JP6014517B2 - Actinic ray-sensitive or radiation-sensitive resin composition, actinic ray-sensitive or radiation-sensitive film, pattern formation method, and electronic device manufacturing method - Google Patents

Description

  The present invention relates to an actinic ray-sensitive or radiation-sensitive resin composition, an actinic ray-sensitive or radiation-sensitive film using the same, a pattern forming method, an electronic device, and an electronic device manufacturing method. More specifically, the present invention relates to an ultra-microlithographic process applicable to a manufacturing process of a VLSI and a high-capacity microchip, a process for producing a mold for nanoimprinting, a manufacturing process of a high-density information recording medium, and other photofabrication. The present invention relates to an actinic ray-sensitive or radiation-sensitive resin composition suitably used in a process, an actinic ray-sensitive or radiation-sensitive film using the same, a pattern formation method, an electronic device, and a method for manufacturing an electronic device.

  Conventionally, in the manufacturing process of semiconductor devices such as IC and LSI, fine processing by lithography using a photoresist composition has been performed. In recent years, with the high integration of integrated circuits, the formation of ultrafine patterns in the submicron region and the quarter micron region has been required. Along with this trend, the trend of shortening the exposure wavelength from g-line to i-line and further to KrF excimer laser light has been observed. Currently, an exposure machine using an ArF excimer laser having a 193 nm wavelength as a light source has been developed. ing. Further, as a technique for further increasing the resolving power, development of a so-called immersion method, in which a high refractive index liquid (hereinafter also referred to as “immersion liquid”) is filled between the projection lens and the sample, has been developed. Documents 1 to 3 disclose chemically amplified resist compositions having hydrophobicity suitable for immersion exposure.

  At present, in addition to excimer laser light, lithography using electron beams, X-rays, extreme ultraviolet rays (EUV light), and the like is also being developed. Accordingly, a chemically amplified resist composition that is sensitive to various types of radiation and has excellent sensitivity and resolution has been developed. These electron beams, X-rays, or EUV lithography are positioned as next-generation or next-generation pattern forming techniques, and high-sensitivity and high-resolution resist compositions are desired. In particular, high sensitivity is a very important issue for shortening the wafer processing time, but when trying to achieve high sensitivity, not only does the resolution decrease in the ultrafine region of 0.25 μm or less, The problem of pattern collapse accompanying pattern miniaturization becomes significant.

  Furthermore, in EUV lithography, it is known that out-of-band light (ultraviolet light other than the wavelength of EUV) is generated from an exposure light source and the pattern shape is deteriorated (see, for example, Non-Patent Documents 1 and 2). .

JP 2008-96816 A JP 2008-1767 A JP 2007-304537 A

Proc. of SPIE Vol. 7273, 72731W, 2009 Proc. of SPIE Vol. 7636, 763626, 2010

  When the resist composition is hydrophobized in order to improve the problem of pattern collapse due to ultrafine patterning, there is a case where an adverse effect on lithography properties may be observed depending on the hydrophobizing method. It has been found by the present inventors that the affinity and penetrability are lowered, the sensitivity is lowered and roughness characteristics are deteriorated, and development defects are sometimes caused.

  Therefore, it has excellent sensitivity, resolution, pattern shape and ability to suppress development defects, and actinic ray sensitivity that can suppress pattern shape deterioration (film slippage) due to out-of-band light for EUV exposure. Or development of a radiation sensitive resin composition is desired.

  The present invention is excellent in sensitivity, resolution, pattern shape, and development defect suppressing ability, and particularly for EUV exposure, it has excellent ability to suppress pattern shape deterioration (film slippage) due to out-of-band light. An object is to provide a light-sensitive or radiation-sensitive resin composition, an actinic light-sensitive or radiation-sensitive film, a pattern forming method, an electronic device, and a method for manufacturing the electronic device.

For example, the present invention is as follows.
[1] A resin (Aa) that contains a repeating unit represented by the following general formula (Aa1) or (Aa2) as a repeating unit decomposed by the action of an acid, is unevenly distributed on the film surface by film formation, and forms a protective film; An actinic ray-sensitive or radiation-sensitive resin composition containing a resin (Ab), which is different from the resin (Aa) and whose solubility in a developer is changed by the action of an acid.

In general formula (Aa1),
R ′ represents a hydrogen atom or an alkyl group.
L represents a single bond or a divalent linking group.
R ₁ represents a hydrogen atom or a monovalent substituent.
R ₂ represents a monovalent substituent not containing a fluorine atom. R ₁ and R ₂ may be bonded to each other to form a ring together with the oxygen atom in the formula.
R ₃ represents a hydrogen atom, an alkyl group or a cycloalkyl group.

In general formula (Aa2),
Ra represents a hydrogen atom, an alkyl group, a cyano group, or a halogen atom.
L ₁ represents a single bond or a divalent linking group.
R ₁ and R ₂ each independently represents an alkyl group. However, at least one alkyl group has 2 or more carbon atoms.
R ₁₁ and R ₁₂ each independently represents an alkyl group, and R ₁₃ represents a hydrogen atom or an alkyl group. R ₁₁ and R ₁₂ may be connected to each other to form a ring, and R ₁₁ and R ₁₃ may be connected to each other to form a ring.

[2] The actinic ray-sensitive or radiation-sensitive resin composition according to [1], wherein the substituent represented by R ₂ in the general formula (Aa1) is a hydrocarbon group composed of a carbon atom and a hydrogen atom. .

  [3] The resin (Aa) is further a fluorine atom, a group having a fluorine atom, a group having a silicon atom, an alkyl group having 6 or more carbon atoms, a cycloalkyl group having 5 or more carbon atoms, or 6 or more carbon atoms. The actinic ray-sensitive material according to [1] or [2], comprising a repeating unit (Aa3) having one or more groups selected from the group consisting of an aryl group of 1 and an aralkyl group having 7 or more carbon atoms Or a radiation sensitive resin composition.

[4] The actinic ray-sensitive or radiation-sensitive resin composition according to any one of [1] to [3], wherein the resin (Aa) further includes a repeating unit represented by the following general formula (Aa4): object.

In general formula (aa2-1),
Rb represents a hydrogen atom, an alkyl group or a halogen atom.
S _1a represents a substituent, and when a plurality of S _1a are present, each is independent.
p represents an integer of 0 to 5.

[5] The actinic ray-sensitive material according to any one of [1] to [4], wherein the resin (Aa) further includes a repeating unit having a structure represented by the following general formula (KY-3). Radiation sensitive resin composition.

In general formula (KY-3),
Rs represents a chain or cyclic alkylene group, and when there are a plurality of Rs, they may be the same or different.
Ls represents a single bond, an ether bond, an ester bond, an amide bond, a urethane bond or a urea bond, and when there are a plurality of Ls, they may be the same or different.
ns represents the number of repeating linking groups represented by-(Rs-Ls)-, and represents an integer of 0 to 5.
L _ky represents an alkylene group, an oxygen atom or a sulfur atom.
Z _ka represents an alkyl group, a cycloalkyl group, an ether group, a hydroxyl group, an amide group, an aryl group, a lactone ring group, or an electron withdrawing group. If Z _ka there are a plurality, the plurality of Z _ka may be the same or different, may be connected to form a ring Z _ka each other.
nka represents an integer of 0 to 10.
R _kb1 and R _kb2 each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, or an electron withdrawing group, and at least two of R _kb1 , R _kb2, and R _ky5 are connected to each other. A ring may be formed.
nkb represents 0 or 1.
R _ky5 represents an electron withdrawing group.

  [6] The actinic ray-sensitive or radiation-sensitive resin composition according to any one of [1] to [5], further comprising a compound that generates an acid upon irradiation with actinic rays or radiation.

  [7] The active sensitivity according to any one of [1] to [6], wherein the resin (Ab) includes a repeating unit (B) having a structural site that generates an acid upon irradiation with an actinic ray or radiation. A light-sensitive or radiation-sensitive resin composition.

  [8] The content of the resin (Aa) according to any one of [1] to [7], in which the content is in the range of 0.01 to 30% by mass based on the total solid content in the composition. An actinic ray-sensitive or radiation-sensitive resin composition.

  [9] The content of the resin (Aa) according to any one of [1] to [7], in which the content is in a range of 0.01 to 20% by mass based on the total solid content in the composition. An actinic ray-sensitive or radiation-sensitive resin composition.

  [10] The content of the resin (Aa) according to any one of [1] to [7], in which the content is in a range of 0.01 to 10% by mass based on the total solid content in the composition. An actinic ray-sensitive or radiation-sensitive resin composition.

  [11] The content of the resin (Aa) according to any one of [1] to [7], in which the content is in a range of 0.01 to 5% by mass based on the total solid content in the composition. An actinic ray-sensitive or radiation-sensitive resin composition.

  [12] An actinic ray-sensitive or radiation-sensitive film formed using the actinic ray-sensitive or radiation-sensitive resin composition according to any one of [1] to [11].

  [13] Forming an actinic ray-sensitive or radiation-sensitive film using the actinic ray-sensitive or radiation-sensitive resin composition described in any one of [1] to [11], the actinic ray A pattern forming method comprising exposing a light-sensitive or radiation-sensitive film by irradiating with actinic light or radiation and developing the exposed light-sensitive or radiation-sensitive film.

  [14] The pattern forming method according to [13], wherein an electron beam or extreme ultraviolet rays is used as the actinic ray or radiation.

[15] A semiconductor device manufactured through a process including the pattern forming method according to [13] or [14].
[16] A method for manufacturing an electronic device, comprising the pattern forming method according to [13] or [14].

  The present invention is excellent in sensitivity, resolution, pattern shape and ability to suppress development defects, and particularly sensitive to EUV exposure, which has excellent ability to suppress pattern shape deterioration (film slippage) due to out-of-band light. It has become possible to provide a light-sensitive or radiation-sensitive resin composition, an actinic light-sensitive or radiation-sensitive film and a pattern forming method, an electronic device manufacturing method, and an electronic device.

  In the description of the group (atomic group) in this specification, the description which does not indicate substitution and non-substitution includes not only a substituent but also a substituent. For example, the “alkyl group” includes not only an alkyl group having no substituent (unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group).

  Here, “active light” or “radiation” refers to, for example, an emission line spectrum of a mercury lamp, far ultraviolet rays represented by excimer laser, extreme ultraviolet (EUV) rays, X rays, soft X rays, electron rays (EB). Etc. In the present invention, light means actinic rays or radiation.

The term “exposure” as used herein refers to not only exposure with far ultraviolet rays, X-rays, EUV light, etc., typified by mercury lamps and excimer lasers, but also drawing with particle beams such as electron beams and ion beams unless otherwise specified. Include in exposure.
Hereinafter, embodiments of the present invention will be described in detail.
<Actinic ray-sensitive or radiation-sensitive resin composition>
The actinic ray-sensitive or radiation-sensitive resin composition (hereinafter also referred to as “the composition of the present invention”) according to the present invention is represented by the general formula (Aa1) or (Aa2) described later as a repeating unit that decomposes by the action of an acid. The resin (Aa) that contains a repeating unit represented by the following formula is unevenly distributed on the surface of the film and forms a protective film, and the solubility in the developer changes due to the action of an acid, which is different from the resin (Aa). Resin (Ab) is contained.

  In one embodiment, the composition of the present invention comprises at least one selected from a compound that generates an acid upon irradiation with an actinic ray or radiation, an acid proliferating agent, a solvent, a basic compound, a surfactant, and other additives. Furthermore, it contains.

  Hereinafter, each of these components will be described.

[1] Resin (Aa)
Resin (Aa) is a resin that contains a repeating unit represented by the following general formula (Aa1) or (Aa2) as a repeating unit that is decomposed by the action of an acid, is unevenly distributed on the film surface by film formation, and forms a protective film. is there. Here, whether or not the protective film is formed unevenly distributed on the film surface by the film formation is, for example, the surface static contact angle (contact angle by pure water) of the composition film not added with the resin (Aa) and the resin (Aa The surface static contact angle of the composition film to which () is added is compared, and when the contact angle increases, it can be considered that a protective layer has been formed.

Even if a compound whose solubility in a developing solution is changed by the action of an acid and which is unevenly distributed on the film surface by film formation to form a protective film, out-of-band light in EUV lithography (other than the wavelength of EUV) It has been found by the present inventors that even though the pattern shape deterioration (film slippage) due to the ultraviolet rays can be improved to some extent, the sensitivity is lowered. Therefore, a resin containing a repeating unit represented by the general formula (Aa1) or (Aa2) having a high reaction rate (sensitivity) to the action of an acid as a compound that is unevenly distributed on the film surface by film formation to form a protective film ( As a result of the development of Aa), as one of the effects, it has become possible to achieve high sensitivity while improving pattern shape deterioration (film slippage) due to out-band light in EUV lithography.

In general formula (Aa1),
R ′ represents a hydrogen atom or an alkyl group.
L represents a single bond or a divalent linking group.
R ₁ represents a hydrogen atom or a monovalent substituent.
R ₂ represents a monovalent substituent not containing a fluorine atom. R ₁ and R ₂ may be bonded to each other to form a ring together with the oxygen atom in the formula.
R ₃ represents a hydrogen atom, an alkyl group or a cycloalkyl group.

In general formula (Aa2),
Ra represents a hydrogen atom, an alkyl group, a cyano group, or a halogen atom.
L ₁ represents a single bond or a divalent linking group.
R ₁ and R ₂ each independently represents an alkyl group. However, at least one alkyl group has 2 or more carbon atoms.

R ₁₁ and R ₁₂ each independently represents an alkyl group, and R ₁₃ represents a hydrogen atom or an alkyl group. Any two of R ₁₁ , R ₁₂ and R ₁₃ may be connected to each other to form a ring.

A repeating unit represented by the general formula (Aa1) (hereinafter also referred to as “repeating unit (Aa1)”) and a repeating unit represented by the general formula (Aa2) (hereinafter also referred to as “repeating unit (Aa2)”). )), As described above, all have a higher reaction rate with respect to the action of the acid, but the repeating unit (Aa1) has a higher reaction rate with respect to the action of the acid. Therefore, from the viewpoint of increasing the sensitivity, the resin (Aa) more preferably includes a repeating unit (Aa1).
Hereinafter, the repeating unit (Aa1) and the repeating unit (Aa2) will be described in detail.

<Repeating unit (Aa1)>
First, the repeating unit represented by formula (Aa1) will be described.

  In the general formula (Aa1), the alkyl group represented by R ′ is preferably an alkyl group having 1 to 10 carbon atoms, more preferably an alkyl group having 1 to 5 carbon atoms, and an alkyl group having 1 to 3 carbon atoms. An alkyl group is more preferable, and an alkyl group having 1 or 2 carbon atoms (that is, a methyl group or an ethyl group) is preferable. Specific examples of the alkyl group for R ′ include, for example, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, and a t-butyl group. Can do.

  R ′ is preferably a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, more preferably a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, a hydrogen atom, a methyl group or ethyl. It is more preferably a group, and particularly preferably a hydrogen atom.

Examples of the divalent linking group represented by L, an alkylene group, aromatic ring group, a cycloalkylene _{group, -COO-L 1 '-,} - O-L 1' -, - CONH-, these two or more Examples include groups formed in combination. Here, L ₁ ′ is an alkylene group (preferably having 1 to 20 carbon atoms), a cycloalkylene group (preferably having 3 to 20 carbon atoms), a group having a lactone structure, an aromatic ring group, or a combination of an alkylene group and an aromatic ring group. Represents a group.

  The alkylene group as the divalent linking group represented by L is preferably an alkylene group having 1 to 8 carbon atoms such as a methylene group, an ethylene group, a propylene group, a butylene group, a hexylene group or an octylene group. An alkylene group having 1 to 4 carbon atoms is more preferable, and an alkylene group having 1 or 2 carbon atoms is particularly preferable.

  The cycloalkylene group as the divalent linking group represented by L is preferably a cycloalkylene group having 3 to 20 carbon atoms, such as a cyclopropylene group, a cyclobutylene group, a cyclopentylene group, or a cyclohexylene group. , Cycloheptylene group, cyclooctylene group, norbornylene group or adamantylene group.

  The aromatic ring group as the divalent linking group represented by L is an aromatic ring group having 6 to 18 carbon atoms (more preferably 6 to 10 carbon atoms) such as a benzene ring or a naphthalene ring group, or, for example, thiophene. Preferred examples include aromatic ring groups including hetero rings such as rings, furan rings, pyrrole rings, benzothiophene rings, benzofuran rings, benzopyrrole rings, triazine rings, imidazole rings, benzimidazole rings, triazole rings, thiadiazole rings, and thiazole rings. A benzene ring group is particularly preferable.

The definitions and preferred ranges of the alkylene group, cycloalkylene group and aromatic ring group represented by L ₁ ′ are the same as those in the alkylene group, cycloalkylene group and aromatic ring group as the divalent linking group represented by L. .

As the group having a lactone structure represented by L ₁ ′, any group having a lactone structure can be used. However, a 5- to 7-membered ring lactone structure is preferable, and a bicyclo lactone structure is added to the 5- to 7-membered ring lactone structure. A structure in which another ring structure is condensed to form a structure or a spiro structure is preferable. For example, KA-1-1 to KA-1-17 described later can be mentioned, but KA-1-1, KA-1-4, KA-1-5, and KA-1-17 are preferable.

The definitions and preferred ranges of the alkylene group and aromatic group in the group in which the alkylene group and the aromatic ring group represented by L ₁ ′ are combined are those in the alkylene group and aromatic ring group as the divalent linking group represented by L It is the same.

  L is preferably a single bond, aromatic ring group, norbornane ring group or adamantane ring group, more preferably a single bond, norbornane ring group or adamantane ring group, more preferably a single bond or norbornane ring group, and a single bond Particularly preferred.

The monovalent substituent for R ₁ is preferably a group represented by * —C (R ₁₁₁ ) (R ₁₁₂ ) (R ₁₁₃ ). * Represents a bond linked to a carbon atom in the repeating unit represented by the general formula (Aa1). R _{111 to} R ₁₁₃ each independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group or a heterocyclic group.

The alkyl group of R _{111 to} R ₁₁₃ is preferably an alkyl group having 1 to 15 carbon atoms, more preferably an alkyl group having 1 to 10 carbon atoms, and an alkyl group having 1 to 6 carbon atoms. Is more preferable. Specific examples of the alkyl group of R _{111 to} R ₁₁₃ include, for example, methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, sec-butyl group, t-butyl group, neopentyl group, hexyl group, 2 - ethylhexyl group, and a octyl group and a dodecyl group, an alkyl group of R ₁₁₁ to R ₁₁₃ include a methyl group, an ethyl group, a propyl group, and an isopropyl group or t- butyl group.

At least two of R _{111 to} R ₁₁₃ each independently represent an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group or a heterocyclic group, and all of R _{111 to} R ₁₁₃ are an alkyl group, a cycloalkyl group, It preferably represents an aryl group, an aralkyl group or a heterocyclic group.

The cycloalkyl group of R _{111 to} R ₁₁₃ may be monocyclic or polycyclic, and is preferably a cycloalkyl group having 3 to 15 carbon atoms, and a cycloalkyl group having 3 to 10 carbon atoms. It is more preferably an alkyl group, and further preferably a cycloalkyl group having 3 to 6 carbon atoms. Specific examples of the cycloalkyl group represented by R _{111 to} R ₁₁₃ include, for example, a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, a decahydronaphthyl group, a cyclodecyl group, and a 1-adamantyl group. , 2-adamantyl group, 1-norbornyl group, 2-norbornyl group and the like. The cycloalkyl group of R _{111 to} R ₁₁₃ is preferably a cyclopropyl group, a cyclopentyl group, or a cyclohexyl group.

The aryl group of R _{111 to} R ₁₁₃ is preferably an aryl group having 6 to 15 carbon atoms, more preferably an aryl group having 6 to 12 carbon atoms, and a plurality of aromatic rings are mutually bonded via a single bond. It also includes linked structures (eg, biphenyl group, terphenyl group). Specific examples of the aryl group of R _{111 to} R ₁₁₃ include a phenyl group, a naphthyl group, an anthranyl group, a biphenyl group, a terphenyl group, and the like. The aryl group of R _{111 to} R ₁₁₃ is preferably a phenyl group, a naphthyl group, or a biphenyl group.

The aralkyl group of R _{111 to} R ₁₁₃ is preferably an aralkyl group having 6 to 20 carbon atoms, and more preferably an aralkyl group having 7 to 12 carbon atoms. Specific examples of the aralkyl group of R _{111 to} R ₁₁₃ include a benzyl group, a phenethyl group, a naphthylmethyl group, a naphthylethyl group, and the like.

The heterocyclic group of R _{111 to} R ₁₁₃ is preferably a heterocyclic group having 6 to 20 carbon atoms, and more preferably a heterocyclic group having 6 to 12 carbon atoms. Specific examples of the heterocyclic group of R _{111 to} R ₁₁₃ include, for example, a pyridyl group, a pyrazyl group, a tetrahydrofuranyl group, a tetrahydropyranyl group, a tetrahydrothiophene group, a piperidyl group, a piperazyl group, a furanyl group, a pyranyl group, and a chromanyl group. Etc.

The alkyl group, cycloalkyl group, aryl group, aralkyl group and heterocyclic group as R _{111 to} R ₁₁₃ may further have a substituent.

Examples of the substituent that the alkyl group as R _{111 to} R ₁₁₃ may further have include a cycloalkyl group, an aryl group, an amino group, an amide group, a ureido group, a urethane group, a hydroxy group, a carboxy group, a halogen atom, and an alkoxy group. Group, aralkyloxy group, thioether group, acyl group, acyloxy group, alkoxycarbonyl group, cyano group, nitro group and the like. The above substituents may be bonded to each other to form a ring, and examples of the ring when the above substituents are bonded to each other to form a ring include a cycloalkyl group having 3 to 10 carbon atoms or a phenyl group. .

Examples of the substituent which the cycloalkyl group may further have as R ₁₁₁ to R _113, an alkyl group, _and, in each group described above as specific examples of the substituent which the alkyl group may further have as R 111 _{to R 113} Can be mentioned.

  In addition, carbon number of the substituent which the cycloalkyl group may further have is preferably 1-8.

Examples of the substituent that the aryl group, aralkyl group and heterocyclic group as R _{111 to} R ₁₁₃ may further have include a halogen atom such as a nitro group and a fluorine atom, a carboxyl group, a hydroxyl group, an amino group, a cyano group, and an alkyl group. Group (preferably having 1 to 15 carbon atoms), alkoxy group (preferably having 1 to 15 carbon atoms), cycloalkyl group (preferably having 3 to 15 carbon atoms), aryl group (preferably having 6 to 14 carbon atoms), alkoxycarbonyl Examples include a group (preferably having 2 to 7 carbon atoms), an acyl group (preferably having 2 to 12 carbon atoms), an alkoxycarbonyloxy group (preferably having 2 to 7 carbon atoms), and the like.

At least two of R _{111 to} R ₁₁₃ may form a ring with each other.
When at least two of R _{111 to} R ₁₁₃ are bonded to each other to form a ring, examples of the ring formed include a tetrahydropyran ring, a cyclopentane ring, a cyclohexane ring, an adamantane ring, a norbornene ring, and a norbornane ring. . These rings may have a substituent, and examples of the substituent that may be included include the alkyl groups and the groups described above as specific examples of the substituent that the alkyl groups as R _{111 to} R ₁₁₃ may further have. Is mentioned.

When all of R _{111 to} R ₁₁₃ are bonded to each other to form a ring, examples of the formed ring include an adamantane ring, norbornane ring, norbornene ring, bicyclo [2,2,2] octane ring, bicyclo [3, 1,1] heptane ring. Of these, an adamantane ring is particularly preferred. These may have a substituent, and examples of the substituent that may be included include the alkyl groups and the groups described above as specific examples of the substituent that the alkyl groups as R _{111 to} R ₁₁₃ may further have. It is done.

The monovalent substituent of R ₂ does not contain a fluorine atom. If an electron withdrawing group such as a fluorine atom is included, the reaction rate (sensitivity) to the action of the acid is slow, so the desired performance cannot be achieved, while oxygen and nitrogen also act as electron withdrawing groups. It has been found by the present inventors that the desired performance is obtained even if atoms are included.

In one embodiment of the present invention, the monovalent substituent of R ₂ may be a group consisting of two or more atoms selected from a carbon atom, a hydrogen atom, an oxygen atom, a nitrogen atom, a silicon atom, and a sulfur atom. Preferably, it is a group consisting of two or more atoms selected from a carbon atom, a hydrogen atom, an oxygen atom and a nitrogen atom, more preferably from two or more atoms selected from a carbon atom, a hydrogen atom and an oxygen atom. Is more preferable, and a group consisting of a carbon atom and a hydrogen atom is particularly preferable.

In one embodiment of the present invention, the monovalent substituent represented by R ₂ is preferably a group represented by * -MQ. * Represents a bond connected to an oxygen atom in the general formula (Aa1). M represents a single bond or a divalent linking group. Q represents an alkyl group, a cycloalkyl group, an aryl group, or a heterocyclic group (not including a fluorine atom).

The divalent linking group as M is, for example, an alkylene group (preferably an alkylene group having 1 to 8 carbon atoms, such as a methylene group, an ethylene group, a propylene group, a butylene group, a hexylene group or an octylene group), a cycloalkylene group. (preferably cycloalkylene group having 3 to 15 carbon atoms, e.g., a cyclopentylene group or a cyclohexylene group), - S -, - O -, - CO -, - CS -, - SO 2 -, - N (R ₀ )-, or a combination of two or more thereof, and those having a total carbon number of 20 or less are preferred. Here, R ₀ is a hydrogen atom or an alkyl group (for example, an alkyl group having 1 to 8 carbon atoms, specifically, a methyl group, an ethyl group, a propyl group, an n-butyl group, a sec-butyl group, Hexyl group and octyl group).

M is preferably a single bond, an alkylene group, or a divalent linking group composed of a combination of an alkylene group and at least one of —O—, —CO—, —CS—, and —N (R ₀ ) —. A divalent linking group composed of a bond, an alkylene group, or a combination of an alkylene group and —O— is more preferable. Here, R ₀ has the same meaning as R ₀ described above.

M may further have a substituent, and the substituent that M may further have is the same as the substituent that the alkyl group of R _{111 to} R ₁₁₃ described above may have.

Specific examples and preferred examples of the alkyl group as Q are the same as those described for the alkyl groups as R _{111 to} R ₁₁₃ described above, for example.

The cycloalkyl group as Q may be monocyclic or polycyclic. This cycloalkyl group preferably has 3 to 10 carbon atoms. Examples of the cycloalkyl group include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, a 1-adamantyl group, a 2-adamantyl group, a 1-norbornyl group, a 2-norbornyl group, Bornyl group, isobornyl group, 4-tetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] dodecyl group, 8-tricyclo [5.2.1.0 ^2,6 ] decyl group, 2-bicyclo [2.2.1] heptyl group. Of these, a cyclopentyl group, a cyclohexyl group, a 2-adamantyl group, an 8-tricyclo [5.2.1.0 ^2,6 ] decyl group, and a 2-bicyclo [2.2.1] heptyl group are preferable.

Specific examples and preferred examples of the aryl group as Q are the same as those described for the aryl group as R _{111 to} R ₁₁₃ described above, for example.

Specific examples and preferred examples of the heterocyclic group as Q are the same as those described for the heterocyclic group as R _{111 to} R ₁₁₃ described above, for example.

  The alkyl group, cycloalkyl group, aryl group and heterocyclic group (not including a fluorine atom) as Q may have a substituent, for example, an alkyl group, a cycloalkyl group, a cyano group, a halogen atom, Examples thereof include a hydroxyl group, an alkoxy group, a carboxyl group, and an alkoxycarbonyl group.

R ₂ is preferably an alkyl group, an alkyl group substituted with a cycloalkyl group, a cycloalkyl group, an aralkyl group, an aryloxyalkyl group or a heterocyclic group (not including a fluorine atom), and an alkyl group or a cycloalkyl group More preferably, it is a group. Alkyl group, a cycloalkyl group of the "cycloalkyl group" and "alkyl group substituted with a cycloalkyl group" as R ₂ as R _2, and "aralkyl group as the group represented by R ₂ (arylalkyl Specific examples and preferred examples of the aryl group in the “group)” and “aryloxyalkyl group” are the same as those described for the alkyl group, cycloalkyl group and aryl group as Q, respectively.

Specific examples and preferred examples of the alkyl moiety in the “alkyl group substituted by a cycloalkyl group”, “aralkyl group (arylalkyl group)” and “aryloxyalkyl group” as R ₂ are the alkylene group as M, respectively. This is the same as that described in.

Specific examples and preferred examples of the heterocyclic group (not including a fluorine atom) as R _{2 are the same} as those described for the heterocyclic group (not including a fluorine atom) as Q.

Specific examples of the substituent represented by R ₂ include a methyl group, an ethyl group, an isopropyl group, a cyclopentyl group, a cyclohexyl group, a cyclohexylethyl group, a 2-adamantyl group, and 8-tricyclo [5.2.1. 0 ^2,6 ] decyl group, 2-bicyclo [2.2.1] heptyl group, benzyl group, 2-phenethyl group, 2-phenoxyethylene group and the like.

R ₁ and R ₂ may be bonded to each other to form a ring (oxygen-containing heterocycle) together with the oxygen atom in the formula. The oxygen-containing heterocyclic structure may be any of a monocyclic, polycyclic, or spiro ring, and is preferably a monocyclic oxygen-containing heterocyclic structure, preferably having 3 to 10 carbon atoms, more preferably Is 4 or 5.

  Further, as described above, when M is a divalent linking group, Q may be bonded to M via a single bond or another linking group to form a ring. As said another coupling group, an alkylene group (preferably C1-C3 alkylene group) is mentioned, It is preferable that the ring formed is a 5- or 6-membered ring.

R ₃ is preferably a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, more preferably a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, a hydrogen atom, a methyl group or ethyl. It is more preferably a group, and particularly preferably a hydrogen atom.

In one embodiment of the present invention, one of R ₁ and R ₃ is preferably a group containing 2 or more carbon atoms.

The repeating unit represented by the general formula (Aa1) is preferably a repeating unit represented by any one of the following general formulas (Aa1-1) to (Aa1-4).

In general formula (Aa1-1),
R ′ ₁ represents a hydrogen atom or a methyl group, and is preferably a methyl group.

Each of R ₁₁ , R ₁₂ and R ₁₃ has the same meaning as R ₁ , R ₂ and R ₃ in the general formula (Aa1).

In general formula (Aa1-2),
R ′ ₂ represents a hydrogen atom or a methyl group, and is preferably a methyl group.
Each of R ₂₁ , R ₂₂ and R ₂₃ has the same meaning as R ₁ , R ₂ and R ₃ in the general formula (Aa1).

In general formula (Aa1-3),
R ′ ₃ represents a hydrogen atom or a methyl group, and is preferably a methyl group.

Each of R ₃₁ , R ₃₂ and R ₃₃ has the same meaning as R ₁ , R ₂ and R ₃ in the general formula (Aa1).

In general formula (Aa1-4),
L ′ represents a single bond or a divalent linking group. 'Examples of the divalent linking group include an alkylene group, aromatic ring group, a cycloalkylene _{group, -COO-L 1' L -} , - O-L 1 '-, - CONH-, these two or more Examples include groups formed in combination. Here, L ₁ ′ represents an alkylene group (preferably having 1 to 20 carbon atoms), a cycloalkylene group (preferably having 3 to 20 carbon atoms), an aromatic ring group, or a group in which an alkylene group and an aromatic ring group are combined. L ′ is preferably a single bond.

Each of R ₄₁ , R ₄₂ and R ₄₃ has the same meaning as R ₁ , R ₂ and R ₃ in the general formula (Aa1).

  In one embodiment of the present invention, the repeating unit represented by General Formula (Aa1) is preferably a repeating unit represented by any one of General Formulas (Aa1-1) to (Aa1-4). The repeating unit represented by any one of (Aa1-1) to (Aa1-3) is more preferable, and the repeating unit represented by the general formula (Aa1-1) or (Aa1-3). More preferred is a repeating unit represented by formula (Aa1-1).

