramethylcyclohexyl.

[0716] The repeating unit having an acid-decomposable group preferably contains one or more selected from the repeating units represented by the following general formulas (3) to (7), and more preferably contains one or more selected from the repeating unit represented by the following general formula (6) and the repeating unit represented by the following general formula (7).

[0717] [Chemical formula 37]

[0718]

[0719] In general formula (3), R 5 , R 6 and R 7 each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, a cyano group or an alkoxycarbonyl group.

[0720] L 2 represents a single bond or a divalent linking group.

[0721] R 8 to R 10 each independently represent an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group or an alkenyl group. In addition, two of R 8 to R 10 can be bonded to each other to form a ring.

[0722] As the alkyl group represented by R 5 , R 6 and R 7 , it can be either linear or branched. The number of carbon atoms of the alkyl group is not particularly limited, but is preferably 1 to 5, and more preferably 1 to 3.

[0723] As the cycloalkyl group represented by R 5 , R 6 and R 7 , it is preferably a monocyclic cycloalkyl group such as cyclopentyl and cyclohexyl, and a polycyclic cycloalkyl group such as norbornyl, tetracyclodecyl, tetracyclododecyl and adamantyl.

[0724] As the halogen atom represented by R 5 , R 6 and R 7 , examples thereof include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom, and a fluorine atom or an iodine atom is preferred.

[0725] As the alkyl group contained in the alkoxycarbonyl group represented by R 5 , R 6 and R 7 , it can be either linear or branched. The number of carbon atoms of the alkyl group contained in the alkoxycarbonyl group is not particularly limited, and is preferably 1 to 5, and more preferably 1 to 3.

[0726] As the one represented by L 2Examples of the divalent linking group represented include -CO-, -O-, -S-, -SO-, -SO 2 -, a hydrocarbon group (e.g., an alkylene group, a cycloalkylene group, an alkenylene group, an arylene group, etc.), and a linking group formed by linking a plurality of them.

[0727] As the alkyl group represented by R 8 ~R 10 It can be either linear or branched. The number of carbon atoms of the alkyl group is not particularly limited, but is preferably 1 to 5, more preferably 1 to 3. In the alkyl group represented by R 8 ~R 10 , the methylene group can be substituted by -CO- and / or -O-.

[0728] As the cycloalkyl group represented by R 8 ~R 10 It is preferably a monocyclic cycloalkyl group such as cyclopentyl and cyclohexyl, and a polycyclic cycloalkyl group such as norbornyl, tetracyclodecanyl, tetracyclododecanyl, and adamantyl.

[0729] As the aryl group represented by R 8 ~R 10 It is preferably a phenyl group.

[0730] As the aralkyl group represented by R 8 ~R 10 It is preferably a group formed by substituting one hydrogen atom of the above-mentioned alkyl group represented by R 8 ~R 10 with an aryl group having 6 to 10 carbon atoms (preferably a phenyl group), and examples thereof include a benzyl group.

[0731] As the alkenyl group represented by R 8 ~R 10 It is preferably a vinyl group.

[0732] As the ring formed by bonding two of R 8 ~R 10 , it is preferably a cycloalkyl group. As the cycloalkyl group formed by bonding two of R 8 ~R 10 , it is preferably a monocyclic cycloalkyl group such as cyclopentyl or cyclohexyl, or a polycyclic cycloalkyl group such as norbornyl, tetracyclodecanyl, tetracyclododecanyl, or adamantyl, and more preferably a monocyclic cycloalkyl group having 5 to 6 carbon atoms.

[0733] R 8 ~R 10In the cycloalkyl group formed by bonding two of them, for example, one of the methylene groups constituting the ring can be substituted with a heteroatom such as an oxygen atom, a group having a heteroatom such as a carbonyl group, or a vinylene group. Further, in these cycloalkyl groups, one or more of the ethylene groups constituting the cycloalkane ring can be substituted with vinylene.

[0734] Each of the above groups in the general formula (3) may have a substituent, and examples of the substituent include the above substituent T.

[0735] [Chemical formula 38]

[0736]

[0737] In the general formula (4), R 11 ~R 14 each independently represents a hydrogen atom or an organic group. Among them, at least one of R 11 and R 12 represents an organic group.

[0738] X 1 represents -CO-, -SO-, or -SO 2 -.

[0739] Y 1 represents -O-, -S-, -SO-, -SO 2 -, or -NR 34 -. R 34 represents a hydrogen atom or an organic group.

[0740] L 3 represents a single bond or a divalent linking group.

[0741] R 15 ~R 17 each independently represents an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, or an alkenyl group. Further, two of R 15 ~R 17 can bond to each other to form a ring.

[0742] As the organic group represented by R 11 ~R 14 it represents an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, or an alkenyl group.

[0743] As the alkyl group, cycloalkyl group, aryl group, aralkyl group, and alkenyl group represented by R 11 ~R 14 the same groups as those of the alkyl group, cycloalkyl group, aryl group, alkyl group, and alkenyl group represented by R 8 ~R 10 in the above general formula (3) can be cited.

[0744] As X 1, wherein, preferably -CO-.

[0745] As the organic group represented by R 34 is the same as the organic group represented by R in the above, 11 ~R 14 and has the same preferred mode.

[0746] As Y 1 , preferably -O-.

[0747] As the divalent linking group represented by L 3 is the same as the divalent linking group represented by L in the above general formula (3), 2 and has the same preferred mode.

[0748] As the alkyl group, cycloalkyl group, aryl group, aralkyl group and alkenyl group represented by R 15 ~R 17 , groups the same as the alkyl group, cycloalkyl group, aryl group, alkyl group and alkenyl group represented by R in the above general formula (3) can be cited. 8 ~R 10

[0749] As the ring formed by bonding two of R 15 ~R 17 , it is preferably a cycloalkyl group. As the cycloalkyl group formed by bonding two of R 15 ~R 17 , it is preferably a monocyclic cycloalkyl group such as cyclopentyl or cyclohexyl, or a polycyclic cycloalkyl group such as norbornyl, tetracyclodecanyl, tetracyclododecanyl or adamantyl, and more preferably a monocyclic cycloalkyl group having 5 to 6 carbon atoms.

[0750] R 15 ~R 17 In the cycloalkyl group formed by bonding two of them, for example, one of the methylene groups constituting the ring can be substituted with a group having a heteroatom such as an oxygen atom, a heteroatom-containing group such as a carbonyl group, or a vinylidene group. And in these cycloalkyl groups, one or more of the ethylene groups constituting the cycloalkane ring can be substituted with vinylene.

[0751] Each of the above groups in the general formula (4) may have a substituent, and as the substituent, for example, the above substituent T can be cited.

[0752] [Chemical formula 39]

[0753]

[0754] In the general formula (5), R 18 and R 19 each independently represent a hydrogen atom or an organic group.

[0755] R20 and R 21 each independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, or an alkenyl group. Additionally, R 20 and R 21 may bond to each other to form a ring.

[0756] As the organic groups represented by R 18 and R 19 , they have the same meaning and preferred embodiments as the organic groups represented by R 11 to R 14 in the above general formula (4).

[0757] As the alkyl group, cycloalkyl group, aryl group, aralkyl group, and alkenyl group represented by R 20 and R 21 , groups the same as those represented by R 8 to R 10 in the above general formula (3) can be cited.

[0758] The alkyl group, cycloalkyl group, aryl group, aralkyl group, and alkenyl group represented by R 20 and R 21 may have substituents. As the substituents, for example, the above-mentioned substituent T can be cited.

[0759] As the ring formed by the bonding of R 20 and R 21 , it is preferably a cycloalkyl group. As the cycloalkyl group formed by the bonding of R 20 and R 21 , it is preferably a monocyclic cycloalkyl group such as cyclopentyl or cyclohexyl, or a polycyclic cycloalkyl group such as norbornyl, tetracyclodecanyl, tetracyclododecanyl, or adamantyl, and more preferably a monocyclic cycloalkyl group having 5 to 6 carbon atoms.

[0760] R 20 and R 21 In the cycloalkyl group formed by the bonding, for example, one of the methylene groups constituting the ring can be substituted with a group having a heteroatom such as an oxygen atom, a group having a heteroatom such as a carbonyl group, or a vinylidene group. And in these cycloalkyl groups, one or more of the ethylene groups constituting the cycloalkane ring can be substituted with vinylene.

[0761] [Chemical formula 40]

[0762]

[0763] In general formula (6), R 22 , R 23 and R 24 each independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, a cyano group, or an alkoxycarbonyl group.

[0764] L 4 represents a single bond or a divalent linking group.

[0765] Ar 1 represents an aromatic ring group.

[0766] R 25 ~R 27 each independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group or an alkenyl group. Additionally, R 26 and R 27 can bond to each other to form a ring. Also, Ar 1 can bond to R 24 or R 25 to form a ring.

[0767] R 22 、R 23 、R 24 and L 4 have the same meanings as R 5 、R 6 、R 7 and L 2 in the general formula (3), and the preferred embodiments are also the same.

[0768] The aromatic ring group represented by Ar 1 is not particularly limited. For example, a benzene ring or a naphthalene ring can be cited, and a benzene ring is preferred.

[0769] As the alkyl group, cycloalkyl group, aryl group, aralkyl group and alkenyl group represented by R 25 ~R 27 , groups the same as those represented by R 8 ~R 10 in the above general formula (3) can be cited.

[0770] The alkyl group, cycloalkyl group, aryl group, aralkyl group and alkenyl group represented by R 25 ~R 27 can have substituents. As the substituents, for example, the above substituent T can be cited.

[0771] As the rings formed by the bonding of R 26 and R 27 , Ar 1 and R 24 and R 25 and Ar 1 , a cycloalkyl group is preferred. As the rings formed by the bonding of R 26 and R 27 , Ar 1 and R 24 and R 25 and Ar 1A cycloalkyl group formed by bonding, preferably a monocyclic cycloalkyl group such as cyclopentyl or cyclohexyl, or a polycyclic cycloalkyl group such as norbornyl, tetracyclodecyl, tetracyclododecyl or adamantyl, more preferably a monocyclic cycloalkyl group having 5 to 6 carbon atoms.

[0772] R 26 With R 27 、Ar 1 With R 24 And R 25 With Ar 1 In the cycloalkyl group formed by bonding, for example, one of the methylene groups constituting the ring can be substituted with a heteroatom such as an oxygen atom, a group having a heteroatom such as a carbonyl group, or a vinylidene group. And in these cycloalkyl groups, one or more of the ethylene groups constituting the cycloalkane ring can be substituted with vinylene.

[0773] [Chemical formula 41]

[0774]

[0775] In general formula (7), R 28 、R 29 And R 30 Each independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, a cyano group or an alkoxycarbonyl group.

[0776] L 5 Represents a single bond or a divalent linking group.

[0777] R 31 And R 32 Each independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group or an alkenyl group.

[0778] R 33 Represents an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group or an alkenyl group. Additionally, R 32 And R 33 Can bond to each other to form a ring.

[0779] R 28 、R 29 And R 30 And L 5 And R in general formula (3) 5 、R 6 、R 7 And L 2 Have the same meaning and preferably the same preferred manner.

[0780] As the alkyl group, cycloalkyl group, aryl group, aralkyl group and alkenyl group represented by R 31 、R 32 And R 33 Examples thereof include those of R in the above general formula (3) from R 8 ~R10 Groups such as alkyl, cycloalkyl, aryl, aralkyl, and alkenyl represented are the same groups.

[0781] By R 31 , R 32 and R 33 The above-mentioned alkyl, cycloalkyl, aryl, aralkyl, and alkenyl represented may have substituents. As the substituents, for example, the above-mentioned substituent T can be cited.

[0782] As the ring formed by the bonding of R 32 and R 33 , it is preferably a cycloalkyl. As the cycloalkyl formed by the bonding of R 32 and R 33 , it is preferably a monocyclic cycloalkyl such as cyclopentyl or cyclohexyl, or a polycyclic cycloalkyl such as norbornyl, tetracyclodecyl, tetracyclododecyl, or adamantyl, and more preferably a monocyclic cycloalkyl having 5 to 6 carbon atoms.

[0783] R 32 and R 33 In the cycloalkyl formed by the bonding, for example, one of the methylene groups constituting the ring can be substituted with a group having a heteroatom such as an oxygen atom, a group having a heteroatom such as a carbonyl group, or a vinylidene group. And in these cycloalkyls, one or more of the ethylene groups constituting the cycloalkane ring can be substituted with vinylene.

[0784] The repeating unit having an acid-decomposable group may or may not contain a halogen atom, and preferably does not contain a halogen atom.

[0785] Relative to all the repeating units in the resin (A), the content of the repeating unit having an acid-decomposable group is preferably 5 mol% or more, more preferably 10 mol% or more, and further preferably 15 mol% or more. And as its upper limit value, it is preferably 95 mol% or less, more preferably 90 mol% or less, and particularly preferably 85 mol% or less.

[0786] Specific examples of the repeating unit having an acid-decomposable group are shown below, but the present invention is not limited thereto. In addition, in the formula, Xa 1 represents any one of H, CH 3 , CF 3 and CH 2 OH, and Rxa and Rxb each represent a linear or branched alkyl group having 1 to 5 carbon atoms.

[0787] [Chemical formula 42]

[0788]

[0789] [Chemical formula 43]

[0790]

[0791] [Chemical formula 44]

[0792]

[0793] [Chemical formula 45]

[0794]

[0795] [Chemical formula 46]

[0796]

[0797] [Chemical formula 47]

[0798]

[0799] [Chemical formula 48]

[0800]

[0801] [Chemical formula 49]

[0802]

[0803] The resin (A) may also contain repeating units other than the above repeating units.

[0804] For example, the resin (A) may also contain at least one repeating unit selected from the group consisting of the following Group A and / or at least one repeating unit selected from the group consisting of the following Group B.

[0805] Group A: The group consisting of the following repeating units (20) to (29).

[0806] (20) A repeating unit having an acid group described below

[0807] (21) A repeating unit having a fluorine atom or an iodine atom and not showing acid decomposability described below

[0808] (22) A repeating unit having a lactone group, a sultone group or a carbonate group described below

[0809] (23) A repeating unit having a photoacid generator group described below

[0810] (24) A repeating unit represented by the general formula (V-1) or the following general formula (V-2) described below

[0811] (25) A repeating unit represented by the formula (A) described below

[0812] (26) A repeating unit represented by the formula (B) described below

[0813] (27) The repeating unit represented by formula (C) described below

[0814] (28) The repeating unit represented by formula (D) described below

[0815] (29) The repeating unit represented by formula (E) described below

[0816] Group B: A group composed of the following repeating units (30) to (32).

[0817] (30) The repeating unit having at least one group selected from a lactone group, a sultone group, a carbonate group, a hydroxyl group, a cyano group, and a base-soluble group described below

[0818] (31) The repeating unit having an alicyclic hydrocarbon structure and not showing acid decomposability described below

[0819] (32) The repeating unit not having any of a hydroxyl group and a cyano group and represented by general formula (III) described below

[0820] When using the composition of the present invention as a photosensitive radiation-sensitive or radiation-sensitive resin composition for EUV, the resin (A) preferably has at least one repeating unit selected from the group consisting of the above Group A.

[0821] Moreover, when using the composition as a photosensitive radiation-sensitive or radiation-sensitive resin composition for EUV, the resin (A) preferably contains at least one of a fluorine atom and an iodine atom, and more preferably contains a fluorine atom. When the resin (A) contains both a fluorine atom and an iodine atom, the resin (A) may have one repeating unit containing both a fluorine atom and an iodine atom, or the resin (A) may also contain two types of repeating units, namely a repeating unit having a fluorine atom and a repeating unit having an iodine atom.

[0822] Moreover, when using the composition as a photosensitive radiation-sensitive or radiation-sensitive resin composition for EUV, the resin (A) further preferably contains a repeating unit having an aromatic group.

