WO2015129355A1

WO2015129355A1 - Pattern forming method, method for manufacturing electronic device, electronic device, active-light-sensitive or radiation-sensitive resin composition, and resist film

Info

Publication number: WO2015129355A1
Application number: PCT/JP2015/051794
Authority: WO
Inventors: 健志川端; 土村　智孝; 英明椿
Original assignee: 富士フイルム株式会社
Priority date: 2014-02-27
Filing date: 2015-01-23
Publication date: 2015-09-03
Also published as: TW201533778A; JP2015161823A; JP6163438B2; TWI627660B

Abstract

　A pattern forming method having: a step for forming a film using an active-light-sensitive or radiation-sensitive resin composition as indicated by (i) or (ii); a step for exposing the film; and a step for removing the exposed portion of the film that was exposed, and forming a pattern, using an alkali developing fluid or a developing fluid containing an organic solvent. (i) An active light-sensitive or radiation-sensitive resin composition containing a resin (A1) that has: a repeating unit having a group that decomposes to form a polar group due to the action of an acid; and a repeating unit that does not dissociate when irradiated with active light or radiation, said repeating unit having a partial structure that has a monovalent iodine atom (ii) An active light-sensitive or radiation-sensitive resin composition containing: a resin (A2) having a repeating unit that has a group that decomposes to form a polar group due to the action of an acid; and a compound (AD) having a monovalent iodine atom.

Description

Pattern forming method, electronic device manufacturing method, electronic device, actinic ray-sensitive or radiation-sensitive resin composition, and resist film

The present invention relates to a pattern forming method, an electronic device manufacturing method, an electronic device, and a sensitivity, which are suitably used in an ultra microlithography process such as manufacturing an ultra LSI or a high-capacity microchip and other photofabrication processes. The present invention relates to an actinic ray-sensitive or radiation-sensitive resin composition and a resist film.
More specifically, a pattern forming method, an electronic device manufacturing method, an electronic device, and an actinic ray that can be suitably used for microfabrication of a semiconductor element using an electron beam or EUV light (wavelength: around 13 nm). The present invention relates to a photosensitive or radiation-sensitive resin composition and a resist film.

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, there is a tendency to shorten the exposure wavelength from g-line to i-line, and further to KrF excimer laser light. In addition to the excimer laser beam, lithography using electron beams and X-rays is currently being developed (see, for example, Patent Documents 1 and 2).

JP 2002-72483 A JP 2002-174894 A

In recent years, lithography using extreme ultraviolet rays (EUV light) has also been positioned as a next-generation or next-generation pattern formation technique, and it is desired to achieve high sensitivity and high resolution.
When the present inventors examined using the resist composition of patent document 1, 2, it turned out that a sensitivity and resolution may be inadequate.
The present invention has been made in view of the above points, and an object thereof is a pattern forming method capable of achieving high sensitivity and high resolution, a method for manufacturing an electronic device using the same, and an electronic device. The present invention also provides an actinic ray-sensitive or radiation-sensitive resin composition and a resist film using the same.

That is, the present invention provides the following [1] to [16].
[1] A step of forming a film using the actinic ray-sensitive or radiation-sensitive resin composition (i) or (ii) below, a step of exposing the film, and an alkaline developer The pattern formation method which has the process of removing the exposure part of the exposed film | membrane and forming a pattern.
(I) A resin having a repeating unit having a group that decomposes by the action of an acid to generate a polar group, and a repeating unit containing a partial structure having a monovalent iodine atom that is not eliminated by irradiation with actinic rays or radiation ( An actinic ray-sensitive or radiation-sensitive resin composition containing A1) (ii) a resin (A2) having a repeating unit having a group that is decomposed by the action of an acid to generate a polar group, and a monovalent iodine atom Actinic ray-sensitive or radiation-sensitive resin composition containing compound (AD) having [2] A film is formed using the actinic-ray-sensitive or radiation-sensitive resin composition which is (i) or (ii) above A pattern forming method including a step, a step of exposing the film, and a step of forming a pattern by removing an unexposed portion of the exposed film using a developer containing an organic solvent.
[3] The pattern forming method according to [1] or [2], wherein the actinic ray-sensitive or radiation-sensitive resin composition is the actinic ray-sensitive or radiation-sensitive resin composition (i).
[4] The content of the resin (A1) is 25 to 99% by mass based on the total solid content in the actinic ray-sensitive or radiation-sensitive resin composition (i). [3] The pattern forming method according to any one of [3].
[5] The pattern forming method according to any one of [1] to [4], wherein the resin (A1) contains a repeating unit represented by the following general formula (1 ′).

In general formula (1 ′),
R ₁₁ , R ₁₂ and R ₁₃ each independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, a cyano group or an alkoxycarbonyl group. R ₁₃ may be bonded to Ar ₁ to form a ring. When R ₁₃ and Ar ₁ are bonded, R ₁₃ represents an alkylene group.
X ₁ represents a single bond, an alkylene group, aromatic ring group, -O -, - S -, - CO -, - COO -, - SO 2 NH -, - SO 2 O -, - NR-, 2 divalent nitrogen It represents a divalent linking group comprising a non-aromatic heterocyclic group or a combination thereof. R represents a hydrogen atom or an alkyl group.
Ar ₁ represents an aromatic ring group.
RI represents an iodine atom or an organic group containing at least one iodine atom.
n represents an integer of 1 or more.
[6] The pattern forming method according to [5], wherein RI in the general formula (1 ′) is an iodine atom.
[7] The pattern forming method according to [5] or [6], wherein n in the general formula (1 ′) is an integer of 2 or more.
[8] The pattern forming method according to any one of [5] to [7], wherein X ₁ in the general formula (1 ′) is —COO—.
[9] The method according to any one of [1] to [8], wherein the actinic ray-sensitive or radiation-sensitive resin composition further contains a compound (B) that generates an acid upon irradiation with actinic rays or radiation. Pattern forming method.
[10] The pattern forming method according to any one of [3] to [8], wherein the resin (A1) has a repeating unit having a group capable of generating an acid upon irradiation with actinic rays or radiation.
[11] The pattern forming method according to any one of [1] to [10], wherein the exposure is exposure with EUV light.
[12] A method for manufacturing an electronic device, comprising the pattern forming method according to any one of [1] to [11].
[13] An electronic device manufactured by the method for manufacturing an electronic device according to [12].
[14] A step of forming a film using the actinic ray-sensitive or radiation-sensitive resin composition, a step of exposing the film, and an exposed portion of the exposed film are removed using an alkali developer. An actinic ray-sensitive or radiation-sensitive resin composition that is used in a pattern forming method including a step of forming a pattern and is (i) or (ii) above.
[15] A step of forming a film using the actinic ray-sensitive or radiation-sensitive resin composition, a step of exposing the film, and an unexposed portion of the exposed film using a developer containing an organic solvent. An actinic ray-sensitive or radiation-sensitive resin composition which is used in a pattern forming method including a step of forming a pattern by removing a portion and is (i) or (ii) above.
[16] A resist film formed from the actinic ray-sensitive or radiation-sensitive resin composition according to [14] or [15].

ADVANTAGE OF THE INVENTION According to this invention, the pattern formation method which can achieve high sensitivity and high resolution, the manufacturing method of an electronic device using the same, an electronic device, and actinic-ray-sensitive or radiation-sensitive resin composition And a resist film using the same.

Hereinafter, embodiments of the present invention will be described in detail.
In the notation of a group (atomic group) in this specification, a notation that does not indicate substitution or non-substitution refers to a group (atomic group) having a substituent together with a group (atomic group) having no substituent. Is also included. 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).
In this specification, light includes not only extreme ultraviolet rays (EUV light) but also electron beams.
In addition, “exposure” in this specification includes not only exposure by extreme ultraviolet rays (EUV light) but also drawing by electron beams unless otherwise specified.
“Actinic light” or “radiation” in the present specification means, for example, an emission line spectrum of a mercury lamp, far ultraviolet rays represented by an excimer laser, extreme ultraviolet rays (EUV light), X-rays, electron beams and the like. In the present invention, light means actinic rays or radiation. In addition, the term “exposure” in the present specification is not limited to exposure with far ultraviolet rays such as mercury lamps and excimer lasers, X-rays, EUV light, etc., but also particle beams such as electron beams and ion beams, unless otherwise specified. Include drawing in exposure.