The repeating unit represented by the general formula (Aa1) is also preferably a repeating unit represented by any of the following (Aa1-a) to (Aa1-f).

In general formula (Aa1-a),
Each of R _a ′, L _a , R _2a and R _1a is the same as R ′, L, R ₂ and R ₁ in formula (Aa1), and the preferred ranges are also the same.

In general formula (Aa1-b),
Each of R _b ′, L _b , R _2b and R _3b is the same as R ′, L, R ₂ and R ₃ in the general formula (Aa1), and preferred ranges are also the same.

In general formula (Aa1-c),
Each of R _c ′, L _c , R _2c and R _3c is the same as R ′, L, R ₂ and R ₃ in formula (Aa1), and the preferred ranges are also the same.
R _1a ′ is the same as R ₁₁₁ in formula (Aa1), and the preferred range is also the same.

In general formula (Aa1-d),
Each of R _d ′, L _d , R _2d and R _3d is the same as R ′, L, R ₂ and R ₃ in the general formula (Aa1), and preferred ranges are also the same.
Each of R _2a ′ and R _{2b ′} is the same as R ₁₁₁ and R ₁₁₂ in General Formula (Aa1), and the preferred range is also the same.

In general formula (Aa1-e),
Each of R _e ′, L _e , R _2e and R _3e is the same as R ′, L, R ₂ and R ₃ in formula (Aa1), and the preferred range is also the same.
Each of R _3a ′, R _{3b ′} and R _{3c ′} is the same as R ₁₁₁ , R ₁₁₂ and R ₁₁₃ in General Formula (Aa1), and the preferred range is also the same.

In general formula (Aa1-f),
R _f ′ and L _f are the same as R ′ and L in the general formula (Aa1), and preferred ranges are also the same.

R _3f is the same as R ₃ in formula (Aa1), and the preferred range is also the same.

R _4f represents an atomic group necessary for forming an oxygen-containing heterocyclic ring together with the carbon atom and the oxygen atom in the formula. The oxygen-containing heterocyclic structure formed by R _4f together with the carbon atom and the oxygen atom is preferably a monocyclic oxygen-containing heterocyclic structure, and the oxygen-containing heterocyclic ring preferably has 3 to 10 carbon atoms, more preferably 4 or 5.

  In one embodiment of the present invention, the repeating unit represented by General Formula (Aa1) is more preferably a repeating unit represented by any one of General Formulas (Aa1-c) to (Aa1-f). A repeating unit represented by formula (Aa1-e) or (Aa1-f) is more preferable.

Preferred specific examples of each partial structure and each group in the general formula (Aa1) are shown below.
Preferred specific examples of the partial structure represented by the following general formula (Aa1 ′) in the above general formula (Aa1) are as follows. In the general formula (Aa1 ′) and specific examples, * represents a bond connected to the carbon atom to which R1 and R3 in the general formula (Aa1) are bonded, and R ′ and L are each in the general formula (Aa1). R ′ and L are represented.

Specific examples of the monovalent substituent of R ₁ in the general formula (Aa1) include the following. * Represents a bond linked to the carbon atom in the general formula (Aa1).

Specific examples of R ₂ in the general formula (Aa1) are shown below. In the following specific examples, * represents a bond bonded to an oxygen atom in the general formula (Aa1).

In the case where the repeating unit represented by the general formula (Aa1) is the repeating unit represented by the general formula (Aa1-f), R _4f is formed together with the carbon atom and the oxygen atom in the formula. Specific examples of the heterocyclic ring are shown below. * Represents a bond connected to an oxygen atom in the general formula (Aa1-f). R _3f is the same as that in the general formula (Aa1-f).

Specific examples of the repeating unit represented by the general formula (Aa1) are shown below, but the present invention is not limited thereto.

  The content of the repeating unit represented by the above general formula (Aa1) in the resin (Aa) (the total when there are a plurality of types) is 5 to 80 mol% with respect to all the repeating units in the resin (Aa). It is preferable that it is 5-60 mol%, and it is still more preferable that it is 10-40 mol%.

<Repeating unit (Aa2)>
Next, the repeating unit represented by formula (Aa2) will be described in detail.

In General Formula (Aa2), R ₁ and R ₂ represent an alkyl group as described above. However, at least one alkyl group has 2 or more carbon atoms. From the viewpoint of more reliably achieving the effects of the present invention, both R ₁ and R ₂ are preferably alkyl groups having 2 or more carbon atoms, more preferably alkyl groups having 2 to 10 carbon atoms, and R More preferably, both ₁ and R ₂ are ethyl groups.

In General Formula (Aa2), as described above, R ₁₁ and R ₁₂ each independently represent an alkyl group, and R ₁₃ represents a hydrogen atom or an alkyl group. The alkyl group as R _{11 to} R ₁₃ is preferably an alkyl group having 1 to 10 carbon atoms. For example, a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, t -A butyl group, a neopentyl group, a hexyl group, a 2-ethylhexyl group, an octyl group, a dodecyl group, etc. are mentioned.

The alkyl group for R ₁₁ and R ₁₂ is more preferably an alkyl group having 1 to 4 carbon atoms, further preferably a methyl group or an ethyl group, and particularly preferably a methyl group.
R ₁₃ is more preferably a hydrogen atom or a methyl group.

As described above, R ₁₁ and R ₁₂ may be connected to each other to form a ring, and R ₁₁ and R ₁₃ may be connected to each other to form a ring. As the ring to be formed, for example, a monocyclic or polycyclic alicyclic hydrocarbon group is preferable, and in particular, R ₁₁ and R ₁₂ are bonded to each other to form a monocyclic or polycyclic alicyclic hydrocarbon group. It is preferable.

The ring formed by connecting R ₁₁ and R ₁₂ is preferably a 3- to 8-membered ring, more preferably a 5- or 6-membered ring.

The ring formed by connecting R ₁₁ and R ₁₃ is preferably a 3- to 8-membered ring, more preferably a 5- or 6-membered ring.

The ring formed by connecting R ₁₁ and R ₁₂ or R ₁₁ and R ₁₃ is more preferably an alicyclic group described later as X in the general formula (Aa2-1).

The alkyl group as R < ₁ >, R < ₂ > and R < ₁₁ > -R < ₁₃ > may further have a substituent. Examples of such substituents include cycloalkyl groups, aryl groups, amino groups, hydroxy groups, carboxy groups, halogen atoms, alkoxy groups, aralkyloxy groups, thioether groups, acyl groups, acyloxy groups, alkoxycarbonyl groups, cyano groups. Groups and nitro groups.

Moreover, the ring formed by connecting R ₁₁ and R ₁₂ and the ring formed by connecting R ₁₁ and R ₁₃ may further have a substituent, and as such a substituent, Alkyl groups (methyl group, ethyl group, propyl group, butyl group, perfluoroalkyl group (for example, trifluoromethyl group) etc.) and alkyl groups as R ₁ , R ₂ and R _{11 to} R ₁₃ are further present. Specific examples of substituents that can be used include the groups described above.

  The above substituents may be bonded to each other to form a ring, and examples of the ring when the above substituents are bonded to each other to form a ring include a cycloalkyl group having 3 to 10 carbon atoms or a phenyl group. .

  As described above, Ra represents a hydrogen atom, an alkyl group, a cyano group, or a halogen atom.

The alkyl group for Ra is preferably an alkyl group having 1 to 4 carbon atoms, and may have a substituent.
Preferable substituents that the alkyl group of Ra may have include, for example, a hydroxyl group and a halogen atom.

  Examples of the halogen atom for Ra include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

  Ra is preferably a hydrogen atom, a methyl group, a hydroxymethyl group, or a perfluoroalkyl group having 1 to 4 carbon atoms (for example, a trifluoromethyl group), and the glass transition point (Tg) of the resin (A). ) And a methyl group is particularly preferable from the viewpoint of improving resolution and space width roughness.

However, when L ₁ described below is a phenylene group, Ra is preferably a hydrogen atom.

L ₁ represents a single bond or a divalent linking group as described above.
Examples of the divalent linking group represented by L _1, an alkylene group, a divalent aromatic ring _{group, -COO-L 11 -, -} O-L 11 -, group formed by combining two or more of these Etc. Here, L ₁₁ represents an alkylene group, a cycloalkylene group, a divalent aromatic ring group, or a group in which an alkylene group and a divalent aromatic ring group are combined.

Examples of the alkylene group for L ₁ and L ₁₁ include alkylene groups having 1 to 8 carbon atoms such as a methylene group, an ethylene group, a propylene group, a butylene group, a hexylene group, and an octylene group. An alkylene group having 1 to 4 carbon atoms is more preferable, and an alkylene group having 1 or 2 carbon atoms is particularly preferable.

The cycloalkylene group for L ₁₁ is preferably a cycloalkylene group having 3 to 20 carbon atoms, such as a cyclopropylene group, a cyclobutylene group, a cyclopentylene group, a cyclohexylene group, a cycloheptylene group, and a cyclooctylene group. , Norbornylene group or adamantylene group.

In the cycloalkylene group for L ₁₁ , the carbon constituting the ring (carbon contributing to ring formation) may be a carbonyl carbon, a heteroatom such as an oxygen atom, an ester bond, and a lactone A ring may be formed.

The divalent aromatic ring group for L ₁ and L ₁₁ is preferably a phenylene group such as 1,4-phenylene group, 1,3-phenylene group, 1,2-phenylene group, or 1,4-naphthylene group, A 1,4-phenylene group is more preferred.

L ₁ is preferably a single bond, a divalent aromatic ring group, a divalent group having a norbornylene group or a divalent group having an adamantylene group, and particularly preferably a single bond.

Specific examples of preferred divalent linking groups for L ₁ are shown below, but the present invention is not limited thereto.

In one embodiment of the present invention, the repeating unit represented by the general formula (Aa2) is preferably a repeating unit represented by the following general formula (Aa2-1).

In the general formula (Aa2-1),
X represents an alicyclic group.

R _{1, R} 2, Ra and _{L 1,} respectively, have the same meaning as _{R 1,} R 2, Ra and _{L 1} in the general formula (Aa2), specific examples, _{R 1} also in the general formula (Aa2) for preferred embodiments , R ₂ , Ra and L ₁ are the same.

  The alicyclic group as X may be monocyclic, polycyclic or bridged, and preferably represents an alicyclic group having 3 to 25 carbon atoms.

In addition, the alicyclic group may have a substituent, and examples of the substituent are the same as the substituents described above as the substituent that the ring formed by connecting R ₁₁ and R ₁₂ may have. Can be mentioned.

X preferably represents an alicyclic group having 3 to 25 carbon atoms, more preferably an alicyclic group having 5 to 20 carbon atoms, and particularly preferably a cycloalkyl group having 5 to 15 carbon atoms.
X is preferably a 3- to 8-membered alicyclic group or a condensed ring group thereof, more preferably a 5- or 6-membered ring or a condensed ring group thereof.
Below, the structural example of the alicyclic group as X is shown.

  Preferred examples of the alicyclic group include an adamantyl group, a noradamantyl group, a decalin residue, a tricyclodecanyl group, a tetracyclododecanyl group, a norbornyl group, a cedrol group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, A cyclooctyl group, a cyclodecanyl group, and a cyclododecanyl group can be exemplified. A cyclohexyl group, a cyclopentyl group, an adamantyl group and a norbornyl group are more preferred, a cyclohexyl group and a cyclopentyl group are more preferred, and a cyclohexyl group is particularly preferred.

Specific examples of the repeating unit represented by the general formula (Aa2) or (Aa2-1) are shown below, but the present invention is not limited thereto.

  The content of the repeating unit represented by the general formula (Aa2) in the resin (Aa) (the total when there are a plurality of types) is 5 to 80 mol% with respect to all the repeating units in the resin (Aa). Preferably, it is 5 to 60 mol%, more preferably 10 to 40 mol%.

<Repeating unit (Aa3)>
In one embodiment of the present invention, the resin (Aa) includes a fluorine atom, a group having a fluorine atom, a group having a silicon atom, an alkyl group having 6 or more carbon atoms, a cycloalkyl group having 5 or more carbon atoms, and a carbon number It may further include a repeating unit (Aa3) having one or more groups selected from the group consisting of 6 or more aryl groups and an aralkyl group having 7 or more carbon atoms. This repeating unit (Aa3) is a repeating unit different from the above-described repeating units (Aa1) and (Aa2).

  From the viewpoint of sensitivity, the repeating unit (Aa3) preferably has a fluorine atom or a group having a fluorine atom. Since the resin (Aa) has a fluorine atom or a group having a fluorine atom, the absorption coefficient of the resin (Aa) with respect to extreme ultraviolet rays is improved, and the resin (Aa) has a property of being unevenly distributed on the resist film surface. Therefore, it is considered that the energy of the extreme ultraviolet light can be efficiently absorbed on the film surface to which the extreme ultraviolet light is more strongly irradiated at the time of exposure, and as a result, the sensitivity is considered to be improved.

  Examples of the group having a fluorine atom include an alkyl group having a fluorine atom, a cycloalkyl group having a fluorine atom, and an aryl group having a fluorine atom.

  The alkyl group having a fluorine atom preferably includes an alkyl group having 1 to 10 carbon atoms, more preferably 1 to 4 carbon atoms, and a straight chain in which at least one hydrogen atom is substituted with a fluorine atom. Or it is a branched alkyl group and may have substituents other than a fluorine atom.

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

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

Preferred examples of the alkyl group having a fluorine atom, the cycloalkyl group having a fluorine atom, and the aryl group having a fluorine atom include groups represented by the following general formulas (F2) to (F4). The invention is not limited to this.

In general formulas (F2) to (F4),
R _{57 to} R ₆₈ each independently represent a hydrogen atom, a fluorine atom or an alkyl group (straight or branched). However, at least one of R _{57 to} R _61, at least one of R _{62 to} R ₆₄ , and at least one of R _{65 to} R ₆₈ are each independently substituted with a fluorine atom or at least one hydrogen atom. Represents an alkyl group (preferably having 1 to 4 carbon atoms).

R _{57 to} R ₆₁ and R _{65 to} R ₆₇ are preferably all fluorine atoms. R ₆₂ , R ₆₃ and R ₆₈ are preferably an alkyl group (preferably having 1 to 4 carbon atoms) in which at least one hydrogen atom is substituted with a fluorine atom, and preferably a perfluoroalkyl group having 1 to 4 carbon atoms. Further preferred. R ₆₂ and R ₆₃ may be connected to each other to form a ring.

  Specific examples of the group represented by the general formula (F2) include a p-fluorophenyl group, a pentafluorophenyl group, and a 3,5-di (trifluoromethyl) phenyl group.

  Specific examples of the group represented by the general formula (F3) include trifluoromethyl group, pentafluoropropyl group, pentafluoroethyl group, heptafluorobutyl group, hexafluoroisopropyl group, heptafluoroisopropyl group, hexafluoro (2 -Methyl) isopropyl group, nonafluorobutyl group, octafluoroisobutyl group, nonafluorohexyl group, nonafluoro-t-butyl group, perfluoroisopentyl group, perfluorooctyl group, perfluoro (trimethyl) hexyl group, 2,2 , 3,3-tetrafluorocyclobutyl group, perfluorocyclohexyl group and the like. Hexafluoroisopropyl group, heptafluoroisopropyl group, hexafluoro (2-methyl) isopropyl group, octafluoroisobutyl group, nonafluoro-t-butyl group and perfluoroisopentyl group are preferable, and hexafluoroisopropyl group and heptafluoroisopropyl group are preferable. Further preferred.

Specific examples of the group represented by the general formula (F4) include, for example, —C (CF ₃ ) ₂ OH, —C (C ₂ F ₅ ) ₂ OH, —C (CF ₃ ) (CH ₃ ) OH, -CH _(CF 3) OH and the like, -C _{(CF 3)} 2 OH is preferred.

  Examples of the group having a silicon atom include an alkylsilyl structure (preferably a trialkylsilyl group) and a cyclic siloxane structure.

Specific examples of the alkylsilyl structure or cyclic siloxane structure for W _{3 to} W ₆ include groups represented by the following general formulas (CS-1) to (CS-3).

In general formulas (CS-1) to (CS-3),
R _{12 to} R ₂₆ each independently represent a linear or branched alkyl group (preferably having 1 to 20 carbon atoms) or a cycloalkyl group (preferably having 3 to 20 carbon atoms).

L < ₃ > -L < ₅ > represents a single bond or a bivalent coupling group. Examples of the divalent linking group include an alkylene group, a phenylene group, an ether bond, a thioether bond, a carbonyl group, an ester bond, an amide bond, a urethane bond, and a urea bond, or a combination of two or more ( Preferably, the total carbon number is 12 or less).

  n represents an integer of 1 to 5. n is preferably an integer of 2 to 4.

  The alkyl group having 6 or more carbon atoms is preferably a linear or branched alkyl group having 6 to 20 carbon atoms, more preferably 6 to 15 carbon atoms, and a substituent (however, a fluorine atom or a fluorine atom) And does not correspond to a group having a silicon atom).

  The cycloalkyl group having 5 or more carbon atoms is preferably a cycloalkyl group having 5 to 20 carbon atoms, more preferably 5 to 15 carbon atoms, and further a substituent (provided that a fluorine atom or a fluorine atom is substituted). Or a group having a silicon atom).

  The aryl group having 6 or more carbon atoms is preferably an aryl group having 6 to 20 carbon atoms, more preferably an aryl group having 6 to 15 carbon atoms, and further a substituent (provided that it has a fluorine atom or a fluorine atom). Or a group having a silicon atom).

  The aryl group may be substituted with at least one alkyl group having 3 or more carbon atoms, or at least one cycloalkyl group having 5 or more carbon atoms, and may be substituted with other substituents (however, a fluorine atom). Or a group having a fluorine atom or a group having a silicon atom).

  The alkyl group having 3 or more carbon atoms is preferably a linear or branched alkyl group having 3 to 15 carbon atoms, more preferably 3 to 10 carbon atoms. In the aryl group substituted with at least one alkyl group having 3 or more carbon atoms, the aryl group is preferably substituted with 1 to 9 alkyl groups having 3 or more carbon atoms, and preferably has 1 to 7 carbon atoms. It is more preferably substituted by 3 or more alkyl groups, and further preferably substituted by 1 to 5 alkyl groups having 3 or more carbon atoms.

  The cycloalkyl group having 5 or more carbon atoms is preferably a cycloalkyl group having 5 to 20 carbon atoms, more preferably 5 to 15 carbon atoms. In the aryl group substituted with at least one cycloalkyl group having 5 or more carbon atoms, the aryl group is preferably substituted with 1 to 5 cycloalkyl groups having 5 or more carbon atoms, and 1 to 4 It is more preferably substituted with a cycloalkyl group having 5 or more carbon atoms, and further preferably substituted with 1 to 3 cycloalkyl groups having 5 or more carbon atoms.

  The aralkyl group having 7 or more carbon atoms is preferably an aralkyl group having 7 to 20 carbon atoms, more preferably 7 to 15 carbon atoms, and a substituent (however, a group having a fluorine atom or a fluorine atom). And a group having a silicon atom).

The resin (Aa) preferably has at least one repeating unit represented by any one of the following general formulas (C-Ia) to (C-Id) as the repeating unit (Aa3).

In the formula, R ₁₀ and R ₁₁ each independently represent a hydrogen atom, a fluorine atom, or an alkyl group. The alkyl group is preferably a linear or branched alkyl group having 1 to 4 carbon atoms, which may have a substituent, and examples of the alkyl group having a substituent include a fluorinated alkyl group. it can. R ₁₀ and R ₁₁ are preferably each independently a hydrogen atom or a methyl group.

W ₃ , W ₅ and W ₆ are each independently a group having a fluorine atom, a group having a silicon atom, an alkyl group having 6 or more carbon atoms, a cycloalkyl group having 5 or more carbon atoms, or an aryl having 6 or more carbon atoms. And an organic group having at least one selected from the group consisting of a group and an aralkyl group having 7 or more carbon atoms.

W ₄ represents an organic group having one or more selected from the group consisting of a group having a fluorine atom, a group having a silicon atom, an alkyl group having 3 or more carbon atoms, and a cycloalkyl group having 5 or more carbon atoms. .

Ar ₁₁ represents an (r + 1) -valent aromatic ring group.

  r represents an integer of 1 to 10.

As the (r + 1) -valent aromatic ring group Ar ₁₁ , the divalent aromatic ring group when r is 1 may have a substituent, for example, a phenylene group, a tolylene group, a naphthylene group, an anthracenylene group And an arylene group having 6 to 18 carbon atoms such as

  Specific examples of the (r + 1) -valent aromatic ring group in the case where r is an integer of 2 or more include (r-1) arbitrary hydrogen atoms removed from the above-described specific examples of the divalent aromatic ring group. The group formed can be preferably mentioned.

Examples of the group having a fluorine atom for W _{3 to} W ₆ are the same as those described above for the group having a fluorine atom.

The group having a fluorine atom for W _{3 to} W ₆ may be directly bonded to the repeating units represented by the general formulas (C-Ia) to (C-Id), and further includes an alkylene group, a phenylene group, Through the group selected from the group consisting of an ether bond, a thioether bond, a carbonyl group, an ester bond, an amide bond, a urethane bond and a ureylene bond, or a combination of two or more thereof, the above general formula (C-Ia) You may couple | bond with the repeating unit represented by-(C-Id).

Examples of the group having a silicon atom for W _{3 to} W ₆ are the same as those described above for the group having a silicon atom.

The alkyl group having 6 or more carbon atoms, the cycloalkyl group having 5 or more carbon atoms, the aryl group having 6 or more carbon atoms, and the aralkyl group having 7 or more carbon atoms for W ₃ , W ₅ , and W ₆ are described above. It is the same as that.

The alkyl group having 3 or more carbon atoms and the cycloalkyl group having 5 or more carbon atoms for W ₄ are each represented by “the number of carbon atoms in the aromatic ring group substituted with at least one alkyl group having 3 or more carbon atoms”. This is the same as that described for the “3 or more alkyl group” and the “cycloalkyl group having 5 or more carbon atoms” in the aromatic ring group substituted with at least one cycloalkyl group having 5 or more carbon atoms.

When the exposure source is extreme ultraviolet (EUV light), for the reasons described above, W ₃ , W ₅ and W ₆ are each independently a group having a silicon atom, an alkyl group having 6 or more carbon atoms, or a carbon number. It is also preferable to represent an organic group having one or more selected from the group consisting of a cycloalkyl group having 5 or more, an aryl group having 6 or more carbon atoms, and an aralkyl group having 7 or more carbon atoms, and W ₄ represents a silicon atom It is also preferable to represent an organic group having one or more selected from the group consisting of a group having an alkyl group, an alkyl group having 3 or more carbon atoms, and a cycloalkyl group having 5 or more carbon atoms.

W ₃ , W ₅ and W ₆ are each independently an organic group having a fluorine atom, an organic group having a silicon atom, an alkyl group having 6 or more carbon atoms, a cycloalkyl group having 5 or more carbon atoms, or a carbon number having 6 or more. In the case where the exposure source is extreme ultraviolet light (EUV light), an organic group having a silicon atom, 6 carbon atoms or more is preferable. It is also preferably an alkyl group, a cycloalkyl group having 5 or more carbon atoms, an aryl group having 6 or more carbon atoms, or an aralkyl group having 7 or more carbon atoms.

W ₄ is preferably an organic group having a fluorine atom, an organic group having a silicon atom, an alkyl group having 3 or more carbon atoms, or a cycloalkyl group having 5 or more carbon atoms, and the exposure source is extreme ultraviolet light (EUV light). ) Is preferably an organic group having a silicon atom, an alkyl group having 3 or more carbon atoms, or a cycloalkyl group having 5 or more carbon atoms.

Hereinafter, although the specific example of the repeating unit represented by either of the said general formula (C-Ia)-(C-Id) is shown, this invention is not limited to this.
In specific examples, X ₁ represents a hydrogen atom, —CH ₃ , —F or —CF ₃ .

  The resin (Aa) preferably has an aryl group, and more preferably has a repeating unit having an aryl group. Since the resin (Aa) has an aryl group, the aryl group absorbs the out-of-band light of EUV light, and only the surface of the exposed portion is exposed to the out-of-band light, and the surface of the pattern becomes rough ( In particular, in the case of EUV exposure), the cross-sectional shape of the pattern becomes a T-top shape or a reverse taper shape, or the surface of the pattern to be separated is not separated from each other, and a problem that a bridge portion is generated can be further suppressed.

  In this case, the repeating unit (Aa3) may have an aryl group, or the resin (Aa) further has a repeating unit other than the repeating unit (Aa3), and the repeating unit has an aryl group. It may be.

When the repeating unit (Aa3) has an aryl group, the repeating unit (Aa3) is preferably a repeating unit represented by the following general formula (C-II).

In the above general formula,
R ₁₂ represents a hydrogen atom, a methyl group, a trifluoromethyl group, or a fluorine atom.
W ₇ represents an organic group having one or more selected from the group consisting of a group having a fluorine atom, a group having a silicon atom, an alkyl group having 3 or more carbon atoms, and a cycloalkyl group having 5 or more carbon atoms.

L ₁ represents a single bond or a —COOL ₂ — group. L ₂ represents a single bond or an alkylene group.

  n represents an integer of 1 to 5.

The group having a fluorine atom and the group having a silicon atom for W ₇ are the same as those described above for the group having a fluorine atom and the group having a silicon atom, respectively. The alkyl group having 3 or more carbon atoms and the cycloalkyl group having 5 or more carbon atoms for W ₇ are each represented by “the number of carbon atoms in the aromatic ring group substituted with at least one alkyl group having 3 or more carbon atoms”. This is the same as that described for the “3 or more alkyl group” and the “cycloalkyl group having 5 or more carbon atoms” in the aromatic ring group substituted with at least one cycloalkyl group having 5 or more carbon atoms.

W ₇ is a trialkylsilyl group, a trialkoxysilyl group, an alkyl group having a trialkylsilyl group, an alkyl group having a trialkoxysilyl group, an alkyl group having 3 or more carbon atoms, or a cycloalkyl group having 5 or more carbon atoms. Preferably there is.

In the alkyl group having a trialkylsilyl group, trialkoxysilyl group, trialkylsilyl group, and alkyl group having a trialkoxysilyl group as W ₇ , the carbon number of the alkyl group or alkoxy group bonded to the silicon atom is It is preferable that it is 1-5, and it is more preferable that it is 1-3.

In the alkyl group having a trialkylsilyl group as W ₇ and the alkyl group having a trialkoxysilyl group, the alkyl group bonded to the trialkylsilyl group or trialkoxysilyl group has 1 to 5 carbon atoms. It is preferable that it is 1-3, and it is more preferable that it is 1-3.

R ₁₂ is preferably a hydrogen atom or a methyl group.
The alkylene group as L ₂ is preferably an alkylene group having 1 to 5 carbon atoms, and more preferably an alkylene group having 1 to 3 carbon atoms. L ₂ is preferably a single bond.

W ₇ is preferably an organic group having a fluorine atom, an organic group having a silicon atom, an alkyl group having 3 or more carbon atoms, or a cycloalkyl group having 5 or more carbon atoms.
Specific examples of the repeating unit represented by formula (C-II) are shown below, but are not limited thereto.

  When the resin (Aa) contains the repeating unit (Aa3), the content of the repeating unit (Aa3) with respect to all the repeating units of the resin (Aa) is preferably 1 to 95 mol%, preferably 3 to 65 mol%. It is more preferable that it is 5 to 35 mol%.

<Repeating unit (Aa4)>
In one embodiment of the present invention, the resin (Aa) may further contain a repeating unit represented by the following general formula (Aa4) (hereinafter also referred to as “repeating unit (Aa4)”). When the resin (Aa) contains the repeating unit (Aa4), the hydrophobicity can be improved and the uneven distribution can be further improved, and the absorption of the out-band light can be improved.

In general formula (Aa4),
Rb represents a hydrogen atom, an alkyl group or a halogen atom.
S _1a represents a substituent, and when a plurality of S _1a are present, each is independent.
p represents an integer of 0 to 5.

The general formula (Aa4) will be described in detail.
Rb in the formula represents a hydrogen atom, an alkyl group or a halogen atom as described above, and the alkyl group may have a substituent.
Rb is preferably a hydrogen atom, a methyl group, a trifluoromethyl group or a fluorine atom, more preferably a hydrogen atom.

S _1a represents a substituent as described above.
Examples of the substituent represented by S _1a include an alkyl group, a cycloalkyl group, an alkoxy group, an acyl group, an acyloxy group, a halogen atom, a cyano group, an organic group containing a silicon atom, an aryl group, an aryloxy group, and an aralkyl. Group, aralkyloxy group, hydroxy group, nitro group, sulfonylamino group, alkylthio group, arylthio group, aralkylthio group and the like.

The substituent represented by S _1a may be a group in which the above-described group is bonded to a divalent linking group. Examples of the divalent linking group include a substituted or unsubstituted alkylene group, Examples thereof include a substituted or unsubstituted cycloalkylene group, —O—, or a divalent linking group obtained by combining a plurality of these.

As the alkyl group represented by S _1a , for example, an alkyl group having 1 to 20 carbon atoms is preferable, and specifically, a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, an isobutyl group. Group, t-butyl group, pentyl group, hexyl group and the like. The alkyl group may further have a substituent. Further preferred substituents that may have, for example, halogen atom, alkoxy group, cycloalkyl group, hydroxyl group, nitro group, acyl group, acyloxy group, acylamino group, sulfonylamino group, alkylthio group, arylthio group, aralkylthio group, Examples thereof include heterocyclic residues such as a thiophenecarbonyloxy group, a thiophenemethylcarbonyloxy group, and a pyrrolidone residue, and a substituent having 12 or less carbon atoms is preferable.

As the cycloalkyl group represented by S _1a , for example, a cycloalkyl group having 3 to 10 carbon atoms is preferable, and specific examples include a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a norbornel group, an adamantyl group, and the like. Can be mentioned. The cycloalkyl group may further have a substituent. Furthermore, as a preferable substituent which can have, an alkyl group is mentioned in addition to the substituent which the alkyl group as _S1a mentioned above may have, for example.

As the alkoxy group represented by S _1a , for example, an alkoxy group having 1 to 10 carbon atoms is preferable, and specific examples include a methoxy group, an ethoxy group, a propoxy group, and a butoxy group. The alkoxy group may have a further substituent, and examples of such a substituent include the same groups as the preferred substituent that the alkyl group as S _1a described above may have.

As the acyl group represented by S _1a , for example, an acyl group having 2 to 10 carbon atoms is preferable, and specific examples include an acetyl group, a propionyl group, a butyryl group, and an isobutyryl group. The acyl group may have a further substituent, and examples of such a substituent include the same groups as the preferable substituent that the alkyl group as S _1a described above may have.

As the acyloxy group represented by S _1a , for example, those having 2 to 10 carbon atoms are preferable. Examples of the acyl group in the acyloxy group include the same specific examples as those of the acyl group described above, and the substituents that can be included are also the same.

As the aryl group represented by S _1a , for example, an aryl group having 6 to 10 carbon atoms is preferable, and specific examples include phenyl group, xylyl group, toluyl group, cumenyl group, naphthyl group, anthracenyl group and the like. It is done. The aryl group may have a further substituent, and examples of such a substituent include a group similar to the preferable substituent that the alkyl group or cycloalkyl group as S _1a described above may have. Can be mentioned.

As the aryloxy group and arylthio group represented by S _1a , for example, those having 2 to 10 carbon atoms are preferable. Examples of the aryl group in the aryloxy group and the arylthio group include specific examples similar to the above-described aryl group, and the substituents that can be included are also the same.

As the aralkyl group represented by S _1a , for example, those having 7 to 15 carbon atoms are preferred, and specific examples include a benzyl group. These groups may further have a substituent. Examples of such a substituent include the same groups as the preferable substituents that the alkyl group or cycloalkyl group as S _1a described above may have. Is mentioned.

As the aralkyloxy group and aralkylthio group represented by S _1a , for example, those having 7 to 15 carbon atoms are preferable. Examples of the aralkyl group in the aralkyloxy group and the aralkylthio group include specific examples similar to the above-described aralkyl, and the substituents that may be included are also the same.