[0823] (Repeating unit having an acid group)

[0824] The resin (A) may have a repeating unit having an acid group different from the repeating unit represented by general formula (AI).

[0825] As the acid group, for example, a carboxyl group, a fluorinated alcohol group (preferably a hexafluoroisopropanol group), a sulfonic acid group, a sulfonamide group, or an isopropanol group is preferably used.

[0826] Moreover, in the above hexafluoroisopropanol group, one or more (preferably 1 to 2) of the fluorine atoms may be substituted with a group other than a fluorine atom (such as an alkoxycarbonyl group). The thus formed -C(CF 3 )(OH)-CF 2- is also preferably used as an acid group. In addition, one or more of the fluorine atoms may be substituted with a group other than a fluorine atom to form a ring containing -C(CF 3 )(OH)-CF 2 -.

[0827] The repeating unit having an acid group is preferably a repeating unit different from the following repeating units: a repeating unit having a structure in which a polar group is protected by a leaving group that is removed by the action of the above acid; and a repeating unit having a lactone group, a sultone group, or a carbonate group described later.

[0828] The repeating unit having an acid group may have a substituent. As the substituent, for example, the above substituent T can be cited.

[0829] As the repeating unit having an acid group, a repeating unit represented by the formula (B) is preferable.

[0830] [Chemical formula 50]

[0831]

[0832] R 3 represents a hydrogen atom or a monovalent organic group.

[0833] As the monovalent organic group, a group represented by -L 4 -R 8 is preferable. L 4 represents a single bond or an ester group. R 8 may be an alkyl group, a cycloalkyl group, an aryl group, or a group formed by combining these.

[0834] R 4 and R 5 each independently represent a hydrogen atom, a fluorine atom, an iodine atom, or an alkyl group.

[0835] L 2 represents a single bond or an ester group.

[0836] L 3 represents an (n + m + 1)-valent alicyclic hydrocarbon ring group. As the alicyclic hydrocarbon ring group, it may be a monocyclic or polycyclic ring. For example, a cycloalkyl ring group can be cited.

[0837] R 6 represents a hydroxyl group or a fluorinated alcohol group (preferably a hexafluoroisopropanol group).

[0838] R 7 represents a halogen atom. As the halogen atom, a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom can be cited.

[0839] 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.

[0840] n represents an integer of 0 or more. n is preferably an integer of 1 to 4.

[0841] In addition, (n + m + 1) is preferably an integer of 1 to 5.

[0842] Each of the above groups in formula (B) may have a substituent, and examples of the substituent include the above substituent T.

[0843] The following exemplifies the repeating unit having an acid group.

[0844] [Chemical formula 51]

[0845]

[0846] Relative to all the repeating units in resin (A), the content of the repeating unit having an acid group is preferably 5 mol% or more, more preferably 10 mol% or more. And, as its upper limit value, it is preferably 70 mol% or less, more preferably 60 mol% or less, and further preferably 50 mol% or less.

[0847] (Repeating unit having a fluorine atom or an iodine atom and not showing acid decomposability)

[0848] Different from the above-mentioned "(repeating unit having an acid-decomposable group)" and "(repeating unit having an acid group)", resin (A) may also contain a repeating unit having a fluorine atom or an iodine atom. And the "(repeating unit having a fluorine atom or an iodine atom)" mentioned here is preferably different from other types of repeating units belonging to group A such as "(repeating unit having a lactone group, a sultone group or a carbonate group)" and "(repeating unit having a photoacid-generating group)" described later.

[0849] In addition, in the above-mentioned "(repeating unit having a fluorine atom or an iodine atom and not showing acid decomposability)", it is preferable that the main chain does not contain ring atoms (in other words, atoms constituting a ring structure).

[0850] As the repeating unit having a fluorine atom or an iodine atom and not showing acid decomposability, a repeating unit represented by formula (C) is preferred.

[0851] [Chemical formula 52]

[0852]

[0853] L 5 represents a single bond or an ester group.

[0854] R 9 represents a hydrogen atom or an alkyl group which may have a fluorine atom or an iodine atom.

[0855] R 10Represents a hydrogen atom, an alkyl group which may have a fluorine atom or an iodine atom, a cycloalkyl group which may have a fluorine atom or an iodine atom, an aryl group which may have a fluorine atom or an iodine atom, or a group formed by combining them.

[0856] The repeating units having a fluorine atom or an iodine atom and not showing acid decomposability are exemplified below.

[0857] [Chemical formula 53]

[0858]

[0859] Relative to all the repeating units in the resin (A), the content of the repeating units having a fluorine atom or an iodine atom and not showing acid decomposability is preferably 0 mol% or more, more preferably 5 mol% or more, and still more preferably 10 mol% or more. And, as its upper limit value, it is preferably 50 mol% or less, more preferably 45 mol% or less, and still more preferably 40 mol% or less.

[0860] (Repeating units having a lactone group, a sultone group or a carbonate group)

[0861] The resin (A) may contain repeating units having at least one selected from the group consisting of a lactone group, a sultone group and a carbonate group (hereinafter, also collectively referred to as "repeating units having a lactone group, a sultone group or a carbonate group").

[0862] The repeating units having a lactone group, a sultone group or a carbonate group also preferably do not have an acid group such as a hexafluoropropanol group.

[0863] As the lactone group or the sultone group, it is sufficient to have a lactone structure or a sultone structure. The lactone structure or the sultone structure is preferably a 5- to 7-membered ring lactone structure or a 5- to 7-membered ring sultone structure. Among them, more preferably, it is a structure 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 structure 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.

[0864] The resin (A) preferably contains repeating units having a lactone group or a sultone group obtained by extracting one or more hydrogen atoms from the ring member atoms of the lactone structure represented by any one of the following general formulas (LC1-1) to (LC1-21) or the sultone structure represented by any one of the following general formulas (SL1-1) to (SL1-3).

[0865] And, the lactone group or the sultone group may be directly bonded to the main chain. For example, the ring member atoms of the lactone group or the sultone group may constitute the main chain of the resin (A).

[0866] [Chemical formula 54]

[0867]

[0868] The above lactone structure or sultone structure moiety may have a substituent (Rb 2 ). As preferred substituents (Rb 2 ), examples 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, etc. n 2 represents an integer of 0 to 4. When n 2 is 2 or more, there may be a plurality of Rb 2 which may be different, and there may be a plurality of Rb 2 which may bond to each other to form a ring.

[0869] As a repeating unit containing a group having a lactone structure represented by any one of the general formulas (LC1-1) to (LC1-21) or a sultone structure represented by any one of the general formulas (SL1-1) to (SL1-3), for example, a repeating unit represented by the following general formula (AI) etc. can be cited.

[0870] [Chemical formula 55]

[0871]

[0872] In the general formula (AI), Rb 0 represents a hydrogen atom, a halogen atom or an alkyl group having 1 to 4 carbon atoms.

[0873] As preferred substituents that the alkyl group of Rb 0 may have, examples include a hydroxyl group and a halogen atom.

[0874] As the halogen atom of Rb 0 , examples 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.

[0875] 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 subcycloalkyl group, preferably a methylene group, an ethylene group, a cyclohexylene group, an adamantylene group or a norbornylene group.

[0876] V represents a group formed by extracting one hydrogen atom from the ring member atoms of a lactone structure represented by any one of the general formulas (LC1-1) to (LC1-21), or a group formed by extracting one hydrogen atom from the ring member atoms of a sultone structure represented by any one of the general formulas (SL1-1) to (SL1-3).

[0877] When there are optical isomers in the repeating unit having a lactone group or a sultone group, any optical isomer 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.

[0878] As the carbonate group, a cyclic carbonate group is preferred.

[0879] As the repeating unit having a cyclic carbonate group, a repeating unit represented by the following general formula (A-1) is preferred.

[0880] [Chemical formula 56]

[0881]

[0882] In the general formula (A-1), R A 1 represents a hydrogen atom, a halogen atom, or a monovalent organic group (preferably a methyl group).

[0883] n represents an integer of 0 or more.

[0884] R A 2 represents a substituent. When n is 2 or more, there are multiple Rs A 2 which may be the same or different from each other.

[0885] A represents a single bond or a divalent linking group. As the above divalent linking group, 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 is preferred.

[0886] Z represents an atomic group that forms a monocyclic or polycyclic ring together with the group represented by -O-CO-O- in the formula.

[0887] The repeating units having a lactone group, a sultone group, or a carbonate group are exemplified below.

[0888] [Chemical formula 57]

[0889] (In the formula, Rx represents H, CH 3 , CH 2 OH, or CF 3 )

[0890]

[0891] [Chemical Formula 58]

[0892] (In the formula, Rx represents H, CH 3 , CH 2 OH or CF 3 )

[0893]

[0894] [Chemical Formula 59]

[0895] (In the formula, Rx represents H, CH 3 , CH 2 OH or CF 3 )

[0896]

[0897] Relative to all the repeating units in resin (A), the content of the repeating units having a lactone group, a sultone group or a carbonate group is preferably 1 mol% or more, more preferably 10 mol% or more. And, as its upper limit value, it is preferably 85 mol% or less, more preferably 80 mol% or less, further preferably 70 mol% or less, and particularly preferably 60 mol% or less.

[0898] (Repeating unit having a photoacid generator group)

[0899] Resin (A) may also contain a repeating unit having a group that generates an acid upon irradiation with actinic rays or radiation (hereinafter, also referred to as "photoacid generator group") as a repeating unit other than the above.

[0900] At this time, it can be considered that the repeating unit having this photoacid generator group corresponds to a compound that generates an acid upon irradiation with actinic rays or radiation (also referred to as "photoacid generator").

[0901] As such a repeating unit, for example, a repeating unit represented by the following general formula (4) can be cited.

[0902] [Chemical Formula 60]

[0903]

[0904] R 41 represents a hydrogen atom or a methyl group. L 41 represents a single bond or a divalent linking group. L 42 represents a divalent linking group. R 40 represents a structural moiety that decomposes upon irradiation with actinic rays or radiation to generate an acid in the side chain.

[0905] The repeating units having a photoacid - generating group are exemplified below.

[0906] [Chemical formula 61]

[0907]

[0908] [Chemical formula 62]

[0909]

[0910] [Chemical formula 63]

[0911]

[0912] In addition, as the repeating unit represented by the general formula (4), for example, the repeating units described in paragraphs <0094> to <0105> of Japanese Patent Laid - Open No. 2014 - 041327 can be cited.

[0913] Relative to all the repeating units in the resin (A), the content of the repeating unit having a photo - acid - generating group is preferably 1 mol% or more, more preferably 5 mol% or more. And, as its upper limit value, it is preferably 40 mol% or less, more preferably 35 mol% or less, and further preferably 30 mol% or less.

[0914] (Repeating unit represented by the general formula (V - 1) or the following general formula (V - 2))

[0915] The resin (A) may also have a repeating unit represented by the following general formula (V - 1) or the following general formula (V - 2).

[0916] The repeating units represented by the following general formula (V - 1) and the following general formula (V - 2) are preferably different from the above - mentioned repeating units.

[0917] [Chemical formula 64]

[0918]

[0919] In the formula,

[0920] R 6 and R 7 each independently represents a hydrogen atom, a hydroxyl group, an alkyl group, an alkoxy group, an acyloxy group, a cyano group, a nitro group, an amino group, a halogen atom, an ester group (-OCOR or -COOR: R is an alkyl group or a fluorinated alkyl group having 1 to 6 carbon atoms) or a carboxyl group. As the alkyl group, a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms is preferred.

[0921] n 3 represents an integer of 0 to 6.

[0922] n 4 represents an integer from 0 to 4.

[0923] X 4 is a methylene group, an oxygen atom or a sulfur atom.

[0924] The repeating units represented by the general formula (V-1) or (V-2) are exemplified below.

[0925] [Chemical formula 65]

[0926]

[0927] (Repeating unit for reducing the mobility of the main chain)

[0928] From the viewpoint of suppressing excessive diffusion of the generated acid or pattern collapse during development, the resin (A) preferably has a high glass transition temperature (Tg). The Tg is preferably greater than 90 °C, more preferably greater than 100 °C, still more preferably greater than 110 °C, and particularly preferably greater than 125 °C. In addition, an excessively high Tg leads to a decrease in the dissolution rate in the developer, and thus the Tg is preferably 400 °C or lower, more preferably 350 °C or lower.

[0929] In addition, in the present specification, the glass transition temperature (Tg) of polymers such as the resin (A) is calculated by the following method. First, the Tg of the homopolymer composed only of each repeating unit contained in the polymer is calculated by the Bicerano method. After that, the calculated Tg is referred to as "repeating unit Tg". Next, the mass ratio (%) of each repeating unit to all the repeating units in the polymer is calculated. Then, the Tg in each mass ratio is calculated using the Fox formula (described in Materials Letters 62 (2008) 3152, etc.), and the sum of them is set as the Tg (°C) of the polymer.

[0930] The Bicerano method is described in Prediction of polymer properties, Marcel Dekker Inc, New York (1993), etc. And the calculation of Tg by the Bicerano method can be carried out using the polymer physical property estimation software MDL Polymer (MDL Information Systems, Inc.).

[0931] In order to increase the Tg of the resin CA) (preferably making the Tg exceed 90 °C), it is preferable to reduce the mobility of the main chain of the resin (A). The methods for reducing the mobility of the main chain of the resin (A) include the following methods (a) to (e).

[0932] (a) Introducing a bulky substituent into the main chain

[0933] (b) Introduction of multiple substituents into the main chain

[0934] (c) Introduction of substituents that induce interactions between resins (A) near the main chain

[0935] (d) Formation of the main chain in a cyclic structure

[0936] (e) Connection of the cyclic structure to the main chain

[0937] In addition, resin (A) preferably has a repeating unit in which the Tg of the homopolymer shows 130 °C or higher.

[0938] In addition, the type of the repeating unit in which the Tg of the homopolymer shows 130 °C or higher is not particularly limited as long as the Tg of the homopolymer calculated by the Bicerano method is 130 °C or higher. In addition, depending on the type of functional group in the repeating unit represented by the following formulas (A) to (E), it corresponds to the repeating unit in which the Tg of the homopolymer shows 130 °C or higher.

[0939] (Repeating unit represented by formula (A))

[0940] As an example of a specific implementation means of the above (a), a method of introducing a repeating unit represented by formula (A) into resin (A) can be cited.

[0941] [Chemical formula 66]

[0942]

[0943] In formula (A), R A represents a group having a polycyclic structure. R x represents a hydrogen atom, a methyl group, or an ethyl group. The group having a polycyclic structure is a group having a plurality of ring structures, and the plurality of ring structures may be fused or unfused.

[0944] As a specific example of the repeating unit represented by formula (A), the following repeating units can be cited.

[0945] [Chemical formula 67]

[0946]

[0947] [Chemical formula 68]

[0948]

[0949] [Chemical formula 69]

[0950]

[0951] In the above formulas, R represents a hydrogen atom, a methyl group, or an ethyl group.

[0952] Ra represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, an alkenyl group, a hydroxyl group, an alkoxy group, an acyloxy group, a cyano group, a nitro group, an amino group, a halogen atom, an ester group (-OCOR''' or -COOR''': R''' is an alkyl group or a fluorinated alkyl group having 1 to 20 carbon atoms) or a carboxyl group. Further, the above alkyl group, the above cycloalkyl group, the above aryl group, the above aralkyl group and the above alkenyl group may each have a substituent. Also, a hydrogen atom bonded to a carbon atom in the group represented by Ra may be substituted with a fluorine atom or an iodine atom.

[0953] Also, R' and R'' each independently represent an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, an alkenyl group, a hydroxyl group, an alkoxy group, an acyloxy group, a cyano group, a nitro group, an amino group, a halogen atom, an ester group (-OCOR''' or -COOR''': R''' is an alkyl group or a fluorinated alkyl group having 1 to 20 carbon atoms) or a carboxyl group. Further, the above alkyl group, the above cycloalkyl group, the above aryl group, the above aralkyl group and the above alkenyl group may each have a substituent. Also, a hydrogen atom bonded to a carbon atom in the group represented by R' and R'' may be substituted with a fluorine atom or an iodine atom.