The actinic ray-sensitive or radiation-sensitive resin composition of the present invention is the following actinic ray-sensitive or radiation-sensitive resin composition (i) or (ii) used in a pattern forming method described later.
(I) a resin having a repeating unit having a group capable of decomposing by the action of an acid to generate a polar group, and a repeating unit containing a partial structure having a monovalent iodine atom that is not eliminated by irradiation with actinic rays or radiation Actinic ray-sensitive or radiation-sensitive resin composition to be contained (ii) Resin (A2) having a repeating unit having a group that decomposes by the action of an acid to generate a polar group, and a compound having a monovalent iodine atom ( AD) containing actinic ray-sensitive or radiation-sensitive resin composition

High sensitivity and resolution can be achieved by the actinic ray-sensitive or radiation-sensitive resin composition of the present invention. The reason is not clear, but is presumed as follows.
First, when exposed using EUV light, it is considered that the resin composition absorbs light to generate electrons, and the generated electrons are decomposed by the generated electrons to generate an acid.
At this time, since the actinic ray-sensitive or radiation-sensitive resin composition of the present invention contains iodine atoms having a high EUV light absorption coefficient, it can be considered that it can absorb a lot of EUV light and has high sensitivity.
Further, even when exposed using an electron beam, the actinic ray-sensitive or radiation-sensitive resin composition of the present invention contains iodine atoms, so that a large amount of electrons are generated and the sensitivity is considered high.
Furthermore, it is considered that high resolution can be obtained by reducing the exposure amount and suppressing the diffusion of the acid generated by exposure to the non-exposed portion.

<Actinic ray-sensitive or radiation-sensitive resin composition>
First, the actinic ray-sensitive or radiation-sensitive resin composition of the present invention (hereinafter also referred to as “the composition of the present invention”) will be described.
The composition of the present invention is typically a resist composition. The composition of the present invention is typically a chemically amplified resist composition.
The composition of this invention is used for the pattern formation method mentioned later, Comprising: It is the actinic-ray sensitive or radiation sensitive resin composition of any of following (i) or (ii).
(I) A resin having a repeating unit having a group that decomposes by the action of an acid to generate a polar group, and a repeating unit having a partial structure having a monovalent iodine atom that is not eliminated by irradiation with actinic rays or radiation ( A1) (hereinafter also referred to as “resin (A1)”) Actinic ray-sensitive or radiation-sensitive resin composition (hereinafter also referred to as “composition (i)”)
(Ii) Resin (A2) (hereinafter also referred to as “resin (A2)”) having a repeating unit having a group that decomposes by the action of an acid to generate a polar group, and a compound having a monovalent iodine atom (AD ) (Hereinafter also referred to as “compound (AD)”) containing actinic ray-sensitive or radiation-sensitive resin composition (hereinafter also referred to as “composition (ii)”)

<Compositions (i) and (ii), and resin (A1) and resin (A2)>
The resin (A1) contained in the composition (i) and the resin (A2) contained in the composition (ii) have in common a repeating unit having a group that decomposes by the action of an acid to generate a polar group. Have.
Therefore, hereinafter, the resin (A) having a repeating unit having a group that decomposes by the action of an acid to generate a polar group will be described.
The resin (A) described below corresponds to the resin (A2), and a “repeating unit having a partial structure having a monovalent iodine atom that is not desorbed by irradiation with actinic rays or radiation” described later on the resin (A). (Hereinafter, also referred to as “repeating unit (s)”) corresponds to the resin (A1).

<Resin (A)>
Resin (A) has an acid-decomposable repeating unit. The acid-decomposable repeating unit has, for example, a group (hereinafter also referred to as “acid-decomposable group”) that is decomposed by the action of an acid in the main chain or side chain of the resin, or in both the main chain and the side chain. It is a repeating unit.
The composition of the present invention may be used as a positive resist composition or a negative resist composition.
When the composition of the present invention is used as a negative resist composition, the group generated by decomposition is a polar group, which has a low affinity with a developer containing an organic solvent and is insoluble or hardly soluble ( (Negative) is preferred. The polar group is more preferably an acidic group. The definition of the polar group is synonymous with the definition described in the section of the repeating unit (c) described later. Examples of the polar group generated by the decomposition of the acid-decomposable group include an alcoholic hydroxyl group, an amino group, and an acidic group Is mentioned.

The polar group generated by the decomposition of the acid-decomposable group is preferably an acidic group.
The acidic group is not particularly limited as long as it is a group that is insolubilized in a developer containing an organic solvent, but is preferably a phenolic hydroxyl group, a carboxylic acid group, a sulfonic acid group, a fluorinated alcohol group, a sulfonamide group, a sulfonyl group. Imido group, (alkylsulfonyl) (alkylcarbonyl) methylene group, (alkylsulfonyl) (alkylcarbonyl) imide group, bis (alkylcarbonyl) methylene group, bis (alkylcarbonyl) imide group, bis (alkylsulfonyl) methylene group, bis (Alkylsulfonyl) imide group, tris (alkylcarbonyl) methylene group, tris (alkylsulfonyl) methylene group, more preferably carboxylic acid group, fluorinated alcohol group (preferably hexafluoroisopropanol group), phenolic hydride Hexyl group, (used as a developer for conventional resist, a group dissociated in 2.38 mass% tetramethylammonium hydroxide aqueous solution) acidic group such as a sulfonic acid group include.

A preferable group as the acid-decomposable group is a group in which the hydrogen atom of these groups is substituted with a group capable of leaving with an acid.
Examples of the group leaving with an acid include —C (R ₃₆ ) (R ₃₇ ) (R ₃₈ ), —C (R ₃₆ ) (R ₃₇ ) (OR ₃₉ ), —C (R ₀₁ ) (R ₀₂ ). ) (OR ₃₉ ) and the like.
In the formula, each of R ₃₆ to R ₃₉ independently represents an alkyl group, a cycloalkyl group, an aryl group, a group in which an alkylene group and an aryl group are combined, 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 represent a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, a group in which an alkylene group and an aryl group are combined, or an alkenyl group.
The acid-decomposable group is preferably a cumyl ester group, an enol ester group, an acetal ester group, a tertiary alkyl ester group or the like.

(A) Repeating unit having acid-decomposable group The resin (A) has, for example, a repeating unit (a) having an acid-decomposable group in the main chain or side chain of the resin, or in both the main chain and side chain. It is preferable. As the repeating unit (a), a repeating unit represented by the following general formula (V) is more preferable.

In general formula (V),
R ₅₁ , R ₅₂ , and R ₅₃ each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, a cyano group, or an alkoxycarbonyl group. R ₅₂ may be bonded to L ₅ to form a ring, and when R ₅₂ and L ₅ are bonded, R ₅₂ represents an alkylene group.
L ₅ represents a single bond or a divalent linking group, and in the case of forming a ring with R ₅₂ , represents a trivalent linking group.
R ₅₄ represents an alkyl group, and R ₅₅ and R ₅₆ each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, or an aralkyl group. R ₅₅ and R ₅₆ may combine with each other to form a ring. _However, no and _{R 55} and _{R 56} are hydrogen atoms at the same time.

The general formula (V) will be described in more detail.
The alkyl group of R ₅₁ to R ₅₃ in the general formula (V) is preferably a methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, sec-butyl group, which may have a substituent, Examples thereof include alkyl groups having 20 or less carbon atoms such as hexyl group, 2-ethylhexyl group, octyl group and dodecyl group, more preferably alkyl groups having 8 or less carbon atoms, and particularly preferably alkyl groups having 3 or less carbon atoms.
The alkyl group contained in the alkoxycarbonyl group is preferably the same alkyl group as the alkyl group in R ₅₁ to R ₅₃ described above.
The cycloalkyl group may be monocyclic or polycyclic. Preferred examples include a monocyclic cycloalkyl group having 3 to 10 carbon atoms such as a cyclopropyl group, a cyclopentyl group, and a cyclohexyl group, which may have a substituent.
Examples of the halogen atom include a fluorine atom, a chlorine atom, and a bromine 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. Group, acyloxy group, alkoxycarbonyl group, cyano group, nitro group and the like, and the substituent preferably has 8 or less carbon atoms.

When R ₅₂ is an alkylene group and forms a ring with L ₅ , the alkylene group 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. Groups. An alkylene group having 1 to 4 carbon atoms is more preferable, and an alkylene group having 1 to 2 carbon atoms is particularly preferable. The ring formed by combining R ₅₂ and L ₅ is particularly preferably a 5- or 6-membered ring.

R ₅₁ and R ₅₃ in Formula (V) are more preferably a hydrogen atom, an alkyl group, or a halogen atom, and a hydrogen atom, a methyl group, an ethyl group, a trifluoromethyl group (—CF ₃ ), a hydroxymethyl group (—CH ₃ ). _2- OH), a chloromethyl group (—CH ₂ —Cl), and a fluorine atom (—F) are particularly preferred. R ₅₂ is more preferably a hydrogen atom, an alkyl group, a halogen atom or an alkylene group (forming a ring with L ₅ ), a hydrogen atom, a methyl group, an ethyl group, a trifluoromethyl group (—CF ₃ ), a hydroxymethyl group Particularly preferred are (—CH ₂ —OH), chloromethyl group (—CH ₂ —Cl), fluorine atom (—F), methylene group (forms a ring with L ₅ ), and ethylene group (forms a ring with L ₅ ). .