As the alkylthio group represented by S _1a , for example, an alkylthio group having 1 to 10 carbon atoms is preferable. Examples of the alkyl group in the alkylthio group include the same specific examples as the alkyl described above, and the substituents that can be included are also the same.

Examples of the halogen atom represented by S _1a include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. A fluorine atom and a chlorine atom are preferable, and a fluorine atom is most preferable.

The organic group in the organic group containing a silicon atom represented by S _1a is a group containing at least one carbon atom, and an oxygen atom, a nitrogen atom, a sulfur atom, a silicon atom, a halogen atom (for example, a fluorine atom, a chlorine atom) A hetero atom such as an atom or a bromine atom). This organic group preferably has 1 to 30 carbon atoms.

In one embodiment, the organic group containing a silicon atom is preferably represented by the following general formula (S).

Where
R ₁ , R ₂ and R ₃ each independently represents a hydrogen atom, an alkyl group, an alkenyl group, a cycloalkyl group, an alkoxy group, an aryl group, an aralkyl group or a halogen atom.
L represents a single bond or a divalent linking group.

The alkyl group in R _{1, R 2} and _{R 3,} for example, preferably an alkyl group having 1 to 20 carbon atoms, which may have a substituent.
The alkenyl group for R _{1, R 2} and _{R 3,} for example, carbon atoms preferably an alkenyl group having 2 to 10, which may have a substituent.
The cycloalkyl group in R _1, R ₂ and R _3, for example, carbon atoms preferably a cycloalkyl group having from 3 to 10, which may have a substituent.
The alkoxy group in R _{1, R 2} and _{R 3,} for example, preferably an alkoxy group having 1 to 10 carbon atoms, which may have a substituent.
As an aryl group in R < ₁ >, R < ₂ > and R < ₃ >, a C6-C10 aryl group is preferable, for example, and you may have a substituent.
As the aralkyl group in R ₁ , R ₂ and R ₃ , for example, an aralkyl group having 7 to 15 carbon atoms is preferable and may have a substituent.
Examples of the divalent linking group represented by L include a substituted or unsubstituted alkylene group, —O—, —S—, — (C═O) —, or a divalent linking in which a plurality of these are combined. Groups.

In one embodiment, S _1a is preferably an alkyl group which may have a substituent, an organic group containing a halogen atom or a silicon atom, and an alkyl group, an alkyl group substituted with a halogen atom, or a silicon atom. Is more preferable, and it is still more preferable that it is an alkyl group or group represented by the following general formula (S-1).

Where
R ₁₁ , R ₂₁ and R ₃₁ each independently represents an alkyl group.
L ₁ represents a single bond or a divalent linking group.

The alkyl group as R ₁₁ , R ₂₁ and R ₃₁ has the same definition as the alkyl group as R ₁ , R ₂ and R ₃ in the general formula (S) described above, and a divalent linking group as L _1. Is synonymous with the divalent linking group as L in formula (S).
p represents an integer of 0 to 5 as described above. p is preferably an integer of 1 to 5.

Specific examples of the repeating unit (Aa4) are shown below, but the present invention is not limited thereto, and the position of the substituent on the benzene ring (corresponding to the S _1a group) is also limited to the following specific examples. It is not what is done.

  When the resin (Aa) contains a repeating unit (Aa4), the content of the repeating unit (Aa4) is preferably from 1 to 99 mol%, more preferably from 1 to 70 mol, based on all repeating units in the resin (Aa). %, More preferably 1 to 50 mol%, and particularly preferably 1 to 30 mol%.

<Repeating unit (Aa5)>
In one embodiment of the present invention, the resin (Aa) may further contain a repeating unit (Aa5) having at least two or more polar conversion groups.

  The repeating unit (Aa5) is preferably a repeating unit (Aa5-1) having at least two or more polar conversion groups and at least one of a fluorine atom and a silicon atom on one side chain. That is, it is a repeating unit having a structure having at least one of a fluorine atom and a silicon atom on a side chain having a plurality of polarity converting groups. The fluorine atom may be a fluorine atom as an electron withdrawing group in a polarity conversion group described later, or may be a fluorine atom different from the fluorine atom as the electron withdrawing group.

  The repeating unit (Aa5) is a repeating unit (Aa5-2) having at least two or more polar conversion groups and not having a fluorine atom and a silicon atom, and the resin (Aa) is a fluorine atom and It is also preferable to further have the above repeating unit (Aa3) having at least one of silicon atoms.

Alternatively, the repeating unit (Aa5) has at least two or more polar conversion groups on one side chain, and a fluorine atom and a silicon atom on a side chain different from the side chain in the same repeating unit. A repeating unit (Aa5-3) having at least one of them is also preferred. In this case, the side chain having a polarity converting group and the side chain having at least one of a fluorine atom and a silicon atom are in the α-position via the main chain carbon atom, that is, as shown in the following formula (4): It is preferable that they are in a positional relationship. In the formula, B1 represents a partial structure having a polarity converting group, and B2 represents a partial structure having at least one of a fluorine atom and a silicon atom.

  Among these resin (Aa) embodiments, it is more preferable to have a repeating unit (Aa5-1).

  Here, the polar conversion group is a group that decomposes by the action of an alkali developer and increases the solubility in the alkali developer, and in the structure represented by the general formula (KA-1) or (KB-1). It is a partial structure represented by COO-.

  The lactone structure represented by the general formula (KA-1) may be any group as long as it has a lactone ring, but is preferably a group having a 5- to 7-membered ring lactone structure, and 5 to 7-membered. Those in which other ring structures are condensed so as to form a bicyclo structure or a spiro structure in the ring lactone structure are preferred.

  In addition, since the ester group (for example, -COO- in acrylate) directly bonded to the main chain of the resin in the repeating unit has a poor function as a polarity conversion group, it is not included in the polarity conversion group in this case.

  Further, the repeating unit (Aa5) may not have two separate entire structures represented by (KA-1) or (KB-1). It is understood that two attracting groups are included, whether in a form in which two ester structures are sandwiched or in a form of formula (KY-1) described later.

In the repeating unit (Aa5-2) and the repeating unit (Aa5-3), the polarity conversion group is more preferably a partial structure represented by —COO— in the structure represented by the general formula (KA-1). preferable.

In general formula (KA-1),
Z _ka represents an alkyl group, a cycloalkyl group, an ether group, a hydroxyl group, an amide group, an aryl group, a lactone ring group, or an electron withdrawing group, if Z _ka there are a plurality, the plurality of Z _ka same But it can be different.

Z _ka may be linked together to form a ring. Examples of the ring formed by linking Z _ka together include a cycloalkyl ring and a hetero ring (a cyclic ether ring, a lactone ring, etc.).

  nka represents an integer of 0 to 10. Preferably it is an integer of 0 to 8, more preferably an integer of 0 to 5, more preferably an integer of 1 to 4, and most preferably an integer of 1 to 3.

  Q represents an atomic group necessary for forming a lactone ring together with atoms in the formula. The lactone ring is not particularly limited as long as it is a group having a lactone structure as described above, but is preferably a group having a 5- to 7-membered ring lactone structure, and the bicyclo structure or spiro structure is added to the 5- to 7-membered ring lactone structure. Those in which other ring structures are condensed in a form to form are preferable.

In general formula (KB-1),
X _kb1 and X _kb2 are each independently an electron withdrawing group.

nkb and nkb ′ each independently represents 0 or 1. When nkb and nkb ′ are 0, X _kb1 and X _kb2 are directly connected to an ester group (—COO—).

R _{kb1 to} R _kb4 each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, or an electron withdrawing group, and at least two of R _kb1 , R _kb2 and X _kb1 are connected to each other to form a ring _And at least two of R _kb3 , R _kb4 and X _kb2 may be connected to each other to form a ring.

The ring that may be formed by linking at least two of R _kb3 , R _kb4, and X _kb2 is preferably a cycloalkyl group or a heterocyclic group, and the heterocyclic group is preferably a lactone ring group. Examples of the lactone ring include structures represented by formulas (KA-1-1) to (KA-1-17) described later.

Note that the structure represented by the general formula (KA-1) or (KB-1) is the structure represented by the general formula (KA-1) ( _KB- ) when X _kb1 and X _kb2 are monovalent. When it does not have a bond as in the structure represented by 1), it is a monovalent or higher-valent partial structure obtained by removing at least one arbitrary hydrogen atom in the structure.

As an electron withdrawing group in Z _ka , X _kb1 , X _kb2 , R _{kb1 to} R _kb4 , a halogen atom, a cyano group, an oxy group, a carbonyl group, a carbonyloxy group, an oxycarbonyl group, a nitrile group, a nitro group, a sulfonyl group A halo (cyclo) alkyl group or a haloaryl group represented by a group, a sulfinyl group, or —C (R _f1 ) (R _f2 ) —R _f3 , and combinations thereof.

  The “halo (cyclo) alkyl group” represents an alkyl group or a cycloalkyl group that is at least partially halogenated. When the electron-withdrawing group is a divalent or higher valent group, the remaining bond forms a bond with an arbitrary atom or substituent, and the main chain of the resin (Aa) through a further substituent It may be connected to.

Here, R _f1 represents a halogen atom, a perhaloalkyl group, a perhalocycloalkyl group, or a perhaloaryl group, more preferably a fluorine atom, a perfluoroalkyl group, or a perfluorocycloalkyl group, still more preferably a fluorine atom or a trialkyl group. Represents a fluoromethyl group.

R _f2 and R _f3 each independently represent a hydrogen atom, a halogen atom or an organic group, and R _f2 and R _f3 may be linked to form a ring. Examples of the organic group include an alkyl group, a cycloalkyl group, and an alkoxy group.

At least two of R _{f1 to} R _f3 may be linked to form a ring, and examples of the ring formed include a (halo) cycloalkyl ring and a (halo) aryl ring.

Examples of the (halo) alkyl group in R _{f1 to} R _f3 include an alkyl group in Z _ka and a structure in which this is halogenated.

In R _f1 to R _{f3, or,} as the (per) halocycloalkyl groups and (per) haloaryl groups in the ring and _{R f2} and _{R f3} is formed by connecting, halogenated cycloalkyl groups such as in the _{Z ka} And more preferably a fluorocycloalkyl group represented by -C _(n) F _(2n-2) H and a perfluoroaryl group represented by -C _(n) F _(n-1). It is done. Although carbon number n is not specifically limited here, the thing of 5-13 is preferable and 6 is more preferable.

More preferably, R _f2 represents the same group as R _f1 or is linked to R _f3 to form a ring.

The electron withdrawing group is preferably a halogen atom, or a halo (cyclo) alkyl group or haloaryl group represented by —C (R _f1 ) (R _f2 ) —R _f3 , more preferably —C ( CF _{3) 2} H or -C _{(CF 3)} a 2 CH _3.

  In the electron withdrawing group, a part of fluorine atoms may be substituted with another electron withdrawing group.

Z _ka is preferably an alkyl group, a cycloalkyl group, an ether group, a hydroxyl group or an electron withdrawing group, more preferably an alkyl group, a cycloalkyl group or an electron withdrawing group. In addition, as an ether group, the thing substituted by the alkyl group or the cycloalkyl group, ie, the alkyl ether group, etc. are preferable. The electron withdrawing group has the same meaning as described above.

Examples of the halogen atom as Z _ka include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom, and a fluorine atom is preferable.

The alkyl group as Z _ka may have a substituent and may be linear or branched. The linear alkyl group preferably has 1 to 30 carbon atoms, more preferably 1 to 20, for example, methyl group, ethyl group, n-propyl group, n-butyl group, n-pentyl group, n-hexyl. Group, n-heptyl group, n-octyl group, n-nonyl group, n-decanyl group and the like. As a branched alkyl group, Preferably it is C3-C30, More preferably, it is 3-20, for example, i-propyl group, i-butyl group, sec-butyl group, t-butyl group, i-pentyl group, Examples include t-pentyl group, i-hexyl group, t-hexyl group, i-heptyl group, t-heptyl group, i-octyl group, t-octyl group, i-nonyl group, t-decanoyl group and the like. C1-C4 things, such as a methyl group, an ethyl group, n-propyl group, i-propyl group, n-butyl group, i-butyl group, t-butyl group, are preferable.

The cycloalkyl group of Z _ka may be monocyclic or polycyclic. In the latter case, the cycloalkyl group may be bridged. That is, in this case, the cycloalkyl group may have a bridged structure. A part of carbon atoms in the cycloalkyl group may be substituted with a hetero atom such as an oxygen atom.

  The monocyclic cycloalkyl group preferably has 3 to 8 carbon atoms, and examples thereof include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, and a cyclooctyl group.

Examples of the polycyclic cycloalkyl group include groups having a bicyclo, tricyclo, or tetracyclo structure having 5 or more carbon atoms. The polycyclic cycloalkyl group preferably has 6 to 20 carbon atoms. For example, an adamantyl group, norbornyl group, isobornyl group, camphanyl group, dicyclopentyl group, α-pinel group, tricyclodecanyl group , Tetocyclododecyl group and androstanyl group.
Examples of these cycloalkyl groups include those represented by the following formula.

  Preferred examples of the alicyclic moiety include adamantyl group, noradamantyl group, decalin group, tricyclodecanyl group, tetracyclododecanyl group, norbornyl group, cedrol group, cyclohexyl group, cycloheptyl group, cyclooctyl group, cyclodecanyl group. And cyclododecanyl group. More preferred are an adamantyl group, a decalin group, a norbornyl group, a cedrol group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, a cyclodecanyl group, a cyclododecanyl group, and a tricyclodecanyl group.

  Examples of the substituent of these alicyclic structures include an alkyl group, a halogen atom, a hydroxyl group, an alkoxy group, a carboxyl group, and an alkoxycarbonyl group. The alkyl group is preferably a lower alkyl group such as a methyl group, an ethyl group, a propyl group, an isopropyl group, or a butyl group, and more preferably a methyl group, an ethyl group, a propyl group, or an isopropyl group. Preferred examples of the alkoxy group include those having 1 to 4 carbon atoms such as a methoxy group, an ethoxy group, a propoxy group, and a butoxy group. Examples of the substituent that the alkyl group and the alkoxy group may have include a hydroxyl group, a halogen atom, and an alkoxy group (preferably having 1 to 4 carbon atoms).

Examples of the Z _ka aryl group include a phenyl group and a naphthyl group.
Examples of the substituent that the alkyl group, cycloalkyl group, and aryl group of Z _ka may further include, for example, a hydroxyl group; a halogen atom; a nitro group; a cyano group; the above alkyl group; a methoxy group, an ethoxy group, a hydroxyethoxy group, Alkoxy groups such as propoxy group, hydroxypropoxy group, n-butoxy group, isobutoxy group, sec-butoxy group and t-butoxy group; alkoxycarbonyl groups such as methoxycarbonyl group and ethoxycarbonyl group; benzyl group, phenethyl group and cumyl group Aralkyloxy group; Aralkyloxy group; Acyl group such as formyl group, acetyl group, butyryl group, benzoyl group, cyanamyl group and valeryl group; Acyloxy group such as butyryloxy group; Alkenyl group; Vinyloxy group, propenyloxy group, allyloxy group And butenylo An alkenyloxy group such as a xy group; the above aryl group; an aryloxy group such as a phenoxy group; and an aryloxycarbonyl group such as a benzoyloxy group.

  When the polarity conversion group is decomposed by the action of an alkali developer and converted in polarity, the receding contact angle with water of the resin composition film after alkali development can be lowered.

  The receding contact angle with water of the resin composition film after alkali development is preferably 50 ° or less, more preferably 40 ° or less at the temperature at the time of exposure, usually room temperature 23 ± 3 ° C. and humidity 45 ± 5%. More preferably, it is 35 ° or less, and most preferably 30 ° or less.

  The receding contact angle is a contact angle measured when the contact line at the droplet-substrate interface recedes, and is useful for simulating the ease of movement of the droplet in a dynamic state. It is generally known. In simple terms, it can be defined as the contact angle when the droplet interface recedes when the droplet discharged from the needle tip is deposited on the substrate and then sucked into the needle again. It can be measured by using a contact angle measuring method generally called an expansion / contraction method.

  The hydrolysis rate of the resin (Aa) with respect to the alkaline developer is preferably 0.001 nm / sec or more, more preferably 0.01 nm / sec or more, and further preferably 0.1 nm / sec or more. Most preferably, it is 1 nm / sec or more.

  Here, the hydrolysis rate of the resin (Aa) with respect to the alkaline developer was 23.degree. C. TMAH (tetramethylammonium hydroxide aqueous solution) (2.38 mass%), and the resin film was formed only with the resin (Aa). This is the rate at which the film thickness decreases.

As the lactone ring structure in the general formula (KA-1), a group having a lactone structure represented by any one of the following (KA-1-1) to (KA-1-17) is more preferable. Further, a group having a lactone structure may be directly bonded to the main chain. Preferred lactone structures include (KA-1-1), (KA-1-4), (KA-1-5), (KA-1-6), (KA-1-13), (KA-1) -14) and (KA-1-17).
Specific examples of the skeleton having a lactone structure are shown below, but are not limited thereto.

  The lactone structure portion may or may not have a substituent. Preferred substituents include alkyl groups having 1 to 8 carbon atoms, cycloalkyl groups having 4 to 7 carbon atoms, alkoxy groups having 1 to 8 carbon atoms, alkoxycarbonyl groups having 2 to 8 carbon atoms, carboxyl groups, halogen atoms, Examples include a hydroxyl group, a cyano group, and an acid-decomposable group. More preferred are an alkyl group having 1 to 4 carbon atoms, a cycloalkyl group having 5 to 6 carbon atoms, a cyano group, an alkoxycarbonyl group having 2 to 4 carbon atoms, a carboxyl group, a halogen atom, a hydroxyl group, and an acid-decomposable group. When a plurality of substituents are present, they may be the same or different, and the substituents may be bonded to form a ring.

  Some lactone structures have optically active substances, but any optically active substance may be used. One optically active substance may be used alone or a plurality of optically active substances may be mixed and used. When one kind of optically active substance is mainly used, its optical purity (ee) is preferably 90% or more, more preferably 95% or more, and most preferably 98% or more.

Since the structure represented by (KB-1) has a structure in which an electron withdrawing group is present at a position close to the ester structure, it has a high polarity conversion ability.
X _kb2 is preferably a halogen atom, or a halo (cyclo) alkyl group or haloaryl group represented by the above-mentioned —C (R _f1 ) (R _f2 ) —R _f3 .

The at least two polarity conversion groups contained in the repeating unit (Aa5) are more preferably a partial structure having two polarity conversion groups represented by the following general formula (KY-1). Note that the structure represented by the general formula (KY-1) is a group having a monovalent or higher group obtained by removing at least one arbitrary hydrogen atom in the structure.

In general formula (KY-1),
R _ky1 and R _ky4 are each independently a hydrogen atom, halogen atom, alkyl group, cycloalkyl group, carbonyl group, carbonyloxy group, oxycarbonyl group, ether group, hydroxyl group, cyano group, amide group, or aryl group Represents. Alternatively, R _ky1 and R _ky4 may be bonded to the same atom to form a double bond. For example, R _ky1 and R _ky4 are bonded to the same oxygen atom to form a part of a carbonyl group (═O). May be formed.

R _ky2 and R _ky3 are each independently an electron withdrawing group, or R _ky1 and R _ky3 are linked to form a lactone ring, and R _ky2 is an electron withdrawing group. As the lactone ring to be formed, the structures (KA-1-1) to (KA-1-17) are preferable. _{Examples of the} electron withdrawing group include the same groups as those of X _kb1 in the formula (KB-1), and are preferably a halogen atom or represented by -C (R _f1 ) (R _f2 ) -R _f3. A halo (cyclo) alkyl group or a haloaryl group.

At least two of R _ky1 , R _ky3 and R _ky4 may be linked to each other to form a monocyclic or polycyclic structure.

R _{kb1 to} R _kb4 , nkb, and nkb ′ are respectively synonymous with those in the formula (KB-1).

Specific examples of R _ky1 and R _ky4 include the same groups as Z _ka in formula (KA-1).
As the lactone ring formed by linking R _ky1 and R _ky3 , the structures (KA-1-1) to (KA-1-17) are preferable. _{Examples of the} electron withdrawing group include the same groups as those in X _kb1 in the formula (KB-1).

The structure represented by the general formula (KY-1) is more preferably a structure represented by the following general formula (KY-2). Note that the structure represented by the general formula (KY-2) is a group having a monovalent or higher group obtained by removing at least one arbitrary hydrogen atom in the structure.

In formula (KY-2),
R _{ky6 to} R _ky10 are each independently a hydrogen atom, halogen atom, alkyl group, cycloalkyl group, carbonyl group, carbonyloxy group, oxycarbonyl group, ether group, hydroxyl group, cyano group, amide group, or aryl. Represents a group.
Two or more of R _{ky6 to} R _ky10 may be connected to each other to form a monocyclic or polycyclic structure.

R _ky5 represents an electron withdrawing group. _Examples of the electron withdrawing group include the same groups as those described above for X _kb1 in the formula (KB-1), and are preferably a halogen atom or represented by -C (R _f1 ) (R _f2 ) -R _f3. A halo (cyclo) alkyl group or a haloaryl group.
R _kb1 , R _kb2 and nkb have the same _meanings as those in formula (KB-1).
Specific examples of R _{ky5 to} R _ky10 include the same groups as Z _ka in formula (KA-1).

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

In general formula (KY-3),
Rs represents a chain or cyclic alkylene group, and when there are a plurality of Rs, they may be the same or different.
Ls represents a single bond, an ether bond, an ester bond, an amide bond, a urethane bond or a urea bond, and when there are a plurality of Ls, they may be the same or different.
ns represents the number of repeating linking groups represented by-(Rs-Ls)-, and represents an integer of 0 to 5.
L _ky represents an alkylene group, an oxygen atom or a sulfur atom.

Z _ka represents an alkyl group, a cycloalkyl group, an ether group, a hydroxyl group, an amide group, an aryl group, a lactone ring group, or an electron withdrawing group. If Z _ka there are a plurality, the plurality of Z _ka may be the same or different, may be connected to form a ring Z _ka each other.
nka represents an integer of 0 to 10.
R _kb1 and R _kb2 each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, or an electron withdrawing group, and at least two of R _kb1 , R _kb2, and R _ky5 are connected to each other. A ring may be formed.
nkb represents 0 or 1.
R _ky5 represents an electron withdrawing group.
* Represents a binding site with the remainder of the repeating unit.

General formula (KY-3) will be described in more detail.
Z _ka and nka are each synonymous with the formula (KA-1). R _ky5 has the same _{meaning as} in formula (KY-2).
R _kb1 , R _kb2 and nkb have the same _meanings as those in formula (KB-1).
L _ky represents an alkylene group, an oxygen atom, or a sulfur atom as described above. _Examples of the alkylene group for L _ky include a methylene group and an ethylene group. L _ky is preferably an oxygen atom or a methylene group, and more preferably a methylene group.

As described above, Rs represents a chain or cyclic alkylene group, and when there are a plurality of Rs, they may be the same or different.
As described above, Ls represents a single bond, an ether bond, an ester bond, an amide bond, a urethane bond or a urea bond, and when there are a plurality of Ls, they may be the same or different.
ns represents the number of repeating linking groups represented by-(Rs-Ls)-, and represents an integer of 0 to 5. ns is preferably 0 or 1.

The repeating unit (Aa5) preferably has a structure represented by the formula (K0).

In the formula, R _k1 represents a hydrogen atom, a halogen atom, a hydroxyl group, an alkyl group, a cycloalkyl group, an aryl group, or a group having a polarity converting group.
R _k2 represents an alkyl group, a cycloalkyl group, an aryl group, or a group having a polarity converting group. However, R _k1 and R _k2 as a whole have two or more polarity conversion groups.
In addition, as described above, the ester group directly connected to the main chain of the repeating unit represented by the general formula (K0) is not included in the polar conversion group in the present invention.

  The repeating unit (Aa5) is not limited as long as it is a repeating unit obtained by polymerization such as addition polymerization, condensation polymerization, addition condensation, etc., but is a repeating unit obtained by addition polymerization of a carbon-carbon double bond. Preferably there is. Examples include acrylate-based repeating units (including those having substituents at the α-position and β-position), styrene-based repeating units (including those having substituents at the α-position and β-position), vinyl ether-based repeating units, norbornene-based Repeating units, maleic acid derivatives (maleic anhydride and derivatives thereof, maleimides, etc.), and the like, acrylate-based repeating units, styrene-based repeating units, vinyl ether-based repeating units, norbornene-based repeating units Preferred are acrylate repeat units, vinyl ether repeat units, and norbornene repeat units, with acrylate repeat units being most preferred.

  Moreover, it is preferable that resin (Aa) contained in the actinic-ray sensitive or radiation sensitive resin composition of this invention contains the repeating unit which has at least any one of a fluorine atom and a silicon atom.

  As a result, when the resin (Aa) is unevenly distributed on the surface layer of the actinic ray-sensitive or radiation-sensitive resin film and the immersion medium is water, the resist film surface with respect to water when the actinic ray-sensitive or radiation-sensitive resin film is used The receding contact angle can be improved, and the immersion water followability can be improved.

  The receding contact angle of the actinic ray-sensitive or radiation-sensitive resin film is preferably 60 ° to 90 °, more preferably 65 ° or more, even more preferably at the temperature at exposure, usually room temperature 23 ± 3 ° C. and humidity 45 ± 5%. Is 70 ° or more.

  The content of the resin (Aa) in the actinic ray-sensitive or radiation-sensitive resin composition can be appropriately adjusted and used so that the receding contact angle of the actinic ray-sensitive or radiation-sensitive resin film falls within the above range, Based on the total solid content of the actinic ray-sensitive or radiation-sensitive resin composition, 0.01 to 30% by mass is preferable, 0.01 to 20% by mass is more preferable, and 0.01 to More preferably, it is 10 mass%, Most preferably, it is 0.1-5 mass%. The resin (Aa) is ubiquitous at the interface as described above, but unlike the surfactant, it does not necessarily have a hydrophilic group in the molecule, and the polar / nonpolar substance is mixed uniformly. You don't have to contribute.

  In the immersion exposure process, the immersion head needs to move on the wafer following the movement of the exposure head to scan the wafer at high speed to form the exposure pattern. In this case, the contact angle of the immersion liquid with respect to the resist film is important, and the resist is required to follow the high-speed scanning of the exposure head without remaining droplets.

  In one embodiment of the present invention, the resin (Aa) contains at least one of a fluorine atom and a silicon atom, whereby the hydrophobicity (water followability) of the resist surface is improved and the development residue (scum) is reduced.

Note that in one embodiment of the present invention, the resin (Aa) may be a resin having a plurality of polarity conversion groups and at least one of a fluorine atom and a silicon atom, and the fluorine atom has the general formula (KB) It may be an electron-withdrawing group of X _kb1 and X _kb2 in -1).

  In one embodiment of the present invention, the fluorine atom or silicon atom in the resin (Aa) may be present in the main chain of the resin or may be substituted on the side chain.

Hereinafter, although the specific example of a repeating unit (Aa5) is shown, this invention is not limited to this. Ra represents a hydrogen atom, a fluorine atom, a methyl group or a trifluoromethyl group.

  When the resin (Aa) contains a repeating unit (Aa5), the content of the repeating unit (Aa5) is preferably from 10 to 90 mol%, more preferably from 30 to 85 mol, based on all repeating units in the resin (Aa). %, More preferably 50 to 80 mol%.

  As for the content rate of a repeating unit (Aa5-1), 10-90 mol% is preferable with respect to all the repeating units in resin (Aa), More preferably, it is 30-85 mol%, More preferably, it is 50-80 mol%.

  As for the content rate of a repeating unit (Aa5-2), 10-90 mol% is preferable with respect to all the repeating units in resin (Aa), More preferably, it is 30-85 mol%, More preferably, it is 50-80 mol%.

  As for the content rate of a repeating unit (Aa5-3), 10-90 mol% is preferable with respect to all the repeating units in resin (Aa), More preferably, it is 30-85 mol%, More preferably, it is 50-80 mol%.

<Repeating unit (Aa6)>
In one embodiment of the present invention, the resin (Aa) may further contain a repeating unit corresponding to the polymerizable compound represented by the following general formula (ca-1) or (cb-1).

  In General Formulas (ca-1) and (cb-1), A may have a methacryl group which may have a substituent, an acrylic group which may have a substituent, or a substituent. Represents a good norbornene group.

Z ₁ each independently represents a single bond, an ether bond (—O—), an ester bond, an amide bond, a urethane bond or a urea bond. When q is 2 or more, the plurality of groups represented by Z ₁ may be the same or different.

Z ₂ each independently represents a single bond or a chain or cyclic alkylene group which may have a substituent. When q is 2 or more, the plurality of groups represented by Z ₂ may be the same or different.

  Ta and Tb are each independently a halogen atom, an alkyl group which may have a substituent, a cycloalkyl group which may have a substituent, an alkoxy group which may have a substituent, a substituent An acyl group which may have a group, an alkyloxycarbonyl group which may have a substituent, a carboxy group, a nitrile group, a hydroxyl group, an amide group which may have a substituent or a substituent. Represents an optionally substituted aryl group.

  When there are a plurality of Tas, Tas may be bonded to form a ring.

  When there are a plurality of Tb, Tb may be bonded to each other to form a condensed ring which may contain a hetero atom together with the benzene ring substituted by Tb.

  Tc is a hydrogen atom, a halogen atom, an alkyl group which may have a substituent, a cycloalkyl group which may have a substituent, a nitrile group, a hydroxyl group or an amide which may have a substituent. Represents an aryl group which may have a group or a substituent.

  L represents a carbonyl group, a carbonyloxy group or an ether bond (—O—). When r is an integer of 2 or more, (L) r represents a group formed by combining L with r, and a plurality of L may be the same or different.

m represents an integer of 1 to 28.
n represents an integer of 0 to 11.
p represents an integer of 0 to 5.
q represents an integer of 0 to 5.
r represents an integer of 0 to 5.

  Paragraphs [0026] to [0053] of JP 2010-159413 A are preferred forms, production methods, and specific examples of the polymerizable compounds represented by the general formulas (ca-1) and (cb-1). Can be referred to.

  When the resin (Aa) contains the repeating unit (Aa6), the content of the repeating unit (Aa6) is preferably 10 to 90 mol% with respect to all the repeating units in the resin (Aa). Preferably it is 30-85 mol%, More preferably, it is 50-80 mol%.

<Repeating unit (Aa7)>
In one embodiment of the present invention, the resin (Aa) may further contain at least one repeating unit (Aa7) derived from a monomer represented by the following general formula (aa1-1).

In general formula (aa1-1),
Q ₁ represents an organic group containing a polymerizable group.
L ₁ and L ₂ each independently represents a single bond or a divalent linking group.
Rf represents an organic group having a fluorine atom.
The organic group containing a polymerizable group represented by Q ₁ in the formula is not particularly limited as long as it is a group containing a polymerizable group. Examples of the polymerizable group include an acryl group, a methacryl group, a styryl group, a norbornenyl group, a maleimide group, and a vinyl ether group, and an acryl group, a methacryl group, and a styryl group are particularly preferable.

Examples of the divalent linking group represented by L ₁ and L ₂ include a substituted or unsubstituted arylene group, a substituted or unsubstituted alkylene group, a substituted or unsubstituted cycloalkylene group, —O—, and —CO. -Or a divalent linking group obtained by combining a plurality of these.

  As an arylene group, a C6-C14 thing is preferable, for example, and a phenylene group, a naphthylene group, an anthrylene group, a phenanthrylene group, a biphenylene group, a terphenylene group etc. are mentioned as a specific example.

  As an alkylene group and a cycloalkylene group, for example, those having 1 to 15 carbon atoms are preferable. As a specific example, one hydrogen atom in a linear, branched or cyclic alkyl group described below is extracted. Examples include: methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, tert-butyl group, tert-amyl group, n-pentyl group, and n-hexyl group. N-heptyl group, n-octyl group, n-nonyl group, n-decyl group, cyclopentyl group, cyclohexyl group, cyclopentylmethyl group, cyclopentylethyl group, cyclopentylbutyl group, cyclohexylmethyl group, cyclohexylethyl group, cyclohexylbutyl group An adamantyl group.