[0954] L represents a single bond or a divalent linking group. As the divalent linking group, for example, -COO-, -CO-, -O-, -S-, -SO-, -SO2-, an alkylene group, a cycloalkylene group, an alkenylene group and a linking group formed by linking a plurality of them can be cited.

[0955] m and n each independently represent an integer of 0 or more. The upper limits of m and n are not particularly limited, but are usually 2 or less, and more often 1 or less.

[0956] (Repeating unit represented by formula (B))

[0957] As an example of a specific implementation means of the above (b), a method of introducing a repeating unit represented by formula (B) into resin (A) can be cited.

[0958] [Chemical formula 70]

[0959]

[0960] In formula (B), R b1 ~R b4 each independently represent a hydrogen atom or an organic group, and at least two or more of R b1 ~R b4 represent an organic group.

[0961] Also, when at least one of the organic groups is a group in which a ring structure is directly connected to the main chain of the repeating unit, the types of the other organic groups are not particularly limited.

[0962] Further, when none of the organic groups is a group in which a ring structure is directly connected to the main chain in the repeating unit, at least two or more of the organic groups are substituents having three or more constituent atoms other than hydrogen atoms.

[0963] As specific examples of the repeating unit represented by the formula (B), the following repeating units can be mentioned.

[0964] [Chemical formula 71]

[0965]

[0966] In the above formula, each R independently represents a hydrogen atom or an organic group. As the organic group, organic groups such as an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, and an alkenyl group which may have a substituent can be mentioned.

[0967] Each R' independently represents an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, an alkenyl group, a hydroxyl group, an alkoxy group, an acyloxy group, a cyano group, a nitro group, an amino group, a halogen atom, an ester group (-OCOR'' or -COOR'': R'' is an alkyl group or a fluorinated alkyl group having 1 to 20 carbon atoms) or a carboxyl group. Further, the above alkyl group, the above cycloalkyl group, the above aryl group, the above aralkyl group, and the above alkenyl group may each have a substituent. Also, a hydrogen atom bonded to a carbon atom in the group represented by R' may be substituted with a fluorine atom or an iodine atom.

[0968] m represents an integer of 0 or more. The upper limit of m is not particularly limited, but is usually 2 or less, and more often 1 or less.

[0969] (Repeating unit represented by formula (C))

[0970] As an example of a specific implementation means of the above (c), a method of introducing the repeating unit represented by the formula (C) into the resin (A) can be mentioned.

[0971] [Chemical formula 72]

[0972]

[0973] In formula (C), R c1 ~R c4 each independently represents a hydrogen atom or an organic group, and at least one of R c1 ~R c4 is a group having a hydrogen atom with hydrogen bonding property within 3 atoms from the main chain carbon. Among them, it is preferable to have a hydrogen atom with hydrogen bonding property within 2 atoms (closer to the main chain side) on the basis of causing the interaction between the main chains of the resin (A).

[0974] As specific examples of the repeating unit represented by the formula (C), the following repeating units can be mentioned.

[0975] [Chemical Formula 73]

[0976]

[0977] In the above formula, R represents an organic group. As the organic group, examples include an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, an alkenyl group, and an ester group (-OCOR or -COOR: R is an alkyl group or a fluorinated alkyl group having 1 to 20 carbon atoms), etc., which may have substituents.

[0978] R’ represents a hydrogen atom or an organic group. As the organic group, examples include organic groups such as an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, and an alkenyl group. In addition, a hydrogen atom in the organic group may be substituted with a fluorine atom or an iodine atom.

[0979] (Repeating unit represented by formula (D))

[0980] As an example of a specific implementation means of the above (d), a method of introducing a repeating unit represented by formula (D) into resin (A) can be cited.

[0981] [Chemical Formula 74]

[0982]

[0983] In formula (D), “Cyclic” represents a group having a cyclic structure as the main chain. The number of atoms constituting the ring is not particularly limited.

[0984] As a specific example of the repeating unit represented by formula (D), the following repeating units can be cited.

[0985] [Chemical Formula 75]

[0986]

[0987] In the above formula, R independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, an alkenyl group, a hydroxyl group, an alkoxy group, an acyloxy group, a cyano group, a nitro group, an amino group, a halogen atom, an ester group (-OCOR” or -COOR”: R” is an alkyl group or a fluorinated alkyl group having 1 to 20 carbon atoms) or a carboxyl group. In addition, the above alkyl group, the above cycloalkyl group, the above aryl group, the above aralkyl group, and the above alkenyl group may each have a substituent. And a hydrogen atom bonded to a carbon atom in the group represented by R may also be substituted with a fluorine atom or an iodine atom.

[0988] In the above formula, each R' independently represents an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, an alkenyl group, a hydroxyl group, an alkoxy group, an acyloxy group, a cyano group, a nitro group, an amino group, a halogen atom, an ester group (-OCOR" or -COOR": R" is an alkyl group or a fluorinated alkyl group having 1 to 20 carbon atoms) or a carboxyl group. In addition, the above alkyl group, the above cycloalkyl group, the above aryl group, the above aralkyl group and the above alkenyl group may each have a substituent. Further, a hydrogen atom bonded to a carbon atom in the group represented by R' may also be substituted with a fluorine atom or an iodine atom.

[0989] m represents an integer of 0 or more. The upper limit of m is not particularly limited, but is usually 2 or less, and more often 1 or less.

[0990] (Repeating unit represented by formula (E))

[0991] As an example of a specific implementation means of the above (e), a method of introducing a repeating unit represented by formula (E) into the resin (A) can be cited.

[0992] [Chemical formula 76]

[0993]

[0994] In formula (E), each Re independently represents a hydrogen atom or an organic group. As the organic group, an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, an alkenyl group, etc., which may have a substituent, can be cited.

[0995] "Cyclic" is a cyclic group containing a carbon atom in the main chain. The number of atoms contained in the cyclic group is not particularly limited.

[0996] As a specific example of the repeating unit represented by formula (E), the following repeating units can be cited.

[0997] [Chemical formula 77]

[0998]

[0999] [Chemical formula 78]

[1000]

[1001] Further, as a specific example of the repeating unit represented by formula (E), a repeating unit derived from the following monomer can also be preferably used.

[1002] [Chemical formula 79]

[1003]

[1004] In the above formulae, R independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, an alkenyl group, a hydroxyl group, an alkoxy group, an acyloxy group, a cyano group, a nitro group, an amino group, a halogen atom, an ester group (-OCOR" or -COOR": R" is an alkyl group or a fluorinated alkyl group having 1 to 20 carbon atoms) or a carboxyl group. Additionally, the above alkyl group, the above cycloalkyl group, the above aryl group, the above aralkyl group, and the above alkenyl group may each have a substituent. Also, a hydrogen atom bonded to a carbon atom in the group represented by R may be substituted with a fluorine atom or an iodine atom.

[1005] R' independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, an alkenyl group, a hydroxyl group, an alkoxy group, an acyloxy group, a cyano group, a nitro group, an amino group, a halogen atom, an ester group (-OCOR" or -COOR": R" is an alkyl group or a fluorinated alkyl group having 1 to 20 carbon atoms) or a carboxyl group. Additionally, the above alkyl group, the above cycloalkyl group, the above aryl group, the above aralkyl group, and the above alkenyl group may each have a substituent. Also, a hydrogen atom bonded to a carbon atom in the group represented by R' may be substituted with a fluorine atom or an iodine atom.

[1006] m represents an integer of 0 or more. The upper limit of m is not particularly limited, but is usually 2 or less, and more often 1 or less.

[1007] Also, in formula (E-2), formula (E-4), formula (E-6), and formula (E-8), two Rs may bond to each other to form a ring.

[1008] Relative to all the repeating units in resin (A), the content of the repeating units represented by formula (A) to formula (E) is preferably 5 mol% or more, more preferably 10 mol% or more. And as its upper limit value, it is preferably 60 mol% or less, more preferably 55 mol% or less.

[1009] (A repeating unit having at least one group selected from a lactone group, a sultone group, a carbonate group, a hydroxyl group, a cyano group, and a base-soluble group)

[1010] Resin (A) may contain a repeating unit having at least one group selected from a lactone group, a sultone group, a carbonate group, a hydroxyl group, a cyano group, and a base-soluble group.

[1011] As the repeating unit having a lactone group, a sultone group, or a carbonate group in resin (A), the repeating units described in the above "(A repeating unit having a lactone group, a sultone group, or a carbonate group)" can be cited. The preferred content is also as described in the above "(A repeating unit having a lactone group, a sultone group, or a carbonate group)".

[1012] Resin (A) may also contain a repeating unit having a hydroxyl group or a cyano group. Thereby, the substrate adhesion and the developer affinity are improved.

[1013] 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.

[1014] The repeating unit having a hydroxyl group or a cyano group preferably does not have an acid-decomposable group. Examples of the repeating unit having a hydroxyl group or a cyano group include repeating units represented by the following general formulas (AIIa) to (AIId).

[1015] [Chemical formula 80]

[1016]

[1017] In general formulas (AIIa) to (AIId),

[1018] R 1c represents a hydrogen atom, a methyl group, a trifluoromethyl group, or a hydroxymethyl group.

[1019] R 2c to R 4c each independently represent a hydrogen atom, a hydroxyl group, or a cyano group. Among them, at least one of R 2c to R 4c represents a hydroxyl group or a cyano group. Preferably, one or two of R 2c to R 4c are hydroxyl groups, and the rest are hydrogen atoms. More preferably, two of R 2c to R 4c are hydroxyl groups, and the rest are hydrogen atoms.

[1020] Relative to all the repeating units in resin (A), the content of the repeating unit having a hydroxyl group or a cyano group is preferably 5 mol% or more, more preferably 10 mol% or more. And, as its upper limit value, it is preferably 40 mol% or less, more preferably 35 mol% or less, and further preferably 30 mol% or less.

[1021] Specific examples of the repeating unit having a hydroxyl group or a cyano group are given below, but the present invention is not limited to these.

[1022] [Chemical formula 81]

[1023]

[1024] Resin (A) may also contain a repeating unit having an alkali-soluble group.

[1025] Examples of the alkali-soluble group include a carboxyl group, a sulfonamide group, a sulfimide group, a bis-sulfimide group, and an aliphatic alcohol group substituted with an electron-withdrawing group at the α-position (for example, a hexafluoroisopropanol group), and a carboxyl group is preferred. By making resin (A) contain a repeating unit having an alkali-soluble group, the resolution in contact hole applications is improved.

[1026] As the repeating unit having an alkali-soluble group, there can be mentioned a repeating unit in which an alkali-soluble group is directly bonded to the main chain of the resin, such as a repeating unit formed from acrylic acid and methacrylic acid, or a repeating unit in which an alkali-soluble group is bonded to the main chain of the resin through a linking group. In addition, the linking group may have a monocyclic or polycyclic alicyclic hydrocarbon structure.

[1027] As the repeating unit having an alkali-soluble group, a repeating unit formed from acrylic acid or methacrylic acid is preferred.

[1028] Relative to all the repeating units in the resin (A), the content of the repeating unit having an alkali-soluble group is preferably 0 mol% or more, more preferably 3 mol% or more, and still more preferably 5 mol% or more. As the upper limit value, it is preferably 20 mol% or less, more preferably 15 mol% or less, and still more preferably 10 mol% or less.

[1029] Specific examples of the repeating unit having an alkali-soluble group are shown below, but the present invention is not limited thereto. In the specific examples, Rx represents H, CH 3 , CH 2 OH or CF 3 .

[1030] [Chemical formula 82]

[1031]

[1032] As the repeating unit having at least one group selected from a lactone group, a hydroxyl group, a cyano group, and an alkali-soluble group, a repeating unit having at least two groups selected from a lactone group, a hydroxyl group, a cyano group, and an alkali-soluble group is preferred, a repeating unit having a cyano group and a lactone group is more preferred, and a repeating unit having a structure in which a cyano group is substituted in the lactone structure represented by the general formula (LC1-4) is still more preferred.

[1033] (Repeating unit having an alicyclic hydrocarbon structure and not showing acid decomposability)

[1034] The resin (A) may also contain a repeating unit having an alicyclic hydrocarbon structure and not showing acid decomposability. Thereby, it is possible to reduce the elution of low molecular components from the resist film into the immersion liquid during immersion exposure. As such a repeating unit, for example, a repeating unit derived from 1-adamantyl (meth)acrylate, diadamantyl (meth)acrylate, tricyclodecanyl (meth)acrylate, or cyclohexyl (meth)acrylate, etc. can be mentioned.

[1035] (Repeating unit represented by the general formula (III) and not having any of a hydroxyl group and a cyano group)

[1036] The resin (A) may also contain a repeating unit represented by the general formula (III) and not having any of a hydroxyl group and a cyano group.

[1037] [Chemical Formula 83]

[1038]

[1039] In general formula (III), R 5 represents a hydrocarbon group having at least one ring structure and not having any of a hydroxyl group and a cyano group.

[1040] Ra represents a hydrogen atom, an alkyl group or -CH 3 -O-Ra 2 group. In the formula, Ra 2 represents a hydrogen atom, an alkyl group or an acyl group.

[1041] R 5 The ring structure of 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 (more preferably 3 to 7 carbon atoms) or a cycloalkenyl group having 3 to 12 carbon atoms can be mentioned.

[1042] As the polycyclic hydrocarbon group, a ring-aggregated hydrocarbon group and a crosslinked cyclic hydrocarbon group can be mentioned. As the crosslinked cyclic hydrocarbon ring, a bicyclic hydrocarbon ring, a tricyclic hydrocarbon ring, a tetracyclic hydrocarbon ring, etc. can be mentioned. And, as the crosslinked cyclic hydrocarbon ring, a condensed ring in which a plurality of 5- to 8-membered cycloalkane rings are condensed can also be included.

[1043] As the crosslinked cyclic hydrocarbon group, norbornyl, adamantyl, bicyclooctyl or tricyclo[5,2,1,02,6]decyl is preferable, and norbornyl or adamantyl is more preferable.

[1044] The alicyclic hydrocarbon group may have a substituent. As the substituent, a halogen atom, an alkyl group, a hydroxyl group protected by a protecting group, and an amino group protected by a protecting group can be mentioned.

[1045] As the halogen atom, a bromine atom, a chlorine atom or a fluorine atom is preferable.

[1046] As the alkyl group, a methyl group, an ethyl group, a butyl group or a tert-butyl group is preferable. The above alkyl group may further have a substituent. As the substituent, a halogen atom, an alkyl group, a hydroxyl group protected by a protecting group or an amino group protected by a protecting group can be mentioned.

[1047] As the protecting group, for example, an alkyl group, a cycloalkyl group, an aralkyl group, a substituted methyl group, a substituted ethyl group, an alkoxycarbonyl group and an aralkyloxycarbonyl group can be mentioned.

[1048] As the alkyl group, an alkyl group having 1 to 4 carbon atoms is preferable.

[1049] As the substituted methyl group, methoxymethyl, methoxythiomethyl, benzyloxymethyl, tert-butoxymethyl or 2-methoxyethoxymethyl is preferable.

[1050] As the substituted ethyl group, 1-ethoxyethyl or 1-methyl-1-methoxyethyl is preferred.

[1051] As the acyl group, aliphatic acyl groups having 1 to 6 carbon atoms such as formyl, acetyl, propionyl, butyryl, isobutyryl, valeryl, and pivaloyl are preferred.

[1052] As the alkoxycarbonyl group, an alkoxycarbonyl group having 1 to 4 carbon atoms is preferred.

[1053] The content of the repeating unit represented by the general formula (III) which has neither a hydroxyl group nor a cyano group relative to all the repeating units in the resin (A) is preferably 0 to 40 mol%, more preferably 0 to 20 mol%.