Examples of the divalent linking group represented by L _5, an alkylene group, a divalent aromatic ring _{group, -COO-L 1 -, -} O-L 1 -, a group formed by combining two or more of these Etc. Here, L ₁ 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.
L ₅ is preferably a single bond, a group represented by —COO—L ₁ —, or a divalent aromatic ring group. L ₁ is preferably an alkylene group having 1 to 5 carbon atoms, more preferably a methylene or propylene group. As the divalent aromatic ring group, a 1,4-phenylene group, a 1,3-phenylene group, a 1,2-phenylene group, and a 1,4-naphthylene group are preferable, and a 1,4-phenylene group is more preferable.
In the case of which L ₅ to form a ring with R _52, examples of the trivalent linking group represented by L _5, a specific example described above divalent linking group represented by L ₅ 1 single Preferable examples include groups formed by removing any hydrogen atom.
The alkyl group of R ₅₄ to R ₅₆ is preferably one having 1 to 20 carbon atoms, more preferably one having 1 to 10 carbon atoms, and includes a methyl group, an ethyl group, an n-propyl group, an isopropyl group, and an n-butyl group. Particularly preferred are those having 1 to 4 carbon atoms such as a group, isobutyl group and t-butyl group.
The cycloalkyl group represented by R ₅₅ and R ₅₆ is preferably one having 3 to 20 carbon atoms, and may be monocyclic such as cyclopentyl group, cyclohexyl group, norbornyl group, adamantyl group, Polycyclic ones such as a tetracyclodecanyl group and a tetracyclododecanyl group may be used.

The ring formed by combining R ₅₅ and R ₅₆ with each other preferably has 3 to 20 carbon atoms, and may be monocyclic such as a cyclopentyl group or a cyclohexyl group, or a norbornyl group. A polycyclic group such as an adamantyl group, a tetracyclodecanyl group, or a tetracyclododecanyl group. When R ₅₅ and R ₅₆ are bonded to each other to form a ring, R ₅₄ is preferably an alkyl group having 1 to 3 carbon atoms, more preferably a methyl group or an ethyl group.
The aryl group represented by R ₅₅ and R ₅₆ preferably has 6 to 20 carbon atoms, and may be monocyclic or polycyclic and may have a substituent. For example, a phenyl group, 1-naphthyl group, 2-naphthyl group, 4-methylphenyl group, 4-methoxyphenyl group and the like can be mentioned. When one of R ₅₅ and R ₅₆ is a hydrogen atom, the other is preferably an aryl group.
The aralkyl group represented by R ₅₅ and R ₅₆ may be monocyclic or polycyclic and may have a substituent. Preferably, it has 7 to 21 carbon atoms, and examples thereof include a benzyl group and a 1-naphthylmethyl group.

As a method for synthesizing a monomer corresponding to the repeating unit represented by the general formula (V), a general method for synthesizing a polymerizable group-containing ester can be applied and is not particularly limited.
Specific examples of the repeating unit (a) represented by the general formula (V) are shown below, but the present invention is not limited thereto.
In specific examples, Rx and Xa ₁ represent a hydrogen atom, CH ₃ , CF ₃ , or CH ₂ OH. Rxa and Rxb each independently represent an alkyl group having 1 to 4 carbon atoms, an aryl group having 6 to 18 carbon atoms, or an aralkyl group having 7 to 19 carbon atoms. Z represents a substituent. p represents 0 or a positive integer, preferably 0 to 2, and more preferably 0 or 1. When a plurality of Z are present, they may be the same as or different from each other. Z is preferably a group consisting of only hydrogen atoms and carbon atoms from the viewpoint of increasing the dissolution contrast with respect to a developer containing an organic solvent before and after acid decomposition (hereinafter also referred to as “organic developer”). For example, a linear or branched alkyl group or cycloalkyl group is preferable.

The resin (A) may contain a repeating unit represented by the following general formula (VI) as the repeating unit (a).

In general formula (VI),
R ₆₁ , R ₆₂ and R ₆₃ each independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, a cyano group or an alkoxycarbonyl group. However, R ₆₂ may be bonded to Ar ₆ to form a ring, and R ₆₂ in this case represents a single bond or an alkylene group.
X ₆ represents a single bond, —COO—, or —CONR ₆₄ —. R ₆₄ represents a hydrogen atom or an alkyl group.
L ₆ represents a single bond or an alkylene group.
Ar ₆ represents an (n + 1) -valent aromatic ring group, and represents an (n + 2) -valent aromatic ring group when bonded to R ₆₂ to form a ring.
Y ₂ represents a group capable of leaving by the action of an acid when n = 1. In the case of n ≧ 2, each independently represents a hydrogen atom or a group capable of leaving by the action of an acid. However, at least one of Y ₂ represents a group capable of leaving by the action of an acid.
n represents an integer of 1 to 4.

General formula (VI) will be described in more detail.
The alkyl group of R ₆₁ to R ₆₃ in the general formula (VI) is preferably a methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, sec-butyl group, which may have a substituent, An alkyl group having 20 or less carbon atoms such as a hexyl group, 2-ethylhexyl group, octyl group or dodecyl group is exemplified, and an alkyl group having 8 or less carbon atoms is more preferred.
The alkyl group contained in the alkoxycarbonyl group is preferably the same alkyl group as the alkyl group in R ₆₁ to R ₆₃ described above.
The cycloalkyl group may be monocyclic or polycyclic, and is preferably a monocyclic type having 3 to 10 carbon atoms such as a cyclopropyl group, cyclopentyl group or cyclohexyl group which may have a substituent. A cycloalkyl group is mentioned.
Examples of the halogen atom include a fluorine atom, a chlorine atom, and a bromine atom, and a fluorine atom is more preferable.

When R ₆₂ represents an alkylene group, the alkylene group preferably has 1 to 8 carbon atoms such as an optionally substituted methylene group, ethylene group, propylene group, butylene group, hexylene group, octylene group, etc. Of the alkylene group.
_-CONR 64 represented by X ₆ - _{(R 64} represents a hydrogen atom, an alkyl group) The alkyl group for _{R 64} in _include the same alkyl group and the alkyl group of _R 61 _~ R _63.
X ₆ is preferably a single bond, —COO— or —CONH—, and more preferably a single bond or —COO—.
The alkylene group for L ₆ 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 or octylene group. .
Ar ₆ represents an (n + 1) -valent aromatic ring group. The divalent aromatic ring group when 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, or a naphthylene group, or, for example, Preferred examples include divalent aromatic ring groups containing heterocycles such as thiophene, furan, pyrrole, benzothiophene, benzofuran, benzopyrrole, triazine, imidazole, benzimidazole, triazole, thiadiazole, and thiazole. The ring formed by combining R ₆₂ and Ar ₆ is particularly preferably a 5- or 6-membered ring.

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.

Examples of the substituent that the alkyl group, cycloalkyl group, alkoxycarbonyl group, alkylene group, and (n + 1) -valent aromatic ring group may have are represented by R ₅₁ to R ₅₃ in the general formula (V). Specific examples similar to the substituents that the group may have are exemplified.
n is preferably 1 or 2, and more preferably 1.
n Y ₂ each independently represents a hydrogen atom or a group capable of leaving by the action of an acid. However, at least one of n represents a group capable of leaving by the action of an acid.
Examples of the group Y ₂ leaving by the action of an acid include —C (R ₃₆ ) (R ₃₇ ) (R ₃₈ ), —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 ) , —CH (R ₃₆ ) (Ar) and the like.
In the formula, each of R ₃₆ to R ₃₉ independently represents an alkyl group, a cycloalkyl group, an aryl group, a group in which an alkylene group and an aryl group are combined, 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 represent a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, a group in which an alkylene group and an aryl group are combined, or an alkenyl group.

Ar represents an aryl group.
The alkyl group of R ₃₆ to R ₃₉ , R ₀₁ and R ₀₂ may be linear or branched and is preferably an alkyl group having 1 to 8 carbon atoms, such as a methyl group, an ethyl group, A propyl group, n-butyl group, sec-butyl group, hexyl group, octyl group and the like can be mentioned.
The cycloalkyl group of R ₃₆ to R ₃₉ , R ₀₁ and R ₀₂ may be monocyclic or polycyclic. The monocyclic type is preferably a cycloalkyl group having 3 to 10 carbon atoms, and examples thereof include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, and a cyclooctyl group. The polycyclic type is preferably a cycloalkyl group having 6 to 20 carbon atoms. For example, an adamantyl group, norbornyl group, isobornyl group, camphanyl group, dicyclopentyl group, α-pinel group, tricyclodecanyl group, tetracyclododecyl group. Group, androstanyl group and the like. A part of carbon atoms in the cycloalkyl group may be substituted with a hetero atom such as an oxygen atom.