  Examples of the substituent that the arylene group, alkylene group, and cycloalkylene group may have include an alkyl group, an aralkyl group, an alkoxy group, and a fluorine atom.

In one embodiment of the present invention, L ₁ is more preferably a single bond, a phenylene group, an ether group, a carbonyl group, or a carbonyloxy group, and L ₂ is more preferably an alkylene group, an ether group, a carbonyl group, or a carbonyloxy group.

  The organic group in the organic group having a fluorine atom as Rf is a group containing at least one carbon atom, and an organic group containing a carbon-hydrogen bond portion is preferable. Rf is, for example, an alkyl group substituted with a fluorine atom or a cycloalkyl group substituted with a fluorine atom.

In one embodiment, the repeating unit (Aa7) is preferably a repeating unit represented by the following general formula (aa1-2-1) or (aa1-3-1).

In general formulas (aa1-2-1) and (aa1-3-1),
Ra ₁ and Ra ₂ each independently represents a hydrogen atom or an alkyl group. Ra ₁ and Ra ₂ are preferably a hydrogen atom or a methyl group.
L ₂₁ and L ₂₂ each independently represent a single bond or a divalent linking group, and have the same meaning as L ₂ in General Formula (aa1-1) described above.
Rf ₁ and Rf ₂ each independently represent an organic group having a fluorine atom, and have the same meaning as Rf in formula (aa1-1).

Moreover, it is preferable that a repeating unit (Aa7) is a repeating unit represented by the following general formula (aa1-2-2) or (aa1-3-2) in one aspect | mode.

In general formulas (aa1-2-2) and (aa1-3-2),
Ra ₁ and Ra ₂ each independently represents a hydrogen atom or an alkyl group.
R ₁ , R ₂ , R ₃ and R ₄ each independently represents a hydrogen atom or an alkyl group.
m ₁ and m ₂ each independently represents an integer of 0 to 5.
Rf ₁ and Rf ₂ each independently represents an organic group having a fluorine atom.

Ra ₁ and Ra ₂ are preferably a hydrogen atom or a methyl group.
As the alkyl group represented by R ₁ , R ₂ , R ₃ and R ₄ , for example, a linear or branched alkyl group having 1 to 10 carbon atoms is preferable, and specific examples include a methyl group, an ethyl group, A propyl group, an isopropyl group, a butyl group, a t-butyl group, etc. are mentioned. This alkyl group may have a substituent, and examples of the substituent include an alkoxy group, an aryl group, and a halogen atom.

m ₁ and m ₂ are preferably integers of 0 to 3, more preferably 0 or 1, and most preferably 1.
The organic group having a fluorine atom as Rf ₁ and Rf ₂ has the same meaning as Rf in formula (aa1-1).

Moreover, it is preferable that a repeating unit (Aa7) is a repeating unit represented by the following general formula (aa1-2-3) or (aa1-3-3) in one aspect | mode.

In general formulas (aa1-2-3) and (aa1-3-3),
Ra ₁ represents a hydrogen atom or a methyl group.
Rf ₁ and Rf ₂ each independently represent an organic group having a fluorine atom, and have the same meaning as Rf in formula (aa1-1).

Specific examples of the repeating unit (Aa7) are shown below, but the present invention is not limited thereto.

  When the resin (Aa) contains the repeating unit (Aa7), the content of the repeating unit (Aa7) is preferably 10 to 90 mol% with respect to all the repeating units in the resin (Aa). Preferably it is 30-85 mol%, More preferably, it is 50-80 mol%.

  In one embodiment, the resin (Aa) may further have at least one group selected from the following groups (x) to (z).

(X) an alkali-soluble group,
(Y) a group that decomposes by the action of an alkali developer and increases the solubility in the alkali developer;
(Z) A group that decomposes by the action of an acid.
Regarding the groups (x) to (z), the description in paragraphs [0323] to [0358] of JP2011-118318A can be referred to.

  When resin (Aa) has a fluorine atom, it is preferable that the content rate of a fluorine atom is 5-80 mass% with respect to the molecular weight of resin (Aa), and it is more preferable that it is 10-80 mass%. Moreover, it is preferable that the repeating unit containing a fluorine atom is 10-100 mass% with respect to all the repeating units in resin (Aa), and it is more preferable that it is 30-100 mass%.

  When resin (Aa) has a silicon atom, it is preferable that the content rate of a silicon atom is 2-50 mass% with respect to the molecular weight of resin (Aa), and it is more preferable that it is 2-30 mass%. Moreover, it is preferable that it is 10-90 mass%, and, as for the repeating unit containing a silicon atom with respect to all the repeating units of resin (Aa), it is more preferable that it is 20-80 mass%.

  The weight average molecular weight in terms of standard polystyrene of the resin (Aa) is preferably 1,000 to 100,000, more preferably 1,000 to 50,000, and still more preferably 2,000 to 20,000.

  As with the resin (Ab) described later, the resin (Aa) preferably has 0 to 10% by mass of residual monomer and oligomer components, and more preferably has few impurities such as metals. 0-5 mass% and 0-1 mass% are still more preferable. Thereby, a resist composition having no change over time such as foreign matter in liquid or sensitivity can be obtained. The molecular weight distribution (Mw / Mn, also referred to as dispersity) is preferably in the range of 1 to 3, more preferably 1 to 2, and still more preferably, in terms of resolution, resist shape, resist pattern side walls, roughness, and the like. It is in the range of 1 to 1.8, most preferably 1 to 1.5.

  Various commercially available products can be used as the resin (Aa), and the resin (Aa) can be synthesized according to a conventional method (for example, radical polymerization or anionic polymerization). For example, it can be synthesized by the same method as the general synthesis method of the resin (Ab) described in the resin (Ab) described later.

Although the specific example of resin (Aa) is shown below, this invention is not limited to this.

[2] Resin (Ab) whose solubility in a developing solution is changed by the action of an acid
The composition according to the present invention contains a resin (Ab) whose solubility in a developer is changed by the action of an acid.
Resin (Ab) is a resin whose solubility in a developer changes due to the action of an acid. Specifically, the solubility in an alkali developer increases due to the action of an acid, or an organic solvent as a main component. Solubility in developer decreases.

The resin (Ab) is preferably insoluble or hardly soluble in an alkaline developer.
The resin (Ab) preferably has a repeating unit having an acid-decomposable group.

  Examples of the acid-decomposable group include a group in which a hydrogen atom of an alkali-soluble group such as a carboxyl group, a phenolic hydroxyl group, a sulfonic acid group, or a thiol group is protected with a group capable of leaving by the action of an acid. .

Examples of the group capable of leaving by the action of an acid include —C (R ₃₆ ) (R ₃₇ ) (R ₃₈ ), —C (R ₃₆ ) (R ₃₇ ) (OR ₃₉ ), —C (═O) — _{O-C (R 36) (} R 37) (R 38), - C (R 01) (R 02) (OR 39), - C (R 01) (R 02) -C (= O) -O- C (R ₃₆ ) (R ₃₇ ) (R ₃₈ ) and the like can be mentioned.

In the formula, R _{36 to} R ₃₉ each independently represents an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, or an alkenyl group. R ₃₆ and R ₃₇ may be bonded to each other to form a ring. R _{01 and} R ₀₂ each independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group or an alkenyl group.

In one embodiment, the resin (Ab) preferably contains at least one repeating unit represented by the following general formulas (A1) and (A2).

In general formula (A1),
n represents an integer of 1 to 5, and m represents an integer of 0 to 4 that satisfies the relationship 1 ≦ m + n ≦ 5.
S ₁ represents a substituent (excluding a hydrogen atom), and when m is 2 or more, the plurality of S ₁ may be the same as or different from each other.
A ₁ represents a hydrogen atom or a group capable of leaving by the action of an acid. However, at least one A ₁ represents a group capable of leaving by the action of an acid. When n ≧ 2, the plurality of A ₁ may be the same as or different from each other.

In general formula (A2),
X is hydrogen atom, alkyl group, hydroxyl group, alkoxy group, halogen atom, cyano group, nitro group, acyl group, acyloxy group, cycloalkyl group, cycloalkyloxy group, aryl group, carboxy group, alkyloxycarbonyl group, alkyl Represents a carbonyloxy group or an aralkyl group.
T represents a single bond or a divalent linking group.
A ₂ represents a group capable of leaving by the action of an acid.

First, the repeating unit represented by formula (A1) will be described.
As described above, n represents an integer of 1 to 5, preferably 1 or 2, and particularly preferably 1.
As described above, m represents an integer of 0 to 4 that satisfies the relationship of 1 ≦ m + n ≦ 5, preferably 0 to 2, more preferably 0 or 1, and particularly preferably 0.
S ₁ represents a substituent (excluding a hydrogen atom) as described above. Examples of the substituent include those similar to the substituents described for S ₁ in the general formula (Ab3) to be described later.

As described above, A ₁ represents a hydrogen atom or a group capable of leaving by the action of an acid, and at least one A ₁ is a group capable of leaving by the action of an acid.

Examples of the group capable of leaving by the action of an acid include tertiary alkyl groups such as t-butyl group and t-amyl group, t-butoxycarbonyl group, t-butoxycarbonylmethyl group, and formula -C (L ₁ ) (L ₂ ) —O—Z ₂ represents an acetal group.

Hereinafter, the acetal group represented by the formula —C (L ₁ ) (L ₂ ) —O—Z ₂ will be described. In the formula, L ₁ and L ₂ each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, or an aralkyl group. Z ₂ represents an alkyl group, a cycloalkyl group, or an aralkyl group. Z ₂ and L ₁ may be bonded to each other to form a 5-membered or 6-membered ring.

The alkyl group may be a linear alkyl group or a branched alkyl group.
As a linear alkyl group, a C1-C30 thing is preferable and a C1-C20 thing is more preferable. Examples of such linear alkyl groups include methyl, ethyl, n-propyl, n-butyl, sec-butyl, t-butyl, n-pentyl, n-hexyl, and n- A heptyl group, n-octyl group, n-nonyl group, and n-decanyl group are mentioned.

  As a branched alkyl group, a C3-C30 thing is preferable and a C3-C20 thing is more preferable. Examples of such branched alkyl groups include i-propyl group, i-butyl group, t-butyl group, i-pentyl group, t-pentyl group, i-hexyl group, thexyl group, i-heptyl group. , T-heptyl group, i-octyl group, t-octyl group, inonyl group and t-decanoyl group.

  These alkyl groups may further have a substituent. Examples of the substituent include a hydroxyl group; a halogen atom such as fluorine, chlorine, bromine and iodine atoms; a nitro group; a cyano group; an amide group; a sulfonamide group; a methyl group, an ethyl group, a propyl group, an isopropyl group, n- Alkyl groups such as butyl, sec-butyl, hexyl, 2-ethylhexyl, octyl and dodecyl; alkoxy groups such as methoxy, ethoxy, hydroxyethoxy, propoxy, hydroxypropoxy and butoxy; Examples include alkoxycarbonyl groups such as methoxycarbonyl group and ethoxycarbonyl group; acyl groups such as formyl group, acetyl group and benzoyl group; acyloxy groups such as acetoxy group and butyryloxy group, and carboxy group.

  As the alkyl group, an ethyl group, an isopropyl group, an isobutyl group, a cyclohexylethyl group, a phenylmethyl group, or a phenylethyl group is particularly preferable.

  The cycloalkyl group may be monocyclic or polycyclic. In the latter case, the cycloalkyl group may be bridged. That is, in this case, the cycloalkyl group may have a bridged structure. A part of carbon atoms in the cycloalkyl group may be substituted with a hetero atom such as an oxygen atom.

  As the monocyclic cycloalkyl group, those having 3 to 8 carbon atoms are preferable. Examples of such a cycloalkyl group include a cyclopropyl group, a cyclopentyl group, a cyclohexyl group, a cyclobutyl group, and a cyclooctyl group.

  Examples of the polycyclic cycloalkyl group include groups having a bicyclo, tricyclo or tetracyclo structure. The polycyclic cycloalkyl group preferably has 6 to 20 carbon atoms. Examples of such a cycloalkyl group include an adamantyl group, norbornyl group, isobornyl group, camphanyl group, dicyclopentyl group, α-pinanyl group, tricyclodecanyl group, tetocyclododecyl group, and androstanyl group.

Examples of the aralkyl group in L ₁ , L ₂ and Z ₂ include those having 7 to 15 carbon atoms such as a benzyl group and a phenethyl group.

  These aralkyl groups may further have a substituent. Preferred examples of the substituent include an alkoxy group, a hydroxyl group, a halogen atom, a nitro group, an acyl group, an acylamino group, a sulfonylamino group, an alkylthio group, an arylthio group, and an aralkylthio group. Examples of the aralkyl group having a substituent include an alkoxybenzyl group, a hydroxybenzyl group, and a phenylthiophenethyl group. In addition, carbon number of the substituent which these aralkyl groups may have is preferably 12 or less.

Examples of the 5-membered or 6-membered ring that can be formed by bonding Z ₂ and L ₁ to each other include a tetrahydropyran ring and a tetrahydrofuran ring. Of these, a tetrahydropyran ring is particularly preferred.

Z ₂ is preferably a linear or branched alkyl group. Thereby, the effect of the present invention becomes more remarkable.
Although the specific example of the repeating unit represented by general formula (A1) below is given, it is not limited to these.

Next, the repeating unit represented by general formula (A2) is demonstrated.
X is hydrogen atom, alkyl group, hydroxyl group, alkoxy group, halogen atom, cyano group, nitro group, acyl group, acyloxy group, cycloalkyl group, cycloalkyloxy group, aryl group, carboxy group, alkyl as described above. An oxycarbonyl group, an alkylcarbonyloxy group or an aralkyl group is represented.

  The alkyl group as X may have a substituent, and may be linear or branched. As a linear alkyl group, Preferably it is C1-C30, More preferably, it is 1-20, For example, a methyl group, an ethyl group, n-propyl group, n-butyl group, sec-butyl group, t-butyl Group, n-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, n-nonyl group, n-decanyl group and the like. As a branched alkyl group, Preferably it is C3-C30, More preferably, it is 3-20, for example, i-propyl group, i-butyl group, t-butyl group, i-pentyl group, t-pentyl group, Examples include i-hexyl group, t-hexyl group, i-heptyl group, t-heptyl group, i-octyl group, t-octyl group, i-nonyl group, t-decanoyl group and the like.

  The alkoxy group as X may have a substituent, for example, the above alkoxy group having 1 to 8 carbon atoms, for example, a methoxy group, an ethoxy group, a propoxy group, a butoxy group, a pentyloxy group, a hexyloxy group. And a cyclohexyloxy group.

  Examples of the halogen atom as X include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom, and a fluorine atom is preferred.

  The acyl group as X may have a substituent, for example, an acyl group having 2 to 8 carbon atoms, specifically, a formyl group, an acetyl group, a propanoyl group, a butanoyl group, a pivaloyl group. Preferred examples include benzoyl group.

  The acyloxy group as X may have a substituent, and is preferably an acyloxy group having 2 to 8 carbon atoms. For example, an acetoxy group, a propionyloxy group, a butyllioxy group, a valeryloxy group, a pivaloyloxy group, hexanoyl An oxy group, an octanoyloxy group, a benzoyloxy group, etc. can be mentioned.

  The cycloalkyl group as X may have a substituent, may be monocyclic, polycyclic, or bridged. For example, the cycloalkyl group may have a bridged structure. The monocyclic type is preferably a cycloalkyl group having 3 to 8 carbon atoms, and examples thereof include a cyclopropyl group, a cyclopentyl group, a cyclohexyl group, a cyclobutyl group, and a cyclooctyl group. Examples of the polycyclic type include groups having a bicyclo, tricyclo, tetracyclo structure or the like having 5 or more carbon atoms, and a cycloalkyl group having 6 to 20 carbon atoms is preferable. For example, an adamantyl group, norbornyl group, isobornyl group, Examples thereof include a camphanyl group, a dicyclopentyl group, an α-pinanyl group, a tricyclodecanyl group, a tetocyclododecyl group, and an androstanyl group. A part of carbon atoms in the cycloalkyl group may be substituted with a hetero atom such as an oxygen atom.

  The aryl group as X may have a substituent, and preferably has 6 to 14 carbon atoms, and examples thereof include a phenyl group, a xylyl group, a toluyl group, a cumenyl group, a naphthyl group, and an anthracenyl group. .

  The alkyloxycarbonyl group as X may have a substituent, and preferably has 2 to 8 carbon atoms, and examples thereof include a methoxycarbonyl group, an ethoxycarbonyl group, and a propoxycarbonyl group.

  The alkylcarbonyloxy group as X may have a substituent, and preferably has 2 to 8 carbon atoms, and examples thereof include a methylcarbonyloxy group and an ethylcarbonyloxy group.

  The aralkyl group as X may have a substituent and is preferably an aralkyl group having 7 to 16 carbon atoms, for example, a benzyl group.

  Substituents that the alkyl group, alkoxy group, acyl group, cycloalkyl group, aryl group, alkyloxycarbonyl group, alkylcarbonyloxy group, aralkyl group as X may further have include a hydroxyl group, a fluorine atom, chlorine Atom, bromine atom, iodine atom, alkyl group, hydroxyl group, alkoxy group, halogen atom, cyano group, nitro group, acyl group, acyloxy group, cycloalkyl group, aryl group, carboxyl group, alkyloxycarbonyl group, alkylcarbonyloxy group Or an aralkyl group etc. are mentioned.

T represents a single bond or a divalent linking group as described above.
Examples of the divalent linking group for T include an alkylene group, —COO—Rt— group, —O—Rt— group, and the like. In the formula, Rt represents an alkylene group or a cycloalkylene group.
T is preferably a single bond or a —COO—Rt— group. Rt is preferably an alkylene group having 1 to 5 carbon atoms, more preferably a —CH ₂ — group or a — (CH ₂ ) ₃ — group.

A ₂ represents a group capable of leaving by the action of an acid as described above. That is, the repeating unit represented by the general formula (A2) includes a group represented by “—COOA ₂ ” as an acid-decomposable group. The A _2, for example, those previously described for A ₁ in the general formula (A1) similar to the.

A ₂ is preferably a hydrocarbon group (preferably having a carbon number of 20 or less, more preferably 4 to 12), and a t-butyl group, a t-amyl group, or a hydrocarbon group having an alicyclic structure (for example, an alicyclic ring). The group itself and a group in which an alicyclic group is substituted on the alkyl group) are more preferable.
A ₂ is preferably a tertiary alkyl group or a tertiary cycloalkyl group.

The alicyclic structure may be monocyclic or polycyclic. Specific examples include monocyclo, bicyclo, tricyclo, and tetracyclo structures having 5 or more carbon atoms. The carbon number is preferably 6-30, and particularly preferably 7-25. These hydrocarbon groups having an alicyclic structure may have a substituent.
Examples of the alicyclic structure include the alicyclic structures (1) to (50) listed as examples of the cycloalkyl group of Z _ka in the general formula (KA-1) in the above resin (Aa). . Further, specific examples of preferable alicyclic structures and specific examples of substituents that the alicyclic structures may have are the same as the specific examples described in the alicyclic structures as Z _ka in the general formula (KA-1). Examples are given.

As the acid-decomposable group having an alicyclic structure, groups represented by the following general formula (pI) to general formula (pV) are preferable.

In the general formulas (pI) to (pV),
R ₁₁ represents a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group or a sec-butyl group, and Z forms an alicyclic hydrocarbon group together with a carbon atom. Represents the necessary atomic group.

R _{12 to} R ₁₆ each independently represents a linear or branched alkyl group or alicyclic hydrocarbon group having 1 to 4 carbon atoms, provided that at least one of R _{12 to} R ₁₄ , or Either R ₁₅ or R ₁₆ represents an alicyclic hydrocarbon group.

R _{17 to} R ₂₁ each independently represents a hydrogen atom, a linear or branched alkyl group having 1 to 4 carbon atoms, or an alicyclic hydrocarbon group, provided that at least one of R _{17 to} R ₂₁ Represents an alicyclic hydrocarbon group. Further, either R ₁₉ or R ₂₁ represents a linear or branched alkyl group or alicyclic hydrocarbon group having 1 to 4 carbon atoms.

R _{22 to} R ₂₅ each independently represents a hydrogen atom, a linear or branched alkyl group having 1 to 4 carbon atoms, or an alicyclic hydrocarbon group, provided that at least one of R _{22 to} R ₂₅ Represents an alicyclic hydrocarbon group. R ₂₃ and R ₂₄ may be bonded to each other to form a ring.

In the general formulas (pI) to (pV), the alkyl group in R _{12 to} R ₂₅ may be either substituted or unsubstituted, and a linear or branched alkyl group having 1 to 4 carbon atoms Represents. Examples of the alkyl group include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, and a t-butyl group.

  Further, the further substituent of the alkyl group includes an alkoxy group having 1 to 4 carbon atoms, a halogen atom (a fluorine atom, a chlorine atom, a bromine atom, an iodine atom), an acyl group, an acyloxy group, a cyano group, a hydroxyl group, A carboxy group, an alkoxycarbonyl group, a nitro group, etc. can be mentioned.

Examples of the alicyclic hydrocarbon group in R _{11 to} R _{25 or} the alicyclic hydrocarbon group formed by Z and a carbon atom include those described above as the alicyclic structure.

In one embodiment, the repeating unit represented by the general formula (A2) is preferably a repeating unit represented by the following formula.

Moreover, the repeating unit represented by the general formula (A2) is preferably a repeating unit represented by the following general formula (A3) in another embodiment.

In general formula (A3),
AR represents an aryl 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.
R represents a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, a cyano group or an alkyloxycarbonyl group.
The repeating unit represented by formula (A3) will be described in detail.
AR represents an aryl group as described above. The aryl group for AR is preferably a group having 6 to 20 carbon atoms such as a phenyl group, a naphthyl group, an anthryl group, or a fluorene group, and more preferably a group having 6 to 15 carbon atoms.

  When AR is a naphthyl group, anthryl group, or fluorene group, the bonding position between the carbon atom to which Rn is bonded and AR is not particularly limited. For example, when AR is a naphthyl group, this carbon atom may be bonded to the α-position of the naphthyl group or may be bonded to the β-position. Alternatively, when AR is an anthryl group, this carbon atom may be bonded to the 1-position, the 2-position, or the 9-position of the anthryl group.

  The aryl group as AR may have one or more substituents. Specific examples of such substituents include, for example, methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, isobutyl group, t-butyl group, pentyl group, hexyl group, octyl group and dodecyl group. A linear or branched alkyl group having 1 to 20 carbon atoms, an alkoxy group containing these alkyl group parts, a cycloalkyl group such as a cyclopentyl group and a cyclohexyl group, a cycloalkoxy group containing these cycloalkyl group parts, a hydroxyl group , Halogen atom, aryl group, cyano group, nitro group, acyl group, acyloxy group, acylamino group, sulfonylamino group, alkylthio group, arylthio group, aralkylthio group, thiophenecarbonyloxy group, thiophenemethylcarbonyloxy group, and pyrrolidone residue And heterocyclic residues such as groups. As this substituent, a linear or branched alkyl group having 1 to 5 carbon atoms and an alkoxy group containing the alkyl group portion are preferable, and a paramethyl group or a paramethoxy group is more preferable.

  When the aryl group as AR has a plurality of substituents, at least two of the plurality of substituents may be bonded to each other to form a ring. The ring is preferably a 5- to 8-membered ring, and more preferably a 5- or 6-membered ring. Moreover, this ring may be a heterocycle containing a heteroatom such as an oxygen atom, a nitrogen atom, or a sulfur atom as a ring member.

  Furthermore, this ring may have a substituent. As this substituent, the thing similar to what is mentioned later about the further substituent which Rn may have is mentioned.

  Moreover, it is preferable that the repeating unit represented by general formula (A3) contains two or more aromatic rings from a viewpoint of roughness performance. The number of aromatic rings contained in this repeating unit is usually preferably 5 or less, and more preferably 3 or less.

  In the repeating unit represented by formula (A3), from the viewpoint of roughness performance, AR preferably contains two or more aromatic rings, and AR is more preferably a naphthyl group or a biphenyl group. . The number of aromatic rings possessed by AR is usually preferably 5 or less, and more preferably 3 or less.

As described above, Rn represents an alkyl group, a cycloalkyl group, or an aryl group.
The alkyl group of Rn may be a straight chain alkyl group or a branched chain alkyl group. The alkyl group is preferably a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a t-butyl group, a pentyl group, a hexyl group, a cyclohexyl group, an octyl group or a dodecyl group. A thing with 1-20 carbon atoms is mentioned. The alkyl group of Rn preferably has 1 to 5 carbon atoms, and more preferably has 1 to 3 carbon atoms.

  Examples of the cycloalkyl group represented by Rn include those having 3 to 15 carbon atoms such as a cyclopentyl group and a cyclohexyl group.

  As the aryl group of Rn, for example, those having 6 to 14 carbon atoms such as phenyl group, xylyl group, toluyl group, cumenyl group, naphthyl group and anthryl group are preferable.

  Each of the alkyl group, cycloalkyl group and aryl group as Rn may further have a substituent. Examples of the substituent include an alkoxy group, a hydroxyl group, a halogen atom, a nitro group, an acyl group, an acyloxy group, an acylamino group, a sulfonylamino group, a dialkylamino group, an alkylthio group, an arylthio group, an aralkylthio group, and a thiophenecarbonyloxy group. , Thiophenemethylcarbonyloxy group, and heterocyclic residues such as pyrrolidone residues. Among these, an alkoxy group, a hydroxyl group, a halogen atom, a nitro group, an acyl group, an acyloxy group, an acylamino group, and a sulfonylamino group are particularly preferable.

  As described above, R represents a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, a cyano group or an alkyloxycarbonyl group.

  Examples of the alkyl group and cycloalkyl group of R include the same as those described above for Rn. Each of these alkyl groups and cycloalkyl groups may have a substituent. Examples of this substituent include the same as those described above for Rn.

  When R is an alkyl group or a cycloalkyl group having a substituent, particularly preferable R is, for example, a trifluoromethyl group, an alkyloxycarbonylmethyl group, an alkylcarbonyloxymethyl group, a hydroxymethyl group, or an alkoxymethyl group. Can be mentioned.

  Examples of the halogen atom for R include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. Among these, a fluorine atom is particularly preferable.

  As the alkyl group moiety contained in the alkyloxycarbonyl group of R, for example, the configuration described above as the alkyl group of R can be employed.

Rn and AR are preferably bonded to each other to form a non-aromatic ring, and in particular, roughness performance can be further improved.
The non-aromatic ring that may be formed by bonding Rn and AR to each other is preferably a 5- to 8-membered ring, more preferably a 5- or 6-membered ring.

The non-aromatic ring may be an aliphatic ring or a heterocycle containing a hetero atom such as an oxygen atom, a nitrogen atom, or a sulfur atom as a ring member.
The non-aromatic ring may have a substituent. As this substituent, the thing similar to having demonstrated previously about the further substituent which Rn may have is mentioned, for example.
Although the specific example of the monomer corresponding to the repeating unit represented by general formula (A2) and the specific example of this repeating unit are given to the following, it is not limited to these.

Although the specific example of the structure of the repeating unit represented by general formula (A3) below is given, it is not limited to these.

Especially, the repeating unit shown below is more preferable.

  In one embodiment, the repeating unit represented by formula (A2) is preferably a repeating unit of t-butyl methacrylate or ethylcyclopentyl methacrylate.

  The monomer corresponding to the repeating unit represented by the general formula (A2) includes (meth) acrylic acid chloride and an alcohol compound in a solvent such as THF, acetone and methylene chloride, and a basic catalyst such as triethylamine, pyridine and DBU. It can be synthesized by esterification below. A commercially available product may be used.

The resin (Ab) may further contain a repeating unit represented by the following general formula (A5).

In formula (A5),
X is a hydrogen atom, alkyl group, hydroxyl group, alkoxy group, halogen atom, cyano group, nitro group, acyl group, acyloxy group, cycloalkyl group, aryl group, carboxyl group, alkyloxycarbonyl group, alkylcarbonyloxy group, or Represents an aralkyl group and is the same as X in formula (A2b).
A ₄ represents a hydrocarbon group that is not eliminated by the action of an acid.

In the general formula (A5), examples of the hydrocarbon group that is not eliminated by the action of the acid A ₄ include hydrocarbon groups other than the acid-decomposable groups, such as an alkyl that is not eliminated by the action of the acid. A group (preferably having 1 to 15 carbon atoms), a cycloalkyl group (preferably having 3 to 15 carbon atoms) which is not eliminated by the action of an acid, an aryl group (preferably having 6 to 15 carbon atoms) which is not eliminated by the action of an acid Can be mentioned.

The hydrocarbon group that is not eliminated by the action of the acid of A ₄ may be further substituted with a hydroxyl group, an alkyl group, a cycloalkyl group, an aryl group, or the like.

It is also preferred that the resin (Ab) further has a repeating unit represented by the general formula (A6).

In general formula (A6),
R ₂ represents a hydrogen atom, a methyl group, a cyano group, a halogen atom, or a perfluoro group having 1 to 4 carbon atoms.
R ₃ represents a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, an aryl group, an alkoxy group or an acyl group.
q represents an integer of 0 to 4.
Ar represents a q + 2 valent aromatic ring.
W represents a group or a hydrogen atom that is not decomposed by the action of an acid.

  As the aromatic ring represented by Ar, a benzene ring, a naphthalene ring and an anthracene ring are preferable, and a benzene ring is more preferable.

  W represents a group that is not decomposed by the action of an acid (also referred to as an acid-stable group), and examples include groups other than the above-mentioned acid-decomposable groups. Specifically, a halogen atom, an alkyl group, a cycloalkyl group, an alkenyl group, An aryl group, an acyl group, an alkylamide group, an arylamidomethyl group, an arylamide group, etc. are mentioned. The acid stabilizing group is preferably an acyl group or an alkylamide group, more preferably an acyl group, an alkylcarbonyloxy group, an alkyloxy group, a cycloalkyloxy group, or an aryloxy group.

In the acid stable group of W, the alkyl group is preferably an alkyl group having 1 to 4 carbon atoms such as methyl group, ethyl group, propyl group, n-butyl group, sec-butyl group and t-butyl group. As the alkyl group, those having 3 to 10 carbon atoms such as cyclopropyl group, cyclobutyl group, cyclohexyl group and adamantyl group are preferable, and as the alkenyl group, carbon number such as vinyl group, propenyl group, allyl group and butenyl group. Those having 2 to 4 carbon atoms are preferable, those having 2 to 4 carbon atoms such as vinyl group, propenyl group, allyl group and butenyl group are preferable as alkenyl groups, and phenyl group, xylyl group and toluyl group are preferable as aryl groups. And those having 6 to 14 carbon atoms such as cumenyl group, naphthyl group and anthracenyl group are preferable. W may be at any position on the benzene ring, but is preferably a meta position or a para position of the styrene skeleton, particularly preferably a para position.
Specific examples of the repeating unit represented by formula (A6) are shown below, but are not limited thereto.

The resin (Ab) preferably further has a repeating unit composed of a (meth) acrylic acid derivative that is not decomposed by the action of acid. Although a specific example is given below, it is not limited to this.

  The content of the repeating unit having an acid-decomposable group in the resin (Ab) is preferably 5 to 95 mol%, more preferably 10 to 60 mol%, and particularly preferably 15 to 50 mol% in all repeating units. It is.

The content of the repeating unit represented by the general formula (A1) in the resin (Ab) is preferably from 0 to 90 mol%, more preferably from 10 to 70 mol%, particularly preferably from 20 to 20 in all repeating units. 50 mol%.
The content of the repeating unit represented by the general formula (A2) in the resin (Ab) is preferably 0 to 90 mol%, more preferably 5 to 75 mol%, and particularly preferably 10 to 10 mol% in all repeating units. 60 mol%.

  The content of the repeating unit represented by the general formula (A3) in the resin (Ab) is preferably 0 to 90 mol%, more preferably 5 to 75 mol%, and particularly preferably 10 to 10 mol% in all repeating units. 60 mol%.

  The content of the repeating unit represented by the general formula (A5) in the resin (Ab) is preferably 0 to 50 mol%, more preferably 0 to 40 mol%, and particularly preferably 0 to 40 mol% in all repeating units. 30 mol%.