[1054] Specific examples of the repeating unit represented by the general formula (III) are shown below, but the present invention is not limited to these. In the specific examples, Ra represents H, CH 3 、CH 2 OH or CF 3 。

[1055] [Chemical formula 84]

[1056]

[1057] (Other repeating units)

[1058] The resin (A) may also contain repeating units other than the above-mentioned repeating units.

[1059] For example, the resin (A) may contain repeating units selected from the group consisting of repeating units having an oxathiane ring group, repeating units having an oxazolone ring group, repeating units having a dioxane ring group, and repeating units having a hydantoin ring group.

[1060] Specific examples of such repeating units are shown below.

[1061] [Chemical formula 85]

[1062]

[1063] In addition to the above-mentioned repeating structural units, for the purpose of adjusting dry etching resistance, adaptability to standard developing solutions, substrate adhesion, resist profile, resolution, heat resistance, sensitivity, etc., the resin (A) may also have various repeating structural units.

[1064] The resin (A) can be synthesized according to a conventional method (for example, radical polymerization).

[1065] As the conversion value of polystyrene based on the GPC method, the weight average molecular weight of the resin (A) is preferably 1,000 to 200,000, more preferably 2,000 to 30,000, and still more preferably 3,000 to 20,000. By setting the weight average molecular weight of the resin (A) to 1,000 to 200,000, the deterioration of heat resistance and dry etching resistance can be further suppressed. Further, the deterioration of film forming properties due to the deterioration of developability and the increase in viscosity can be further suppressed.

[1066] The dispersity (molecular weight distribution) of the resin (A) is usually 1.0 to 5.0, preferably 1.0 to 3.0, more preferably 1.0 to 2.5, and still more preferably 1.0 to 2.0. The smaller the dispersity, the more excellent the resolution and the shape of the resist, and the smoother the side wall of the resist pattern and the more excellent the roughness.

[1067] In the composition of the present invention, the content of the resin (A) is preferably 50 to 99.9% by mass, more preferably 60 to 99.0% by mass, based on the total solid content of the composition.

[1068] In addition, the solid content means the components other than the solvent in the composition, and as long as it is a component other than the solvent, even a liquid component is regarded as a solid component.

[1069] Moreover, one kind of the resin (A) can be used, or a plurality of them can be used in combination.

[1070] [Acid diffusion control agent]

[1071] 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 or the like during exposure and functions as a quencher, and this quencher suppresses the reaction of the acid-decomposable resin in the unexposed portion due to the excessive generation of acid.

[1072] As an acid diffusion control agent, for example, a basic compound (DA), a basic compound (DB) whose basicity is reduced or disappears by irradiation with actinic rays or radiation, an onium salt (DC) that is a relatively weak acid with respect to the acid generator, a low-molecular compound (DD) having a nitrogen atom and a group that is cleaved by the action of an acid, or an onium salt compound (DE) having a nitrogen atom in the cationic part 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, it is preferable to use the known compounds disclosed in paragraphs

[0627] to

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

[0095] to

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

[0403] to

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

[0259] to

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

[1073] As the basic compound (DA), a compound having a structure represented by the following general formulas (A) to (E) is preferable.

[1074] [Chemical formula 86]

[1075]

[1076] In general formulas (A) and (E),

[1077] 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.

[1078] 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.

[1079] The alkyl group in general formulas (A) and (E) may have a substituent or may be unsubstituted.

[1080] Regarding the above alkyl group, as the alkyl group having a substituent, an aminoalkyl group having 1 to 20 carbon atoms, a hydroxyalkyl group having 1 to 20 carbon atoms, or a cyanoalkyl group having 1 to 20 carbon atoms is preferable.

[1081] The alkyl group in general formula (A) and general formula (E) is more preferably unsubstituted.

[1082] 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 compound having a thiazole structure, a benzothiazole structure, an oxazole structure, a benzoxazole structure, an imidazole structure, a diazabicyclic structure, an oxonium hydroxide structure, a carboxonium structure, a trialkylamine structure, an aniline structure or a pyridine structure, an alkylamine derivative having a hydroxyl group and / or an ether bond, or an aniline derivative having a hydroxyl group and / or an ether bond is more preferred.

[1083] The basic compound (DB) whose basicity is reduced or disappears by irradiation with actinic rays or radiation (hereinafter, also referred to as "compound (DB)") is a compound having a proton-accepting functional group and decomposing by irradiation with actinic rays or radiation to reduce, disappear or change from proton-accepting to acidic the proton-accepting property.

[1084] 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 having an unshared electron pair that does not contribute to π conjugation. The nitrogen atom having an unshared electron pair that does not contribute to π conjugation is, for example, a nitrogen atom having a partial structure represented by the following formula.

[1085] [Chemical formula 87]

[1086] Unshared electron pair

[1087] As a preferred partial structure of the proton-accepting functional group, 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 can be cited.

[1088] Compound (DB) generates a compound that decomposes by irradiation with actinic rays or radiation to reduce or disappear the proton-accepting property or change from proton-accepting to acidic. Here, the reduction or disappearance of the proton-accepting property or the change from proton-accepting to acidic is a change in the proton-accepting property due to 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.

[1089] The proton-accepting property can be confirmed by measuring the pH.

[1090] The acid dissociation constant pKa of the compound produced by the decomposition of the compound (DB) upon irradiation with actinic rays or radioactive rays preferably satisfies pKa < -1, more preferably satisfies -13 < pKa < -1, and still more preferably satisfies -13 < pKa < -3.

[1091] 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.

[1092] 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 used in combination, if the acid generated from the photoacid generator upon irradiation with actinic rays or radioactive rays collides with the onium salt having an unreacted weak acid anion, the weak acid is released by salt exchange and an onium salt having a strong acid anion is generated. In this process, the strong acid is exchanged for a weak acid with lower catalytic ability, so that the acid is apparently inactivated and the control of acid diffusion can be carried out.

[1093] As the onium salt that is a relatively weak acid with respect to the photoacid generator, compounds represented by the following general formulas (d1-1) to (d1-3) are preferred.

[1094] [Chemical formula 88]

[1095]

[1096] In the formula, R 51 is a hydrocarbon group that may have a substituent, Z 2 c is a hydrocarbon group having 1 to 30 carbon atoms that may have a substituent (wherein the fluorine atom in the carbon adjacent to S is unsubstituted), R 52 is an organic group, Y 3 is a linear, branched or cyclic alkylene or arylene group, Rf is a fluorine atom-containing hydrocarbon group, and M + are each independently an ammonium cation, a sulfonium cation or an iodonium cation.

[1097] As preferred examples of the sulfonium cation or iodonium cation represented by M + , a sulfonium cation exemplified by the general formula (ZIA) and an iodonium cation exemplified by the general formula (ZIIA) can be cited.

[1098] The onium salt (DC) that is a relatively weak acid with respect to the photoacid generator may 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)").

[1099] As the compound (DCA), compounds represented by any one of the following general formulas (C-1) to (C-3) are preferred.

[1100] [Chemical formula 89]

[1101]

[1102] In general formulas (C-1) to (C-3),

[1103] R 1 、R 2 and R 3 each independently represent a substituent having 1 or more carbon atoms.

[1104] L 1 represents a divalent linking group or a single bond that connects the cationic moiety and the anionic moiety.

[1105] -X - represents an anionic moiety selected from -COO - , -SO 3 - , -SO 2 - and -N - -R 4 . 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 linking position with an adjacent N atom.

[1106] R 1 , R 2 , R 3 , R 4 and L 1 may bond to each other to form a ring structure. Further, in general formula (C-3), two of R 1 to R 3 together represent a divalent substituent and may bond to the N atom through a double bond.

[1107] Examples of the substituent having 1 or more carbon atoms as R 1 to R 3 include alkyl, cycloalkyl, aryl, alkoxycarbonyl, cycloalkoxycarbonyl, aryloxycarbonyl, alkylaminocarbonyl, cycloalkylaminocarbonyl, and arylaminocarbonyl. Preferred are alkyl, cycloalkyl, or aryl.

[1108] Examples of the divalent linking group L 1 include linear or branched alkylene, cycloalkylene, arylene, carbonyl, ether bond, ester bond, amide bond, urethane bond, urea bond, and a group formed by combining two or more of these. L 1 is preferably alkylene, arylene, ether bond, ester bond, or a group formed by combining two or more of these.

[1109] A low-molecular compound (DD) having a nitrogen atom and a group detachable by the action of an acid (hereinafter, also referred to as "compound (DD)") is preferably an amine derivative having a group detachable by the action of an acid on the nitrogen atom.

[1110] As the group detachable by the action of an acid, an acetal group, a carbonate group, a carbamate group, a tertiary ester group, a tertiary hydroxyl group or a hemiacetal amine ether group is preferred, and a carbamate group or a hemiacetal amine ether group is more preferred.

[1111] The molecular weight of the compound (DD) is preferably 100 to 1000, more preferably 100 to 700, and still more preferably 100 to 500.

[1112] The compound (DD) may also have a carbamate group having a protecting group on the nitrogen atom. As the protecting group constituting the carbamate group, it is represented by the following general formula (d-1).

[1113] [Chemical formula 90]

[1114]

[1115] In the general formula (d-1),

[1116] Rb 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). Rb may be bonded to each other to form a ring.

[1117] The alkyl group, cycloalkyl group, aryl group and aralkyl group represented by Rb may each independently be substituted by a functional group such as a hydroxyl group, a cyano group, an amino group, a pyrrolidino group, a piperidino group, a morpholino group, an oxo group, an alkoxy group or a halogen atom. The same applies to the alkoxyalkyl group represented by Rb.

[1118] As Rb, a linear or branched alkyl group, a cycloalkyl group or an aryl group is preferred, and a linear or branched alkyl group or a cycloalkyl group is more preferred.

[1119] Examples of the ring formed by the connection of two Rb include an alicyclic hydrocarbon, an aromatic hydrocarbon, a heterocyclic hydrocarbon and their derivatives.

[1120] 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.

[1121] The compound (DD) is preferably a compound having a structure represented by the following general formula (6).

[1122] [Chemical Formula 91]

[1123]

[1124] In general formula (6),

[1125] l represents an integer from 0 to 2, m represents an integer from 1 to 3, and l + m = 3 is satisfied.

[1126] Ra represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, or an aralkyl group. When l is 2, the two Ras may be the same or different, and the two Ras may also be connected to each other to form a heterocycle together with the nitrogen atom in the formula. The heterocycle may also contain heteroatoms other than the nitrogen atom in the formula.

[1127] Rb has the same meaning as Rb in the above general formula (d - 1), and the preferred examples are also the same.

[1128] In general formula (6), the alkyl group, cycloalkyl group, aryl group, and aralkyl group as Ra may each be independently substituted by the same groups as the following groups, and the following groups are the groups by which the alkyl group, cycloalkyl group, aryl group, and aralkyl group as Rb may be substituted.

[1129] Specific examples of the alkyl group, cycloalkyl group, aryl group, and aralkyl group (these groups may be substituted by the above groups) as the above Ra may be the same groups as the above specific examples for Rb.

[1130] As specific examples of the particularly preferred compound (DD) in the present invention, compounds disclosed in paragraph

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

[1131] The onium salt compound (DE) having a nitrogen atom in the cationic part (hereinafter, also referred to as "compound (DE)") is preferably a compound having a basic site containing a nitrogen atom in the cationic part. The basic site is preferably an amino group, more preferably an aliphatic amino group. Further preferably, all atoms adjacent to the nitrogen atom in the basic site are hydrogen atoms or carbon atoms. And from the viewpoint of improving basicity, it is preferred that an electron-withdrawing functional group (carbonyl group, sulfonyl group, cyano group, halogen atom, etc.) is not directly connected to the nitrogen atom.

[1132] As preferred specific examples of compound (DE), compounds disclosed in paragraph

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

[1133] The following shows preferred examples of the acid diffusion control agent, but the present invention is not limited to these. Me represents a methyl group.

[1134] [Chemical Formula 92]

[1135]

[1136] [Chemical Formula 93]

[1137]

[1138] [Chemical Formula 94]

[1139]

[1140] [Chemical Formula 95]

[1141]

[1142] [Chemical Formula 96]

[1143]

[1144] [Chemical Formula 97]

[1145]

[1146] [Chemical Formula 98]

[1147]

[1148] In the composition of the present invention, the acid diffusion control agent can be used alone in one kind, or two or more kinds can be used in combination.

[1149] The content of the acid diffusion control agent in the composition of the present invention (the total when there are multiple kinds) is preferably 0.001 to 20% by mass, more preferably 0.01 to 5% by mass, based on the total solid content of the composition.

[1150] [Solvent]

[1151] The composition of the present invention preferably contains a solvent.

[1152] In the composition of the present invention, known resist solvents can be appropriately used. For example, the known solvents 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 can be preferably used.

[1153] As solvents that can be used in the preparation of the composition, examples include organic solvents such as alkylene glycol monoalkyl ether carboxylates, alkylene glycol monoalkyl ethers, alkyl lactates, alkyl alkoxypropionates, cyclic lactones (preferably having 4 to 10 carbon atoms), monoketone compounds that may have a ring (preferably having 4 to 10 carbon atoms), alkylene carbonates, alkyl alkoxyacetates, and alkyl pyruvates.

[1154] 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.

[1155] As the solvent having a hydroxyl group and the solvent not having a hydroxyl group, the above-exemplified compounds can be appropriately selected. However, 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 may have a ring, cyclic lactones, or alkyl acetates are preferred, among which 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.

[1156] The mixing ratio (mass ratio) of the solvent having a hydroxyl group to 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.

[1157] The solvent preferably contains propylene glycol monomethyl ether acetate, and 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.

[1158] [Surfactant]

[1159] The composition of the present invention can further contain a surfactant. By containing a surfactant, when using an exposure light source having a wavelength of 250 nm or less, especially 220 nm or less, a pattern with better sensitivity, resolution, less adhesion, and fewer development defects can be formed.

[1160] As the surfactant, a fluorine-based and / or silicon-based surfactant is particularly preferably used.

[1161] As the fluorine-based and / or silicon-based surfactant, for example, the surfactants described in

[0276] of the specification of U.S. 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.

[1162] Moreover, in addition to the well-known surfactants as shown above, a fluorinated aliphatic compound produced by adjusting the telomerization method (also called the telomer method) or the oligomerization method (also called the oligomer method) can be used as the surfactant. 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 Laid-Open No. 2002-90991.

[1163] Further, surfactants other than those described in

[0280] of the specification of U.S. Patent Application Publication No. 2008 / 0248425, i.e., fluorine-based and / or silicon-based surfactants, may also be used.

[1164] These surfactants may be used alone or in combination of two or more.

[1165] When the composition of the present invention contains a surfactant, its content is preferably more than 0 to 2% by mass, more preferably 0.0001 to 2% by mass, and further preferably 0.0005 to 1% by mass based on the total solid content of the composition.

[1166] [Other Additives]

[1167] In addition to the components described above, the composition of the present invention can also 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), etc., dyes, plasticizers, photosensitizers, light absorbers, antioxidants, etc.

[1168] 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.

[1169] 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 further preferably 0.01 to 3% by mass based on the total solid content of the composition.

[1170] 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 further preferably 30 to 100 nm. By setting the solid content concentration in the composition within an appropriate range to have an appropriate viscosity, coatability and film-forming property can be improved, and thus such a film thickness can be formed.

[1171] 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 1.5 to 5.7% by mass, and further preferably 1.8 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.

[1172] The solid content concentration is 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.

[1173] [Use]

[1174] The composition of the present invention relates to a photosensitive or radiation-sensitive resin composition whose properties change upon reaction by irradiation with actinic rays or radiation. More specifically, the composition of the present invention relates to a photosensitive or radiation-sensitive resin composition used in semiconductor manufacturing processes such as IC (Integrated Circuit), the manufacture of circuit boards for liquid crystals or thermal heads, the production of imprint mold structures, other photosensitive etching processes, or the manufacture of lithographic printing plates or acid-curable compositions. The pattern formed in the present invention can be used in etching processes, ion implantation processes, bump electrode formation processes, rewiring formation processes, and MEMS (Micro Electro Mechanical Systems), etc.