The aryl group of R ₃₆ to R ₃₉ , R ₀₁ , R ₀₂ and Ar is preferably an aryl group having 6 to 10 carbon atoms, such as an aryl group such as a phenyl group, a naphthyl group and an anthryl group, thiophene, furan, pyrrole, Mention may be made of divalent aromatic ring groups containing heterocycles such as benzothiophene, benzofuran, benzopyrrole, triazine, imidazole, benzimidazole, triazole, thiadiazole, thiazole and the like.
The group in which the alkylene group of R ₃₆ to R ₃₉ , R ₀₁ and R ₀₂ and the aryl group are combined is preferably an aralkyl group having 7 to 12 carbon atoms, and examples thereof include a benzyl group, a phenethyl group, and a naphthylmethyl group. be able to.
The alkenyl group of R ₃₆ to R ₃₉ , R ₀₁ and R ₀₂ is preferably an alkenyl group having 2 to 8 carbon atoms, and examples thereof include a vinyl group, an allyl group, a butenyl group, and a cyclohexenyl group.

The ring formed by combining R ₃₆ and R ₃₇ with each other may be monocyclic or polycyclic. The monocyclic type is preferably a cycloalkyl structure having 3 to 10 carbon atoms, and examples thereof include a cyclopropane structure, a cyclobutane structure, a cyclopentane structure, a cyclohexane structure, a cycloheptane structure, and a cyclooctane structure. The polycyclic type is preferably a cycloalkyl structure having 6 to 20 carbon atoms, and examples thereof include an adamantane structure, a norbornane structure, a dicyclopentane structure, a tricyclodecane structure, and a tetracyclododecane structure. A part of carbon atoms in the cycloalkyl structure may be substituted with a hetero atom such as an oxygen atom.
Each of the groups as R ₃₆ to R ₃₉ , R ₀₁ , R ₀₂ , and Ar may have a substituent. Examples of the substituent include an alkyl group, a cycloalkyl group, an aryl group, and an amino group. Amide group, ureido group, urethane group, hydroxyl group, carboxyl group, halogen atom, alkoxy group, thioether group, acyl group, acyloxy group, alkoxycarbonyl group, cyano group, nitro group, etc. The number of carbon atoms is preferably 8 or less.
As the group Y ₂ leaving by the action of an acid, a structure represented by the following general formula (VI-A) is more preferable.

Here, L ₁ and L ₂ each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, or a group in which an alkylene group and an aryl group are combined.
M represents a single bond or a divalent linking group.
Q represents an alkyl group, a cycloalkyl group which may contain a hetero atom, an aryl group which may contain a hetero atom, an amino group, an ammonium group, a mercapto group, a cyano group or an aldehyde group.
At least two of Q, M, and L ₁ may combine to form a ring (preferably a 5-membered or 6-membered ring).
The alkyl group as L ₁ and L ₂ is, for example, an alkyl group having 1 to 8 carbon atoms, and specifically includes a methyl group, an ethyl group, a propyl group, an n-butyl group, a sec-butyl group, a hexyl group. Preferred examples include a group and an octyl group.
The cycloalkyl group as L ₁ and L ₂ is, for example, a cycloalkyl group having 3 to 15 carbon atoms, and specific examples thereof include a cyclopentyl group, a cyclohexyl group, a norbornyl group, an adamantyl group, and the like. Can do.

The aryl group as L ₁ and L ₂ is, for example, an aryl group having 6 to 15 carbon atoms, and specific examples include a phenyl group, a tolyl group, a naphthyl group, an anthryl group, and the like. .
The group combining the alkylene group and the aryl group as L ₁ and L ₂ has, for example, 6 to 20 carbon atoms, and examples thereof include aralkyl groups such as benzyl group and phenethyl group.
The divalent linking group as M is, for example, an alkylene group (for example, methylene group, ethylene group, propylene group, butylene group, hexylene group, octylene group, etc.), cycloalkylene group (for example, cyclopentylene group, cyclohexylene group). Group, adamantylene group, etc.), alkenylene group (eg, ethenylene group, propenylene group, butenylene group, etc.), divalent aromatic ring group (eg, phenylene group, tolylene group, naphthylene group, etc.), —S—, —O A divalent linking group in which —, —CO—, —SO ₂ —, —N (R ₀ ) —, and a combination thereof are combined. R ₀ is a hydrogen atom or an alkyl group (eg, 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, a hexyl group). Octyl group, etc.).

The alkyl group as Q are the same as each group of L ₁ and L _2.
In the cycloalkyl group which may contain a hetero atom as Q and the aryl group which may contain a hetero atom, an aliphatic hydrocarbon ring group containing no hetero atom and an aryl group containing no hetero atom Includes the cycloalkyl group as L ₁ and L ₂ described above, an aryl group, and the like, and preferably has 3 to 15 carbon atoms.
Examples of the cycloalkyl group containing a hetero atom and the aryl group containing a hetero atom include, for example, thiirane, cyclothiolane, thiophene, furan, pyrrole, benzothiophene, benzofuran, benzopyrrole, triazine, imidazole, benzimidazole, triazole, thiadiazole, thiazole, Examples thereof include groups having a heterocyclic structure such as pyrrolidone, but are not limited thereto as long as the structure is generally called a heterocyclic ring (a ring formed of carbon and a heteroatom or a ring formed of a heteroatom).

Q, M, as a ring which may be formed by combining at least two L _1, Q, M, by combining at least two L _1, for example, a propylene group, to form a butylene group, an oxygen atom The case where a 5-membered or 6-membered ring containing is formed is mentioned.
Each group represented by L ₁ , L ₂ , M, Q in the general formula (VI-A) may have a substituent. For example, R ₃₆ to R ₃₉ , R ₀₁ , R ₀₂ described above And the substituents described as the substituent that Ar may have, and the number of carbon atoms of the substituent is preferably 8 or less.
The group represented by —MQ is preferably a group composed of 1 to 30 carbon atoms, more preferably a group composed of 5 to 20 carbon atoms.

The repeating unit represented by the general formula (VI) is preferably a repeating unit represented by the following general formula (3).

In general formula (3),
Ar ₃ represents an aromatic ring group.
R ₃ represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, an alkoxy group, an acyl group, or a heterocyclic group.
M ₃ represents a single bond or a divalent linking group.
Q ₃ represents an alkyl group, a cycloalkyl group, an aryl group or a heterocyclic group.
At least two of Q ₃ , M ₃ and R ₃ may be bonded to form a ring.

The aromatic ring group represented by Ar ₃ is the same as Ar ₆ in the general formula (VI) when n in the general formula (VI) is 1, more preferably a phenylene group or a naphthylene group. More preferred is a phenylene group.
Ar ₃ may have a substituent, and examples of the substituent that Ar ₃ may have include the same substituents as the substituent that Ar ₆ in General Formula (VI) may have.

The alkyl group or cycloalkyl group represented by R ₃ has the same meaning as the alkyl group or cycloalkyl group represented by the aforementioned R ₃₆ to R ₃₉ , R ₀₁ and R ₀₂ .
The aryl group represented by R ₃ has the same meaning as the aryl group represented by R ₃₆ to R ₃₉ , R ₀₁ and R ₀₂ described above, and the preferred range is also the same.
The aralkyl group represented by R ₃ is preferably an aralkyl group having 7 to 12 carbon atoms, and examples thereof include a benzyl group, a phenethyl group, and a naphthylmethyl group.
The alkyl group portion of the alkoxy group represented by R ₃ is the same as the alkyl group represented by R ₃₆ to R ₃₉ , R ₀₁ and R ₀₂ described above, and the preferred range is also the same.
Examples of the acyl group represented by R ₃ include an aliphatic acyl group having 1 to 10 carbon atoms such as formyl group, acetyl group, propionyl group, butyryl group, isobutyryl group, valeryl group, pivaloyl group, benzoyl group and naphthoyl group. , An acetyl group or a benzoyl group is preferred.
Examples of the heterocyclic group represented by R ₃ include the aforementioned cycloalkyl groups containing a hetero atom and aryl groups containing a hetero atom, and a pyridine ring group or a pyran ring group is preferable.

R ₃ is preferably an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, an alkoxy group, an acyl group or a heterocyclic group, and a linear or branched alkyl group having 1 to 8 carbon atoms (specifically, Is a methyl group, ethyl group, propyl group, i-propyl group, n-butyl group, sec-butyl group, tert-butyl group, neopentyl group, hexyl group, 2-ethylhexyl group, octyl group), 3 to More preferably, it is 15 cycloalkyl groups (specifically, cyclopentyl group, cyclohexyl group, norbornyl group, adamantyl group, etc.). R ₃ is more preferably a methyl group, an ethyl group, an i-propyl group, a sec-butyl group, a tert-butyl group, a neopentyl group, a cyclohexyl group, an adamantyl group, a cyclohexylmethyl group or an adamantanemethyl group, , Sec-butyl group, neopentyl group, cyclohexylmethyl group or adamantanemethyl group is particularly preferable.

The alkyl group, cycloalkyl group, aryl group, aralkyl group, alkoxy group, acyl group or heterocyclic group described above may further have a substituent, and examples of the substituent that may be included include the aforementioned R _36- Examples of the substituent that R ₃₉ , R ₀₁ , R ₀₂ , and Ar may have include the substituents described above.

The divalent linking group represented by M ₃ has the same meaning as M in the structure represented by the above general formula (VI-A), and the preferred range is also the same. M ₃ may have a substituent, and the substituent that M ₃ may have is the same group as the substituent that M in the structure represented by the general formula (VI-A) can have Is mentioned.