  The resin (Ab) may further have a repeating unit represented by the general formula (A6), which is preferable from the viewpoints of improving the film quality and suppressing the decrease in the film thickness of the unexposed area. The content of the repeating unit represented by the general formula (A5) is preferably 0 to 50 mol%, more preferably 0 to 40 mol%, and particularly preferably 0 to 40 mol% in each of all the repeating units. 30 mol%.

  In addition, the resin (Ab) is copolymerized with other polymerizable monomers suitable so that an alkali-soluble group such as a phenolic hydroxyl group or a carboxyl group can be introduced in order to maintain good developability for an alkali developer. In order to improve the film quality, other hydrophobic polymerizable monomers such as alkyl acrylate and alkyl methacrylate may be copolymerized.

  The monomer corresponding to the repeating unit represented by the general formula (A2) includes (meth) acrylic acid chloride and an alcohol compound in a solvent such as THF, acetone and methylene chloride, and a basic catalyst such as triethylamine, pyridine and DBU. It can be synthesized by esterification below. A commercially available product may be used.

  The monomer corresponding to the repeating unit represented by the general formula (A1) is a hydroxy-substituted styrene monomer and a vinyl ether compound in a solvent such as THF and methylene chloride, such as p-toluenesulfonic acid and p-toluenesulfonic acid pyridine salt. It can be synthesized by acetalization in the presence of an acidic catalyst or by t-Boc protection using t-butyl dicarbonate in the presence of a basic catalyst such as triethylamine, pyridine, DBU or the like. A commercially available product may be used.

The resin (Ab) preferably has a repeating unit represented by the following general formula (A).

In the above general formula,
R ₂₁ , R ₂₂ and R ₂₃ each independently represents a hydrogen atom, an alkyl group, a halogen atom, a cyano group or an alkoxycarbonyl group. However, R ₂₂ may be bonded to Ar ₂ to form a ring, in which case R ₂₂ represents a single bond or an alkylene group.

X ₂ represents a single bond, —COO—, or —CONR ₃₀ —, and R ₃₀ represents a hydrogen atom or an alkyl group.

L ₂ represents a single bond or an alkylene group.

Ar ₂ represents an (n + 1) -valent aromatic ring group, and represents an (n + 2) -valent aromatic ring group when bonded to R ₂₂ to form a ring.

  n represents an integer of 1 to 4.

The alkyl group of R ₂₁ , R ₂₂ and R ₂₃ in the general formula (A) is preferably a methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, sec, which may have a substituent. -Alkyl groups having 20 or less carbon atoms such as butyl group, hexyl group, 2-ethylhexyl group, octyl group and dodecyl group are mentioned, more preferably alkyl groups having 8 or less carbon atoms, particularly preferably alkyl groups having 3 or less carbon atoms. Is mentioned.

As the alkyl group contained in the alkoxycarbonyl group, the same alkyl groups as those described above for R ₂₁ , R ₂₂ and R ₂₃ are preferable.

  Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom, and a fluorine atom is particularly preferable.

  Preferred substituents in each of the above groups include, for example, alkyl groups, cycloalkyl groups, aryl groups, amino groups, amide groups, ureido groups, urethane groups, hydroxyl groups, carboxyl groups, halogen atoms, alkoxy groups, thioether groups, acyls. Groups, acyloxy groups, alkoxycarbonyl groups, cyano groups, nitro groups and the like, and the substituent preferably has 8 or less carbon atoms.

Ar ₂ represents an (n + 1) -valent aromatic ring group. The divalent aromatic ring group in the case where n is 1 may have a substituent, for example, an arylene group having 6 to 18 carbon atoms such as a phenylene group, a tolylene group, a naphthylene group, and an anthracenylene group, or Examples of preferred aromatic ring groups include heterocycles such as thiophene, furan, pyrrole, benzothiophene, benzofuran, benzopyrrole, triazine, imidazole, benzimidazole, triazole, thiadiazole, thiazole.

  Specific examples of the (n + 1) -valent aromatic ring group in the case where n is an integer of 2 or more include (n-1) arbitrary hydrogen atoms removed from the above-described specific examples of the divalent aromatic ring group. The group formed can be preferably mentioned.

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

_-CONR 30 represented by X ₂ - _{(R 30} represents a hydrogen atom, an alkyl group) The alkyl group for _{R 30 in,} the same as the alkyl group of R 21 _{to R 23.}

X ₂ is preferably a single bond, —COO—, or —CONH—, and more preferably a single bond or —COO—.

The alkylene group for L ₂ is preferably an alkylene group having 1 to 8 carbon atoms, such as an optionally substituted methylene group, ethylene group, propylene group, butylene group, hexylene group, and octylene group.

Ar ₂ is more preferably an aromatic ring group having 6 to 18 carbon atoms which may have a substituent, and particularly preferably a benzene ring group, a naphthalene ring group or a biphenylene ring group.

This repeating unit preferably has a hydroxystyrene structure. That is, Ar ₂ is preferably a benzene ring group.

Specific examples of the repeating unit represented by formula (A) are shown below, but the present invention is not limited thereto. In the formula, a represents 1 or 2.

The repeating unit represented by the general formula (A) is preferably a repeating unit represented by the following formula (Ab1) or Ab2), and more preferably a repeating unit represented by the formula (A1). .

Wherein _{(Ab2), R 23} has the same meaning as _{R 23} in the general formula (A).
The resin (Ab) may contain two or more types of repeating units represented by the general formula (A).

In one embodiment, the resin (Ab) preferably contains a repeating unit represented by the following general formula (Ab3).

  In the formula, n represents an integer of 1 to 5, and m represents an integer of 0 to 4 that satisfies the relationship 1 ≦ m + n ≦ 5. n is preferably 1 or 2, more preferably 1. m is preferably 0 to 2, more preferably 0 or 1, and particularly preferably 0.

S ₁ represents a substituent. When m is 2 or more, the plurality of S ₁ may be the same as or different from each other.
Examples of the substituent represented by S ₁ include an alkyl group, an alkoxy group, an acyl group, an acyloxy group, an aryl group, an aryloxy group, an aralkyl group, an aralkyloxy group, a hydroxy group, a halogen atom, a cyano group, and a nitro group. , A sulfonylamino group, an alkylthio group, an arylthio group, and an aralkylthio group.

  For example, as an alkyl group and a cycloalkyl group, a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a t-butyl group, a pentyl group, a cyclopentyl group, a hexyl group, a cyclohexyl group, an octyl group, A linear or branched alkyl group having 1 to 20 carbon atoms such as a dodecyl group or a cycloalkyl group is preferable. These groups may further have a substituent.

  Further preferred substituents that may be included are alkyl group, alkoxy group, hydroxyl group, halogen atom, nitro group, acyl group, acyloxy group, acylamino group, sulfonylamino group, alkylthio group, arylthio group, aralkylthio group, thiophenecarbonyloxy Group, a thiophenemethylcarbonyloxy group, a heterocyclic residue such as a pyrrolidone residue, and the like, and a substituent having 12 or less carbon atoms is preferable.

  Examples of the alkyl group having a substituent include a cyclohexylethyl group, an alkylcarbonyloxymethyl group, an alkylcarbonyloxyethyl group, a cycloalkylcarbonyloxymethyl group, a cycloalkylcarbonyloxyethyl group, an arylcarbonyloxyethyl group, and an aralkylcarbonyloxyethyl group. , Alkyloxymethyl group, cycloalkyloxymethyl group, aryloxymethyl group, aralkyloxymethyl group, alkyloxyethyl group, cycloalkyloxyethyl group, aryloxyethyl group, aralkyloxyethyl group, alkylthiomethyl group, cycloalkylthiomethyl Group, arylthiomethyl group, aralkylthiomethyl group, alkylthioethyl group, cycloalkylthioethyl group, arylthioethyl group, aralkyl Oechiru group, and the like.

  The alkyl group and cycloalkyl group in these groups are not particularly limited, and may further have a substituent such as the aforementioned alkyl group, cycloalkyl group, or alkoxy group.

  Examples of the alkylcarbonyloxyethyl group and cycloalkylcarbonyloxyethyl group include cyclohexylcarbonyloxyethyl group, t-butylcyclohexylcarbonyloxyethyl group, n-butylcyclohexylcarbonyloxyethyl group, and the like.

The aryl group is not particularly limited, but generally includes those having 6 to 14 carbon atoms such as a phenyl group, a xylyl group, a toluyl group, a cumenyl group, a naphthyl group, an anthracenyl group, and the above-mentioned alkyl groups and cycloalkyl groups. And may have a substituent such as an alkoxy group.
Examples of the aryloxyethyl group include a phenyloxyethyl group, a cyclohexylphenyloxyethyl group, and the like. These groups may further have a substituent.

Aralkyl is not particularly limited, and examples thereof include a benzyl group.
Examples of the aralkylcarbonyloxyethyl group include a benzylcarbonyloxyethyl group. These groups may further have a substituent.

Examples of the repeating unit represented by the general formula (Ab3) include the following.

In one embodiment, the resin (Ab) contains at least a repeating unit represented by the following formula as the repeating unit represented by the general formula (Ab3).

  The content of the repeating unit represented by the general formula (A) in the resin (Ab) (the total when there are plural types) is high resolution, sensitivity, PEB temperature dependency and dry etching resistance, and good pattern shape. Is more preferably from 10 mol% to 75 mol%, and more preferably from 15 mol% to 70 mol%, based on all the repeating units in the resin (Ab). More preferably, it is 20 mol% or more and 65 mol% or less.

  The content of the repeating unit represented by the general formula (Ab3) in the resin (Ab) is preferably 0 to 90 mol%, more preferably 5 to 80 mol%, based on all repeating units in the resin (Ab). More preferably, it is 10-70 mol%, Most preferably, it is 20-60 mol%.

The resin (Ab) preferably has a repeating unit represented by the following general formula. In the following general formula, j represents an integer of 0 to 3, preferably an integer of 0 to 2, and more preferably 0 or 1.

Specific examples of the repeating unit represented by these general formulas include the following.

In one embodiment, the resin (Ab) is a repeating unit (B) (hereinafter referred to as “acid generating repeating unit (B)” or “repeating” having a structural site that decomposes upon irradiation with actinic rays or radiation to generate an acid. Unit (B) ”).
This structural site may be, for example, a structural site that generates an acid anion in the repeating unit (B) by being decomposed by irradiation with an actinic ray or radiation, or the repeating unit (B ) May be a structural site that generates a cation structure.

  Moreover, it is preferable that this structure site | part is an ionic structure site | part provided with the sulfonium salt structure or the iodonium salt structure, for example.

  This structural site may be, for example, a structural site similar to the structural site represented by A in the general formulas (B1), (B2), and (B3) described below.

In one aspect, the repeating unit (B) is preferably at least one selected from the group consisting of repeating units represented by the following general formulas (B1), (B2), and (B3). Among these, the repeating unit represented by the following general formula (B1) or (B3) is more preferable, and the repeating unit represented by the following general formula (B1) is particularly preferable.

In general formulas (B1), (B2) and (B3),
A represents a structural site that decomposes upon irradiation with actinic rays or radiation to generate an acid anion.
R ₀₄ , R ₀₅ and R _{07 to} R ₀₉ each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, a cyano group or an alkoxycarbonyl group.
R ₀₆ represents a cyano group, a carboxy group, —CO—OR ₂₅ or —CO—N (R ₂₆ ) (R ₂₇ ). R ₂₅ represents an alkyl group, a cycloalkyl group, an alkenyl group, a cycloalkenyl group, an aryl group or an aralkyl group. R ₂₆ and R ₂₇ each independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, an alkenyl group, a cycloalkenyl group, an aryl group or an aralkyl group. R ₂₆ and R ₂₇ may be bonded to each other to form a ring together with the nitrogen atom.

X ₁ , X ₂ and X ₃ are each independently a single bond, an arylene group, an alkylene group, a cycloalkylene group, —O—, —SO ₂ —, —CO—, —N (R ₃₃ ) —, or these Represents a divalent linking group in combination of a plurality. R ₃₃ represents a hydrogen atom, an alkyl group, a cycloalkyl group, an alkenyl group, a cycloalkenyl group, an aryl group or an aralkyl group.

The alkyl group of R _{04, R 05} and _R 07 _{to R 09,} preferably one having 20 or less carbon atoms, more preferably those having a carbon number of 8 or less. Examples of such an alkyl group include a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, a hexyl group, a 2-ethylhexyl group, an octyl group, and a dodecyl group. These alkyl groups may further have a substituent.

The cycloalkyl group of R ₀₄ , R ₀₅ and R _{07 to} R ₀₉ may be monocyclic or polycyclic. As this cycloalkyl group, a C3-C8 thing is preferable. Examples of such a cycloalkyl group include a cyclopropyl group, a cyclopentyl group, and a cyclohexyl group.

Examples of the halogen atom for R ₀₄ , R ₀₅ and R _{07 to} R ₀₉ include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. Of these, a fluorine atom is particularly preferable.

As the alkyl group contained in the alkoxycarbonyl group of R ₀₄ , R ₀₅ and R _{07 to} R ₀₉ , for example, those exemplified above as the alkyl group of R ₀₄ , R ₀₅ and R _{07 to} R ₀₉ are preferable.

As the alkyl group for R _{25 to} R ₂₇ and R ₃₃ , for example, those exemplified above as the alkyl groups for R ₀₄ , R ₀₅ and R _{07 to} R ₀₉ are preferable.
As the cycloalkyl group represented by R _{25 to} R ₂₇ and R ₃₃ , for example, those exemplified above as the cycloalkyl groups represented by R ₀₄ , R ₀₅ and R _{07 to} R ₀₉ are preferable.

The alkenyl group of R ₂₅ to R ₂₇ and _{R 33,} preferably having a carbon number of 2-6. Examples of such an alkenyl group include a vinyl group, a propenyl group, an allyl group, a butenyl group, a pentenyl group, and a hexenyl group.

The cycloalkenyl group R ₂₅ to R ₂₇ and _{R 33,} preferably having a carbon number of 3-6. Examples of such a cycloalkenyl group include a cyclohexenyl group.

The aryl group represented by R _{25 to} R ₂₇ and R ₃₃ may be a monocyclic aromatic group or a polycyclic aromatic group. As this aryl group, a C6-C14 thing is preferable. This aryl group may further have a substituent. In addition, aryl groups may be bonded to each other to form a multicycle. Examples of the aryl group of R _{25 to} R ₂₇ and R ₃₃ include a phenyl group, a tolyl group, a chlorophenyl group, a methoxyphenyl group, and a naphthyl group.

As the aralkyl group of R _{25 to} R ₂₇ and R ₃₃ , those having 7 to 15 carbon atoms are preferable. This aralkyl group may further have a substituent. Examples of the aralkyl group of R _{25 to} R ₂₇ and R ₃₃ include a benzyl group, a phenethyl group, and a cumyl group.

The ring formed by combining R ₂₆ and R ₂₇ together with the nitrogen atom is preferably a 5- to 8-membered ring, and specific examples include pyrrolidine, piperidine, and piperazine.

The arylene group X ₁ to X _3, preferably having a carbon number of 6-14. Examples of such an arylene group include a phenylene group, a tolylene group, and a naphthylene group. These arylene groups may further have a substituent.

Examples of the alkylene group of X ₁ to X _3, preferably having a carbon number of 1-8. Examples of such an alkylene group include a methylene group, an ethylene group, a propylene group, a butylene group, a hexylene group, and an octylene group. These alkylene groups may further have a substituent.

The cycloalkylene group X ₁ to X _3, is preferably from 5 to 8 carbon atoms. Examples of such a cycloalkylene group include a cyclopentylene group and a cyclohexylene group. These cycloalkylene groups may further have a substituent.

  Preferred substituents that each group in the general formulas (B1) to (B3) may have include, for example, a hydroxyl group; a halogen atom (fluorine, chlorine, bromine, iodine); a nitro group; a cyano group; an amide group; Groups; alkyl groups as R04, R05 and R07 to R09; alkoxy groups such as methoxy, ethoxy, hydroxyethoxy, propoxy, hydroxypropoxy and butoxy; methoxycarbonyl and ethoxycarbonyl An alkoxy group such as a formyl group, an acetyl group and a benzoyl group; an acyloxy group such as an acetoxy group and a butyryloxy group; and a carboxy group. These substituents preferably have 8 or less carbon atoms.

  A represents a structural site that decomposes upon irradiation with actinic rays or radiation to generate an acid anion. Specifically, photoinitiator of photocationic polymerization, photoinitiator of photoradical polymerization, photodecoloration of pigments Examples thereof include structural sites possessed by compounds that generate acid by known light used in agents, photochromic agents, and microresists.

Moreover, as A, the ionic structure site | part provided with the sulfonium salt structure or the iodonium salt structure is more preferable. More specifically, A is preferably a group represented by the following general formula (ZI) or (ZII).

In general formula (ZI),
R ₂₀₁ , R ₂₀₂ and R ₂₀₃ each independently represents an organic group.
The carbon number of the organic group as R ₂₀₁ , R ₂₀₂ and R ₂₀₃ is generally 1-30, preferably 1-20. Two of R _{201 to} R ₂₀₃ may be bonded to form a ring structure, and the ring may contain an oxygen atom, a sulfur atom, an ester bond, an amide bond, or a carbonyl group. Examples of the group formed by combining two of R _{201 to} R ₂₀₃ include alkylene groups such as a butylene group and a pentylene group.

Z ⁻ represents an acid anion generated by decomposition upon irradiation with actinic rays or radiation. Z ⁻ is preferably a non-nucleophilic anion. Examples of the non-nucleophilic anion include a sulfonate anion, a carboxylate anion, a sulfonylimide anion, a bis (alkylsulfonyl) imide anion, and a tris (alkylsulfonyl) methyl anion.

  The non-nucleophilic anion means an anion having an extremely low ability to cause a nucleophilic reaction. When a non-nucleophilic anion is used, degradation with time due to intramolecular nucleophilic reaction can be suppressed. This makes it possible to improve the temporal stability of the resin and the composition.

Examples of the organic group for R ₂₀₁ , R ₂₀₂ and R ₂₀₃ include corresponding groups in the groups represented by (ZI-1), (ZI-2) and (ZI-3) described later.

  More preferable examples of the group represented by (ZI) include the (ZI-1) group, (ZI-2) group, (ZI-3) group and (ZI-4) group described below.

The (ZI-1) group is a group having an arylsulfonium as a cation, wherein at least one of R _{201 to} R ₂₀₃ in the general formula (ZI) is an aryl group.

All of R _{201 to} R ₂₀₃ may be an aryl group, or a part of R _{201 to} R ₂₀₃ may be an aryl group, and the rest may be an alkyl group or a cycloalkyl group.

  Examples of the (ZI-1) group include groups corresponding to triarylsulfonium, diarylalkylsulfonium, aryldialkylsulfonium, diarylcycloalkylsulfonium, and aryldicycloalkylsulfonium.

  The aryl group in the arylsulfonium is preferably a phenyl group or a naphthyl group, and more preferably a phenyl group. The aryl group may have a heterocyclic structure containing a hetero atom such as an oxygen atom, a nitrogen atom and a sulfur atom. Examples of this heterocyclic structure include pyrrole, furan, thiophene, indole, benzofuran and benzothiophene. When arylsulfonium has two or more aryl groups, these aryl groups may be the same as or different from each other.

  The alkyl group or cycloalkyl group which arylsulfonium has as necessary is preferably a linear or branched alkyl group having 1 to 15 carbon atoms or a cycloalkyl group having 3 to 15 carbon atoms. Examples of such an alkyl group or cycloalkyl group include a methyl group, an ethyl group, a propyl group, an n-butyl group, a sec-butyl group, a t-butyl group, a cyclopropyl group, a cyclobutyl group, and a cyclohexyl group. .

The aryl group, alkyl group or cycloalkyl group of R _{201 to} R ₂₀₃ is an alkyl group (eg, having 1 to 15 carbon atoms), a cycloalkyl group (eg, having 3 to 15 carbon atoms), or an aryl group (eg, having 6 to 14 carbon atoms). , An alkoxy group (for example, having 1 to 15 carbon atoms), a halogen atom, a hydroxyl group or a phenylthio group may be substituted.

Preferred examples of the substituent include a linear or branched alkyl group having 1 to 12 carbon atoms, a cycloalkyl group having 3 to 12 carbon atoms, and a linear, branched or cyclic alkoxy group having 1 to 12 carbon atoms. It is done. More preferable substituents include, for example, an alkyl group having 1 to 4 carbon atoms and an alkoxy group having 1 to 4 carbon atoms. The substituent may be substituted with any one of the three R _{201 to} R ₂₀₃ , or may be substituted with two or more of these. _Also, when R 201 _{to R 203} is a phenyl group, these substituents are preferably substituted at the p- position of the phenyl group.

Next, the (ZI-2) group will be described.
The (ZI-2) group is a group in which R _{201 to} R ₂₀₃ in the general formula (ZI) each independently represents an organic group having no aromatic ring. Here, the aromatic ring includes a heterocycle containing a hetero atom.

The organic group not containing an aromatic ring as R _{201 to} R ₂₀₃ generally has 1 to 30 carbon atoms, preferably 1 to 20 carbon atoms.

R _{201 to} R ₂₀₃ are each independently preferably an alkyl group, a cycloalkyl group, an allyl group, or a vinyl group, and more preferably a linear or branched 2-oxoalkyl group, 2-oxocyclo group. An alkyl group or an alkoxycarbonylmethyl group, more preferably a linear or branched 2-oxoalkyl group.

The alkyl group and cycloalkyl group represented by R _{201 to} R ₂₀₃ are preferably a linear or branched alkyl group having 1 to 10 carbon atoms (for example, a methyl group, an ethyl group, a propyl group, a butyl group, or a pentyl group), and And a cycloalkyl group having 3 to 10 carbon atoms (for example, a cyclopentyl group, a cyclohexyl group, or a norbornyl group). More preferred examples of the alkyl group include a 2-oxoalkyl group and an alkoxycarbonylmethyl group. As the cycloalkyl group, a 2-oxocycloalkyl group is more preferable.

  The 2-oxoalkyl group may be linear or branched. As the 2-oxoalkyl group, a group having> C═O at the 2-position of the above alkyl group is preferable. As the 2-oxocycloalkyl group, a group having> C═O at the 2-position of the cycloalkyl group is preferably exemplified.

  The alkoxy group in the alkoxycarbonylmethyl group is preferably an alkoxy group having 1 to 5 carbon atoms (for example, a methoxy group, an ethoxy group, a propoxy group, a butoxy group, or a pentoxy group).

R _{201 to} R ₂₀₃ may be further substituted with, for example, a halogen atom, an alkoxy group (eg, having 1 to 5 carbon atoms), a hydroxyl group, a cyano group, or a nitro group.

Next, the (ZI-3) group will be described.
The (ZI-3) group is a group represented by the following general formula (ZI-3), which is a group having a phenacylsulfonium salt structure.

In General Formula (ZI-3), R _{1c to} R _5c each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, an alkoxy group, or a halogen atom.
R _6c and R _7c each independently represents a hydrogen atom, an alkyl group or a cycloalkyl group.
R _x and R _y each independently represents an alkyl group, a cycloalkyl group, an allyl group, or a vinyl group.

Two or more of R _{1c to} R _5c , R _6c and R _7c , and R _x and R _y may be bonded to each other to form a ring structure. This ring structure may contain an oxygen atom, a sulfur atom, an ester bond and / or an amide bond. Examples of the group formed by bonding these to each other include a butylene group and a pentylene group.

Zc ^- represents a non-nucleophilic anion, for example, Z in formula (ZI) ^- the same as the like.

  Specific examples of the structure of the cation moiety of the general formula (ZI-3) include acids exemplified in paragraphs 0047 and 0048 of JP-A No. 2004-233661 and paragraphs 0040 to 0046 of JP-A No. 2003-35948. See the structure of the cation moiety of the generator.

Subsequently, the (ZI-4) group will be described.
The (ZI-4) group is a group represented by the following general formula (ZI-4). This group is effective for suppressing outgas.

In General Formula (ZI-4), R _{1 to} R ₁₃ each independently represents a hydrogen atom or a substituent.
At least one of R _{1 to} R ₁₃ is preferably a substituent containing an alcoholic hydroxyl group. Here, “alcoholic hydroxyl group” means a hydroxyl group bonded to a carbon atom of an alkyl group.
Z is a single bond or a divalent linking group.
Z _c ⁻ represents a non-nucleophilic anion, and examples thereof include the same as Z ⁻ in the general formula (ZI).

When R _{1 to} R ₁₃ are substituents containing an alcoholic hydroxyl group, R _{1 to} R ₁₃ are preferably groups represented by — (WY). Here, Y is an alkyl group substituted with a hydroxyl group, and W is a single bond or a divalent linking group.

  Preferable examples of the alkyl group represented by Y include an ethyl group, a propyl group, and an isopropyl group. Y particularly preferably includes a structure represented by -CH2CH2OH.

  The divalent linking group represented by W is not particularly limited, but preferably a single bond, an alkoxy group, an acyloxy group, an acylamino group, an alkyl and arylsulfonylamino group, an alkylthio group, an alkylsulfonyl group, an acyl group, A divalent group in which an arbitrary hydrogen atom in an alkoxycarbonyl group or a carbamoyl group is replaced by a single bond, and more preferably an arbitrary hydrogen atom in a single bond, an acyloxy group, an alkylsulfonyl group, an acyl group or an alkoxycarbonyl group. It is a divalent group replaced by a single bond.

When R _{1 to} R ₁₃ are substituents containing an alcoholic hydroxyl group, the number of carbons contained is preferably 2 to 10, more preferably 2 to 6, and particularly preferably 2 to 4.

The substituent containing an alcoholic hydroxyl group as R _{1 to} R ₁₃ may have two or more alcoholic hydroxyl groups. R The number of alcoholic hydroxyl groups in substituent containing an alcoholic hydroxyl group as ₁ to R ₁₃ is a 1-6, preferably 1-3, more preferably 1.

The number of alcoholic hydroxyl groups contained in the (ZI-4) group is preferably 1 to 10, more preferably 1 to 6, more preferably 1 to 3 in total for all of R _{1 to} R _13. .

When R _{1 to} R ₁₃ do not contain an alcoholic hydroxyl group, R _{1 to} R ₁₃ are, for example, a hydrogen atom, a halogen atom, an alkyl group, a cycloalkyl group, an alkenyl group, a cycloalkenyl group, an alkynyl group, an aryl group, a complex Ring group, cyano group, nitro group, carboxy group, alkoxy group, aryloxy group, silyloxy group, heterocyclic oxy group, acyloxy group, carbamoyloxy group, alkoxycarbonyloxy group, aryloxycarbonyloxy group, amino group (anilino group) ), Ammonio group, acylamino group, aminocarbonylamino group, alkoxycarbonylamino group, aryloxycarbonylamino group, sulfamoylamino group, alkyl and arylsulfonylamino group, mercapto group, alkylthio group, arylthio group, complex Thio group, sulfamoyl group, sulfo group, alkyl and arylsulfinyl group, alkyl and arylsulfonyl group, acyl group, aryloxycarbonyl group, alkoxycarbonyl group, carbamoyl group, aryl and heterocyclic azo group, imide group, phosphino group, phosphinyl Group, phosphinyloxy group, phosphinylamino group, phosphono group, silyl group, hydrazino group, ureido group, boronic acid group [—B (OH) ₂ ], phosphato group [—OPO (OH) ₂ ], sulfato Examples include the group (—OSO ₃ H), as well as other known substituents.

When R _{1 to} R ₁₃ do not contain an alcoholic hydroxyl group, R _{1 to} R ₁₃ are preferably a hydrogen atom, a halogen atom, an alkyl group, a cycloalkyl group, a cyano group, an alkoxy group, an acyloxy group, an acylamino group, an amino group. A carbonylamino group, an alkoxycarbonylamino group, an alkyl and arylsulfonylamino group, an alkylthio group, a sulfamoyl group, an alkyl and arylsulfonyl group, an alkoxycarbonyl group or a carbamoyl group.

When R _{1 to} R ₁₃ do not contain an alcoholic hydroxyl group, R _{1 to} R ₁₃ are particularly preferably a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, or an alkoxy group.

Two adjacent ones of R _{1 to} R ₁₃ may be bonded to each other to form a ring structure. This ring structure includes aromatic and non-aromatic hydrocarbon rings and heterocycles. These ring structures may be further combined to form a condensed ring.

The (ZI-4) group preferably has a structure in which at least one of R _{1 to} R ₁₃ contains an alcoholic hydroxyl group, and more preferably at least one of R _{9 to} R ₁₃ is alcoholic. It has a structure containing a hydroxyl group.

  Z represents a single bond or a divalent linking group as described above. Examples of the divalent linking group include an alkylene group, an arylene group, a carbonyl group, a sulfonyl group, a carbonyloxy group, a carbonylamino group, a sulfonylamide group, an ether bond, a thioether bond, an amino group, a disulfide group, an acyl group, Examples thereof include an alkylsulfonyl group, -CH = CH-, an aminocarbonylamino group, and an aminosulfonylamino group.

This divalent linking group may have a substituent. Examples of these substituents include those similar to those listed above for R _{1 to} R ₁₃ .

  Z is preferably a single bond, an ether bond or a thioether bond, and particularly preferably a single bond.

Next, general formula (ZII) will be described.
In General Formula (ZII), R ₂₀₄ and R ₂₀₅ each independently represents an aryl group, an alkyl group, or a cycloalkyl group.
Specific examples and preferred embodiments of the aryl group, alkyl group and cycloalkyl group of R ₂₀₄ and R ₂₀₅ are the same as those described for R _{201 to} R ₂₀₃ in the aforementioned compound (ZI-1).

The aryl group, alkyl group, and cycloalkyl group of R ₂₀₄ and R ₂₀₅ may have a substituent. Even the substituent include the same as those described for _R 201 _{to R 203} in the compound of the aforementioned (ZI-1).

Z ⁻ represents an acid anion generated by decomposition upon irradiation with actinic rays or radiation, and is preferably a non-nucleophilic anion, and examples thereof include the same as Z ⁻ in formula (ZI).

Preferred examples of A also include groups represented by the following general formula (ZCI) or (ZCII).

In the above general formulas (ZCI) and (ZCII),
R ₃₀₁ and R ₃₀₂ each independently represents an organic group. The organic group generally has 1 to 30 carbon atoms, preferably 1 to 20 carbon atoms. R ₃₀₁ and R ₃₀₂ may be bonded to each other to form a ring structure. This ring structure may contain at least one of an oxygen atom, a sulfur atom, an ester bond, an amide bond and a carbonyl group in the ring. Examples of the group that can be formed by bonding R ₃₀₁ and R ₃₀₂ to each other include alkylene groups such as a butylene group and a pentylene group.

The organic group of R ₃₀₁ and _{R 302,} for example, aryl groups mentioned as examples of _R 201 _{to R 203} in formula (ZI), include alkyl groups and cycloalkyl groups.

  M represents an atomic group that forms an acid when a proton is added thereto. More specifically, a structure represented by any one of the general formulas AN1 to AN3 described later can be given. Of these, the structure represented by the general formula AN1 is particularly preferable.

R ₃₀₃ represents an organic group. The carbon number of the organic group as R ₃₀₃ is generally from 1 to 30, preferably 1 to 20. Specific examples of the organic group for R ₃₀₃ include an aryl group, an alkyl group, a cycloalkyl group, and the like given as specific examples of R ₂₀₄ and R ₂₀₅ in the general formula (ZII).

  Moreover, as a structural site | part which generate | occur | produces an acid by irradiation of actinic light or a radiation, the structural site | part used as the sulfonic acid precursor which the following photoacid generator has can be mentioned, for example. Examples of the photoacid generator include the following compounds (1) to (3).