[1175] [Photosensitive or radiation-sensitive film]

[1176] The present invention also relates to a photosensitive or radiation-sensitive film (preferably a resist film) formed from the photosensitive 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 film is preferably 0.02 to 0.1 μm. As a method of coating on the substrate, it is 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.

[1177] 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.

[1178] An antireflection film can be pre-coated on the substrate before forming the resist film.

[1179] As the antireflection film, any of inorganic film types such as titanium, titanium dioxide, titanium nitride, chromium oxide, carbon, amorphous silicon, and organic film types composed of light absorbers and polymer materials can be used. Also, as the organic antireflection film, commercially available organic antireflection films such as the DUV30 series and DUV-40 series manufactured by Brewer Science Inc., and AR-2, AR-3, AR-5 manufactured by Shipley Company can be used.

[1180] 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. The top coat layer is preferably not mixed with the resist film and can be further uniformly coated on the upper layer of the resist film.

[1181] 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.

[1182] 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-mentioned acid diffusion inhibitor.

[1183] 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.

[1184] Furthermore, the top coat layer preferably contains a resin. There is no particular limitation on the resin that the top coat layer can contain, and the same resin as the hydrophobic resin that can be contained in the photosensitive or radiation-sensitive composition can be used.

[1185] 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.

[1186] The top coat layer preferably contains a resin containing a repeating unit having an aromatic ring. By containing a repeating unit having an aromatic ring, especially during electron beam or EUV exposure, the generation efficiency of secondary electrons and the acid generation efficiency of the compound that generates acid through actinic rays or radiation are improved, and high sensitivity and high resolution can be expected during pattern formation.

[1187] 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 fluorine atom and / or a silicon atom content lower than that of the resin (XA). Thus, when forming the top coat layer film, since the resin (XA) is unevenly distributed on the surface of the top coat layer film, performance such as development characteristics and immersion liquid followability can be improved.

[1188] Moreover, the top coat layer may contain an acid generator and a crosslinking agent.

[1189] The topcoat is typically formed from a topcoat-forming composition.

[1190] The topcoat-forming composition 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, more preferably 0.05 μm or less, and even more preferably 0.03 μm or less is preferred. Also, when the solid component concentration of the composition is high (e.g., 25 mass% or more), the pore size of the filter used for filtration through the filter is preferably 3 μm or less, more preferably 0.5 μm or less, and even more preferably 0.3 μm or less. This filter is preferably a polytetrafluoroethylene, polyethylene, or nylon filter. In filtration through the filter, for example, as disclosed in the specification of Japanese Patent Application Laid-Open No. 2002-62667 (Japanese Unexamined Patent Application Publication No. 2002-62667), circulation filtration can be performed, or multiple filters can be connected in series or in parallel for filtration. Also, the composition can be filtered multiple times. In addition, degassing treatment or the like can be performed on the composition before and after filtration through the filter.

[1191] The topcoat-forming composition preferably does not contain impurities such as metals. As the content of the metal components contained in these materials, it is preferably 10 ppm or less, more preferably 5 ppm or less, even more preferably 1 ppm or less, and particularly preferably substantially does not contain (below the detection limit of the measuring device).

[1192] In order to make the content of metal impurities in the resist composition small (e.g., in the mass ppm level), it is also preferred to perform glass lining treatment on a part or all of the inside of the devices 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.

[1193] When the exposure described later is immersion exposure, the topcoat also functions as a layer disposed between the resist film and the immersion liquid and does not allow the resist film to directly contact the immersion liquid. At this time, the preferred characteristics of the topcoat (topcoat-forming composition) are coatability on the resist film, transparency to radiation, particularly 193 nm, and low solubility in the immersion liquid (preferably water). Also, the topcoat preferably does not mix with the resist film and can be further uniformly coated on the surface of the resist film.

[1194] In addition, in order to uniformly coat the composition for forming the top coat without dissolving the resist film on the surface of the resist film, the composition for forming the top coat preferably contains a solvent that does not dissolve the resist film. As the solvent that does not dissolve the resist film, a solvent having a different component from the developer (organic developer) containing an organic solvent described in detail later is further preferably used.

[1195] The coating method of the composition for forming the top coat is not particularly limited, and spin coating, spraying, roll coating, dipping, etc., which are conventionally known, can be used.

[1196] The film thickness of the top coat is not particularly limited, and from the viewpoint of transparency to the exposure light source, it is usually formed to a thickness of 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.

[1197] After forming the top coat, the (PB) substrate is heated as needed.

[1198] From the viewpoint of resolution, the refractive index of the top coat is preferably close to the refractive index of the resist film.

[1199] The top coat is preferably insoluble in the immersion liquid, and more preferably insoluble in water.

[1200] 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.

[1201] In immersion exposure, it is necessary for the immersion liquid to follow the exposure head and move on the wafer at high speed to form an exposure pattern, so the contact angle of the immersion liquid in the dynamic state with respect to the top coat becomes important. In order to obtain better resist performance, a receding contact angle within the above range is preferred.

[1202] When stripping the top coat, an organic developer can be used, or a stripper can be used alone. As the stripper, a solvent with low penetration into the resist film is preferred. From the viewpoint of being able to strip the top coat simultaneously with the development of the resist film, the top coat is preferably strippable with an organic developer. As the organic developer used for stripping, as long as it can dissolve and remove the low-exposure part of the resist film, there is no particular limitation.

[1203] 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.

[1204] Here, the dissolution rate of the top coat to the organic-based developer is the film thickness reduction rate when the top coat film is exposed to the developer after film formation, and in the present invention, it is set to the rate when immersed in butyl acetate at 23°C.

[1205] By setting the dissolution rate of the top coat to the organic-based developer to 1 / sec or more, preferably 10 nm / sec or more, there is an effect of reducing the occurrence of development defects after developing the resist film. Also, by setting it to 300 nm / sec or less, preferably 100 nm / sec, due to the influence of reducing exposure non-uniformity during liquid immersion exposure, there is an effect of further improving the line edge roughness of the pattern after developing the resist film.

[1206] The top coat 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.

[1207] [Pattern formation method]

[1208] The present invention also relates to a pattern formation method, which includes: a resist film formation 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.

[1209] In the present invention, the above exposure is preferably performed using an electron beam, an ArF excimer laser, or extreme ultraviolet light, and more preferably using an electron beam or extreme ultraviolet light.

[1210] In the manufacture of precision integrated circuit elements, etc., for the exposure on the resist film (pattern formation step), first, it is preferable to irradiate the resist film of the present invention with an ArF excimer laser, an electron beam, or extreme ultraviolet light (EUV) in a pattern shape. Regarding the exposure amount, in the case of an ArF excimer laser, it is set to be about 1 to 100 mJ / cm 2 about, preferably about 20 to 60 mJ / cm 2 about, in the case of an electron beam, it becomes about 0.1 to 20 μC / cm 2 about, preferably about 3 to 10 μC / cm 2 about, in the case of extreme ultraviolet light, it becomes about 0.1 to 20 mJ / cm 2 about, preferably about 3 to 15 mJ / cm 2 about for exposure.

[1211] Next, after exposure, heating (post-exposure baking) is preferably carried out on a hot plate at 60°C to 150°C for 5 seconds to 20 minutes, more preferably at 80°C to 120°C for 15 seconds to 10 minutes, and further preferably at 80°C to 120°C for 1 to 10 minutes. Then, development, rinsing, and drying are carried out to form a pattern. Here, the post-exposure heating is appropriately adjusted by the acid decomposability of the repeating unit having an acid-decomposable group in the resin (A). In the case of low acid decomposability, it is also preferable that the temperature of the post-exposure heating is 110°C or higher and the heating time is 45 seconds or longer.

[1212] The developer can be appropriately selected. Preferably, an alkaline developer (typically an alkaline aqueous solution) or a developer containing an organic solvent (also referred to as an organic-based developer) is used. When the developer is an alkaline aqueous solution, a 0.1 to 5 mass%, preferably 2 to 3 mass% alkaline aqueous 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. In the alkaline developer, an appropriate amount of an alcohol-based and / or surfactant can be added. 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. 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.

[1213] When the pattern formation method of the present invention has a step of developing using an alkaline developer, as the alkaline developer, for example, inorganic bases such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, and ammonia water, 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.

[1214] In addition, an appropriate amount of an alcohol-based and surfactant can also be added to the above alkaline aqueous solution for use.

[1215] The alkali concentration of the alkaline developer is usually 0.1 to 20 mass%.

[1216] The pH of the alkaline developer is generally 10.0 to 15.0.

[1217] In particular, an aqueous solution of 2.38% by mass of tetramethylammonium hydroxide is preferably used.

[1218] As the rinsing liquid in the rinsing process after alkali development, pure water can be used, and an appropriate amount of surfactant can be added for use.

[1219] Moreover, after the development process or the rinsing process, a process of removing the developer or the rinsing liquid adhering to the pattern using a supercritical fluid can be performed.

[1220] 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 solvents, ether solvents, and hydrocarbon solvents can be used.

[1221] 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 alcoholic hydroxyl group in the molecule, an amide 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 these, there are also solvents having a plurality of the above functional groups in one molecule, but in this case, it is assumed to be a solvent corresponding to any solvent type including the functional groups possessed by the solvent. For example, diethylene glycol monomethyl ether corresponds to either an alcohol solvent or an ether solvent in the above classification. And a hydrocarbon solvent means a hydrocarbon solvent having no substituent.

[1222] In particular, a developer containing at least one solvent selected from ketone solvents, ester solvents, alcohol solvents, and ether solvents is preferably used.

[1223] From the viewpoint of being able to suppress the 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.

[1224] The heteroatom of the above ester solvent is an atom other than a carbon atom and a hydrogen atom, and examples thereof may include an oxygen atom, a nitrogen atom, a sulfur atom, etc. The number of heteroatoms is preferably 2 or less.

[1225] Preferred examples of the ester solvent having 7 or more carbon atoms and 2 or less heteroatoms may include amyl acetate, isoamyl acetate, 2-methylbutyl acetate, 1-methylbutyl acetate, hexyl acetate, pentyl propionate, hexyl propionate, heptyl propionate, butyl butyrate, isobutyl isobutyrate, etc., and isoamyl acetate or isobutyl isobutyrate is particularly preferably used.

[1226] The developing solution can use a mixed solvent of the above ester-based solvent and the above hydrocarbon-based solvent or a mixed solvent of the above ketone-based solvent and the above hydrocarbon solvent to replace the above ester-based solvent having 7 or more carbon atoms and 2 or less heteroatoms. At this time, it is also effective in suppressing the swelling of the resist film.

[1227] When the ester-based solvent and the hydrocarbon-based solvent are used in combination, isopentyl acetate is preferably used as the ester-based solvent. And, as the hydrocarbon-based solvent, 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.

[1228] Examples of the ketone-based solvent include 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, diisobutyl ketone, cyclohexanone, methylcyclohexanone, phenylacetone, methyl ethyl ketone, methyl isobutyl ketone, acetylacetone, acetonylacetone, ionone, diacetonyl alcohol, acetylmethanol, acetophenone, methyl naphthyl ketone, isophorone, propylene carbonate, etc. Among them, diisobutyl ketone and 2,5-dimethyl-4-hexanone are particularly preferably used.

[1229] Examples of the ester-based solvent include methyl acetate, butyl acetate, ethyl acetate, isopropyl acetate, pentyl acetate, isopentyl acetate, amyl acetate, propylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, diethylene glycol monoethyl ether acetate, ethyl-3-ethoxypropionate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, methyl formate, ethyl formate, butyl formate, propyl formate, ethyl lactate, butyl lactate, propyl lactate, butyl butyrate, methyl 2-hydroxyisobutyrate, etc.

[1230] Examples of the alcohol-based solvent include 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., diol-based solvents such as ethylene glycol, diethylene glycol, triethylene glycol, etc., and ethylene glycol ether-based 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.

[1231] Examples of the ether-based solvent include anisole, dioxane, tetrahydrofuran, etc., in addition to the above ethylene glycol ether-based solvents.

[1232] 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.

[1233] As hydrocarbon solvents, for example, aromatic hydrocarbon solvents such as toluene and xylene, and aliphatic hydrocarbon solvents such as pentane, hexane, octane, decane, undecane, etc. can be cited.

[1234] In addition, among the aliphatic hydrocarbon solvents as hydrocarbon solvents, it can be a mixture of compounds having the same number of carbon atoms and different structures. For example, when decane is used as the aliphatic hydrocarbon solvent, compounds having the same number of carbon atoms and different structures, namely 2-methylnonane, 2,2-dimethyloctane, 4-ethyloctane, isooctane, etc. can be included in the aliphatic hydrocarbon solvent.

[1235] And, the above-mentioned compounds having the same number of carbon atoms and different structures can contain only one kind, or can contain multiple kinds as described above.

[1236] A plurality 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 exhibit the effects of the present invention, the water content of the developer as a whole is preferably less than 10% by mass, and more preferably substantially free of water.

[1237] The concentration of the organic solvent (when a plurality are mixed, the total) in the organic developer is preferably 50% by mass or more, more preferably 50 to 100% by mass, further preferably 85 to 100% by mass, further more preferably 90 to 100% by mass, and particularly preferably 95 to 100% by mass. The most preferred is the case where it consists essentially of only an organic solvent. In addition, the case where it consists essentially of only an organic solvent means including the case where a small amount of a surfactant, antioxidant, stabilizer, antifoaming agent, etc. are contained.

[1238] In particular, the organic developer is preferably a developer containing at least one organic solvent selected from ketone solvents, ester solvents, alcohol solvents, amide solvents, and ether solvents.

[1239] The vapor pressure of the organic developer is preferably 5 kPa or less at 20°C, more preferably 3 kPa or less, and particularly preferably 2 kPa or less. 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, and the temperature uniformity in the plane of the wafer is improved. As a result, the size uniformity in the plane of the wafer is improved.

[1240] Specific examples of those 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-propyl alcohol, isopropyl alcohol, n-butyl alcohol, sec-butyl alcohol, tert-butyl alcohol, isobutyl alcohol, n-hexyl alcohol, n-heptyl alcohol, n-octyl alcohol, and n-decyl alcohol; diol solvents such as ethylene glycol, diethylene glycol, and triethylene glycol; ethylene 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.

[1241] Specific examples of those having a vapor pressure in a particularly preferred range of 2 kPa or less include ketone solvents such as 1-octanone, 2-octanone, 1-nonanone, 2-nonanone, 2-heptanone, 4-heptanone, 2-hexanone, diisobutyl ketone, cyclohexanone, methylcyclohexanone, and phenylacetone; 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-butyl alcohol, sec-butyl alcohol, tert-butyl alcohol, isobutyl alcohol, n-hexyl alcohol, n-heptyl alcohol, n-octyl alcohol, and n-decyl alcohol; diol solvents such as ethylene glycol, diethylene glycol, and triethylene glycol; ethylene 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; 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.

[1242] The organic developing solution may 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 the specific examples and preferred examples of the basic compound that the radiation-sensitive or radiation-sensitive composition may contain.

[1243] An appropriate amount of surfactant can be added as needed to the organic developer.

[1244] There is no particular limitation on the surfactant. For example, ionic or non-ionic fluorine-based and / or silicon-based surfactants can be used. As these fluorine and / or silicon-based surfactants, for example, the surfactants described in Japanese Patent Laid-Open No. 62-36663, Japanese Patent Laid-Open No. 61-226746, Japanese Patent Laid-Open No. 61-226745, Japanese Patent Laid-Open No. 62-170950, Japanese Patent Laid-Open No. 63-34540, Japanese Patent Laid-Open No. 7-230165, Japanese Patent Laid-Open No. 8-62834, Japanese Patent Laid-Open No. 9-54432, Japanese Patent 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 can be cited. 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 further preferably used.