The alkyl group, cycloalkyl group and aryl group represented by Q ₃ have the same meanings as those in Q in the structure represented by the above general formula (VI-A), and preferred ranges thereof are also the same.
Examples of the heterocyclic group represented by Q ₃ include a cycloalkyl group containing a hetero atom as Q and an aryl group containing a hetero atom in the structure represented by the aforementioned general formula (VI-A). It is the same.
Q ₃ may have a substituent, and the substituent that Q ₃ may have is the same group as the substituent that Q in the group represented by the general formula (VI-A) may have Is mentioned.

A ring formed by combining at least two of Q ₃ , M ₃ and R ₃ is a ring which may be formed by combining at least two of Q, M and L ₁ in the general formula (VI-A). It is synonymous and the preferable range is also the same.

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

Resin (A) preferably contains a repeating unit represented by the following general formula (4).

In general formula (4),
R ₄₁ , R ₄₂ and R ₄₃ each independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, a cyano group or an alkoxycarbonyl group. R ₄₂ may be bonded to L ₄ to form a ring, and when R ₄₂ and L ₄ are bonded, R ₄₂ represents an alkylene group.
L ₄ represents a single bond or a divalent linking group, and in the case of forming a ring with R ₄₂ , represents a trivalent linking group.
R ₄₄ and R ₄₅ represent a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, an alkoxy group, an acyl group, or a heterocyclic group.
M ₄ represents a single bond or a divalent linking group.
Q ₄ represents an alkyl group, a cycloalkyl group, an aryl group, or a heterocyclic group.
At least two of Q ₄ , M ₄ and R ₄₄ may be bonded to form a ring.
R ₄₁ , R ₄₂ and R ₄₃ have the same meanings as R ₅₁ , R ₅₂ and R _{53 in} the general formula (V), and preferred ranges are also the same.
L ₄ has the same meaning as L _{5 in} the general formula (V), and the preferred range is also the same.
R ₄₄ and R ₄₅ have the same meaning as R _{3 in} the general formula (3), and the preferred range is also the same.
M ₄ has the same meaning as M _{3 in} the general formula (3), and the preferred range is also the same.
Q ₄ has the same meaning as Q _{3 in} the general formula (3), and the preferred range is also the same. Examples of the ring formed by combining at least two of Q ₄ , M ₄ and R ₄₄ include rings formed by combining at least two of Q ₃ , M ₃ and R ₃ , and the preferred range is the same. It is.
Specific examples of the repeating unit represented by the general formula (4) are shown below, but the present invention is not limited thereto.

Further, the resin (A) may contain a repeating unit represented by the following general formula (BZ) as the repeating unit (a).

In general formula (BZ), 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 ₁ represents a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, a cyano group or an alkyloxycarbonyl group.

The aryl group for AR is preferably an aryl 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 an aryl 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.
Each of the aryl groups 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 moiety 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, 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 (a) represented by general formula (BZ) 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 (a) represented by the general formula (BZ), from the viewpoint of roughness performance, AR preferably contains two or more aromatic rings, and AR is a naphthyl group or a biphenyl group. Is more preferable. 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, ethyl group, propyl group, isopropyl group, n-butyl group, isobutyl group, t-butyl group, pentyl group, hexyl group, cyclohexyl group, octyl group, dodecyl group, etc. Examples thereof include alkyl groups having 1 to 20 carbon atoms. The alkyl group represented by Rn is preferably an alkyl group having 1 to 5 carbon atoms, and more preferably an alkyl group having 1 to 3 carbon atoms.
Examples of the cycloalkyl group represented by Rn include cycloalkyl groups having 3 to 15 carbon atoms such as a cyclopentyl group and a cyclohexyl group.
As the aryl group of Rn, for example, aryl groups 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.
R ₁ represents a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, a cyano group, or an alkyloxycarbonyl group as described above.
Examples of the alkyl group and cycloalkyl group of R ₁ include the same alkyl group and cycloalkyl group as described above for Rn. Each of these alkyl groups and cycloalkyl groups may have a substituent. Examples of the substituent include the same substituents as those described above for Rn.

When R ₁ is an alkyl group or a cycloalkyl group having a substituent, particularly preferable R ₁ includes, for example, a trifluoromethyl group, an alkyloxycarbonylmethyl group, an alkylcarbonyloxymethyl group, a hydroxymethyl group, and an alkoxymethyl group. Groups.
Examples of the halogen atom for R ₁ include a fluorine atom, a chlorine atom, and a bromine atom. Among these, a fluorine atom is particularly preferable.
The alkyl group moiety contained in the alkyloxycarbonyl group of R _1, for example, it is possible to adopt a configuration in which previously mentioned as the alkyl group of R _1.
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.

Specific examples of the repeating unit (a) represented by the general formula (BZ) are shown below, but are not limited thereto.

Further, the embodiment of the repeating unit having an acid-decomposable group different from the repeating unit exemplified above may be an embodiment of a repeating unit that produces an alcoholic hydroxyl group. In this case, it is preferably represented by at least one selected from the group consisting of the following general formulas (I-1) to (I-10). This repeating unit is more preferably represented by at least one selected from the group consisting of the following general formulas (I-1) to (I-3), and is represented by the following general formula (I-1) More preferably.

Where
Each Ra independently represents a hydrogen atom, an alkyl group or a group represented by —CH ₂ —O—Ra ₂ . Here, Ra ₂ represents a hydrogen atom, an alkyl group, or an acyl group.
R ₁ represents a (n + 1) -valent organic group.
R ₂ independently represents a single bond or an (n + 1) -valent organic group when m ≧ 2.
OP each independently represents a group (acid-decomposable group) that decomposes by the action of an acid to generate an alcoholic hydroxy group. When n ≧ 2 and / or m ≧ 2, two or more OPs may be bonded to each other to form a ring.
W represents a methylene group, an oxygen atom or a sulfur atom.
n and m represent an integer of 1 or more. In the general formula (I-2), (I-3) or (I-8), n is 1 when R ₂ represents a single bond.
l represents an integer of 0 or more.
L ₁ represents a linking group represented by —COO—, —OCO—, —CONH—, —O—, —Ar—, —SO ₃ — or —SO ₂ NH—. Here, Ar represents a divalent aromatic ring group.
Each R independently represents a hydrogen atom or an alkyl group.
R ₀ represents a hydrogen atom or an organic group.
L ₃ represents a (m + 2) -valent linking group.
R ^L each independently represents an (n + 1) -valent linking group when m ≧ 2.
R ^S each independently represents a substituent when p ≧ 2. For p ≧ 2, plural structured R ^S may be bonded to each other to form a ring.
p represents an integer of 0 to 3.

Ra represents a hydrogen atom, an alkyl group, or a group represented by —CH ₂ —O—Ra ₂ . Ra is preferably a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, more preferably a hydrogen atom or a methyl group.
W represents a methylene group, an oxygen atom or a sulfur atom. W is preferably a methylene group or an oxygen atom.
R ₁ represents a (n + 1) -valent organic group. R ₁ is preferably a non-aromatic hydrocarbon group. In this case, R ₁ may be a chain hydrocarbon group or an alicyclic hydrocarbon group. R ₁ is more preferably an alicyclic hydrocarbon group.
R ₂ represents a single bond or an (n + 1) valent organic group. R ₂ is preferably a single bond or a non-aromatic hydrocarbon group. In this case, R ₂ may be a chain hydrocarbon group or an alicyclic hydrocarbon group.
When R ₁ and / or R ₂ is a chain hydrocarbon group, the chain hydrocarbon group may be linear or branched. In addition, the chain hydrocarbon group preferably has 1 to 8 carbon atoms. For example, when R ₁ and / or R ₂ is an alkylene group, R ₁ and / or R ₂ is a methylene group, ethylene group, n-propylene group, isopropylene group, n-butylene group, isobutylene group or sec- A butylene group is preferred.
When R ₁ and / or R ₂ is an alicyclic hydrocarbon group, the alicyclic hydrocarbon group may be monocyclic or polycyclic. This alicyclic hydrocarbon group has, for example, a monocyclo, bicyclo, tricyclo or tetracyclo structure. The carbon number of the alicyclic hydrocarbon group is usually 5 or more, preferably 6 to 30, and more preferably 7 to 25.

Examples of the alicyclic hydrocarbon group include those having the partial structures listed below. Each of these partial structures may have a substituent. In each of these partial structures, the methylene group (—CH ₂ —) includes an oxygen atom (—O—), a sulfur atom (—S—), a carbonyl group [—C (═O) —], a sulfonyl group [— —S (═O) ₂ —], sulfinyl group [—S (═O) —], or imino group [—N (R) —] (where R is a hydrogen atom or an alkyl group) may be substituted.