(1) M.M. TUNOOKA et al. , PolymerPreprints Japan, 35 (8); Berneteral. , J .; Rad. Curing, 13 (4); J. et al. Mijsetal. , CoatingTechnol. 55
(697), 45 (1983); Adachietal. , Polymer Preprints, Japan, 37 (3); European Patent Nos. 0199,672, 84515, 199,672, 044,115, 0101,122, US Pat. Nos. 618,564, 4 , 371, 605, 4,431, 774, JP-A 64-18143, JP-A-2-245756, and JP-A-4-365048. A compound that generates sulfonic acid by photolysis, such as

(2) Disulfone compounds described in JP-A No. 61-166544.
(3) V. N. R. Pilla, Synthesis, (1), 1 (1980); Abadetal, Tetrahedron Lett. (47) 4555 (1971); H. R. Bartonetal. , J .; Chem. Soc. , (C), 329 (1970); U.S. Pat. No. 3,779,778; and European Patent No. 126,712 and the like.

  The repeating unit (B) preferably has a structural site that is converted to an acid anion by irradiation with actinic rays or radiation. For example, A in the general formulas (B1) to (B3) is preferably a structural site that is converted into an acid anion by irradiation with actinic rays or radiation.

  That is, it is more preferable that the repeating unit (B) has a structure in which an acid anion is generated in the side chain of the resin by irradiation with actinic rays or radiation. By adopting such a structure, the diffusion of the generated acid anions is suppressed, and the resolution and roughness characteristics can be further improved.

Formula sites _-X 1 -A in (B1), the general formula (B2) site _-X 2 -A in, and each of the sites _-X 3 -A in formula (B3), the following formula (L1), It is preferably represented by either (L2) or (L3).

_{-X 11 -L 11 -X 12 -Ar 1} -X 13 -L 12 -Z 1 (L1)
_{-Ar 2 -X 21 -L 21 -X 22} -L 22 -Z 2 (L2)
_{-X 31 -L 31 -X 32 -L 32} -Z 3 (L3)
First, the site | part represented by general formula (L1) is demonstrated.
X ₁₁ is —O—, —S—, —CO—, —SO ₂ —, —NR— (R is a hydrogen atom or an alkyl group), a divalent nitrogen-containing non-aromatic heterocyclic group, or these Represents a combined group.
X ₁₂ and X ₁₃ each independently represent a single bond, —O—, —S—, —CO—, —SO ₂ —, —NR— (R is a hydrogen atom or an alkyl group), divalent nitrogen-containing non- An aromatic heterocyclic group or a group obtained by combining them is represented.

  The alkyl group of R may be linear or branched. Moreover, the alkyl group of R may further have a substituent. The alkyl group preferably has 20 or less carbon atoms, more preferably 8 or less carbon atoms, and still more preferably 3 or less carbon atoms. Examples of such an alkyl group include a methyl group, an ethyl group, a propyl group, and an isopropyl group. R is particularly preferably a hydrogen atom, a methyl group or an ethyl group.

  The divalent nitrogen-containing non-aromatic heterocyclic group means a 3- to 8-membered non-aromatic heterocyclic group having at least one nitrogen atom.

X ₁₁ is more preferably —O—, —CO—, —NR— (R is a hydrogen atom or an alkyl group), or a combination thereof, and —COO— or —CONR— (R is hydrogen). Particularly preferred is an atom or an alkyl group.

L ₁₁ represents an alkylene group, an alkenylene group, a divalent aliphatic hydrocarbon ring group, or a group obtained by combining two or more thereof. In the combined group, two or more groups to be combined may be the same as each other or different from each other. These groups, O -, - S -, - CO -, - SO 2 -, - NR- (R is a hydrogen atom or an alkyl group), a divalent nitrogen-containing non-aromatic heterocyclic group, a divalent They may be linked via an aromatic ring group or a group obtained by combining these.

The alkylene group for L ₁₁ may be linear or branched. As this alkylene group, a C1-C8 thing is preferable, a C1-C6 thing is more preferable, and a C1-C4 thing is still more preferable.

As the alkenylene group for L ₁₁ , for example, a group having a double bond at any position of the above alkylene group can be mentioned.

The divalent aliphatic hydrocarbon ring group as L ₁₁ may be monocyclic or polycyclic. The divalent aliphatic hydrocarbon ring group preferably has 5 to 12 carbon atoms, and more preferably 6 to 10 carbon atoms.

  The divalent aromatic ring group as the linking group may be an arylene group or a heteroarylene group. The aromatic ring group preferably has 6 to 14 carbon atoms. This aromatic ring group may further have a substituent.

In addition, —NR— as a linking group and a divalent nitrogen-containing non-aromatic heterocyclic group are the same as, for example, each of X ₁₁ described above.

L ₁₁ is an alkylene group, a divalent aliphatic hydrocarbon ring group, or a combination of an alkylene group and a divalent aliphatic hydrocarbon ring group via —OCO—, —O— or —CONH—. Group (for example, -alkylene group-O-alkylene group-, -alkylene group-OCO-alkylene group- or -valent aliphatic hydrocarbon ring group-O-alkylene group-, -alkylene group-CONH-alkylene group- Is particularly preferred.

Specific examples of —NR— and divalent nitrogen-containing non-aromatic heterocyclic group in X ₁₂ and X ₁₃ are the same as those in X ₁₁ described above, and preferred examples are also the same.

X ₁₂ is more preferably a single bond, —S—, —O—, —CO—, —SO ₂ — or a combination thereof, and a single bond, —S—, —OCO— or —OSO ₂ —. Is particularly preferred.

X ₁₃ is more preferably —O—, —CO—, —SO ₂ —, or a combination thereof, and particularly preferably —OSO ₂ —.

Ar ₁ represents a divalent aromatic ring group. The divalent aromatic ring group may be an arylene group or a heteroarylene group. This divalent aromatic ring group may further have a substituent. Examples of the substituent include an alkyl group, an alkoxy group, and an aryl group.

Ar ₁ is more preferably an arylene group having 6 to 18 carbon atoms which may have a substituent, or an aralkylene group in which an arylene group having 6 to 18 carbon atoms and an alkylene having 1 to 4 carbon atoms are combined. A phenylene group, a naphthylene group, a biphenylene group, or a phenylene group substituted with a phenyl group is particularly preferable.

L ₁₂ represents an alkylene group, an alkenylene group, a divalent aliphatic hydrocarbon ring group, a divalent aromatic ring group, or a group obtained by combining two or more of these, and these groups are a part of hydrogen atoms or All are substituted with a substituent selected from a fluorine atom, a fluorinated alkyl group, a nitro group, and a cyano group. In the combined group, two or more groups to be combined may be the same as each other or different from each other. These groups, -O -, - S -, - CO -, - SO 2 -, - NR- (R is a hydrogen atom or an alkyl group), a divalent nitrogen-containing non-aromatic heterocyclic group, a divalent May be connected via a group of aromatic rings or a combination thereof.

As L ₁₂ , an alkylene group, a divalent aromatic ring group, or a combination thereof, in which some or all of the hydrogen atoms are substituted with a fluorine atom or a fluorinated alkyl group (more preferably a perfluoroalkyl group) A group is more preferable, and an alkylene group or a divalent aromatic ring group in which part or all of hydrogen atoms are substituted with fluorine atoms is particularly preferable. L ₁₂ is particularly preferably an alkylene group or a divalent aromatic ring group in which 30 to 100% of the number of hydrogen atoms are substituted with fluorine atoms.

The alkylene group for L ₁₂ may be linear or branched. The alkylene group preferably has 1 to 6 carbon atoms, and more preferably 1 to 4 carbon atoms.

Examples of the alkenylene group for L ₁₂ include a group having a double bond at an arbitrary position of the alkylene group.

The divalent aliphatic hydrocarbon ring group represented by L ₁₂ may be monocyclic or polycyclic. The divalent aliphatic hydrocarbon ring group is preferably one having 3 to 17 carbon atoms.

Examples of the divalent aromatic ring group for L ₁₂ include the same groups as those described above as the linking group for L ₁₁ .

Specific examples of the linking group —NR— and the divalent nitrogen-containing non-aromatic heterocyclic group in L ₁₂ include the same specific examples as in X ₁₁ described above, and preferred examples are also the same.

Z ₁ represents a site that becomes a sulfonic acid group upon irradiation with actinic rays or radiation, and specifically includes, for example, a structure represented by the above formula (ZI).

Next, the site | part represented by general formula (L2) is demonstrated.
Ar ₂ represents a divalent aromatic ring group. The divalent aromatic ring group may be an arylene group or a heteroarylene group. These divalent aromatic ring groups preferably have 6 to 18 carbon atoms. These divalent aromatic ring groups may further have a substituent.

X ₂₁ represents —O—, —S—, —CO—, —SO ₂ —, —NR— (R represents a hydrogen atom or an alkyl group), a divalent nitrogen-containing non-aromatic heterocyclic group, or these Represents a combined group.
Examples of —NR— and divalent nitrogen-containing non-aromatic heterocyclic group in X ₂₁ include the same as those described above for X ₁₁ .

The _{X 21, -O -, - S} -, - CO -, - SO 2 -, or, more preferably a group composed of a combination of these, -O -, - OCO- or -OSO ₂ - is particularly preferred.

X ₂₂ represents a single bond, —O—, —S—, —CO—, —SO ₂ —, —NR— (R represents a hydrogen atom or an alkyl group), a divalent nitrogen-containing non-aromatic heterocyclic group, or And represents a combination of these. Examples of —NR— and divalent nitrogen-containing non-aromatic heterocyclic group in X ₂₂ include the same as those described above for X ₁₁ .

The _{X 22, -O -, - S} -, - CO -, - SO 2 -, or, more preferably a group composed of a combination of these, -O -, - OCO- or -OSO ₂ - is particularly preferred.

L ₂₁ represents a single bond, an alkylene group, an alkenylene group, a divalent aliphatic hydrocarbon ring group, a divalent aromatic ring group, or a group obtained by combining two or more thereof. In the combined group, two or more groups to be combined may be the same as each other or different from each other. These groups, -O -, - S -, - CO -, - SO 2 -, - NR- (R is a hydrogen atom or an alkyl group), a divalent nitrogen-containing non-aromatic heterocyclic group, a divalent May be connected via a group of aromatic rings or a combination thereof.

Examples of the alkylene group, alkenylene group, and divalent aliphatic hydrocarbon ring group for L ₂₁ include the same groups as those described above for L ₁₁ .

The divalent aromatic ring group of L ₂₁ may be an arylene group or a heteroarylene group. The divalent aromatic ring group preferably has 6 to 14 carbon atoms.

Examples of —NR— and divalent nitrogen-containing non-aromatic heterocyclic group in L ₂₁ include the same as those described above for X ₁₁ .

L ₂₁ includes, for example, a single bond, an alkylene group, a divalent aliphatic hydrocarbon ring group, a divalent aromatic ring group, or a group obtained by combining two or more of these (for example, -alkylene group-2 divalent aromatic ring group- Or a group in which two or more of these are combined through a linking group such as -OCO-, -COO-, -O-, and -S- For example, -alkylene group-OCO-2 valent aromatic ring group-, -alkylene group-S-2 valent aromatic ring group-, or -alkylene group-O-alkylene group-2 valent aromatic ring group-). Particularly preferred.

L ₂₂ represents an alkylene group, an alkenylene group, a divalent aliphatic hydrocarbon ring group, a divalent aromatic ring group, or a group obtained by combining two or more of these, and these groups are a part of hydrogen atoms or All may be substituted with a substituent selected from a fluorine atom, a fluorinated alkyl group, a nitro group, and a cyano group. In the combined group, two or more groups to be combined may be the same as each other or different from each other. These groups, -O-, S -, - CO -, - SO 2 -, - NR- (R is a hydrogen atom or an alkyl group), a divalent nitrogen-containing non-aromatic heterocyclic group, a divalent They may be linked via an aromatic ring group or a group obtained by combining these.

L ₂₂ is an alkylene group, a divalent aromatic ring group, or a combination of these, in which part or all of the hydrogen atoms are substituted with a fluorine atom or a fluorinated alkyl group (more preferably a perfluoroalkyl group). Are more preferable, and an alkylene group or a divalent aromatic ring group in which part or all of the hydrogen atoms are substituted with fluorine atoms is particularly preferable.

Specific examples of the alkylene group, the alkenylene group, the group aliphatic hydrocarbon ring group, the divalent aromatic ring group, and a combination of two or more of these represented by L ₂₂ include L ₁₂ in the general formula (L1). The same group as the specific example illustrated previously is mentioned.

Specific examples of the linking group —NR— and the divalent nitrogen-containing non-aromatic heterocyclic group in L ₂₂ include the same specific examples as in X ₁₁ described above, and preferred examples are also the same.

Z ₂ represents a site that becomes a sulfonic acid group upon irradiation with actinic rays or radiation. Specific examples of Z ₂ are the same as those described above for Z 1.

Then, the site | part represented by general formula (L3) is demonstrated.
X ₃₁ and X ₃₂ are each independently a single bond, —O—, —S—, —CO—, —SO ₂ —, —NR— (R is a hydrogen atom or an alkyl group), divalent nitrogen-containing non- An aromatic heterocyclic group or a group obtained by combining them is represented.

Examples of —NR— and a divalent nitrogen-containing non-aromatic heterocyclic group in each of X ₃₁ and X ₃₂ include the same as those described above for X ₁₁ .

X ₃₁ is preferably a single bond, —O—, —CO—, —NR— (wherein R is a hydrogen atom or an alkyl group), or a combination thereof, and more preferably a single bond, —COO— or —CONR—. (R is a hydrogen atom or an alkyl group) is particularly preferred.

X ₃₂ is more preferably —O—, —S—, —CO—, —SO ₂ —, a divalent nitrogen-containing non-aromatic heterocyclic group, or a combination thereof, —O—, — OCO- or -OSO ₂ - is particularly preferred.

L ₃₁ represents a single bond, an alkylene group, an alkenylene group, a divalent aliphatic hydrocarbon ring group, a divalent aromatic ring group, or a group obtained by combining two or more thereof. In the combined group, two or more groups to be combined may be the same as each other or different from each other. These groups, -O -, - S -, - CO -, - SO 2 -, - NR- (R is a hydrogen atom or an alkyl group), a divalent nitrogen-containing non-aromatic heterocyclic group, a divalent May be connected via a group of aromatic rings or a combination thereof.

Examples of the alkylene group, alkenylene group, divalent aliphatic hydrocarbon ring group, and divalent aromatic ring group of L ₃₁ include the same as those described above for L ₂₁ .

Specific examples of -NR- and a divalent nitrogen-containing non-aromatic heterocyclic group in L ₃₁ include the same specific examples as those in X ₁₁ described above, and preferred examples are also the same.

L ₃₂ represents an alkylene group, an alkenylene group, a divalent aliphatic hydrocarbon ring group, a divalent aromatic ring group, or a group obtained by combining two or more of these. In the combined group, two or more groups to be combined may be the same as each other or different from each other. These groups, -O -, - S -, - CO -, - SO 2 -, - NR- (R is a hydrogen atom or an alkyl group), a divalent nitrogen-containing non-aromatic heterocyclic group, a divalent May be connected via a group of aromatic rings or a combination thereof.

L _{32 is} an alkylene group, alkenylene group, divalent aliphatic hydrocarbon ring group, divalent aromatic ring group, or a combination of two or more thereof, wherein a part or all of the hydrogen atoms are fluorine atoms, It is preferably substituted with a substituent selected from a fluorinated alkyl group, a nitro group, and a cyano group.

L ₃₂ is an alkylene group, a divalent aromatic ring group, or a combination of these, in which part or all of the hydrogen atoms are substituted with a fluorine atom or a fluorinated alkyl group (more preferably a perfluoroalkyl group). Are more preferable, and an alkylene group or a divalent aromatic ring group in which part or all of the hydrogen atoms are substituted with fluorine atoms is particularly preferable.

Examples of the L ₃₂ alkylene group, alkenylene group, divalent aliphatic hydrocarbon ring group, divalent aromatic ring group, and a group obtained by combining two or more of these include L ₁₂ described above. The same thing is mentioned. Specific examples of the —NR— of the linking group and the divalent nitrogen-containing non-aromatic heterocyclic group in L ₃₂ include the same specific examples as in X ₁₁ described above, and preferred examples are also the same.

In the case where X ₃ is a single bond and L ₃₁ is an aromatic ring group, when R ₃₂ forms a ring with the aromatic ring group of L ₃₁ , the alkylene group represented by R ₃₂ has 1 carbon atom -8 are preferable, those having 1 to 4 carbon atoms are more preferable, and those having 1 to 2 carbon atoms are still more preferable.

Z ₃ represents an onium salt that becomes an imido acid group or a methide acid group by irradiation with actinic rays or radiation. The onium salt represented by Z ₃ is preferably a sulfonium salt or an iodonium salt, and a structure represented by the following general formula (ZIII) or (ZIV) is preferred.

In general formulas (ZIII) and (ZIV), Z ₁ , Z ₂ , Z ₃ , Z ₄ , and Z ₅ each independently represent —CO— or —SO ₂ —, and more preferably —SO ₂ —. It is.

Rz ₁ , Rz ₂ and Rz ₃ each independently represents an alkyl group, a monovalent aliphatic hydrocarbon ring group, an aryl group or an aralkyl group. An embodiment in which part or all of the hydrogen atoms are substituted with a fluorine atom or a fluoroalkyl group (more preferably a perfluoroalkyl group) is more preferable.

The alkyl groups of Rz ₁ , Rz ₂ and Rz ₃ may be linear or branched. The alkyl group preferably has 1 to 8 carbon atoms, more preferably 1 to 6 carbon atoms, and still more preferably 1 to 4 carbon atoms.

The monovalent aliphatic hydrocarbon ring group represented by Rz ₁ , Rz ₂ and Rz ₃ preferably has 3 to 10 carbon atoms, and more preferably 3 to 6 carbon atoms.

The aryl group of Rz ₁ , Rz ₂ and Rz ₃ preferably has 6 to 18 carbon atoms, and more preferably an aryl group having 6 to 10 carbon atoms. As this aryl group, a phenyl group is particularly preferable.

Preferable examples of the aralkyl group of Rz ₁ , Rz ₂ and Rz ₃ include those in which an alkylene group having 1 to 8 carbon atoms and the aryl group are bonded. An aralkyl group formed by bonding an alkylene group having 1 to 6 carbon atoms and the aryl group is more preferable, and an aralkyl group formed by bonding an alkylene group having 1 to 4 carbon atoms and the aryl group is particularly preferable.

A ⁺ represents a sulfonium cation or an iodonium cation. Preferable examples of A ⁺ include a sulfonium cation in the general formula (ZI) or an iodonium cation structure in the general formula (ZII).

Specific examples of the repeating unit (B) are shown below, but the scope of the present invention is not limited thereto.

  When the resin (Ab) contains the repeating unit (B), the content of the repeating unit (B) in the resin (Ab) is 0.1 to 80 mol% with respect to all the repeating units in the resin (Ab). Preferably, it is 0.5-60 mol%, More preferably, it is 1-40 mol%.

  The weight average molecular weight (Mw) of the resin (Ab) is preferably in the range of 1000 to 200,000, respectively. 200,000 or less is preferable from the viewpoint of the dissolution rate and sensitivity of the resin itself with respect to alkali. The dispersity (Mw / Mn) is preferably 1.0 to 3.0, more preferably 1.0 to 2.5, and particularly preferably 1.0 to 2.0.

Among them, the weight average molecular weight (Mw) of the resin is preferably in the range of 1,000 to 200,000, more preferably in the range of 1,000 to 100,000, and particularly preferably 1,000. Is in the range of ~ 50,000, most preferably in the range of 1,000-25,000.
Here, the weight average molecular weight is defined by a polystyrene conversion value of gel permeation chromatography. Specifically, the weight average molecular weight (Mw) and the number average molecular weight (Mn) of the resin (Ab) are, for example, HLC-8120 (manufactured by Tosoh Corporation), and TSK gel Multipore HXL-M (Tosoh ( 7.8 mm ID × 30.0 cm can be obtained by using THF (tetrahydrofuran) as an eluent.

  (Ab) can use various commercially available products, and can be synthesized according to a conventional method (for example, radical polymerization or anionic polymerization method). For example, as a general synthesis method, a monomer polymerization method in which a monomer species and an initiator are dissolved in a solvent and heating is performed, and a solution of the monomer species and the initiator is dropped into the heating solvent over 1 to 10 hours. The dropping polymerization method is added, and the dropping polymerization method is preferable. Examples of the reaction solvent include ethers such as tetrahydrofuran, 1,4-dioxane, diisopropyl ether, ketones such as methyl ethyl ketone and methyl isobutyl ketone, ester solvents such as ethyl acetate, amide solvents such as dimethylformamide and dimethylacetamide, Further, the composition of the present invention such as propylene glycol monomethyl ether acetate (PGMEA, also known as 1-methoxy-2-acetoxypropane), propylene glycol monomethyl ether (PGME, also known as 1-methoxy-2-propanol), and cyclohexanone described later is used. Solvents that dissolve are mentioned. More preferably, the polymerization is performed using the same solvent as the solvent used in the actinic ray-sensitive or radiation-sensitive resin composition of the present invention. Thereby, the generation of particles during storage can be suppressed.

The resin (Ab) is preferably polymerized by a known anionic polymerization method or radical polymerization method.
The anionic polymerization method is usually performed at a temperature of −100 to 90 ° C. in an organic solvent in an inert gas atmosphere such as nitrogen or argon using an alkali metal or an organic alkali metal as a polymerization initiator. In the copolymerization, a block copolymer is obtained by sequentially adding monomers to the reaction system for polymerization, and a random copolymer is obtained by adding a mixture of monomers to the reaction system for polymerization. can get.

  Examples of the alkali metal of the polymerization initiator include lithium, sodium, potassium, cesium and the like, and examples of the organic alkali metal include alkylated products, allylated products and arylated products of the alkali metals, specifically Is ethyl lithium, n-butyl lithium, sec-butyl lithium, tert-butyl lithium, ethyl sodium, lithium biphenyl, lithium naphthalene, lithium triphenyl, sodium naphthalene, α-methylstyrene sodium dianion, 1,1-diphenylhexyl lithium 1,1-diphenyl-3-methylpentyl lithium and the like can be mentioned.

  The radical polymerization method is a known radical polymerization start such as azo compounds such as azobisisobutyronitrile and azobisisovaleronitrile, and organic oxides such as benzoyl peroxide, methyl ethyl ketone peroxide and cumene hydroperoxide. If necessary, a known chain transfer agent such as 1-dodecanethiol is used in combination with an inert gas atmosphere such as nitrogen or argon in an organic solvent at a temperature of 50 to 200 ° C. .

  Examples of organic solvents include aliphatic hydrocarbons such as n-hexane and n-heptane, alicyclic hydrocarbons such as cyclohexane and cyclopentane, aromatic hydrocarbons such as benzene and toluene, and ketones such as methyl ethyl ketone and cyclohexanone. Propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, ethylene glycol monobutyl ether acetate, ethylene glycol monobutyl ether, ethylene glycol monoethyl ether acetate, ethylene glycol monoethyl ether, propylene glycol monoethyl ether acetate, propylene glycol monoethyl ether, etc. Polyhydric alcohol derivatives, ethers such as diethyl ether, tetrahydrofuran and dioxane, anisole, hex It can be mentioned organic solvents which are usually used in anionic polymerization such as methyl phosphoramide, which are used as a single solvent or two or more kinds of mixed solvents. More preferable solvents include propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, and cyclohexanone.

    As the radical initiator, an azo initiator is preferable, and an azo initiator having an ester group, a cyano group, or a carboxyl group is preferable. Preferred initiators include azobisisobutyronitrile, azobisdimethylvaleronitrile, dimethyl 2,2'-azobis (2-methylpropionate) and the like. The concentration of the reaction is usually 5 to 50% by mass, preferably 30 to 50% by mass. The reaction temperature is usually from 10 ° C to 150 ° C, preferably from 30 ° C to 120 ° C, more preferably from 60 ° C to 100 ° C. Resin (Ab) having a dispersity of 2.0 or less can be synthesized by performing radical polymerization using an azo polymerization initiator. A resin (Ab) having a more preferable dispersity of 1.0 to 1.5 can be synthesized by living radical polymerization, for example.

  After completion of the reaction, the mixture is allowed to cool to room temperature and purified. Purification can be accomplished by a liquid-liquid extraction method that removes residual monomers and oligomer components by combining water and an appropriate solvent, and a purification method in a solution state such as ultrafiltration that extracts and removes only those having a specific molecular weight or less. , Reprecipitation method that removes residual monomer by coagulating resin in poor solvent by dripping resin solution into poor solvent and purification in solid state such as washing filtered resin slurry with poor solvent A normal method such as a method can be applied. For example, the resin is precipitated as a solid by contacting a solvent (poor solvent) in which the resin is hardly soluble or insoluble in a volume amount of 10 times or less, preferably 10 to 5 times that of the reaction solution.

  The solvent (precipitation or reprecipitation solvent) used in the precipitation or reprecipitation operation from the polymer solution may be a poor solvent for the polymer, and may be a hydrocarbon, halogenated hydrocarbon, nitro, depending on the type of polymer. A compound, ether, ketone, ester, carbonate, alcohol, carboxylic acid, water, a mixed solvent containing these solvents, and the like can be appropriately selected for use. Among these, as a precipitation or reprecipitation solvent, a solvent containing at least an alcohol (particularly methanol or the like) or water is preferable.

  The amount of the precipitation or reprecipitation solvent used can be appropriately selected in consideration of efficiency, yield, and the like, but generally 100 to 10000 parts by mass, preferably 200 to 2000 parts by mass with respect to 100 parts by mass of the polymer solution, More preferably, it is 300-1000 mass parts.

  The temperature for precipitation or reprecipitation can be appropriately selected in consideration of efficiency and operability, but is usually about 0 to 50 ° C., preferably around room temperature (for example, about 20 to 35 ° C.). The precipitation or reprecipitation operation can be performed by a known method such as a batch method or a continuous method using a conventional mixing vessel such as a stirring tank.

  The precipitated or re-precipitated polymer is usually subjected to conventional solid-liquid separation such as filtration and centrifugation, and dried before use. Filtration is performed using a solvent-resistant filter medium, preferably under pressure. Drying is performed at a temperature of about 30 to 100 ° C., preferably about 30 to 50 ° C. under normal pressure or reduced pressure (preferably under reduced pressure).

  In addition, once the resin is precipitated and separated, it may be dissolved again in a solvent, and the resin may be brought into contact with a hardly soluble or insoluble solvent. That is, after completion of the radical polymerization reaction, a solvent in which the polymer is hardly soluble or insoluble is brought into contact, the resin is precipitated (step a), the resin is separated from the solution (step b), and dissolved again in the solvent. (Step c), and then contact the resin solution A with a solvent in which the resin is hardly soluble or insoluble in a volume amount less than 10 times that of the resin solution A (preferably 5 times or less volume). This may be a method including precipitating a resin solid (step d) and separating the precipitated resin (step e).

  Moreover, when exposing the positive resist of this invention with an ArF excimer laser, it is preferable to use resin which does not have an aromatic ring as resin (Ab) from a transparency viewpoint with respect to ArF excimer laser. As a resin (Ab) suitable for ArF excimer laser exposure, for example, the resin (A ′) described in paragraphs 0446 to 0477 of JP2013-15590A can be used.

Two or more types of resins (Ab) may be used in combination.
The total content of the resin (Ab) is generally 10 to 99% by mass, preferably 20 to 99% by mass, and particularly preferably 30 to 99% by mass, based on the total solid content of the composition of the present invention. %.
Although the specific example of resin (Ab) is shown below, it is not limited to these.

  When the resin (Ab) does not contain the acid generating repeating unit (B), the content of the repeating unit containing a fluorine atom is preferably 1 mol% or less, and more preferably no fluorine atom is contained. When the resin (Ab) has a repeating unit (B), the content of the repeating unit other than the repeating unit (B) and containing a fluorine atom is more preferably 1 mol% or less. Most preferably, no atoms are contained.

[3] Compound that generates acid upon irradiation with actinic ray or radiation In one embodiment, the composition of the present invention includes a compound that generates acid upon irradiation with actinic ray or radiation (hereinafter also referred to as “acid generator”). May be contained.
The acid generator is not particularly limited as long as it is a publicly known acid generator, but upon irradiation with actinic rays or radiation, at least any of organic acids such as sulfonic acid, bis (alkylsulfonyl) imide, and tris (alkylsulfonyl) methide. Compounds that generate such are preferred.

More preferred examples include compounds represented by the following general formulas (ZI), (ZII), and (ZIII).

In the general formula (ZI),
R ₂₀₁ , R ₂₀₂ and R ₂₀₃ each independently represents an organic group.
The carbon number of the organic group as R ₂₀₁ , R ₂₀₂ and R ₂₀₃ is generally 1 to 30, preferably 1 to 20.
Two of R _{201 to} R ₂₀₃ may be bonded to form a ring structure, and the ring may contain an oxygen atom, a sulfur atom, an ester bond, an amide bond, or a carbonyl group. Examples of the group formed by combining two of R _{201 to} R ₂₀₃ include an alkylene group (eg, butylene group, pentylene group).
Z ⁻ represents a non-nucleophilic anion (an anion having an extremely low ability to cause a nucleophilic reaction).

  Non-nucleophilic anions include, for example, sulfonate anions (aliphatic sulfonate anions, aromatic sulfonate anions, camphor sulfonate anions, etc.), carboxylate anions (aliphatic carboxylate anions, aromatic carboxylate anions, aralkyls). Carboxylate anion, etc.), sulfonylimide anion, bis (alkylsulfonyl) imide anion, tris (alkylsulfonyl) methide anion and the like.

  The aliphatic moiety in the aliphatic sulfonate anion and the aliphatic carboxylate anion may be an alkyl group or a cycloalkyl group, preferably a linear or branched alkyl group having 1 to 30 carbon atoms and a carbon number. 3-30 cycloalkyl groups are mentioned.

  The aromatic group in the aromatic sulfonate anion and aromatic carboxylate anion is preferably an aryl group having 6 to 14 carbon atoms such as a phenyl group, a tolyl group, and a naphthyl group.

  The alkyl group, cycloalkyl group and aryl group mentioned above may have a substituent. Specific examples thereof include nitro groups, halogen atoms such as fluorine atoms, carboxyl groups, hydroxyl groups, amino groups, cyano groups, alkoxy groups (preferably having 1 to 15 carbon atoms), cycloalkyl groups (preferably having 3 to 15 carbon atoms). ), An aryl group (preferably 6 to 14 carbon atoms), an alkoxycarbonyl group (preferably 2 to 7 carbon atoms), an acyl group (preferably 2 to 12 carbon atoms), an alkoxycarbonyloxy group (preferably 2 to 2 carbon atoms). 7), an alkylthio group (preferably 1 to 15 carbon atoms), an alkylsulfonyl group (preferably 1 to 15 carbon atoms), an alkyliminosulfonyl group (preferably 2 to 15 carbon atoms), an aryloxysulfonyl group (preferably carbon) Number 6-20), alkylaryloxysulfonyl group (preferably C7-20), cycloalkylary Examples thereof include an oxysulfonyl group (preferably having 10 to 20 carbon atoms), an alkyloxyalkyloxy group (preferably having 5 to 20 carbon atoms), a cycloalkylalkyloxyalkyloxy group (preferably having 8 to 20 carbon atoms), and the like. . About the aryl group and ring structure which each group has, an alkyl group (preferably C1-C15) can further be mentioned as a substituent.

  The aralkyl group in the aralkyl carboxylate anion is preferably an aralkyl group having 7 to 12 carbon atoms, such as a benzyl group, a phenethyl group, a naphthylmethyl group, a naphthylethyl group, and a naphthylbutyl group.

  Examples of the sulfonylimide anion include saccharin anion.

  The alkyl group in the bis (alkylsulfonyl) imide anion and tris (alkylsulfonyl) methide anion is preferably an alkyl group having 1 to 5 carbon atoms. Examples of substituents for these alkyl groups include halogen atoms, alkyl groups substituted with halogen atoms, alkoxy groups, alkylthio groups, alkyloxysulfonyl groups, aryloxysulfonyl groups, cycloalkylaryloxysulfonyl groups, and the like. A fluorine atom or an alkyl group substituted with a fluorine atom is preferred.

  The alkyl groups in the bis (alkylsulfonyl) imide anion may be bonded to each other to form a ring structure. This increases the acid strength.