[1245] The usage amount of the surfactant 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 based on the total amount of the developer.

[1246] As a developing method, for example, the following methods can be applied: a method of immersing a substrate in a tank filled with a developer for a certain period of time (dip method); a method of making the developer bulge on the substrate surface by surface tension and standing for a certain period of time for development (puddle method); a method of spraying a developer on the substrate surface (spray method); a method of continuously ejecting a developer while scanning a nozzle for ejecting the developer at a certain speed on a substrate rotating at a certain speed (dynamic dispense method), etc.

[1247] When the above various developing methods include a step of ejecting a developer from a developing nozzle of a developing apparatus toward a resist film, the ejection pressure of the ejected developer (the flow rate per unit area of the ejected developer) is preferably 2 mL / sec / mm 2 More preferably, it is 1.5 mL / sec / mm or less 2 Further preferably, it is 1 mL / sec / mm or less 2Hereinafter, there is no particular lower limit for the flow rate, but considering the production volume, it is preferably 0.2 mL / sec / mm 2 or more.

[1248] By setting the ejection pressure of the ejected developer within the above range, it is possible to significantly reduce the defects of the pattern originating from the resist residue after development.

[1249] Although the detailed situation of this mechanism is not certain, it is generally considered that the reason is that by setting the ejection pressure within the above range, the pressure exerted by the developer on the resist film becomes smaller, and the situation where the resist film / pattern is inadvertently shaved or damaged is suppressed.

[1250] In addition, the ejection pressure of the developer (mL / sec / mm 2 ) is the value at the outlet of the developing nozzle in the developing apparatus.

[1251] As a method for 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 adjusting the supply from a pressurized tank, etc. can be cited.

[1252] Moreover, after the step of developing using a developer containing an organic solvent, a step of stopping development while replacing with another solvent can be implemented.

[1253] After the step of developing using a developer containing an organic solvent, a step of cleaning with a rinsing liquid can be included, but from the viewpoints of production volume (productivity), amount of rinsing liquid used, etc., the step of cleaning with a rinsing liquid can be excluded.

[1254] 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 solution containing a general organic solvent can be used. As the above 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.

[1255] 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, and particularly preferably, butyl acetate and methyl isobutyl carbinol can be cited.

[1256] After the step of developing using a developer containing an organic solvent, it is more preferable to perform a step of cleaning with a rinsing liquid containing at least one organic solvent selected from ester solvents, alcohol solvents, and hydrocarbon solvents, and further preferably to perform a step of cleaning with a rinsing liquid containing an alcohol solvent or a hydrocarbon solvent.

[1257] As the organic solvent contained in the rinse liquid, a hydrocarbon solvent is preferably used among organic solvents, and an aliphatic hydrocarbon solvent is more preferably used. As the aliphatic hydrocarbon solvent used in the rinse 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 preferred, an aliphatic hydrocarbon solvent having 8 or more carbon atoms is preferred, and an aliphatic hydrocarbon solvent having 10 or more carbon atoms is more preferred.

[1258] In addition, the upper limit value of the number of carbon atoms of the above-mentioned aliphatic hydrocarbon solvent is not particularly limited, and for example, 16 or less, preferably 14 or less, and more preferably 12 or less can be cited.

[1259] Among the above-mentioned aliphatic hydrocarbon solvents, decane, undecane, and dodecane are particularly preferred, and undecane is most preferred.

[1260] Thus, by using a hydrocarbon solvent (especially an aliphatic hydrocarbon solvent) as the organic solvent contained in the rinse liquid, the developer slightly infiltrated into the resist film after development is rinsed, further suppressing swelling, and the effect of suppressing pattern collapse is further exerted.

[1261] A plurality of the above components can be mixed, or they can be mixed with organic solvents other than the above.

[1262] 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.

[1263] The vapor pressure of the rinse liquid used after the step of developing using a developer containing an organic solvent is preferably 0.05 kPa or more and 5 kPa or less at 20°C, 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. By setting the vapor pressure of the rinse liquid to 0.05 kPa or more and 5 kPa or less, the temperature uniformity in the plane of the wafer is improved, and further, the swelling caused by the penetration of the rinse liquid is suppressed, and the size uniformity in the plane of the wafer is improved.

[1264] An appropriate amount of surfactant can also be added to the rinse liquid for use.

[1265] In the rinsing step, a rinsing liquid containing the above-mentioned organic solvent is used to clean a wafer developed with a developing solution containing an organic solvent. The method of the cleaning treatment is not particularly limited. For example, a method of continuously spraying the rinsing liquid onto a substrate rotating at a certain speed (spin coating method), a method of immersing the substrate in a tank filled with the rinsing liquid for a certain time (dipping method), a method of spraying the rinsing liquid onto the surface of the substrate (spray coating method), etc. Among them, it is preferred to perform the cleaning treatment by the spin coating method. After cleaning, the substrate is rotated at a speed of 2000 rpm to 4000 rpm to remove the rinsing liquid from the substrate. Further, it is also preferred to include a heating step (Post Bake) after the rinsing step. By baking, the developing solution and the rinsing liquid remaining between and inside the patterns can be removed. The heating step of the rinsing step is usually carried out at 40 to 160 °C, preferably 70 to 95 °C, and usually for 10 seconds to 3 minutes, preferably 30 seconds to 90 seconds.

[1266] In the case where there is no step of cleaning with a rinsing liquid, for example, the developing treatment method described in paragraphs

[0014] to

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

[1267] Moreover, the pattern forming method of the present invention may have a developing step using an organic developing solution and a developing step using an alkaline developing solution. By developing with the organic developing solution, the portions with weak exposure intensity are removed, and by developing with the alkaline developing solution, the portions with strong exposure intensity are also removed. Thus, through the multiple developing process of performing multiple developments, since only the region with an intermediate exposure intensity that is insoluble can be used for pattern formation, a pattern finer than usual can be formed (the same mechanism as in paragraph

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

[1268] In the photosensitive radiation 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, developing solutions, rinsing liquids, compositions for forming anti-reflection films, compositions for forming top coats, etc.), it is preferred that they do not contain impurities such as metals, metal salts containing halogens, components containing acids, bases, 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.

[1269] Regarding 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 not contained (below the detection limit of the measuring device).

[1270] As a method for removing impurities such as metals from various materials, for example, filtration using a filter can be cited. As the pore size of the filter, a pore size of 10 nm or less is preferred, more preferably 5 nm or less, and still more 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 formed by combining these materials and an ion exchange medium. A filter that has been pre-cleaned with an organic solvent can be used. In the filter filtration step, multiple filters can be connected in series or in parallel for use. When using multiple filters, filters with different pore sizes and / or materials can be used in combination. Also, various materials can be filtered multiple times, and the step of performing multiple filtrations can be a cyclic filtration step.

[1271] Moreover, as a method for reducing impurities such as metals contained in various materials, methods such as selecting raw materials with a low metal content as raw materials constituting various materials, subjecting the raw materials constituting various materials to filter filtration, and performing distillation under conditions that suppress contamination as much as possible, such as lining the inside of the apparatus with Teflon (registered trademark), can be cited. The preferred conditions for filter filtration of the raw materials constituting various materials are the same as the above conditions.

[1272] In addition to filter filtration, impurities can be removed by an adsorbent material, and filter filtration and an adsorbent material can also be used in combination. As the adsorbent material, known adsorbent materials can be used. For example, inorganic adsorbent materials such as silica gel and zeolite, and organic adsorbent materials such as activated carbon can be used.

[1273] Furthermore, as a method for reducing impurities such as metals contained in the organic treatment liquid of the present invention, methods such as selecting raw materials with a low metal content as raw materials constituting various materials, subjecting the raw materials constituting various materials to filter filtration, and performing distillation under conditions that suppress contamination as much as possible, such as lining the inside of the apparatus with Teflon (registered trademark), can be cited. The preferred conditions for filter filtration of the raw materials constituting various materials are the same as the above conditions.

[1274] In addition to filter filtration, impurities can be removed by an adsorbent material, and filter filtration and an adsorbent material can also be used in combination. As the adsorbent material, known adsorbent materials can be used. For example, inorganic adsorbent materials such as silica gel and zeolite, and organic adsorbent materials such as activated carbon can be used.

[1275] [Receiving container]

[1276] As an organic solvent (also referred to as an "organic-based treatment liquid") that can be used in a developing solution and a rinsing solution, it is preferably a solvent stored in a storage container for an organic-based treatment liquid for patterning a chemically amplified or non-chemically amplified resist film, which has a storage portion. As such a storage container, for example, it is preferably a storage container for an organic-based treatment liquid for patterning a resist film, in which the inner wall of the storage portion that comes into contact with the organic-based treatment liquid is formed of a resin different from any of polyethylene resin, polypropylene resin, and polyethylene-polypropylene resin, or a metal that has been subjected to rust prevention and metal elution prevention treatment. A predetermined organic solvent used as an organic-based treatment liquid for patterning a resist film is stored in the above-mentioned storage portion of the storage container, and the organic solvent discharged from the above-mentioned storage portion can be used during patterning of the resist film.

[1277] In the case where the above-mentioned storage container further has a sealing portion for sealing the above-mentioned storage portion, the sealing portion is also preferably formed of a resin different from one or more resins selected from polyethylene resin, polypropylene resin, and polyethylene-polypropylene resin, or a metal that has been subjected to rust prevention and metal elution prevention treatment.

[1278] Here, the sealing portion refers to a component that can block the storage portion from external air, and seals, O-rings, etc. can be preferably selected.

[1279] A resin different from one or more resins selected from polyethylene resin, polypropylene resin, and polyethylene-polypropylene resin is preferably a perfluororesin.

[1280] 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), vinyl fluoride resin (PVF), etc.

[1281] Particularly preferred perfluororesins include tetrafluoroethylene resin, tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer, and tetrafluoroethylene-hexafluoropropylene copolymer resin.

[1282] Examples of the metal in the metal that has been subjected to rust prevention and metal elution prevention treatment include carbon steel, alloy steel, nickel-chromium steel, nickel-chromium-molybdenum steel, chromium steel, chromium-molybdenum steel, manganese steel, etc.

[1283] As the rust prevention and metal elution prevention treatment, film technology is preferably applied.

[1284] Coating technology is roughly divided into three types: metal coating (various plating), inorganic coating (various chemical conversion treatments, glass, concrete, ceramics, etc.) and organic coating (rust-proof oil, paint, rubber, plastic).

[1285] Preferred coating techniques include surface treatment using rust preventive oil, rust preventive agent, corrosion inhibitor, chelate compound, strippable plastic, and lining agent.

[1286] Among them, various chromates, nitrites, silicates, phosphates, carboxylic acids such as oleic acid, dimer acid, cyclopentane acid, corrosion inhibitors such as carboxylic acid metal soaps, sulfonates, amine salts, esters (glycerides or phosphates of higher fatty acids), chelate compounds such as ethylenediaminetetraacetic acid, gluconic acid, nitrilotriacetic acid, hydroxyethylethylenediaminetriacetic acid, diethylenetriaminepentaacetic acid, and fluororesin linings are preferred. Phosphate treatment and fluororesin linings are particularly preferred.

[1287] Furthermore, although it cannot directly prevent rust as compared with direct coating treatment, it is also preferable to adopt "pretreatment" as a stage before rust prevention treatment as a treatment method for extending the rust prevention period by coating treatment.

[1288] 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 washing or polishing can be preferably mentioned.

[1289] Specific examples of the storage container include the following.

[1290] Entegris FluoroPure PFA composite roller (wetted inner surface; PFA resin lining)

[1291] · JFE steel cylinder (liquid contact inner surface: zinc phosphate film)

[1292] Furthermore, examples of storage containers that can be used in the present invention include containers described in Japanese Patent Application Laid-Open Nos. 11-021393

[0013] to 0030] and Japanese Patent Application Laid-Open Nos. 10-45961

[0012] to 24].

[1293] In order to prevent failures of liquid medicine pipes 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 liquid medicine pipe, 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 filter and O-ring, polyethylene, polypropylene, or fluororesin (polytetrafluoroethylene, perfluoroalkoxy resin, etc.) subjected to antistatic treatment can be used.

[1294] In addition, usually, after use, the developer and the rinsing liquid are collected in a waste liquid tank through pipes. At this time, if a hydrocarbon-based solvent is used as the rinsing 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 pipe, etc., there is a method of passing the solvent that dissolves the resist through the pipe again. As the method of passing through the pipe, there can be cited a method of cleaning with the rinsing liquid and then cleaning with the solvent that dissolves the resist and flowing it through the back surface and side surface of the substrate, etc., or a method of flowing the solvent that dissolves the resist through the pipe without contacting the resist.

[1295] As the solvent passing through the pipe, as long as it is a solvent that can dissolve the resist, there is no particular limitation. For example, the above-mentioned organic solvents can be cited, 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 can be preferably used.

[1296] [Method for manufacturing an electronic device]

[1297] Furthermore, the present invention also relates to a method for manufacturing an electronic device including the above-mentioned pattern forming method. The electronic device manufactured by the method for manufacturing an electronic device of the present invention can be preferably mounted on electrical and electronic devices (for example, home appliances, OA (Office Automation) related devices, media related devices, optical devices, and communication devices, etc.).

[1298] Furthermore, the present invention also relates to a photosensitive actinic or radiation-sensitive resin composition described below.

[1299] A photosensitive actinic ray- or radiation-sensitive resin composition containing: resin (A) whose polarity increases by the action of an acid; and compound (B) which generates an acid upon irradiation with actinic rays or radiation and is represented by the following general formula (I), wherein the resin (A) contains a repeating unit represented by the following general formula (AI).

[1300] [Chemical formula 99]

[1301]

[1302] In general formula (AI),

[1303] R A , R B and R C each independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, a cyano group, or an alkoxycarbonyl group. Among them, R C may bond with Ar A to form a ring, and in this case, R C represents a single bond or an alkylene group.

[1304] L A represents a single bond or a divalent linking group.

[1305] Ar A represents an (n + 1)-valent aromatic ring group. When Ar A bonds with R C to form a ring, it represents an (n + 2)-valent aromatic ring group.

[1306] n represents an integer from 1 to 5.

[1307] [Chemical formula 100]

[1308]

[1309] In general formula (I),

[1310] M 1 + and M 2 + each independently represents a cation.

[1311] X represents an (m + 1)-valent linking group.

[1312] A 1 - and A 2 - are each independently a group selected from the groups represented by the following formulas (B-1) to (B-27).

[1313] [Chemical formula 101]

[1314]

[1315] [Chemical formula 102]

[1316]

[1317] In general formula (B-1),

[1318] Y F1 represents a fluorine atom or a perfluoroalkyl group.

[1319] Y 1 represents a hydrogen atom or a substituent having no fluorine atom.

[1320] In general formula (B-2),

[1321] Y 2 each independently represents a hydrogen atom or a substituent having no fluorine atom.

[1322] In general formula (B-3),

[1323] Y F2 represents a fluorine atom or a perfluoroalkyl group.

[1324] Y 3 represents a hydrogen atom or a substituent having no fluorine atom.

[1325] Ra represents an organic group.

[1326] In general formula (B-4),

[1327] Y 4 each independently represents a hydrogen atom or a substituent having no fluorine atom.

[1328] Ra 1 represents an organic group.

[1329] In general formula (B-5),

[1330] Y F3 represents a fluorine atom or a perfluoroalkyl group.

[1331] Y 5 represents a hydrogen atom or a substituent having no fluorine atom.

[1332] Rb represents a hydrogen atom or an organic group.

[1333] In general formula (B-6),

[1334] Y 6 each independently represents a hydrogen atom or a substituent having no fluorine atom.

[1335] Rb 1 represents a hydrogen atom or an organic group.