For example, when R ₁ and / or R ₂ is a cycloalkylene group, R ₁ and / or R ₂ may be an adamantylene group, a noradamantylene group, a decahydronaphthylene group, a tricyclodecanylene group, a tetracyclododeca group. Nylene group, norbornylene group, cyclopentylene group, cyclohexylene group, cycloheptylene group, cyclooctylene group, cyclodecanylene group, or cyclododecanylene group are preferable, and adamantylene group, norbornylene group, cyclohexylene group, cyclopentylene It is more preferable that they are a len group, a tetracyclododecanylene group, or a tricyclodecanylene group.
The non-aromatic hydrocarbon group of R ₁ and / or R ₂ may have a substituent. Examples of the substituent include an alkyl group having 1 to 4 carbon atoms, a halogen atom, a hydroxy group, an alkoxy group having 1 to 4 carbon atoms, a carboxy group, and an alkoxycarbonyl group having 2 to 6 carbon atoms. The above alkyl group, alkoxy group and alkoxycarbonyl group may further have a substituent. As this substituent, a hydroxy group, a halogen atom, and an alkoxy group are mentioned, for example.
L ₁ represents a linking group represented by —COO—, —OCO—, —CONH—, —O—, —Ar—, —SO ₃ — or —SO ₂ NH—. Here, Ar represents a divalent aromatic ring group. L ₁ is preferably a linking group represented by —COO—, —CONH— or —Ar—, and more preferably a linking group represented by —COO— or —CONH—.
R represents a hydrogen atom or an alkyl group. The alkyl group may be linear or branched. The alkyl group preferably has 1 to 6 carbon atoms, more preferably 1 to 3 carbon atoms. R is preferably a hydrogen atom or a methyl group, and more preferably a hydrogen atom.

R ₀ represents a hydrogen atom or an organic group. Examples of the organic group include an alkyl group, a cycloalkyl group, an aryl group, an alkynyl group, and an alkenyl group. R ₀ is preferably a hydrogen atom or an alkyl group, more preferably a hydrogen atom or a methyl group.
L ₃ represents a (m + 2) -valent linking group. That is, L ₃ represents a trivalent or higher linking group. Examples of such a linking group include corresponding groups in specific examples described later.
R ^L represents a (n + 1) -valent linking group. That is, R ^L represents a divalent or higher linking group. Examples of such a linking group include an alkylene group, a cycloalkylene group, and corresponding groups in the specific examples described below. R ^L may be bonded to each other or bonded to the following R ^S to form a ring structure.
R ^S represents a substituent. Examples of the substituent include an alkyl group, an alkenyl group, an alkynyl group, an aryl group, an alkoxy group, an acyloxy group, an alkoxycarbonyl group, and a halogen atom.
n is an integer of 1 or more. n is preferably an integer of 1 to 3, and more preferably 1 or 2. When n is 2 or more, it is possible to further improve the dissolution contrast with respect to a developer containing an organic solvent. Accordingly, in this way, the limit resolution and roughness characteristics can be further improved.
m is an integer of 1 or more. m is preferably an integer of 1 to 3, and more preferably 1 or 2.
l is an integer of 0 or more. l is preferably 0 or 1.
p is an integer of 0 to 3.
Specific examples of the repeating unit having a group that decomposes by the action of an acid to generate an alcoholic hydroxy group are shown below. In the specific examples, Ra and OP have the same meanings as in general formulas (I-1) to (I-3). In addition, when a plurality of OPs are bonded to each other to form a ring, the corresponding ring structure is represented as “OPO” for convenience.

The group that decomposes by the action of an acid to produce an alcoholic hydroxy group is preferably represented by at least one selected from the group consisting of the following general formulas (II-1) to (II-4).

Where
R ₃ each independently represents a hydrogen atom or a monovalent organic group. R ₃ may be bonded to each other to form a ring.
R ₄ each independently represents a monovalent organic group. R ₄ may be bonded to each other to form a ring. R ₃ and R ₄ may be bonded to each other to form a ring.
R ₅ each independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an alkenyl group, or an alkynyl group. At least two R ₅ may be bonded to each other to form a ring. However, when one or two of the three R ₅ are hydrogen atoms, at least one of the remaining R ₅ represents an aryl group, an alkenyl group, or an alkynyl group.
The group capable of decomposing by the action of an acid to produce an alcoholic hydroxy group is also preferably represented by at least one selected from the group consisting of the following general formulas (II-5) to (II-9).

Where
R ₄ is formula (II-1) is synonymous with _{R 4} a ~ (II-3).
R ₆ each independently represents a hydrogen atom or a monovalent organic group. R ₆ may be bonded to each other to form a ring.
The group that decomposes by the action of an acid to produce an alcoholic hydroxy group is more preferably represented by at least one selected from the general formulas (II-1) to (II-3). More preferably, it is represented by 1) or (II-3), and particularly preferably represented by formula (II-1).

R ₃ represents a hydrogen atom or a monovalent organic group as described above. R ₃ is preferably a hydrogen atom, an alkyl group or a cycloalkyl group, more preferably a hydrogen atom or an alkyl group.
The alkyl group for R ₃ may be linear or branched. The number of carbon atoms of the alkyl group represented by R ₃ is preferably 1 to 10, and more preferably 1 to 3. Examples of the alkyl group for R ₃ include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, and an n-butyl group.
The cycloalkyl group for R ₃ may be monocyclic or polycyclic. The number of carbon atoms of the cycloalkyl group represented by R ₃ is preferably 3 to 10, and more preferably 4 to 8. Examples of the cycloalkyl group represented by R ₃ include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a norbornyl group, and an adamantyl group.

In general formula (II-1), at least one of R ₃ is preferably a monovalent organic group. When such a configuration is employed, particularly high sensitivity can be achieved.
R ₄ represents a monovalent organic group. R ₄ is preferably an alkyl group or a cycloalkyl group, and more preferably an alkyl group. These alkyl groups and cycloalkyl groups may have a substituent.
The alkyl group represented by R ₄ preferably has no substituent, or preferably has one or more aryl groups and / or one or more silyl groups as substituents. The carbon number of the unsubstituted alkyl group is preferably 1-20. The alkyl group moiety in the alkyl group substituted with one or more aryl groups preferably has 1 to 25 carbon atoms. The number of carbon atoms of the alkyl group moiety in the alkyl group substituted with one or more silyl groups is preferably 1-30. Further, when the cycloalkyl group of R ₄ has no substituent, the carbon number thereof is preferably 3-20.
R ₅ represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an alkenyl group, or an alkynyl group. However, when one or two of the three R ₅ are hydrogen atoms, at least one of the remaining R ₅ represents an aryl group, an alkenyl group, or an alkynyl group. R ₅ is preferably a hydrogen atom or an alkyl group. The alkyl group may have a substituent or may not have a substituent. When the alkyl group has no substituent, the number of carbon atoms is preferably 1 to 6, and more preferably 1 to 3.
R ₆ represents a hydrogen atom or a monovalent organic group as described above. R ₆ is preferably a hydrogen atom, an alkyl group or a cycloalkyl group, more preferably a hydrogen atom or an alkyl group, and further preferably a hydrogen atom or an alkyl group having no substituent. R ₆ is preferably a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, and more preferably a hydrogen atom or an alkyl group having 1 to 10 carbon atoms and having no substituent.
Examples of the alkyl group and cycloalkyl group of R ₄ , R _5, and R ₆ include the same alkyl group and cycloalkyl group as those described above for R ₃ .
Below, the specific example of the group which decomposes | disassembles by the effect | action of an acid and produces an alcoholic hydroxy group is shown.

Specific examples of the repeating unit having a group that decomposes by the action of an acid to generate an alcoholic hydroxy group are shown below. In the following specific examples, Xa ₁ represents a hydrogen atom, CH ₃ , CF ₃ , or CH ₂ OH.

The above repeating unit having an acid-decomposable group may be one type or a combination of two or more types.

The content of the repeating unit having an acid-decomposable group in the resin (A) (when there are a plurality of types) is 5 mol% or more and 80 mol% or less with respect to all repeating units in the resin (A) It is preferably 5 mol% or more and 75 mol% or less, more preferably 10 mol% or more and 65 mol% or less.

(B) Repeating Unit Represented by General Formula (1) The resin (A) is preferably a resin having a repeating unit represented by the following general formula (1).

In general formula (1),
R ₁₁ , R ₁₂ and R ₁₃ each independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, a cyano group or an alkoxycarbonyl group. R ₁₃ may be bonded to Ar ₁ to form a ring, in which case R ₁₃ represents an alkylene group.
X ₁ represents a single bond or a divalent linking group.
Ar ₁ represents an (n + 1) -valent aromatic ring group, and when bonded to R ₁₃ to form a ring, represents an (n + 2) -valent aromatic ring group.
n represents an integer of 1 to 4.

Specific examples of the alkyl group, cycloalkyl group, halogen atom, alkoxycarbonyl group of R ₁₁ , R ₁₂ , and R ₁₃ in formula (1), and the substituents that these groups may have are the above general formula (V) Are the same as the specific examples described for each group represented by R ₅₁ , R ₅₂ and R ₅₃ .