Examples of other non-nucleophilic anions include fluorinated phosphorus (eg, PF ₆ ⁻ ), fluorinated boron (eg, BF ₄ ⁻ ), and fluorinated antimony (eg, SbF ₆ ⁻ ). .

Examples of the non-nucleophilic anion include an aliphatic sulfonate anion in which at least α-position of the sulfonic acid is substituted with a fluorine atom, an aromatic sulfonate anion substituted with a fluorine atom or a group having a fluorine atom, and an alkyl group having a fluorine atom And a tris (alkylsulfonyl) methide anion in which the alkyl group is substituted with a fluorine atom. The non-nucleophilic anion is more preferably a perfluoroaliphatic sulfonate anion (more preferably 4 to 8 carbon atoms), a benzenesulfonate anion having a fluorine atom, still more preferably a nonafluorobutanesulfonate anion, or perfluorooctane. A sulfonate anion, a pentafluorobenzenesulfonate anion, and a 3,5-bis (trifluoromethyl) benzenesulfonate anion.
From the viewpoint of acid strength, the pKa of the generated acid is preferably −1 or less in order to improve sensitivity.

Moreover, as a non-nucleophilic anion, the anion represented with the following general formula (AN1) is also mentioned as a preferable aspect.

Where
Xf each independently represents a fluorine atom or an alkyl group substituted with at least one fluorine atom.
R ¹ and R ² each independently represent a hydrogen atom, a fluorine atom or an alkyl group, and when there are a plurality of R ¹ and R ² , they may be the same or different.
L represents a divalent linking group, and when there are a plurality of L, L may be the same or different.
A represents a cyclic organic group.
x represents an integer of 1 to 20, y represents an integer of 0 to 10, and z represents an integer of 0 to 10.

The general formula (AN1) will be described in more detail.
The alkyl group in the alkyl group substituted with the fluorine atom of Xf preferably has 1 to 10 carbon atoms, more preferably 1 to 4 carbon atoms. The alkyl group substituted with a fluorine atom of Xf is preferably a perfluoroalkyl group.

Xf is preferably a fluorine atom or a perfluoroalkyl group having 1 to 4 carbon atoms. Specific examples of Xf include fluorine atom, CF ₃ , C ₂ F ₅ , C ₃ F ₇ , C ₄ F ₉ , CH ₂ CF ₃ , CH ₂ CH ₂ CF ₃ , CH ₂ C ₂ F ₅ , CH ₂ CH ₂ C ₂ F ₅ , CH ₂ C ₃ F ₇ , CH ₂ CH ₂ C ₃ F ₇ , CH ₂ C ₄ F ₉ , CH ₂ CH ₂ C ₄ F ₉ may be mentioned, among which a fluorine atom and CF ₃ are preferable. In particular, it is preferable that both Xf are fluorine atoms.

The alkyl group of R ¹ and R ² may have a substituent (preferably a fluorine atom), and preferably has 1 to 4 carbon atoms. More preferably, it is a C1-C4 perfluoroalkyl group. Specific examples of the alkyl group having a substituent for R ¹ and R ² include CF ₃ , C ₂ F ₅ , C ₃ F ₇ , C ₄ F ₉ , C ₅ F ₁₁ , C ₆ F ₁₃ , and C ₇ F _{15. , C 8 F 17, CH 2} CF 3, CH 2 CH 2 CF 3, CH 2 C 2 F 5, CH 2 CH 2 C 2 F 5, CH 2 C 3 F 7, CH 2 CH 2 C 3 F 7, CH ₂ C ₄ F ₉ and CH ₂ CH ₂ C ₄ F ₉ can be mentioned, among which CF ₃ is preferable.
R ¹ and R ² are preferably a fluorine atom or CF ₃ .

x is preferably 1 to 10, and more preferably 1 to 5.
y is preferably 0 to 4, and more preferably 0.
z is preferably 0 to 5, and more preferably 0 to 3.
The divalent linking group of L is not particularly limited, and is —COO—, —OCO—, —CO—, —O—, —S—, —SO—, —SO ₂ —, an alkylene group, a cycloalkylene group, An alkenylene group or a linking group in which a plurality of these groups are linked can be exemplified, and a linking group having a total carbon number of 12 or less is preferred. Among these, —COO—, —OCO—, —CO—, and —O— are preferable, and —COO— and —OCO— are more preferable.

  The cyclic organic group of A is not particularly limited as long as it has a cyclic structure, and is not limited to alicyclic groups, aryl groups, and heterocyclic groups (not only those having aromaticity but also aromaticity). And the like).

  The alicyclic group may be monocyclic or polycyclic, and may be a monocyclic cycloalkyl group such as a cyclopentyl group, a cyclohexyl group, or a cyclooctyl group, a norbornyl group, a tricyclodecanyl group, a tetracyclodecanyl group, or a tetracyclododecane group. A polycyclic cycloalkyl group such as a nyl group and an adamantyl group is preferred. Among them, an alicyclic group having a bulky structure having 7 or more carbon atoms, such as a norbornyl group, a tricyclodecanyl group, a tetracyclodecanyl group, a tetracyclododecanyl group, an adamantyl group, or the like is present in the film in the post-exposure heating step. Diffusivity can be suppressed, which is preferable from the viewpoint of improving MEEF.

Examples of the aryl group include a benzene ring, a naphthalene ring, a phenanthrene ring, and an anthracene ring.
Examples of the heterocyclic group include those derived from a furan ring, a thiophene ring, a benzofuran ring, a benzothiophene ring, a dibenzofuran ring, a dibenzothiophene ring, and a pyridine ring. Of these, those derived from a furan ring, a thiophene ring and a pyridine ring are preferred.

  In addition, examples of the cyclic organic group may include a lactone structure, and specific examples include those represented by the general formulas (LC1-1) to (LC1-17) that the above-described resin (P) may have. Can be mentioned.

  The cyclic organic group may have a substituent, and examples of the substituent include an alkyl group (which may be linear, branched or cyclic, preferably 1 to 12 carbon atoms), cyclo Alkyl group (which may be monocyclic, polycyclic or spirocyclic, preferably 3 to 20 carbon atoms), aryl group (preferably 6 to 14 carbon atoms), hydroxy group, alkoxy group, ester group, amide Group, urethane group, ureido group, thioether group, sulfonamide group, sulfonic acid ester group and the like. The carbon constituting the cyclic organic group (carbon contributing to ring formation) may be a carbonyl carbon.

_Examples of the organic group for R ₂₀₁ , R _202, and R ₂₀₃ include an aryl group, an alkyl group, and a cycloalkyl group.

Of R ₂₀₁ , R ₂₀₂ and R ₂₀₃ , at least one is preferably an aryl group, more preferably all three are aryl groups. As the aryl group, in addition to a phenyl group, a naphthyl group, and the like, a heteroaryl group such as an indole residue and a pyrrole residue can be used. Preferred examples of the alkyl group and cycloalkyl group represented by R _{201 to} R ₂₀₃ include a linear or branched alkyl group having 1 to 10 carbon atoms and a cycloalkyl group having 3 to 10 carbon atoms. More preferable examples of the alkyl group include a methyl group, an ethyl group, an n-propyl group, an i-propyl group, and an n-butyl group. More preferable examples of the cycloalkyl group include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, and a cycloheptyl group. These groups may further have a substituent. Examples of the substituent include halogen atoms such as nitro groups and fluorine atoms, carboxyl groups, hydroxyl groups, amino groups, cyano groups, alkoxy groups (preferably having 1 to 15 carbon atoms), cycloalkyl groups (preferably having 3 to 15 carbon atoms). ), An aryl group (preferably 6 to 14 carbon atoms), an alkoxycarbonyl group (preferably 2 to 7 carbon atoms), an acyl group (preferably 2 to 12 carbon atoms), an alkoxycarbonyloxy group (preferably 2 to 2 carbon atoms). 7) and the like, but are not limited thereto.

In _the case of forming the two members ring structure of R 201 _{to R 203,} it is preferably a structure represented by the following general formula (A1).

In general formula (A1),
R ^{1a to} R ^13a each independently represents a hydrogen atom or a substituent.

It is preferable that 1-3 are not a hydrogen atom among R ^{< 1a} > -R < ^13a >, and it is more preferable that any one of R ^{< 9a} > -R < ^13a > is not a hydrogen atom.

  Za is a single bond or a divalent linking group.

X ⁻ has the same meaning as Z ⁻ in formula (ZI).

Specific examples when R ^{1a to} R ^13a are not a hydrogen atom include a halogen atom, a linear, branched, cyclic alkyl group, alkenyl group, alkynyl group, aryl group, heterocyclic group, cyano group, nitro group, carboxyl group , Alkoxy group, aryloxy group, silyloxy group, heterocyclic oxy group, acyloxy group, carbamoyloxy group, alkoxycarbonyloxy group, aryloxycarbonyloxy group, amino group (including anilino group), ammonio group, acylamino group, amino Carbonylamino group, alkoxycarbonylamino group, aryloxycarbonylamino group, sulfamoylamino group, alkyl and arylsulfonylamino group, mercapto group, alkylthio group, arylthio group, heterocyclic thio group, sulfamoyl group, sulfo group, alkyl And arylsulfinyl groups, alkyl and arylsulfonyl groups, acyl groups, aryloxycarbonyl groups, alkoxycarbonyl groups, carbamoyl groups, aryl and heterocyclic azo groups, imide groups, phosphino groups, phosphinyl groups, phosphinyloxy groups, phosphini Ruamino group, phosphono group, silyl group, hydrazino group, ureido group, boronic acid group (—B (OH) ₂ ), phosphato group (—OPO (OH) ₂ ), sulfato group (—OSO ₃ H), other Known substituents are listed as examples.

As a case where R ^{1a to} R ^13a are not a hydrogen atom, a linear, branched or cyclic alkyl group substituted with a hydroxyl group is preferable.

Examples of the divalent linking group for Za include an alkylene group, an arylene group, a carbonyl group, a sulfonyl group, a carbonyloxy group, a carbonylamino group, a sulfonylamide group, an ether bond, a thioether bond, an amino group, a disulfide group, and — (CH _{2 ) n -CO -, - (CH} 2) n -SO 2 -, - CH = CH-, an aminocarbonylamino group, and an amino sulfonylamino group (n is an integer of 1 to 3).

In addition, as a preferable structure when at least one of R ₂₀₁ , R ₂₀₂ and R ₂₀₃ is not an aryl group, paragraphs 0046, 0047 and 0048 of JP-A-2004-233661, paragraphs of JP-A-2003-35948 0040-0046, compounds exemplified as formulas (I-1) to (I-70) in US 2003/0224288 A1, US Pat. No. 2003/0077540 A1 in formula (IA) -1) to (IA-54) and cation structures such as compounds exemplified as formulas (IB-1) to (IB-24).

In general formulas (ZII) and (ZIII),
R ₂₀₄ to R ₂₀₇ each independently represents an aryl group, an alkyl group or a cycloalkyl group.

The aryl group, alkyl group, and cycloalkyl group of R _{204 to} R ₂₀₇ are the same as the aryl group described as the aryl group, alkyl group, and cycloalkyl group of R _{201 to} R ₂₀₃ in the aforementioned compound (ZI).

The aryl group, alkyl group, and cycloalkyl group of R _{204 to} R ₂₀₇ may have a substituent. Even the substituent, an aryl group of R ₂₀₁ to R ₂₀₃ in the above compound (ZI), alkyl groups include those which may have a cycloalkyl group.

Z ⁻ represents a non-nucleophilic anion, and examples thereof include the same as the non-nucleophilic anion of Z ^{− in} formula (ZI).

Examples of the acid generator further include compounds represented by the following general formulas (ZIV), (ZV), and (ZVI).

In general formulas (ZIV) to (ZVI),
Ar ₃ and Ar ₄ each independently represents an aryl group.
R ₂₀₈ , R ₂₀₉ and R ₂₁₀ each independently represents an alkyl group, a cycloalkyl group or an aryl group.
A represents an alkylene group, an alkenylene group or an arylene group.
Specific examples of the aryl group represented by Ar ₃ , Ar ₄ , R ₂₀₈ , R _209, and R ₂₁₀ are the same as the specific examples of the aryl group represented by R ₂₀₁ , R _202, and R ₂₀₃ in the general formula (ZI). Can be mentioned.

Specific examples of the alkyl group and cycloalkyl group represented by R ₂₀₈ , R ₂₀₉ and R ₂₁₀ include specific examples of the alkyl group and cycloalkyl group represented by R ₂₀₁ , R ₂₀₂ and R ₂₀₃ in the general formula (ZI), respectively. The same can be mentioned.

The alkylene group of A is an alkylene group having 1 to 12 carbon atoms (for example, methylene group, ethylene group, propylene group, isopropylene group, butylene group, isobutylene group, etc.), and the alkenylene group of A is 2 carbon atoms. ˜12 alkenylene groups (for example, ethenylene group, propenylene group, butenylene group, etc.), and as the arylene group of A, C 6-10 arylene groups (for example, phenylene group, tolylene group, naphthylene group, etc.) Each can be mentioned.
Among acid generators, particularly preferred examples are given below.

An acid generator can be used individually by 1 type or in combination of 2 or more types.
The content of the photoacid generator is preferably 0.1 to 50% by mass, more preferably 0.5 to 45% by mass, and still more preferably 1 based on the total solid content of the composition. -40 mass%.

[4] Compound that decomposes by the action of an acid to generate an acid The actinic ray-sensitive or radiation-sensitive composition of the present invention further comprises a compound that decomposes by the action of an acid to generate an acid (hereinafter referred to as an acid proliferating agent). 1 type or 2 types or more). The acid generated by the acid proliferating agent is preferably sulfonic acid, methide acid or imide acid. The content of the acid proliferating agent is preferably 0.1 to 50% by mass, more preferably 0.5 to 30% by mass, based on the total solid content of the composition, and 1.0 to More preferably, it is 20 mass%.

  As a quantitative ratio between the acid proliferator and the acid generator (solid content of the acid proliferator based on the total solid content in the composition / solid content of the acid generator based on the total solid content in the composition) Although not particularly limited, 0.01 to 50 is preferable, 0.1 to 20 is more preferable, and 0.2 to 1.0 is particularly preferable.

Although the example of the compound which can be used for this invention below is shown, it is not limited to these.

[5] Solvent The solvent that can be used in preparing the composition of the present invention is not particularly limited as long as it dissolves each component. For example, alkylene glycol monoalkyl ether carboxylate (propylene glycol monomethyl ether acetate ( PGMEA; also known as 1-methoxy-2-acetoxypropane), alkylene glycol monoalkyl ether (propylene glycol monomethyl ether (PGME; 1-methoxy-2-propanol), etc.), lactate alkyl ester (ethyl lactate, methyl lactate, etc.) A cyclic lactone (γ-butyrolactone, preferably 4 to 10 carbon atoms), a chain or cyclic ketone (2-heptanone, cyclohexanone, etc., preferably 4 to 10 carbon atoms), an alkylene carbonate (ethylene carbonate). Over DOO, propylene carbonate), alkyl acetate such as carboxylic acid alkyl (butyl acetate is preferred), and the like alkoxy alkyl acetates (ethyl ethoxypropionate). Other usable solvents include, for example, the solvents described in US Patent Application Publication No. 2008 / 0248425A1 after [0244].

  Of the above, alkylene glycol monoalkyl ether carboxylate and alkylene glycol monoalkyl ether are preferred.

  These solvents may be used alone or in combination of two or more. When mixing 2 or more types, it is preferable to mix the solvent which has a hydroxyl group, and the solvent which does not have a hydroxyl group. The mass ratio of the solvent having a hydroxyl group and the solvent having no hydroxyl group is from 1/99 to 99/1, preferably from 10/90 to 90/10, and more preferably from 20/80 to 60/40.

  The solvent having a hydroxyl group is preferably an alkylene glycol monoalkyl ether, and the solvent having no hydroxyl group is preferably an alkylene glycol monoalkyl ether carboxylate.

[6] Basic compound The actinic ray-sensitive or radiation-sensitive resin composition according to the present invention may further contain a basic compound. The basic compound is preferably a compound having a stronger basicity than phenol. Moreover, this basic compound is preferably an organic basic compound, and more preferably a nitrogen-containing basic compound.

  Although the nitrogen-containing basic compound which can be used is not specifically limited, For example, the compound classified into the following (1)-(7) can be used.

(1) Compound represented by general formula (BS-1)

In general formula (BS-1),
Each R independently represents a hydrogen atom or an organic group. However, at least one of the three Rs is an organic group. This organic group is a linear or branched alkyl group, a monocyclic or polycyclic cycloalkyl group, an aryl group, or an aralkyl group.

  Although carbon number of the alkyl group as R is not specifically limited, Usually, it is 1-20, Preferably it is 1-12.

  Although carbon number of the cycloalkyl group as R is not specifically limited, Usually, it is 3-20, Preferably it is 5-15.

  Although carbon number of the aryl group as R is not specifically limited, Usually, it is 6-20, Preferably it is 6-10. Specific examples include a phenyl group and a naphthyl group.

  Although carbon number of the aralkyl group as R is not specifically limited, Usually, it is 7-20, Preferably it is 7-11. Specific examples include a benzyl group.

  In the alkyl group, cycloalkyl group, aryl group and aralkyl group as R, a hydrogen atom may be substituted with a substituent. Examples of the substituent include an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, a hydroxy group, a carboxy group, an alkoxy group, an aryloxy group, an alkylcarbonyloxy group, and an alkyloxycarbonyl group.

  In the compound represented by the general formula (BS-1), it is preferable that at least two of R are organic groups.

  Specific examples of the compound represented by the general formula (BS-1) include tri-n-butylamine, tri-n-pentylamine, tri-n-octylamine, tri-n-decylamine, triisodecylamine, dicyclohexyl. Methylamine, tetradecylamine, pentadecylamine, hexadecylamine, octadecylamine, didecylamine, methyloctadecylamine, dimethylundecylamine, N, N-dimethyldodecylamine, methyldioctadecylamine, N, N-dibutylaniline, N , N-dihexylaniline, 2,6-diisopropylaniline, and 2,4,6-tri (t-butyl) aniline.

  Moreover, as a preferable basic compound represented by the general formula (BS-1), a compound in which at least one R is an alkyl group substituted with a hydroxy group can be given. Specific examples include triethanolamine and N, N-dihydroxyethylaniline.

In addition, the alkyl group as R may have an oxygen atom in the alkyl chain. That is, an oxyalkylene chain may be formed. As the oxyalkylene chain, —CH ₂ CH ₂ O— is preferable. Specifically, for example, tris (methoxyethoxyethyl) amine and compounds exemplified in the 60th and subsequent lines of column 3 of US6040112 can be mentioned.

As a basic compound represented by general formula (BS-1), the following are mentioned, for example.

(2) Compound having nitrogen-containing heterocyclic structure This nitrogen-containing heterocyclic ring may have aromaticity or may not have aromaticity. Moreover, you may have two or more nitrogen atoms. Furthermore, you may contain hetero atoms other than nitrogen. Specifically, for example, compounds having an imidazole structure (2-phenylbenzimidazole, 2,4,5-triphenylimidazole, etc.), compounds having a piperidine structure [N-hydroxyethylpiperidine and bis (1,2,2) , 6,6-pentamethyl-4-piperidyl) sebacate], compounds having a pyridine structure (such as 4-dimethylaminopyridine), and compounds having an antipyrine structure (such as antipyrine and hydroxyantipyrine).

  A compound having two or more ring structures is also preferably used. Specific examples include 1,5-diazabicyclo [4.3.0] non-5-ene and 1,8-diazabicyclo [5.4.0] -undec-7-ene.

(3) Amine compound having a phenoxy group An amine compound having a phenoxy group is a compound having a phenoxy group at the terminal opposite to the N atom of the alkyl group contained in the amine compound. The phenoxy group is, for example, a substituent such as an alkyl group, an alkoxy group, a halogen atom, a cyano group, a nitro group, a carboxy group, a carboxylic acid ester group, a sulfonic acid ester group, an aryl group, an aralkyl group, an acyloxy group, and an aryloxy group. You may have.

This compound more preferably has at least one oxyalkylene chain between the phenoxy group and the nitrogen atom. The number of oxyalkylene chains in one molecule is preferably 3-9, more preferably 4-6. Among the oxyalkylene chains, —CH ₂ CH ₂ O— is particularly preferable.

  Specific examples include 2- [2- {2- (2,2-dimethoxy-phenoxyethoxy) ethyl} -bis- (2-methoxyethyl)]-amine, and paragraph [0066] of US2007 / 0224539A1. ] Compounds (C1-1) to (C3-3) exemplified in the above.

  The amine compound having a phenoxy group is prepared by reacting, for example, a primary or secondary amine having a phenoxy group with a haloalkyl ether, and adding an aqueous solution of a strong base such as sodium hydroxide, potassium hydroxide or tetraalkylammonium. And then extracted with an organic solvent such as ethyl acetate and chloroform. In addition, the amine compound having a phenoxy group reacts by heating a primary or secondary amine and a haloalkyl ether having a phenoxy group at the terminal, and a strong base such as sodium hydroxide, potassium hydroxide or tetraalkylammonium. It can also be obtained by adding an aqueous solution and then extracting with an organic solvent such as ethyl acetate and chloroform.

(4) Ammonium salt As the basic compound, an ammonium salt can also be used as appropriate. Examples of the anion of the ammonium salt include halides, sulfonates, borates, and phosphates. Of these, halides and sulfonates are particularly preferred.

As the halide, chloride, bromide and iodide are particularly preferable.
As the sulfonate, an organic sulfonate having 1 to 20 carbon atoms is particularly preferable. Examples of the organic sulfonate include alkyl sulfonates having 1 to 20 carbon atoms and aryl sulfonates.

  The alkyl group contained in the alkyl sulfonate may have a substituent. Examples of the substituent include a fluorine atom, a chlorine atom, a bromine atom, an alkoxy group, an acyl group, and an aryl group. Specific examples of the alkyl sulfonate include methane sulfonate, ethane sulfonate, butane sulfonate, hexane sulfonate, octane sulfonate, benzyl sulfonate, trifluoromethane sulfonate, pentafluoroethane sulfonate, and nonafluorobutane sulfonate.

  Examples of the aryl group contained in the aryl sulfonate include a phenyl group, a naphthyl group, and an anthryl group. These aryl groups may have a substituent. As this substituent, a C1-C6 linear or branched alkyl group and a C3-C6 cycloalkyl group are preferable, for example. Specifically, for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, i-butyl, t-butyl, n-hexyl and cyclohexyl groups are preferable. Examples of the other substituent include an alkoxy group having 1 to 6 carbon atoms, a halogen atom, cyano, nitro, an acyl group, and an acyloxy group.

  The ammonium salt may be hydroxide or carboxylate. In this case, the ammonium salt is a tetraalkylammonium hydroxide having 1 to 8 carbon atoms (tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetra- (n-butyl) ammonium hydroxide, etc.). It is particularly preferred.

  Preferred basic compounds include, for example, guanidine, aminopyridine, aminoalkylpyridine, aminopyrrolidine, indazole, imidazole, pyrazole, pyrazine, pyrimidine, purine, imidazoline, pyrazoline, piperazine, aminomorpholine and aminoalkylmorpholine. . These may further have a substituent.

  Preferred substituents include, for example, amino group, aminoalkyl group, alkylamino group, aminoaryl group, arylamino group, alkyl group, alkoxy group, acyl group, acyloxy group, aryl group, aryloxy group, nitro group, hydroxyl group And a cyano group.

  Particularly preferable basic compounds include, for example, guanidine, 1,1-dimethylguanidine, 1,1,3,3-tetramethylguanidine, imidazole, 2-methylimidazole, 4-methylimidazole, N-methylimidazole, 2 -Phenylimidazole, 4,5-diphenylimidazole, 2,4,5-triphenylimidazole, 2-aminopyridine, 3-aminopyridine, 4-aminopyridine, 2-dimethylaminopyridine, 4-dimethylaminopyridine, 2- Diethylaminopyridine, 2- (aminomethyl) pyridine, 2-amino-3-methylpyridine, 2-amino-4-methylpyridine, 2-amino-5-methylpyridine, 2-amino-6-methylpyridine, 3-aminoethyl Pyridine, 4-aminoethylpyridine, 3-amino Pyrrolidine, piperazine, N- (2-aminoethyl) piperazine, N- (2-aminoethyl) piperidine, 4-amino-2,2,6,6 tetramethylpiperidine, 4-piperidinopiperidine, 2-iminopiperidine 1- (2-aminoethyl) pyrrolidine, pyrazole, 3-amino-5-methylpyrazole, 5-amino-3-methyl-1-p-tolylpyrazole, pyrazine, 2- (aminomethyl) -5 methylpyrazine, Examples include pyrimidine, 2,4-diaminopyrimidine, 4,6-dihydroxypyrimidine, 2-pyrazoline, 3-pyrazoline, N-aminomorpholine and N- (2-aminoethyl) morpholine.

(5) A compound having a proton acceptor functional group and generating a compound which is decomposed by irradiation with actinic rays or radiation to decrease or disappear the proton acceptor property or change from proton acceptor property to acidity ( PA)
The composition according to the present invention has a proton acceptor functional group as a basic compound, and is decomposed by irradiation with actinic rays or radiation, resulting in a decrease, disappearance, or a proton acceptor property. It may further contain a compound that generates a compound that has been changed to acidity (hereinafter also referred to as compound (PA)).

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

  Examples of a preferable partial structure of the proton acceptor functional group include a crown ether, an azacrown ether, a primary to tertiary amine, a pyridine, an imidazole, and a pyrazine structure.

  The compound (PA) is decomposed by irradiation with an actinic ray or radiation to generate a compound in which the proton acceptor property is lowered, disappeared, or changed from proton acceptor property to acidity. Here, the decrease or disappearance of the proton acceptor property or the change from the proton acceptor property to the acid is a change in the proton acceptor property caused by the addition of a proton to the proton acceptor functional group. Specifically, when a proton adduct is formed from a compound having a proton acceptor functional group (PA) and a proton, the equilibrium constant in the chemical equilibrium is reduced.

Hereinafter, although the specific example of a compound (PA) is shown, it is not limited to these.

Moreover, in this invention, compounds (PA) other than the compound which generate | occur | produces the compound represented by general formula (PA-1) can also be selected suitably. For example, an ionic compound that has a proton acceptor moiety in the cation moiety may be used. More specifically, a compound represented by the following general formula (7) is exemplified.

  In the formula, A represents a sulfur atom or an iodine atom.

  m represents 1 or 2, and n represents 1 or 2. However, when A is a sulfur atom, m + n = 3, and when A is an iodine atom, m + n = 2.

  R represents an aryl group.

R _N represents an aryl group substituted with a proton acceptor functional group.

X ⁻ represents a counter anion.

Specific examples of X ⁻ include the same as X− in the general formula (ZI) described above.

Specific examples of the aryl group of R and R _N is a phenyl group are preferably exemplified.

  Specific examples of the proton acceptor functional group possessed by RN are the same as the proton acceptor functional group described in the above formula (PA-1).

  In the composition of the present invention, the compounding ratio of the compound (PA) in the whole composition is preferably 0.1 to 10% by mass, more preferably 1 to 8% by mass in the total solid content.

(6) Guanidine Compound The composition of the present invention may further contain a guanidine compound having a structure represented by the following formula.

The guanidine compound exhibits strong basicity because the positive charge of the conjugate acid is dispersed and stabilized by three nitrogens.

  The basicity of the guanidine compound (A) of the present invention is preferably such that the pKa of the conjugate acid is 6.0 or more, and 7.0 to 20.0 is highly neutralizing reactivity with the acid, Since it is excellent in a roughness characteristic, it is preferable and it is more preferable that it is 8.0-16.0.

  Due to such strong basicity, it is possible to suppress acid diffusibility and contribute to the formation of an excellent pattern shape.

  Here, “pKa” means pKa in an aqueous solution, and is described in, for example, Chemical Handbook (II) (4th revised edition, 1993, edited by The Chemical Society of Japan, Maruzen Co., Ltd.). The lower the value, the higher the acid strength. Specifically, pKa in an aqueous solution can be actually measured by measuring an acid dissociation constant at 25 ° C. using an infinitely diluted aqueous solution, and using the software package 1 below, A value based on a database of constants and known literature values can also be obtained by calculation. The values of pKa described in this specification all indicate values obtained by calculation using this software package.

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

  In the present invention, log P is a logarithmic value of n-octanol / water partition coefficient (P), and is an effective parameter that can characterize the hydrophilicity / hydrophobicity of a wide range of compounds. In general, the distribution coefficient is obtained by calculation without experimentation. In the present invention, CSChemDrawUltraVer. The value calculated by 8.0 software package (Crippen's fragmentation method) is shown.

  Moreover, it is preferable that logP of a guanidine compound (A) is 10 or less. By being below the above value, it can be contained uniformly in the resist film.

  The log P of the guanidine compound (A) in the present invention is preferably in the range of 2 to 10, more preferably in the range of 3 to 8, still more preferably in the range of 4 to 8.

  Moreover, it is preferable that the guanidine compound (A) in this invention does not have a nitrogen atom other than a guanidine structure.

Hereinafter, although the specific example of a guanidine compound is shown, it is not limited to these.

(7) Low molecular weight compound having a nitrogen atom and having a group capable of leaving by the action of an acid The composition of the present invention comprises a low molecular weight compound having a nitrogen atom and having a group capable of leaving by the action of an acid (hereinafter referred to as “low molecular compound” In this case, it is possible to contain “low molecular compound (D)” or “compound (D)”. The low molecular compound (D) preferably has basicity after the group capable of leaving by the action of an acid is eliminated.

  The group capable of leaving by the action of an acid is not particularly limited, but is preferably an acetal group, a carbonate group, a carbamate group, a tertiary ester group, a tertiary hydroxyl group, or a hemiaminal ether group, and a carbamate group or a hemiaminal ether group. It is particularly preferred.

  The molecular weight of the low molecular weight compound (D) having a group capable of leaving by the action of an acid is preferably 100 to 1000, more preferably 100 to 700, and particularly preferably 100 to 500.

  As the compound (D), an amine derivative having a group capable of leaving by the action of an acid on the nitrogen atom is preferable.

Compound (D) may have a carbamate group having a protecting group on the nitrogen atom. The protecting group constituting the carbamate group can be represented by the following general formula (d-1).

In general formula (d-1),
R ′ each independently represents a hydrogen atom, a linear or branched alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, or an alkoxyalkyl group. R ′ may be bonded to each other to form a ring.

  R ′ is preferably a linear or branched alkyl group, cycloalkyl group, or aryl group. More preferably, it is a linear or branched alkyl group or cycloalkyl group.

The specific structure of such a group is shown below.

  The compound (D) can also be constituted by arbitrarily combining the basic compound and the structure represented by the general formula (d-1).

  The compound (D) particularly preferably has a structure represented by the following general formula (D).

The compound (D) may correspond to the basic compound as long as it is a low molecular compound having a group capable of leaving by the action of an acid.

  In the general formula (D), Ra represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group or an aralkyl group. When n = 2, the two Ras may be the same or different, and the two Ras are bonded to each other to form a divalent heterocyclic hydrocarbon group (preferably having 20 or less carbon atoms) or a derivative thereof. May be formed.

  Rb independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, or an alkoxyalkyl group. However, in -C (Rb) (Rb) (Rb), when one or more Rb is a hydrogen atom, at least one of the remaining Rb is a cyclopropyl group, a 1-alkoxyalkyl group or an aryl group.

  At least two Rb may be bonded to form an alicyclic hydrocarbon group, an aromatic hydrocarbon group, a heterocyclic hydrocarbon group or a derivative thereof.

  n represents an integer of 0 to 2, m represents an integer of 1 to 3, and n + m = 3.

  In general formula (D), the alkyl group, cycloalkyl group, aryl group, and aralkyl group represented by Ra and Rb are functional groups such as hydroxyl group, cyano group, amino group, pyrrolidino group, piperidino group, morpholino group, and oxo group. , An alkoxy group and a halogen atom may be substituted. The same applies to the alkoxyalkyl group represented by Rb.