[1336] In general formula (B-7),

[1337] Y F4 represents a fluorine atom or a perfluoroalkyl group.

[1338] Y 7 represents a hydrogen atom or a substituent having no fluorine atom.

[1339] Rc represents an organic group.

[1340] In general formula (B-8),

[1341] Y 8 each independently represents a hydrogen atom or a substituent having no fluorine atom.

[1342] Rc 1 represents an organic group.

[1343] In general formula (B-9), Y F5 represents a fluorine atom or a perfluoroalkyl group.

[1344] Y 9 represents a hydrogen atom or a substituent having no fluorine atom.

[1345] Rd represents an organic group.

[1346] In general formula (B-10),

[1347] Y 10 each independently represents a hydrogen atom or a substituent having no fluorine atom.

[1348] Rd 1 represents an organic group.

[1349] In general formula (B-12),

[1350] Re represents a hydrogen atom, an organic group or a halogen atom.

[1351] o represents an integer of 1 to 4.

[1352] When o represents an integer of 2 or more, multiple Res may be the same or different.

[1353] In general formula (B-13),

[1354] Y F6 represents a fluorine atom or a perfluoroalkyl group.

[1355] Y 11 represents a hydrogen atom or a substituent having no fluorine atom.

[1356] In general formula (B-14),

[1357] Y 12Each independently represents a hydrogen atom or a substituent having no fluorine atom.

[1358] In general formula (B-15),

[1359] Y F7 represents a fluorine atom or a perfluoroalkyl group.

[1360] Y 13 represents a hydrogen atom or a substituent having no fluorine atom.

[1361] Rf represents an organic group.

[1362] In general formula (B-16),

[1363] Y 14 Each independently represents a hydrogen atom or a substituent having no fluorine atom.

[1364] Rf 1 represents an organic group.

[1365] In general formula (B-17),

[1366] Y F8 represents a fluorine atom or a perfluoroalkyl group.

[1367] Y 15 represents a hydrogen atom or a substituent having no fluorine atom.

[1368] Rg represents an organic group.

[1369] Rh represents an organic group.

[1370] In general formula (B-18),

[1371] Y 16 Each independently represents a hydrogen atom or a substituent having no fluorine atom.

[1372] Rg 1 represents an organic group.

[1373] Rh 1 represents an organic group.

[1374] In general formula (B-19),

[1375] Y F9 represents a fluorine atom or a perfluoroalkyl group.

[1376] Y 17 represents a hydrogen atom or a substituent having no fluorine atom.

[1377] In general formula (B-20),

[1378] Y 18 Each independently represents a hydrogen atom or a substituent having no fluorine atom.

[1379] In general formula (B-21),

[1380] Y F10 represents a fluorine atom or a perfluoroalkyl group.

[1381] Y 19 represents a hydrogen atom or a substituent having no fluorine atom.

[1382] Ri represents an organic group.

[1383] Rj represents an organic group.

[1384] In general formula (B-22),

[1385] Y 20 each independently represents a hydrogen atom or a substituent having no fluorine atom.

[1386] Ri 1 represents an organic group.

[1387] Rj 1 represents an organic group.

[1388] In general formula (B-23),

[1389] Rk represents a hydrogen atom or a substituent having no fluorine atom.

[1390] p represents an integer from 1 to 4.

[1391] When p represents an integer of 2 or more, multiple Rk's may be the same or different.

[1392] In general formula (B-24),

[1393] Rl represents a hydrogen atom, an organic group, or a halogen atom.

[1394] q represents an integer from 1 to 4.

[1395] When q represents an integer of 2 or more, multiple R1's may be the same or different.

[1396] Rc 2 represents an organic group.

[1397] In general formula (B-25),

[1398] Y F11 each independently represents a fluorine atom or a perfluoroalkyl group.

[1399] Rc 3 represents an organic group.

[1400] In general formula (B-26),

[1401] YF12 Each independently represents a fluorine atom or a perfluoroalkyl group.

[1402] Rd 2 represents an organic group.

[1403] In general formula (B-27),

[1404] Y F13 Each independently represents a fluorine atom or a perfluoroalkyl group.

[1405] In general formulas (B-1) to (B-27),

[1406] * represents the bonding position.

[1407] A 1 - represents a structure different from the group represented by A 2 - represents.

[1408] m represents 1 or 2. When m represents 2, multiple Ms 1 + can be the same or different. When m represents 2, multiple As 1 - can be the same or different.

[1409] R in general formula (AI) A 、R B 、R C 、L A 、Ar A and n are the same as R A 、R B 、R C 、L A 、Ar A and n in general formula (A1) of the above resin (A), respectively.

[1410] M in general formula (I) 1 + 、M 2 + 、X and each group in general formulas (B-1) to (B-27) are the same as M 1 + 、M 2 + 、X and each group in general formulas (B-1) to (B-27) in the above compound (B), respectively.

[1411] Examples

[1412] Hereinafter, the present invention will be further described in detail based on examples. As long as the gist of the present invention is not departed from, materials, amounts used, ratios, treatment contents, treatment 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.

[1413] <Resin (A)>

[1414] The structure of the repeating unit of the resin (A) used, its content (molar ratio), weight average molecular weight (Mw), and dispersity (Mw / Mn) are shown below.

[1415] In addition, resin A'-1 is not resin (A), but is described below for convenience.

[1416] [Chemical formula 103]

[1417]

[1418] [Chemical formula 104]

[1419]

[1420] [Chemical formula 105]

[1421]

[1422] [Chemical formula 106]

[1423]

[1424] [Chemical formula 107]

[1425]

[1426] [Chemical formula 108]

[1427]

[1428] [Chemical formula 109]

[1429]

[1430] [Chemical formula 110]

[1431]

[1432] In resin (A-30), the numbers of the repeating units attached to the right side represent the contents (molar ratios) of the above repeating units.

[1433] <Photoacid generator (B)>

[1434] Compounds (B-1) to (B-27) are formed by combining the cations described in Table 1 and the anions described in Table 1. In addition, for the cations, the number of cations contained in the compound is also described together.

[1435] In the comparative example, the following compound (B'-1) was used.

[1436] [Chemical formula 111]

[1437]

[1438] [Table 1]

[1439] Table 1

[1440]

[1441] The structures of the cations described in Table 1 are shown below. Me represents methyl, and Bu represents n-butyl.

[1442] [Chemical formula 112]

[1443]

[1444] [Chemical formula 113]

[1445]

[1446] The structures of the anions described in Table 1 are shown below. Me represents methyl, and Bu represents n-butyl.

[1447] [Chemical formula 114]

[1448]

[1449] [Chemical formula 115]

[1450]

[1451] [Chemical formula 116]

[1452]

[1453] (Acid dissociation constant pKa of the acid generated from the photoacid generator)

[1454] Table 2 shows the acid dissociation constant pKa of the acid generated from the photoacid generator.

[1455] In addition, when measuring the acid dissociation constant pKa of the acid generated from the photoacid generator, specifically, each cation moiety in Compounds B-1 to B-27 was replaced with H + to form a compound (for example, when it is Compound B-1, the triphenylsulfonium cation is replaced with H+ For the compounds formed, as described above, using the software package 1 of ACD / Labs, the Hammett-based substituent constants and the values in the database of known literature values were calculated. And when the pKa could not be calculated by the above method, the values obtained by Gaussian16 based on DFT (density functional method) were adopted.

[1456] In the following table, "pKa1" represents the acid dissociation constant in the first stage, "pKa2" represents the acid dissociation constant in the second stage, and "pKa3" represents the acid dissociation constant in the third stage. The smaller the value of pKa, the higher the acidity.

[1457] As described above, Compounds B-1 to B-14 and B-16 to B-27 correspond to the above Compound (B). Here, pKa1 corresponds to the above acid dissociation constant a1, and pKa2 corresponds to the above acid dissociation constant a2.

[1458] And, as described above, Compound B-15 also corresponds to the above Compound (B). Here, pKa1 corresponds to the above acid dissociation constant a1, and pKa3 corresponds to the above acid dissociation constant a2.

[1459] Since the acid generated from Compound B-15 (the compound formed by substituting the sulfonium cation of Compound B-15 with H + is a symmetric structure, the acid dissociation constants pKa of the two first acidic sites (HA 1 ) theoretically become the same value. However, in the above calculation method, the acid dissociation constants of the two first acidic sites (HA 1 ) can be obtained as the acid dissociation constant pKa1 in the first stage and the acid dissociation constant pKa2 in the second stage. Regarding the acid generated from Compound B-15, the smallest value among the acid dissociation constants pKa of the two first acidic sites (HA 1 ), that is, the acid dissociation constant pKa1, corresponds to the above acid dissociation constant a1.

[1460] [Table 2]

[1461] Table 2

[1462] Photoacid generator B pKa1 pKa2 pKa3 B-1 -0.83 4.14 - B-2 -0.92 1.92 - B-3 -0.82 4.24 - B-4 -0.83 3.96 - B-5 -0.86 3.32 - B-6 -0.95 4.58 - B-7 -0.8 3.90 - B-8 0.05 4.15 - B-9 0.07 4.24 - B-10 0.05 3.98 - B-11 0.86 4.49 - B-12 -0.05 4.15 - B-13 -0.05 3.97 - B-14 -0.05 4.24 - B-15 0.79 1.53 4.16 B-16 0.42 4.06 - B-17 -0.82 -0.56 - B-18 -0.92 1.92 - B-19 -0.58 9.09 - B-20 -1.3 4.64 - B-21 1.64 2.3 - B-22 1.44 4.86 - B-23 -1.47 3.89 - B-24 1.01 2.5 - B-25 -0.54 5.72 - B-26 -0.29 4.61 - B-27 1.08 5.68 - B′-1 -3.41 -0.24 -

[1463] <Acid diffusion control agent>

[1464] The structure of the acid diffusion control agent used is shown below.

[1465] [Chemical formula 117]

[1466]

[1467] [Chemical Formula 118]

[1468]

[1469] [Chemical Formula 119]

[1470]

[1471] [Chemical Formula 120]

[1472]

[1473] <Photoacid Generator (B’)>[

[1474] The structure of the photoacid generator (B’) used is shown below.

[1475] [Chemical Formula 121]

[1476]

[1477] [Chemical Formula 122]

[1478]

[1479] <Surfactant>[

[1480] As the surfactant, the following W-1 to W-4 were used.

[1481] W-1: Megaface R08 (manufactured by DIC Corporation; fluorine and silicon-based)

[1482] W-2: Polysiloxane polymer KP-341 (manufactured by Shin-Etsu Chemical Co., Ltd.; silicon-based)

[1483] W-3: Troysol S-366 (manufactured by Troy Chemical Industries Inc.; fluorine-based)

[1484] W-4: PF6320 (manufactured by OMNOVA Solutions Inc.; fluorine-based)

[1485] <Solvent>[

[1486] The solvents used are shown below.

[1487] S-1: Propylene glycol monomethyl ether acetate (PGMEA)

[1488] S-2: Propylene glycol monomethyl ether (PGME)

[1489] S-3: Ethyl lactate (EL)

[1490] S-4: Ethyl 3-ethoxypropionate (EEP)

[1491] S-5: 2-Heptanone (MAK)

[1492] S-6: Methyl 3-methoxypropionate (MMP)

[1493] S-7: Butyl 3-methoxyacetate

[1494] [Preparation and Coating of Resist Composition Coating Liquid]

[1495] (1) Preparation of Support

[1496] An 8-inch wafer vapor-deposited with Cr oxynitride (a material subjected to the shielding film treatment used in a normal blank photomask) was prepared.

[1497] (2) Preparation of Resist Composition

[1498] The components shown in Table 3 were dissolved in the solvent shown in Table 3 to prepare a solution, and the solution was filtered through a polyethylene filter having a pore size of 0.03 μm to prepare a resist composition.

[1499] (3) Fabrication of Resist Film

[1500] The resist composition was coated on the above 8-inch wafer using a spin coater Mark8 manufactured by Tokyo Electron Ltd., 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 resist-coated wafer was obtained.

[1501] [EB Exposure and Development]

[1502] (4) Fabrication of Resist Pattern

[1503] 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 dried.

[1504] [Evaluation]

[1505] (5) Evaluation of Resist Pattern

[1506] For the resolution and roughness performance, the obtained pattern was evaluated by the following method. The results are shown in Table 4 described later.

[1507] The irradiation energy when resolving a 1:1 line and space pattern with a line width of 50 nm is defined as the sensitivity (Eop).

[1508] <L / S resolution>

[1509] The resolution (nm) is defined as the ultimate resolving power (the minimum line width for separating a line and space (line:space = 1:1)) in the exposure amount showing the above sensitivity (Eop).

[1510] <Isolated space pattern (IS) resolution>

[1511] The ultimate resolving power (the minimum space width for separating a line and space) of an isolated space (line:space = 100:1) in the above sensitivity (Eop) is obtained. Then, this value is set as the "isolated space pattern resolution (nm)". A smaller value indicates better performance.

[1512] <Roughness performance (LWR)>

[1513] For a 20 nm (1:1) line and space pattern analyzed for the optimal exposure amount when analyzing a line pattern with an average line width of 30 nm, when observed from above the pattern using a length measurement scanning electron microscope (SEM, S-9380II manufactured by Hitachi, Ltd.), the line width was observed at an arbitrary point, and its measurement deviation was evaluated by 3σ (nm). A smaller value indicates better performance.

[1514] In addition, in Table 3 below, the content (mass%) of each component other than the solvent refers to the content ratio relative to the total solid components. And the content ratio (mass%) of the solvent used relative to all solvents is recorded in Table 3 below.

[1515]

[1516]

[1517] [Table 5]

[1518] Table 4

[1519]

[1520] [Table 6]

[1521] Table 4 (continued)

[1522]

[1523] From the results in Table 4, it can be seen that the patterns obtained by the pattern formation method of the present invention have excellent resolution and roughness performance.

[1524] [Extreme Ultraviolet (EUV) Exposure and Development]

[1525] (4) Fabrication of Resist Pattern

[1526] 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), the wafer coated with a resist film obtained in (3) above was pattern-exposed. After exposure, it was heated on a hot plate 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 and then baked at 95 °C for 60 seconds to dry it.

[1527] [Evaluation]

[1528] (5) Evaluation of Resist Pattern

[1529] For the resolution and roughness performance, the obtained pattern was evaluated by the following method. The results are shown in Table 5 described later.

[1530] The irradiation energy when resolving a 1:1 line and space pattern with a line width of 50 nm was defined as the sensitivity (Eop).

[1531] <L / S Resolution>

[1532] The ultimate resolution (the minimum line width for separating a line and space (line:space = 1:1)) in the exposure dose showing the above sensitivity (Eop) was defined as the resolution (nm).

[1533] <Isolated Space Pattern (IS) Resolution>

[1534] The ultimate resolution (the minimum space width for separating a line and space) of the isolated space (line:space = 100:1) in the above sensitivity (Eop) was determined. Then, this value was set as the "isolated space pattern resolution (nm)". A smaller value indicates better performance.

[1535] <Roughness Performance (LWR)>

[1536] For a 20 nm (1:1) line and space pattern analyzed for the optimum exposure dose when analyzing a line pattern with an average line width of 30 nm, when observed from above the pattern using a length measurement scanning electron microscope (SEM, S-9380II manufactured by Hitachi, Ltd.), the line width was observed at an arbitrary point, and its measurement deviation was evaluated by 3σ (nm). A smaller value indicates better performance.

[1537] [Table 7]

[1538] Table 5

[1539]

[1540] [Table 8]

[1541] Table 5 (continued)

[1542]

[1543] As can be seen from the results in Table 5, the pattern obtained by the pattern forming method of the present invention has excellent resolution and roughness performance.