Ar ₁ 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, an anthracenylene group, or the like. Examples of preferred aromatic ring groups include heterocycles such as thiophene, furan, pyrrole, benzothiophene, benzofuran, benzopyrrole, triazine, imidazole, benzimidazole, triazole, thiadiazole, thiazole.

Examples of the substituent that the above-described alkylene group and (n + 1) -valent aromatic ring group may have include an alkyl group, a methoxy group, an ethoxy group, a hydroxyethoxy group, a propoxy group, a hydroxypropoxy group, a butoxy group and other alkoxy groups, phenyl And aryl groups such as groups.

Examples of the divalent linking group for X ₁ include —COO— or —CONR ₆₄ —.
_-CONR 64 represented by X ₁ - _{(R 64} represents a hydrogen atom, an alkyl group) The alkyl group for _{R 64} in, preferably an optionally substituted 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, a dodecyl group, and the like, and an alkyl group having a carbon number of 8 or less is more preferable. Can be mentioned.
X ₁ is preferably a single bond, —COO— or —CONH—, and more preferably a single bond or —COO—.

As Ar ₁ , an optionally substituted aromatic ring group having 6 to 18 carbon atoms is more preferable, and a benzene ring group, a naphthalene ring group, and a biphenylene ring group are particularly preferable.
The repeating unit (b) preferably has a hydroxystyrene structure. That is,
Ar ₁ is preferably a benzene ring group.

N represents an integer of 1 to 4, preferably 1 or 2, and more preferably 1.

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

Resin (A) may contain two or more types of repeating units represented by general formula (1).

The content of the repeating unit represented by the general formula (1) (the total when containing plural types) is within the range of 3 to 98 mol% with respect to all the repeating units in the resin (A). Is more preferably in the range of 10 to 80 mol%, and still more preferably in the range of 25 to 70 mol%.

(C) Repeating unit having a polar group other than the repeating unit represented by formula (1) The resin (A) preferably contains a repeating unit (c) having a polar group. By including the repeating unit (c), for example, the sensitivity of the composition containing a resin can be improved. The repeating unit (c) is preferably a non-acid-decomposable repeating unit (that is, having no acid-decomposable group).
Examples of the “polar group” that can be contained in the repeating unit (c) include the following (1) to (4). In the following, “electronegativity” means a value by Pauling.

(1) A functional group including a structure in which an oxygen atom and an atom having an electronegativity difference of 1.1 or more are bonded by a single bond. Examples of such a polar group include a hydroxy group and the like. And a group containing a structure represented by O—H.
(2) Functional group including a structure in which a nitrogen atom and an atom having a difference in electronegativity of the nitrogen atom of 0.6 or more are bonded by a single bond. Examples of such a polar group include an amino group and the like. And a group containing a structure represented by NH.
(3) Functional group including a structure in which two atoms having electronegativity different by 0.5 or more are bonded by a double bond or a triple bond. Examples of such a polar group include C≡N, C═O, N = And a group containing a structure represented by O, S═O or C═N.
(4) Examples of the functional group such polar groups having an ionic sites, for example, a group having a moiety represented by N ⁺ or S ^+.
Specific examples of the partial structure that can be included in the “polar group” are given below.

The “polar group” that the repeating unit (c) may contain includes, for example, (I) a hydroxy group, (II) a cyano group, (III) a lactone group or a sultone group (cyclic sulfonate ester), (IV) a carboxylic acid group, or At least selected from the group consisting of a sulfonic acid group, a group corresponding to (V) an amide group, a sulfonamide group or a derivative thereof, (VI) an ammonium group or a sulfonium group, and a group formed by combining two or more thereof. One is preferred.

The polar group is selected from a hydroxyl group, a cyano group, a lactone group, a sultone group, a carboxylic acid group, a sulfonic acid group, an amide group, a sulfonamide group, an ammonium group, a sulfonium group, and a group formed by combining two or more thereof. It is particularly preferably an alcoholic hydroxy group, a cyano group, a lactone group, a sultone group, or a group containing a cyanolactone structure.
When the resin further contains a repeating unit having an alcoholic hydroxy group, the exposure latitude (EL) of the composition containing the resin can be further improved.
When the resin further contains a repeating unit having a cyano group, the sensitivity of the composition containing the resin can be further improved.
If the resin further contains a repeating unit having a lactone group or a sultone group, the dissolution contrast with respect to the developer containing an organic solvent can be further improved. This also makes it possible to further improve the dry etching resistance, coating properties, and adhesion to the substrate of the resin-containing composition.
If the resin further contains a repeating unit having a group containing a lactone structure having a cyano group, the dissolution contrast with respect to the developer containing an organic solvent can be further improved. This also makes it possible to further improve the sensitivity, dry etching resistance, applicability, and adhesion to the substrate of the composition containing the resin. In addition, this makes it possible for a single repeating unit to have a function attributable to each of the cyano group and the lactone group, thereby further increasing the degree of freedom in designing the resin.

When the polar group of the repeating unit (c) is an alcoholic hydroxy group, it is preferably represented by at least one selected from the group consisting of the following general formulas (I-1H) to (I-10H). In particular, it is more preferably represented by at least one selected from the group consisting of the following general formulas (I-1H) to (I-3H), and may be represented by the following general formula (I-1H). Further preferred.

In the formula, Ra, R ₁ , R ₂ , W, n, m, l, L ₁ , R, R ₀ , L ₃ , R ^L , R ^S and p are represented by the general formulas (I-1) to (I− It is synonymous with each of 10).
A repeating unit having a group capable of decomposing by the action of an acid to generate an alcoholic hydroxy group, and a repeating unit represented by at least one selected from the group consisting of the above general formulas (I-1H) to (I-10H) When the unit is used in combination, for example, by suppressing acid diffusion due to an alcoholic hydroxy group and increasing sensitivity due to a group that decomposes by the action of an acid to generate an alcoholic hydroxy group, without degrading other performances, The exposure latitude (EL) can be improved.
The content of the repeating unit having an alcoholic hydroxy group is preferably from 1 to 60 mol%, more preferably from 3 to 50 mol%, still more preferably from 5 to 40 mol%, based on all repeating units in the resin (A). It is.
Specific examples of the repeating unit represented by any one of the general formulas (I-1H) to (I-10H) are shown below. In specific examples, Ra has the same meaning as Ra in formulas (I-1H) to (I-10H).

When the polar group of the repeating unit (c) is an alcoholic hydroxy group or a cyano group, it is a repeating unit having an alicyclic hydrocarbon structure substituted with a hydroxyl group or a cyano group as one embodiment of a preferable repeating unit. Is mentioned. At this time, it is preferable not to have an acid-decomposable group. The alicyclic hydrocarbon structure in the alicyclic hydrocarbon structure substituted with a hydroxyl group or a cyano group is preferably an adamantyl group, a diadamantyl group, or a norbornane group. As the alicyclic hydrocarbon structure substituted with a preferred hydroxyl group or cyano group, partial structures represented by the following general formulas (VIIa) to (VIIc) are preferred. This improves the substrate adhesion and developer compatibility.

In the general formulas (VIIa) to (VIIc),
R ₂ c to R ₄ c each independently represents a hydrogen atom, a hydroxyl group or a cyano group. However, at least one of R ₂ c to R ₄ c represents a hydroxyl group. Preferably, one or two of R ₂ c to R ₄ c are a hydroxyl group and the remaining is a hydrogen atom. In the general formula (VIIa), more preferably, _two of R ₂ c to R ₄ c are a hydroxyl group and the rest are hydrogen atoms.

Examples of the repeating unit having a partial structure represented by the general formulas (VIIa) to (VIIc) include the repeating units represented by the following general formulas (AIIa) to (AIIc).

In the general formulas (AIIa) to (AIIc),
R ₁ c represents a hydrogen atom, a methyl group, a trifluoromethyl group, or a hydroxymethyl group.

_R ₂ c ~ R ₄ c is in the general formula (VIIa) ~ _(VIIc), the same meanings as _R 2 c ~ R ₄ c.

The resin (A) may or may not contain a repeating unit having a hydroxyl group or a cyano group. However, when it is contained, the content of the repeating unit having a hydroxyl group or a cyano group is in the resin (A). The amount is preferably 1 to 60 mol%, more preferably 3 to 50 mol%, still more preferably 5 to 40 mol%, based on all repeating units.

Specific examples of the repeating unit having a hydroxyl group or a cyano group are listed below, but the present invention is not limited thereto.

The repeating unit (c) may be a repeating unit having a lactone structure or a sultone structure as a polar group.
As the repeating unit having a lactone structure or a sultone structure, a repeating unit represented by the following general formula (AII) is more preferable.

In general formula (AII),
Rb ₀ represents a hydrogen atom, a halogen atom or an optionally substituted alkyl group (preferably having 1 to 4 carbon atoms).
Preferable substituents that the alkyl group of Rb ₀ may have include a hydroxyl group and a halogen atom. Examples of the halogen atom for Rb ₀ include a fluorine atom, a chlorine atom, and a bromine atom. Rb ₀ is preferably a hydrogen atom, a methyl group, a hydroxymethyl group or a trifluoromethyl group, and particularly preferably a hydrogen atom or a methyl group.