The alkyl group, cycloalkyl group, aryl group, and aralkyl group of Ra and / or Rb (these alkyl group, cycloalkyl group, aryl group, and aralkyl group are substituted with the above functional group, alkoxy group, or halogen atom). As may be)
For example, a group derived from a linear or branched alkane such as methane, ethane, propane, butane, pentane, hexane, heptane, octane, nonane, decane, undecane, dodecane, etc., a group derived from these alkanes, for example, A group substituted with one or more cycloalkyl groups such as a cyclobutyl group, a cyclopentyl group, and a cyclohexyl group,
Groups derived from cycloalkanes such as cyclobutane, cyclopentane, cyclohexane, cycloheptane, cyclooctane, norbornane, adamantane, noradamantane, groups derived from these cycloalkanes, for example, methyl group, ethyl group, n-propyl group, a group substituted with one or more linear or branched alkyl groups such as i-propyl group, n-butyl group, 2-methylpropyl group, 1-methylpropyl group, t-butyl group and the like,
Groups derived from aromatic compounds such as benzene, naphthalene, anthracene, etc., and groups derived from these aromatic compounds are, for example, methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, 2 A group substituted with one or more linear or branched alkyl groups such as -methylpropyl group, 1-methylpropyl group, t-butyl group, and the like;
Groups derived from heterocyclic compounds such as pyrrolidine, piperidine, morpholine, tetrahydrofuran, tetrahydropyran, indole, indoline, quinoline, perhydroquinoline, indazole, benzimidazole, and groups derived from these heterocyclic compounds are linear or branched A group substituted with one or more groups derived from an alkyl group or aromatic compound, a group derived from a linear or branched alkane, a group derived from a cycloalkane, a phenyl group, a naphthyl group , A group substituted with one or more groups derived from an aromatic compound such as anthracenyl group or the like, or the above substituent is a hydroxyl group, cyano group, amino group, pyrrolidino group, piperidino group, morpholino group, oxo And a group substituted with a functional group such as a group.

  Examples of the divalent heterocyclic hydrocarbon group (preferably having 1 to 20 carbon atoms) or a derivative thereof formed by bonding of Ra to each other include, for example, pyrrolidine, piperidine, morpholine, 1, 4, 5 , 6-tetrahydropyrimidine, 1,2,3,4-tetrahydroquinoline, 1,2,3,6-tetrahydropyridine, homopiperazine, 4-azabenzimidazole, benzotriazole, 5-azabenzotriazole, 1H-1, 2,3-triazole, 1,4,7-triazacyclononane, tetrazole, 7-azaindole, indazole, benzimidazole, imidazo [1,2-a] pyridine, (1S, 4S)-(+)-2 , 5-diazabicyclo [2.2.1] heptane, 1,5,7-triazabicyclo [4.4.0] dec-5-ene Groups derived from heterocyclic compounds such as indole, indoline, 1,2,3,4-tetrahydroquinoxaline, perhydroquinoline, 1,5,9-triazacyclododecane, groups derived from these heterocyclic compounds A group derived from a linear or branched alkane, a group derived from a cycloalkane, a group derived from an aromatic compound, a group derived from a heterocyclic compound, a hydroxyl group, a cyano group, an amino group, a pyrrolidino group, a piperidino And groups substituted with one or more functional groups such as a group, a morpholino group and an oxo group.

A particularly preferred compound (D) in the present invention is specifically shown, but the present invention is not limited thereto.

  The compound represented by the general formula (D) can be synthesized based on JP2007-298869A, JP2009-199021A, and the like.

  In the present invention, the low molecular compound (D) can be used singly or in combination of two or more.

  The composition of the present invention may or may not contain the low molecular compound (D), but when it is contained, the content of the compound (D) is the total solid of the composition combined with the basic compound described above. Based on the minutes, it is usually 0.001 to 20% by mass, preferably 0.001 to 10% by mass, and more preferably 0.01 to 5% by mass.

  When the composition of the present invention contains an acid generator, the ratio of the acid generator and the compound (D) used in the composition is: acid generator / [compound (D) + the following basic compound] (mole Ratio) = 2.5 to 300. In other words, the molar ratio is preferably 2.5 or more from the viewpoint of sensitivity and resolution, and is preferably 300 or less from the viewpoint of suppressing the reduction in resolution due to the thickening of the resist pattern over time until post-exposure heat treatment. The acid generator / [compound (D) + basic compound] (molar ratio) is more preferably 5.0 to 200, and still more preferably 7.0 to 150.

  Other examples that can be used in the composition according to the present invention include compounds synthesized in Examples of JP-A No. 2002-363146, and compounds described in paragraph 0108 of JP-A No. 2007-298869. It is done.

  A photosensitive basic compound may be used as the basic compound. As the photosensitive basic compound, for example, JP-T-2003-524799 and J. Org. Photopolym. Sci & Tech. Vol. 8, P.I. 543-553 (1995) etc. can be used.

  The molecular weight of the basic compound is usually 100-1500, preferably 150-1300, and more preferably 200-1000.

  These basic compounds may be used individually by 1 type, and may be used in combination of 2 or more types.

  When the composition according to the present invention contains a basic compound, the content is preferably 0.01 to 8.0% by mass based on the total solid content of the composition, More preferably, it is 5.0 mass%, and it is especially preferable that it is 0.2-4.0 mass%.

  The molar ratio of the basic compound to the photoacid generator is preferably 0.01 to 10, more preferably 0.05 to 5, and still more preferably 0.1 to 3. If this molar ratio is excessively increased, sensitivity and / or resolution may be reduced. If this molar ratio is excessively small, there is a possibility that pattern thinning occurs between exposure and heating (post-bake). More preferably, it is 0.05-5, More preferably, it is 0.1-3. The photoacid generator at the molar ratio is based on the total amount of the repeating unit (B) of the resin and the photoacid generator that the resin may further contain.

[7] Surfactant The actinic ray-sensitive or radiation-sensitive resin composition according to the present invention may further contain a surfactant. As this surfactant, fluorine-based and / or silicon-based surfactants are particularly preferable.

  Examples of the fluorine-based and / or silicon-based surfactant include Megafac F176 and Megafac R08 manufactured by Dainippon Ink and Chemicals, PF656 and PF6320 manufactured by OMNOVA, and Troisol S manufactured by Troy Chemical Co., Ltd. -366, Fluorard FC430 manufactured by Sumitomo 3M Limited, and polysiloxane polymer KP-341 manufactured by Shin-Etsu Chemical Co., Ltd.

  Surfactants other than fluorine and / or silicon may be used. Examples of the surfactant include nonionic surfactants such as polyoxyethylene alkyl ethers and polyoxyethylene alkyl aryl ethers.

  In addition, known surfactants can be used as appropriate. Examples of the surfactant that can be used include surfactants described in [0273] and after in US 2008 / 0248425A1.

One type of surfactant may be used alone, or two or more types may be used in combination.
When the composition according to the present invention further contains a surfactant, the amount used is preferably 0.0001 to 2% by mass, more preferably 0.001 to 2, based on the total solid content of the composition. 1% by mass.

[8] Other Additives In addition to the components described above, the composition of the present invention has a molecular weight of 3000 or less as described in carboxylic acids, carboxylic acid onium salts, Proceeding of SPIE, 2724, 355 (1996), etc. A blocking compound, a dye, a plasticizer, a photosensitizer, a light absorber, an antioxidant, and the like can be appropriately contained.

  In particular, carboxylic acid is preferably used for improving the performance. As the carboxylic acid, aromatic carboxylic acids such as benzoic acid and naphthoic acid are preferable.

  The content of the carboxylic acid is preferably 0.01 to 10% by mass, more preferably 0.01 to 5% by mass, and still more preferably 0.01 to 3% by mass in the total solid content concentration of the composition.

  The actinic ray-sensitive or radiation-sensitive resin composition in the present invention is preferably used at a thickness of 10 to 250 nm, more preferably at a thickness of 20 to 200 nm, from the viewpoint of improving resolution. More preferably, it is preferably used at 30 to 100 nm. Such a film thickness can be obtained by setting the solid content concentration in the composition to an appropriate range to give an appropriate viscosity and improving the coating property and film forming property.

  The solid content concentration of the actinic ray-sensitive or radiation-sensitive resin composition in the present invention is usually 1.0 to 10% by mass, preferably 2.0 to 5.7% by mass, and more preferably 2.0. It is -5.3 mass%. By setting the solid content concentration within the above range, it is possible to uniformly apply the resist solution on the substrate, and it is possible to form a resist pattern having excellent line width roughness. The reason for this is not clear, but perhaps the solid content concentration is 10% by mass or less, preferably 5.7% by mass or less, which suppresses aggregation of the material in the resist solution, particularly the photoacid generator. As a result, it is considered that a uniform resist film was formed.

  The solid content concentration is a weight percentage of the weight of other resist components excluding the solvent with respect to the total weight of the actinic ray-sensitive or radiation-sensitive resin composition.

  In the actinic ray-sensitive or radiation-sensitive resin composition of the present invention, the above components are dissolved in a predetermined organic solvent, preferably the mixed solvent, filtered, and then applied onto a predetermined support (substrate). Use. The pore size of the filter used for filter filtration is preferably 0.1 μm or less, more preferably 0.05 μm or less, and still more preferably 0.03 μm or less made of polytetrafluoroethylene, polyethylene, or nylon. In filter filtration, for example, as in JP-A-2002-62667, circulation filtration may be performed, or filtration may be performed by connecting a plurality of types of filters in series or in parallel. The composition may be filtered multiple times. Furthermore, you may perform a deaeration process etc. with respect to a composition before and behind filter filtration.

<Pattern formation method>
The present invention relates to an actinic ray-sensitive or radiation-sensitive film formed using the above-described composition of the present invention. Moreover, the pattern formation method of this invention has the process of exposing and developing the said actinic-light sensitive or radiation sensitive film | membrane.

  The composition according to the present invention is typically used as follows. That is, the composition according to the present invention is typically applied on a support such as a substrate to form a film. The thickness of this film is preferably 0.02 to 0.1 μm. As a method of coating on the substrate, spin coating is preferable, and the rotation speed is preferably 1000 to 3000 rpm.

  This composition can be applied to, for example, a spinner and a substrate on a substrate (eg, silicon / silicon dioxide coating, silicon nitride and chromium-deposited quartz substrate) used for manufacturing precision integrated circuit elements and imprint molds. It is applied using a coater or the like. Thereafter, this is dried to form an actinic ray-sensitive or radiation-sensitive film (hereinafter also referred to as a resist film). In addition, a known antireflection film can be applied in advance.

  Next, the actinic ray-sensitive or radiation-sensitive film is irradiated with actinic rays or radiation, and preferably baked (usually 80 to 150 ° C., more preferably 90 to 130 ° C.), followed by development. By performing baking, a more favorable pattern can be obtained.

Examples of actinic rays or radiation include infrared light, visible light, ultraviolet light, far ultraviolet light, X-rays, and electron beams. As these actinic rays or radiation, for example, those having a wavelength of 250 nm or less, particularly 220 nm or less are more preferable. Examples of such actinic rays or radiation include KrF excimer laser (248 nm), ArF excimer laser (193 nm), F ₂ excimer laser (157 nm), X-rays, and electron beams. Preferable actinic rays or radiations include, for example, KrF excimer laser, electron beam, X-ray and EUV light. More preferred are electron beam, X-ray and EUV light.

  That is, the present invention also relates to an actinic ray-sensitive or radiation-sensitive resin composition for KrF excimer laser, electron beam, X-ray or EUV light (more preferably for electron beam, X-ray or EUV light).

In the development step, an alkali developer is usually used.
Examples of the alkaline developer include inorganic alkalis such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate and aqueous ammonia, primary amines such as ethylamine and n-propylamine, diethylamine and Secondary amines such as di-n-butylamine, tertiary amines such as triethylamine and methyldiethylamine, alcohol amines such as dimethylethanolamine and triethanolamine, and fourth amines such as tetramethylammonium hydroxide and tetraethylammonium hydroxide. Examples include alkaline aqueous solutions containing a quaternary ammonium salt or cyclic amines such as pyrrole and pihelidine.

An appropriate amount of alcohols and / or surfactant may be added to the alkaline developer.
The concentration of the alkali developer is usually from 0.1 to 20% by mass. PH of alkaline developer
Is usually 10.0 to 15.0.

  The composition of the present invention can also be used in a process for obtaining a negative pattern by coating, film formation, and exposure, followed by development using a developer containing an organic solvent as a main component. As such a process, for example, a process described in JP 2010-217884 A can be used.

  Organic solvents include polar solvents such as ester solvents (eg, butyl acetate, ethyl acetate, etc.), ketone solvents (eg, 2-heptanone, cyclohexanone, etc.), alcohol solvents, amide solvents, ether solvents, etc. In addition, hydrocarbon solvents can be used. The water content of the organic developer as a whole is preferably less than 10% by mass, and more preferably substantially free of moisture.

  The organic developer may have a basic compound, and specific examples thereof include compounds described as basic compounds that can be included in the resin composition of the present invention. “A double development process combining organic solvent development and alkali development may be performed.

  In addition, you may produce the mold for imprint using the composition which concerns on this invention, For the details, for example, the patent 4109085 gazette, Unexamined-Japanese-Patent No. 2008-162101, and "the foundation and technique of nanoimprint" Refer to “Development and Application Development-Nanoimprint Substrate Technology and Latest Technology Development-Editing: Yoshihiko Hirai (Frontier Publishing)".

Hereinafter, the embodiments of the present invention will be described in more detail by way of examples, but the contents of the present invention are not limited thereto.
[Synthesis Example 1: Resin (Aa-22)]

Resin (Aa-22) was synthesized according to the following scheme.
0.43 g of compound (1), 13.32 g of compound (2), 0.94 g of compound (3), and 0.55 g of polymerization initiator V-601 (manufactured by Wako Pure Chemical Industries, Ltd.) Were dissolved in 66.60 g of cyclohexanone. 16.65 g of cyclohexanone was placed in the reaction vessel and dropped into the system at 85 ° C. over 4 hours under a nitrogen gas atmosphere. The reaction solution was heated and stirred for 2 hours, and then allowed to cool to room temperature.

  The above reaction solution was dropped into 1000 g of heptane / ethyl acetate = 8/2 to precipitate a polymer and filtered. The filtered solid was washed with 300 g of heptane / ethyl acetate = 8/2. Thereafter, the washed solid was subjected to vacuum drying to obtain 9.10 g of resin (Aa-22).

For this resin (Aa-22), GPC (manufactured by Tosoh Corporation; HLC-8120; Tsk gel Multipore HXL-M) was used, and the weight average molecular weight and the degree of dispersion were measured using THF as a solvent. In addition, the composition ratio was calculated by ¹ H-NMR or ¹³ C-NMR using NMR (manufactured by Bruker BioSpin Corporation; AVANCE III400 type). The results are shown in Table 1.

[Synthesis Example 2: Resin (Aa-2)]

  7.08 g of compound (4), 4.77 g of compound (5), and 0.58 g of polymerization initiator V-601 (manufactured by Wako Pure Chemical Industries, Ltd.) were dissolved in 43.65 g of cyclohexanone. I let you. 23.50 g of cyclohexanone was placed in the reaction vessel and dropped into the system at 85 ° C. over 4 hours under a nitrogen gas atmosphere. The reaction solution was heated and stirred for 2 hours, and then allowed to cool to room temperature.

  The reaction solution was dropped into 1000 g of heptane / ethyl acetate = 9/1 to precipitate a polymer and filtered. The filtered solid was washed with 300 g of heptane / ethyl acetate = 9/1. Thereafter, the washed solid was subjected to vacuum drying to obtain 5.57 g of resin (Aa-2).

  With respect to this resin (Aa-2), the weight average molecular weight, the degree of dispersion, and the composition ratio were measured by the same method as that described in Synthesis Example 1. The results are shown in Table 1.

[Other resins (Aa)]
From the resins (Aa-1) to (Aa-35) listed above, each of the resins shown in Table 1 was synthesized by the same method as described in Synthesis Example 1 or 2. Furthermore, for comparison, the following resins (Aa′-1), (Aa′-2), (Aa′-3) and (Aa′-4) were synthesized. For these resins, the weight average molecular weight, the degree of dispersion, and the composition ratio were measured in the same manner as described in Synthesis Example 1. The results are shown in Table 1.

[Synthesis Example 3: Resin (Ab-289)]

  46.50 g of compound (6) was dissolved in 263.5 g of n-hexane, 87.19 g of cyclohexanol, 46.50 g of anhydrous magnesium sulfate, 4.81 g of 10-camphorsulfonic acid were added, and at room temperature. Stir for 6 hours. After adding 10.49 g of triethylamine and stirring for 10 minutes, the solid was removed by filtration. 400 g of ethyl acetate was added, and the organic layer was washed 5 times with 200 g of ion-exchanged water and then dried over anhydrous magnesium sulfate, and the solvent was distilled off to obtain 116.27 g of a compound (7) -containing solution.

  8.41 g of acetyl chloride was added to 41.19 g of the compound (7) -containing solution, and the mixture was stirred at room temperature for 2 hours to obtain 49.99 g of a compound (8) -containing solution.

  7.40 g of compound (9) was dissolved in 79.93 g of dehydrated tetrahydrofuran, 7.40 g of anhydrous magnesium sulfate and 60.89 g of triethylamine were added, and the mixture was stirred under a nitrogen atmosphere. The solution was cooled to 0 ° C., 49.99 g of the compound (8) -containing solution was added dropwise, stirred at room temperature for 3 hours, and filtered to remove the solid. 400 g of ethyl acetate was added, the organic layer was washed 5 times with 200 g of ion-exchanged water, dried over anhydrous magnesium sulfate, and the solvent was distilled off. It was isolated and purified by column chromatography to obtain 23.91 g of compound (10).

  6.61 g of compound (11) (50.00 mass% cyclohexanone solution), 6.31 g of compound (10), 0.35 g of polymerization initiator V-601 (manufactured by Wako Pure Chemical Industries, Ltd.) Was dissolved in 32.10 g of cyclohexanone. 19.07 g of cyclohexanone was placed in the reaction vessel and dropped into the system at 85 ° C. in a nitrogen gas atmosphere over 4 hours. The reaction solution was heated and stirred for 2 hours, and then allowed to cool to room temperature.

  The reaction solution was dropped into 450 g of heptane / ethyl acetate = 9/1 (mass ratio) to precipitate a polymer, followed by filtration. The filtered solid was washed with 200 g of heptane / ethyl acetate = 9/1 (mass ratio). Thereafter, the washed solid was subjected to vacuum drying to obtain 4.90 g of a resin (Ab-289).

[Other resins (Ab)]
Of the resins (Ab-1) to (Ab-311) listed above, each of the resins shown in Table 2 was synthesized by the same method as described in Synthesis Example 3. For these resins, the weight average molecular weight, the degree of dispersion, and the composition ratio were measured in the same manner as described in Synthesis Example 1. The results are shown in Table 2.

[Photoacid generator]
The photoacid generator was appropriately selected from the acid generators z1 to z143 listed above.

[Basic compounds]
As the basic compound, any of the following compounds (N-1) to (N-10) was used.

  In addition, the said compound (N-7) corresponds to the compound (PA) mentioned above, and was synthesize | combined based on the description of [0354] of Unexamined-Japanese-Patent No. 2006-330098.

[Surfactant]
The following W-1 to W-4 were used as the surfactant.
W-1: Megafuck R08 (Dainippon Ink Chemical Co., Ltd .; fluorine and silicon)
W-2: Polysiloxane polymer KP-341 (manufactured by Shin-Etsu Chemical Co., Ltd .; silicon-based)
W-3: Troisol S-366 (manufactured by Troy Chemical Co .; fluorine type)
W-4: PF6320 (manufactured by OMNOVA; fluorine-based)
<Electron Beam (EB) Exposure> (Examples 1A to 41A, Comparative Examples 1A to 5A)
(1) Preparation and application of coating solution of actinic ray-sensitive or radiation-sensitive resin composition A coating solution composition having a solid content concentration of 3% by mass having the composition shown in the table below is precisely filtered with a membrane filter having a pore size of 0.1 μm. Filtration gave an actinic ray-sensitive or radiation-sensitive resin composition (resist composition) solution.

  This actinic ray-sensitive or radiation-sensitive resin composition is applied onto a 6-inch Si wafer that has been previously treated with hexamethyldisilazane (HMDS) using a spin coater Mark8 manufactured by Tokyo Electron, and heated at 100 ° C. for 60 seconds. It dried on the plate and obtained the resist film with a film thickness of 100 nm.

(2) EB exposure and development The wafer coated with the resist film obtained in (1) above was subjected to pattern irradiation using an electron beam drawing apparatus (HL750 manufactured by Hitachi, Ltd., acceleration voltage 50 KeV). . At this time, drawing was performed so that a 1: 1 line and space was formed. After the electron beam drawing, the sample was heated on a hot plate at 100 ° C. for 90 seconds, immersed in an aqueous 2.38 mass% tetramethylammonium hydroxide (TMAH) solution for 60 seconds, and then rinsed with water for 30 seconds. . Thereafter, the wafer was rotated at a rotational speed of 4000 rpm for 30 seconds, and then heated at 95 ° C. for 60 seconds to obtain a 1: 1 line and space pattern resist pattern having a line width of 100.

(3) Evaluation of resist pattern (3-1) Sensitivity Irradiation energy when resolving a line / space = 1: 1 pattern with a line width of 100 nm was defined as sensitivity (Eop). The smaller this value, the better the performance.

(3-2) Pattern shape The cross-sectional shape of the pattern having a line width of 100 nm at the exposure amount exhibiting the above sensitivity: space = 1: 1 is observed using a scanning electron microscope (S-4300, manufactured by Hitachi, Ltd.). Then, the following five-level evaluation was performed.

A: No bridge B: Between A and C C: Somewhat bridge D: Between C and E E: Bridge (3-3) Film verification Film slip was evaluated according to the following formula. It means that the smaller the film verification rate (%), the better the remaining film of the pattern and the better the resolution.
Film verification rate (%) = (applied film thickness 100 nm−pattern height) / applied film thickness 100 nm × 100
A: Less than 5.0% B: 5.0% or more and less than 10.0% C: 10.0% or more and less than 15.0% D: 15.0% or more and less than 20.0% E: 20.0% or more <Extreme Ultraviolet (EUV) Exposure> (Examples 1B to 41B, Comparative Examples 1B to 5B)
(1) Preparation and application of actinic ray-sensitive or radiation-sensitive resin composition coating liquid composition having a composition shown in the table below and having a solid content concentration of 1.5% by mass, a membrane filter having a pore size of 0.05 μm Was subjected to microfiltration to obtain an actinic ray-sensitive or radiation-sensitive resin composition (resist composition) solution.

  This actinic ray-sensitive or radiation-sensitive resin composition was applied onto a 6-inch Si wafer that had been previously treated with hexamethyldisilazane (HMDS) using a spin coater Mark8 manufactured by Tokyo Electron, and was hot at 100 ° C. for 60 seconds. It dried on the plate and obtained the resist film with a film thickness of 50 nm.

(2) EUV exposure and development The wafer coated with the resist film obtained in the above (1) is subjected to an EUV exposure apparatus (Micro Exposure Tool, NA 0.3, Quadrupole, outer sigma 0.68, inner sigma 0, manufactured by Exitech) .36) and pattern exposure was performed using an exposure mask (line / space = 1/1). After exposure, the substrate was heated on a hot plate at 100 ° C. for 90 seconds, immersed in an aqueous 2.38 mass% tetramethylammonium hydroxide (TMAH) solution for 60 seconds, and rinsed with water for 30 seconds. Thereafter, the wafer was rotated at 4000 rpm for 30 seconds and then baked at 95 ° C. for 60 seconds to obtain a 1: 1 line and space pattern resist pattern having a line width of 50 nm.

(3) Evaluation of resist pattern (3-1) Sensitivity Irradiation energy when resolving a line / space = 1: 1 pattern with a line width of 50 nm was defined as sensitivity (Eop). The smaller this value, the better the performance.

(3-2) Pattern shape The cross-sectional shape of the pattern having a line width of 50 nm at the exposure amount showing the above sensitivity: space = 1: 1 is observed using a scanning electron microscope (S-4300, manufactured by Hitachi, Ltd.). Then, the following five-level evaluation was performed.

A: No bridge B: Between A and C C: Somewhat bridge D: Between C and E E: Bridge (3-3) Film verification Film slip was evaluated according to the following formula. It means that the smaller the film verification rate (%), the better the remaining film of the pattern and the better the resolution.
Film verification rate (%) = (applied film thickness 50 nm−pattern height) / applied film thickness 50 nm × 100
A: Less than 5.0% B: 5.0% or more and less than 10.0% C: 10.0% or more and less than 15.0% D: 15.0% or more and less than 20.0% E: 20.0% or more <Development defects> (Examples 1C to 41C, Comparative Examples 1C to 5C)
The positive resist solution prepared as described above was applied uniformly onto a substrate coated with a 60 nm antireflection film (DUV44 manufactured by Brewer Sciences) using a spin coater Mark8 manufactured by Tokyo Electron, and was applied at 130 ° C. for 60 seconds. Heat drying was performed to form a positive resist film having an average film thickness of 60 nm. Using a KrF excimer laser scanner (manufactured by ASML, PAS5500 / 850C wavelength 248 nm), this resist film was subjected to a checkered flag exposure in which the exposed area of the open frame and the unexposed area were alternately exposed with a 15 mm square area. (Exposure conditions: NA = 0.80, σ = 0.89, 20 mJ). After irradiation, it was baked at 110 ° C. for 60 seconds, immersed in an aqueous 2.38 mass% tetramethylammonium hydroxide (TMAH) solution for 60 seconds, rinsed with water for 30 seconds and dried. The obtained pattern was evaluated by the following method.
Further, the sensitivity E _{0 at} which the resist film thickness becomes zero was measured.

At the above effective sensitivity E ₀ , a pattern having a mask size of 0.15 μm was exposed at 78 locations within the wafer surface. The number of development defects of the obtained patterned wafer was measured with KLA-2360 manufactured by KLA-Tencor Corporation. In this case, the inspection area was 205 cm ² in total, the pixel size was 0.25 μm, the threshold = 30, and the inspection light was visible light. A value obtained by dividing the obtained numerical value by the inspection area was evaluated as the number of defects (pieces / cm ² ). A with a value less than 1.0, B with 1.0 or more and less than 3.0, C with 3.0 or more and less than 5.0, D with 5.0 or more and less than 10.0, A value of 10.0 or more was designated E. A smaller value indicates better performance. The results are shown in Table 5.

Claims (16)

Resin (Aa) which contains a repeating unit represented by the following general formula (Aa1) or (Aa2) as a repeating unit decomposed by the action of an acid, is unevenly distributed on the film surface by film formation, and forms a protective film; An actinic ray-sensitive or radiation-sensitive resin composition containing a resin (Ab) that is different from Aa) and whose solubility in a developer is changed by the action of an acid.

In general formula (Aa1),
R ′ represents a hydrogen atom or an alkyl group.
L represents a single bond or a divalent linking group.
R ₁ represents a hydrogen atom or a monovalent substituent.
R ₂ represents a monovalent substituent not containing a fluorine atom. R ₁ and R ₂ may be bonded to each other to form a ring together with the oxygen atom in the formula.
R ₃ represents a hydrogen atom, an alkyl group or a cycloalkyl group.
In general formula (Aa2),
Ra represents a hydrogen atom, an alkyl group, a cyano group, or a halogen atom.
L ₁ represents a single bond or a divalent linking group.
R ₁ and R ₂ each independently represents an alkyl group. However, at least one alkyl group has 2 or more carbon atoms.
R ₁₁ and R ₁₂ each independently represents an alkyl group, and R ₁₃ represents a hydrogen atom or an alkyl group. R ₁₁ and R ₁₂ may be connected to each other to form a ring, and R ₁₁ and R ₁₃ may be connected to each other to form a ring. The actinic ray-sensitive or radiation-sensitive resin composition according to claim 1, wherein the substituent represented by R ₂ in the general formula (Aa1) is a hydrocarbon group composed of a carbon atom and a hydrogen atom.   The resin (Aa) is further a fluorine atom, a group having a fluorine atom, a group having a silicon atom, an alkyl group having 6 or more carbon atoms, a cycloalkyl group having 5 or more carbon atoms, or an aryl group having 6 or more carbon atoms. And an actinic ray-sensitive or radiation-sensitive resin according to claim 1 or 2, comprising a repeating unit (Aa3) having one or more groups selected from the group consisting of aralkyl groups having 7 or more carbon atoms. Composition. The actinic-ray sensitive or radiation sensitive resin composition of any one of Claims 1-3 in which resin (Aa) contains the repeating unit further represented by the following general formula (Aa4).

In general formula (aa2-1),
Rb represents a hydrogen atom, an alkyl group or a halogen atom.
S _1a represents a substituent, and when a plurality of S _1a are present, each is independent.
p represents an integer of 0 to 5. The actinic ray-sensitive or radiation-sensitive resin composition according to any one of claims 1 to 4, wherein the resin (Aa) further comprises a repeating unit having a structure represented by the following general formula (KY-3). object.

In general formula (KY-3),
Rs represents a chain or cyclic alkylene group, and when there are a plurality of Rs, they may be the same or different.
Ls represents a single bond, an ether bond, an ester bond, an amide bond, a urethane bond or a urea bond, and when there are a plurality of Ls, they may be the same or different.
ns represents the number of repeating linking groups represented by-(Rs-Ls)-, and represents an integer of 0 to 5.
L _ky represents an alkylene group, an oxygen atom or a sulfur atom.
Z _ka represents an alkyl group, a cycloalkyl group, an ether group, a hydroxyl group, an amide group, an aryl group, a lactone ring group, or an electron withdrawing group. If Z _ka there are a plurality, the plurality of Z _ka may be the same or different, may form a ring by linking to each other ZKA.
nka represents an integer of 0 to 10.
R _kb1 and R _kb2 each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, or an electron withdrawing group, and at least two of R _kb1 , R _kb2, and R _ky5 are connected to each other. A ring may be formed.
nkb represents 0 or 1.
R _ky5 represents an electron withdrawing group.   The active light sensitive or radiation sensitive resin composition of any one of Claims 1-5 which further contains the compound which generate | occur | produces an acid by irradiation of actinic light or a radiation.   The actinic ray sensitive or radiation sensitive substance according to any one of claims 1 to 6, wherein the resin (Ab) comprises a repeating unit (B) having a structural moiety that generates an acid upon irradiation with actinic rays or radiation. Resin composition.   The actinic-ray-sensitive or radiation-sensitive resin composition of any one of Claims 1-7 in which resin (Ab) contains the repeating unit represented by the following general formula (Ab1) or (Ab2).

  In the general formula (Ab2), R ₂₃ Represents a hydrogen atom, an alkyl group, a halogen atom, a cyano group or an alkoxycarbonyl group. The actinic ray-sensitive property according to any one of claims 1 to 8 , wherein the content of the resin (Aa) is in the range of 0.01 to 30% by mass based on the total solid content in the composition. Radiation sensitive resin composition. The actinic ray-sensitive property according to any one of claims 1 to 8 , wherein the content of the resin (Aa) is in the range of 0.01 to 20% by mass based on the total solid content in the composition. Radiation sensitive resin composition. The actinic ray-sensitive property according to any one of claims 1 to 8 , wherein the content of the resin (Aa) is in the range of 0.01 to 10% by mass based on the total solid content in the composition. Radiation sensitive resin composition. The actinic ray-sensitive property according to any one of claims 1 to 8 , wherein the content of the resin (Aa) is in the range of 0.01 to 5 mass% based on the total solid content in the composition. Radiation sensitive resin composition. An actinic ray-sensitive or radiation-sensitive film formed using the actinic ray-sensitive or radiation-sensitive resin composition according to any one of claims 1 to 12 . Forming the actinic ray-sensitive or radiation-sensitive film with actinic ray-sensitive or radiation-sensitive resin composition according to any one of claims 1 to 12, wherein the actinic ray-sensitive or radiation-sensitive A pattern forming method comprising exposing a film to actinic rays or radiation for exposure, and developing the exposed actinic ray-sensitive or radiation-sensitive film. The pattern forming method according to claim 14 , wherein an electron beam or extreme ultraviolet rays is used as the actinic ray or radiation. The manufacturing method of an electronic device containing the pattern formation method of Claim 14 or 15 .