[1544] Industrial applicability

[1545] According to the present invention, it is possible to provide a photosensitive radiation-curable or radiation-sensitive resin composition capable of achieving both an improvement in roughness performance and an improvement in resolution in a high dimension in the formation of ultra-fine patterns (particularly, patterns having a line width or space width of 30 nm or less). According to the present invention, it is possible to provide a photosensitive radiation-curable or radiation-sensitive film, a pattern forming method, and a method for manufacturing an electronic device using the above-mentioned photosensitive radiation-curable or radiation-sensitive resin composition.

[1546] The present invention has been described in detail with reference to specific embodiments, but it is obvious to those skilled in the art that various changes or modifications can be added without departing from the spirit and scope of the present invention.

[1547] In addition, this application is based on a Japanese patent application filed on March 31, 2020 (Japanese Patent Application No. 2020-65191), the content of which is incorporated herein by reference.

Claims

1. A photosensitive actinic ray or radiation-sensitive resin composition, comprising: Resin (A): having increased polarity by the action of an acid; and Compound (B): generating an acid upon irradiation with actinic rays or radiation and represented by the following general formula (I), The resin (A) contains a repeating unit represented by the following general formula (AI), In general formula (AI), R A 、R B and R C each independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, a cyano group or an alkoxycarbonyl group, Wherein, R C Optionally bonded to Ar A to form a ring, where R C represents a single bond or an alkylene group L A represents a single bond or a divalent linking group, Ar A represents an aromatic ring group with a valence of (n + 1). When Ar A is bonded to R C to form a ring, it represents an aromatic ring group with a valence of (n + 2). n represents an integer of 1 to 5, In general formula (I), M 1 + and M 2 + each independently represents a cation, X represents a single bond or an (m + 1)-valent linking group, A 1 - and A 2 - each independently represents an anionic group, A 1 - represents a structure different from the acid anionic group represented by A 2 - represented m represents 1 or 2. When m represents 2, multiple Ms 1 + are the same or different. When m represents 2, multiple As 1 - are the same or different Among them, M of the compound represented by the general formula (I) 1 + and M 2 + The compounds (PI) in which are each replaced by a hydrogen atom have an acid dissociation constant a1 of the group represented by HA 1 and an acid dissociation constant a2 of the group represented by A 2 H. The acid dissociation constant a1 is lower than the acid dissociation constant a2, and the acid dissociation constant a1 is -1.5 or more.

2. The photosensitive actinic ray or radiation-sensitive resin composition according to claim 1, Wherein, In the general formula (I), A 1 - and A 2 - are each independently a group selected from the groups represented by the following general formulas (B-1) to (B-27), In general formula (B-1), Y F1 represents a fluorine atom or a perfluoroalkyl group Y 1 represents a hydrogen atom or a substituent having no fluorine atom, In general formula (B-2), Y 2 each independently represents a hydrogen atom or a substituent having no fluorine atom In general formula (B-3), Y F2 represents a fluorine atom or a perfluoroalkyl group Y 3 represents a hydrogen atom or a substituent having no fluorine atom Ra represents an organic group, In general formula (B-4), Y 4 each independently represents a hydrogen atom or a substituent having no fluorine atom Ra 1 represents an organic group In general formula (B-5), Y F3 represents a fluorine atom or a perfluoroalkyl group, Y 5 represents a hydrogen atom or a substituent having no fluorine atom, Rb represents a hydrogen atom or an organic group, In general formula (B-6), Y 6 each independently represents a hydrogen atom or a substituent having no fluorine atom Rb 1 represents a hydrogen atom or an organic group, In general formula (B-7), Y F4 represents a fluorine atom or a perfluoroalkyl group, Y 7 represents a hydrogen atom or a substituent having no fluorine atom, Rc represents an organic group, In general formula (B-8), Y 8 each independently represents a hydrogen atom or a substituent having no fluorine atom Rc 1 represents an organic group In general formula (B-9), Y F5 represents a fluorine atom or a perfluoroalkyl group Y 9 represents a hydrogen atom or a substituent having no fluorine atom Rd represents an organic group, In general formula (B-10), Y 10 each independently represents a hydrogen atom or a substituent having no fluorine atom Rd 1 represents an organic group In general formula (B-12), Re represents a hydrogen atom, an organic group or a halogen atom, o represents an integer of 1 to 4, When o represents an integer of 2 or more, multiple Res are the same or different, In general formula (B-13), Y F6 represents a fluorine atom or a perfluoroalkyl group Y 11 represents a hydrogen atom or a substituent having no fluorine atom, In general formula (B-14), Y 12 each independently represents a hydrogen atom or a substituent having no fluorine atom In general formula (B-15), Y F7 represents a fluorine atom or a perfluoroalkyl group, Y 13 represents a hydrogen atom or a substituent having no fluorine atom, Rf represents an organic group, In general formula (B-16), Y 14 each independently represents a hydrogen atom or a substituent having no fluorine atom Rf 1 represents an organic group, In general formula (B-17), Y F8 represents a fluorine atom or a perfluoroalkyl group, Y 15 represents a hydrogen atom or a substituent having no fluorine atom Rg represents an organic group, Rh represents an organic group, In general formula (B-18), Y 16 each independently represents a hydrogen atom or a substituent having no fluorine atom Rg 1 represents an organic group Rh 1 represents an organic group, In general formula (B-19), Y F9 represents a fluorine atom or a perfluoroalkyl group, Y 17 represents a hydrogen atom or a substituent having no fluorine atom, In general formula (B-20), Y 18 each independently represents a hydrogen atom or a substituent having no fluorine atom In general formula (B-21), Y F10 represents a fluorine atom or a perfluoroalkyl group, Y 19 represents a hydrogen atom or a substituent having no fluorine atom, Ri represents an organic group, Rj represents an organic group, In general formula (B-22), Y 20 each independently represents a hydrogen atom or a substituent having no fluorine atom Ri 1 represents an organic group Rj 1 represents an organic group In general formula (B-23), Rk represents a hydrogen atom or a substituent without a fluorine atom, p represents an integer of 1 to 4, When p represents an integer of 2 or more, multiple Rks are the same or different, In general formula (B-24), R1 represents a hydrogen atom, an organic group or a halogen atom, q represents an integer of 1 to 4, When q represents an integer of 2 or more, multiple R1s are the same or different, Rc 2 represents an organic group In general formula (B-25), Y F11 each independently represents a fluorine atom or a perfluoroalkyl group Rc 3 represents an organic group In general formula (B-26), Y F12 each independently represents a fluorine atom or a perfluoroalkyl group Rd 2 represents an organic group In general formula (B-27), Y F13 each independently represents a fluorine atom or a perfluoroalkyl group In general formulas (B-1) to (B-27), * represents the bonding position.

3. The photosensitive actinic ray or radiation-sensitive resin composition according to claim 1 or 2, Wherein, In the compound (PI), the difference between the acid dissociation constant a1 and the acid dissociation constant a2 is 2.0 or more.

4. The photosensitive actinic ray or radiation-sensitive resin composition according to claim 1 or 2, Wherein, In the compound (PI), the acid dissociation constant a2 is 2.0 or more.

5. The photosensitive actinic ray or radiation-sensitive resin composition according to claim 2, Wherein, In the general formula (I), A 1 - is a group represented by the general formula (B-2) or (B-23).

6. The photosensitive actinic ray or radiation-sensitive resin composition according to claim 2, Wherein, In the general formula (I), A 1 - is a group represented by the general formula (B-2).

7. The photosensitive actinic ray or radiation-sensitive resin composition according to claim 1 or 2, Wherein, (A) The resin whose polarity is increased by the action of an acid contains a repeating unit having an acid-decomposable group, and the repeating unit having an acid-decomposable group is a repeating unit selected from a repeating unit having a group that decomposes by the action of an acid to generate a carboxyl group and a repeating unit having a group that decomposes by the action of an acid to generate a phenolic hydroxyl group.

8. The photosensitive actinic or radiation-sensitive resin composition according to claim 7, wherein, the repeating unit having an acid-decomposable group contains one or more selected from the repeating units represented by the following general formulas (3) to (7), In general formula (3), R 5 , R 6 and R 7 each independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, a cyano group or an alkoxycarbonyl group, L 2 represents a single bond or a divalent linking group R 8 ~R 10 each independently represents an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group or an alkenyl group, and further, two of 8 ~R 10 optionally bond to each other to form a ring, In general formula (4), R 11 ~R 14 each independently represents a hydrogen atom or an organic group, where at least one of R 11 and R 12 represents an organic group. X 1 represents -CO-, -SO- or -SO 2 -, Y 1 represents -O-, -S-, -SO-, -SO 3 -, or -NR 34 -, where R 34 represents a hydrogen atom or an organic group, L 3 represents a single bond or a divalent linking group, R 15 ~R 17 each independently represents an alkyl group, a cycloalkyl group optionally having a fluorine atom, an aryl group, an aralkyl group or an alkenyl group. Additionally, two of R 15 ~R 17 optionally bond to each other to form a ring, In general formula (5), R 18 and R 19 each independently represents a hydrogen atom or an organic group, R 20 and R 21 each independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group or an alkenyl group. Additionally, R 20 and R 21 optionally bond to each other to form a ring In general formula (6), R 22 , R 23 and R 24 each independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, a cyano group or an alkoxycarbonyl group, L 4 represents a single bond or a divalent linking group Ar 1 represents an aromatic ring group R 25 ~R 27 each independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group or an alkenyl group. Additionally, R 26 and R 27 optionally bond to each other to form a ring, and Ar 1 optionally bonds to R 24 or R 25 to form a ring. In general formula (7), R 28 , R 29 , and R 30 each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, a cyano group, or an alkoxycarbonyl group, L 5 represents a single bond or a divalent linking group R 31 and R 32 each independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group or an alkenyl group, R 33 represents alkyl, cycloalkyl, aryl, aralkyl or alkenyl, and further, R 32 and R 33 are optionally bonded to each other to form a ring.

9. The photosensitive actinic or radiation-sensitive resin composition according to claim 8, wherein, the repeating unit having an acid-decomposable group contains one or more selected from the repeating unit represented by the general formula (6) and the repeating unit represented by the general formula (7).

10. The photosensitive actinic or radiation-sensitive resin composition according to claim 7, wherein, the repeating unit having an acid-decomposable group does not contain a halogen atom.

11. A photosensitive actinic or radiation-sensitive resin composition, which contains: Resin (A): whose polarity is increased by the action of an acid; and Compound (B): which generates an acid by irradiation with actinic rays or radiation and is represented by the following general formula (I), the resin (A) contains a repeating unit represented by the following general formula (AI), In the general formula (AI), R A 、R B and R C each independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, a cyano group or an alkoxycarbonyl group, wherein, R C Optionally bonded to Ar A to form a ring, where R C represents a single bond or an alkylene group L A represents a single bond or a divalent linking group Ar A represents an aromatic ring group having a valence of (n + 1), and when Ar A bonds with R C to form a ring, it represents an aromatic ring group having a valence of (n + 2). n represents an integer of 1 to 5, In the general formula (I), M 1 + and M 2 + each independently represents a cation, X represents an (m + 1)-valent linking group, A 1 - and A 2 - are each independently a group selected from the groups represented by the following general formulas (B-1) to (B-27), In the general formula (B-1), Y F1 represents a fluorine atom or a perfluoroalkyl group Y 1 represents a hydrogen atom or a substituent having no fluorine atom, In the general formula (B-2), Y 2 each independently represents a hydrogen atom or a substituent having no fluorine atom In the general formula (B-3), Y F2 represents a fluorine atom or a perfluoroalkyl group, Y 3 represents a hydrogen atom or a substituent having no fluorine atom, Ra represents an organic group, In the general formula (B-4), Y 4 each independently represents a hydrogen atom or a substituent having no fluorine atom Ra 1 represents an organic group, In the general formula (B-5), Y F3 represents a fluorine atom or a perfluoroalkyl group, Y 5 represents a hydrogen atom or a substituent having no fluorine atom, Rb represents a hydrogen atom or an organic group, In the general formula (B-6), Y 6 each independently represents a hydrogen atom or a substituent having no fluorine atom Rb 1 represents a hydrogen atom or an organic group, In the general formula (B-7), Y F4 represents a fluorine atom or a perfluoroalkyl group Y 7 represents a hydrogen atom or a substituent having no fluorine atom, Rc represents an organic group, In the general formula (B-8), Y 8 each independently represents a hydrogen atom or a substituent having no fluorine atom Rc 1 represents an organic group In the general formula (B-9), Y F5 represents a fluorine atom or a perfluoroalkyl group, Y 9 represents a hydrogen atom or a substituent having no fluorine atom, Rd represents an organic group, In the general formula (B-10), Y 10 each independently represents a hydrogen atom or a substituent having no fluorine atom Rd 1 represents an organic group In the general formula (B-12), Re represents a hydrogen atom, an organic group or a halogen atom, o represents an integer of 1 to 4, when o represents an integer of 2 or more, a plurality of Res are the same or different, In the general formula (B-13), Y F6 represents a fluorine atom or a perfluoroalkyl group, Y 11 represents a hydrogen atom or a substituent having no fluorine atom In the general formula (B-14), Y 12 each independently represents a hydrogen atom or a substituent having no fluorine atom In the general formula (B-15), Y F7 represents a fluorine atom or a perfluoroalkyl group, Y 13 represents a hydrogen atom or a substituent having no fluorine atom Rf represents an organic group, In the general formula (B-16), Y 14 each independently represents a hydrogen atom or a substituent having no fluorine atom Rf 1 represents an organic group In the general formula (B-17), Y F8 represents a fluorine atom or a perfluoroalkyl group, Y 15 represents a hydrogen atom or a substituent having no fluorine atom, Rg represents an organic group, Rh represents an organic group, In the general formula (B-18), Y 16 each independently represents a hydrogen atom or a substituent having no fluorine atom Rg 1 represents an organic group Rh 1 represents an organic group In the general formula (B-19), Y F9 represents a fluorine atom or a perfluoroalkyl group, Y 17 represents a hydrogen atom or a substituent having no fluorine atom, In the general formula (B-20), Y 18 each independently represents a hydrogen atom or a substituent having no fluorine atom In the general formula (B-21), Y F10 represents a fluorine atom or a perfluoroalkyl group, Y 19 represents a hydrogen atom or a substituent having no fluorine atom, Ri represents an organic group, Rj represents an organic group, In the general formula (B-22), Y 20 each independently represents a hydrogen atom or a substituent having no fluorine atom Ri 1 represents an organic group, Rj 1 represents an organic group In the general formula (B-23), Rk represents a hydrogen atom or a substituent having no fluorine atom, p represents an integer of 1 to 4, when p represents an integer of 2 or more, a plurality of Rks are the same or different, In the general formula (B-24), R1 represents a hydrogen atom, an organic group or a halogen atom, q represents an integer of 1 to 4, when q represents an integer of 2 or more, a plurality of R1s are the same or different, Rc 2 represents an organic group In the general formula (B-25), Y F11 each independently represents a fluorine atom or a perfluoroalkyl group Rc 3 represents an organic group In the general formula (B-26), Y F12 each independently represents a fluorine atom or a perfluoroalkyl group Rd 2 represents an organic group In the general formula (B-27), Y F13 each independently represents a fluorine atom or a perfluoroalkyl group In the general formulas (B-1) to (B-27), * represents the bonding position, A 1 - represents a structure different from the group represented by A 2 - ​ m represents 1 or 2. When m represents 2, multiple Ms 1 + are the same or different. When m represents 2, multiple As 1 - are the same or different.

12. A photosensitive radiation-curable or radiation-sensitive film, which is formed from the photosensitive radiation-curable or radiation-sensitive resin composition according to any one of claims 1 to 11.

13. A method for forming a pattern, which comprises: a resist film forming step of forming a resist film using the photosensitive radiation-curable or radiation-sensitive resin composition according to any one of claims 1 to 11; an exposure step of exposing the resist film; and a development step of developing the exposed resist film using a developer.

14. A method for manufacturing an electronic device, which comprises the pattern forming method according to claim 13.

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