Ab represents a single bond, an alkylene group, a divalent linking group having a monocyclic or polycyclic cycloalkyl structure, an ether bond, an ester bond, a carbonyl group, or a divalent linking group obtained by combining these. Ab is preferably a single bond or a divalent linking group represented by —Ab ₁ —CO ₂ —.
Ab ₁ represents a linear or branched alkylene group, a cycloalkylene group or a monocyclic or polycyclic, preferably a methylene group, an ethylene group, a cyclohexylene group, an adamantylene group, norbornylene group.
V represents a group having a lactone structure or a sultone structure.

As the group having a lactone structure or a sultone structure, any group having a lactone structure or a sultone structure can be used, but a 5- to 7-membered lactone structure or a sultone structure is preferable, and a 5- to 7-membered structure is preferable. Those in which other ring structures are condensed in a form forming a bicyclo structure or a spiro structure in the lactone structure or sultone structure of the ring are preferable. Repeat having a lactone structure represented by any one of the following general formulas (LC1-1) to (LC1-17) or a sultone structure represented by any one of the following general formulas (SL1-1) or (SL1-2) More preferably it has units. A lactone structure or a sultone structure may be directly bonded to the main chain. Particularly preferred structures are (LC1-1), (LC1-4), (LC1-5), (LC1-6), (LC1-8), (LC1-13), (LC1-14), (SL1- 1).

The lactone structure portion or sultone structure may or may not have a substituent (Rb ₂ ). Preferred examples of the substituent (Rb ₂ ) include an alkyl group having 1 to 8 carbon atoms, a monovalent cycloalkyl group having 4 to 7 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, and an alkoxycarbonyl group having 2 to 8 carbon atoms. , Carboxyl group, halogen atom, hydroxyl group, cyano group, acid-decomposable group and the like. More preferred are an alkyl group having 1 to 4 carbon atoms, a cyano group, and an acid-decomposable group. n ₂ represents an integer of 0 to 4. When n ₂ is 2 or more, a plurality of substituents (Rb ₂ ) may be the same or different, and a plurality of substituents (Rb ₂ ) may be bonded to form a ring. .

The repeating unit having a lactone structure or a sultone structure usually has an optical isomer, but any optical isomer may be used. One optical isomer may be used alone, or a plurality of optical isomers may be mixed and used. When one kind of optical isomer is mainly used, the optical purity (ee) thereof is preferably 90% or more, more preferably 95% or more.

The resin (A) may or may not contain a repeating unit having a lactone structure or a sultone structure, but when it contains a repeating unit having a lactone structure or a sultone structure, the above repeating unit in the resin (A) The content of is preferably in the range of 1 to 70 mol%, more preferably in the range of 3 to 65 mol%, still more preferably in the range of 5 to 60 mol% with respect to all repeating units.
Specific examples of the repeating unit having a lactone structure or a sultone structure in the resin (A) are shown below, but the present invention is not limited thereto. In the formula, Rx represents H, CH ₃ , CH ₂ OH, or CF ₃ .

Also, it is one of particularly preferable embodiments that the polar group that the repeating unit (c) may have is an acidic group. Preferred acidic groups include phenolic hydroxyl groups, carboxylic acid groups, sulfonic acid groups, fluorinated alcohol groups (eg hexafluoroisopropanol group), sulfonamido groups, sulfonylimide groups, (alkylsulfonyl) (alkylcarbonyl) methylene groups, Alkylsulfonyl) (alkylcarbonyl) imide group, bis (alkylcarbonyl) methylene group, bis (alkylcarbonyl) imide group, bis (alkylsulfonyl) methylene group, bis (alkylsulfonyl) imide group, tris (alkylcarbonyl) methylene group, A tris (alkylsulfonyl) methylene group is mentioned. Of these, the repeating unit (c) is more preferably a repeating unit having a carboxyl group. By containing the repeating unit having an acidic group, the resolution in the contact hole application is increased. The repeating unit having an acidic group includes a repeating unit in which an acidic group is directly bonded to the main chain of the resin, such as a repeating unit of acrylic acid or methacrylic acid, or an acidic group in the main chain of the resin through a linking group. It is preferable to use a polymerization initiator or a chain transfer agent having a repeating unit bonded to each other, or an acidic group, at the time of polymerization and introduce it at the end of the polymer chain. Particularly preferred are repeating units of acrylic acid or methacrylic acid.

The acidic group that the repeating unit (c) may have may or may not contain an aromatic ring, but when it has an aromatic ring, it is preferably selected from acidic groups other than phenolic hydroxyl groups. When the repeating unit (c) has an acidic group, the content of the repeating unit having an acidic group is preferably 30 mol% or less, and 20 mol% or less with respect to all the repeating units in the resin (A). More preferably. When resin (A) contains the repeating unit which has an acidic group, content of the repeating unit which has an acidic group in resin (A) is 1 mol% or more normally.
Specific examples of the repeating unit having an acidic group are shown below, but the present invention is not limited thereto.
In specific examples, Rx represents H, CH ₃ , CH ₂ OH, or CF ₃ .

(D) Repeating unit having a plurality of aromatic rings The resin (A) may have a repeating unit (d) having a plurality of aromatic rings represented by the following general formula (c1).

In general formula (c1),
R ₃ represents a hydrogen atom, an alkyl group, a halogen atom, a cyano group or a nitro group,
Y represents a single bond or a divalent linking group,
Z represents a single bond or a divalent linking group;
Ar represents an aromatic ring group,
p represents an integer of 1 or more.

The alkyl group as R ₃ may be linear or branched. For example, methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, sec-butyl group, t-butyl group Group, n-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, n-nonyl group, n-decanyl group, i-butyl group, and may further have a substituent. Preferred examples of the substituent include an alkoxy group, a hydroxyl group, a halogen atom, and a nitro group. Among them, examples of the alkyl group having a substituent include a CF ₃ group, an alkyloxycarbonylmethyl group, an alkylcarbonyloxymethyl group, and hydroxymethyl. Group, alkoxymethyl group and the like are preferable.

Examples of the halogen atom as R ₃ include a fluorine atom, a chlorine atom, and a bromine atom, and a fluorine atom is particularly preferable.
Y represents a single bond or a divalent linking group, and examples of the divalent linking group include an ether group (oxygen atom), a thioether group (sulfur atom), an alkylene group, an arylene group, a carbonyl group, a sulfide group, Sulfone group, —COO—, —CONH—, —SO ₂ NH—, —CF ₂ —, —CF ₂ CF ₂ —, —OCF ₂ O—, —CF ₂ OCF ₂ —, —SS—, —CH ₂ SO ₂ CH ₂ —, —CH ₂ COCH ₂ —, —COCF ₂ CO—, —COCO—, —OCOO—, —OSO ₂ O—, amino group (nitrogen atom), acyl group, alkylsulfonyl group, —CH═CH And —C—C≡C—, an aminocarbonylamino group, an aminosulfonylamino group, or a combination thereof. Y preferably has 15 or less carbon atoms, more preferably 10 or less carbon atoms.

Y is preferably a single bond, a —COO— group, a —COS— group, a —CONH— group, more preferably a —COO— group or a —CONH— group, and particularly preferably a —COO— group.
Z represents a single bond or a divalent linking group, and examples of the divalent linking group include an ether group (oxygen atom), a thioether group (sulfur atom), an alkylene group, an arylene group, a carbonyl group, a sulfide group, Sulfone group, —COO—, —CONH—, —SO ₂ NH—, amino group (nitrogen atom), acyl group, alkylsulfonyl group, —CH═CH—, aminocarbonylamino group, aminosulfonylamino group, or these Examples include a group consisting of a combination.
Z is preferably a single bond, an ether group, a carbonyl group, or —COO—, more preferably a single bond or an ether group, and particularly preferably a single bond.

Ar represents an aromatic ring group, specifically, phenyl group, naphthyl group, anthracenyl group, phenanthrenyl group, quinolinyl group, furanyl group, thiophenyl group, fluorenyl-9-one-yl group, anthraquinonyl group, phenanthralkyl. A nonyl group, a pyrrole group, etc. are mentioned, A phenyl group is preferable. These aromatic ring groups may further have a substituent. Preferred examples of the substituent include an alkyl group, 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. Group, aryl group such as phenyl group, aryloxy group, arylcarbonyl group, heterocyclic residue, etc. Among them, phenyl group suppresses deterioration of exposure latitude and pattern shape caused by out-of-band light It is preferable from the viewpoint.
p is an integer of 1 or more, preferably an integer of 1 to 3.

More preferred as the repeating unit (d) is a repeating unit represented by the following formula (c2).

In general formula (c2), R ₃ represents a hydrogen atom or an alkyl group. Preferred alkyl groups as the alkyl group R ₃ represents is the same as the alkyl group represented by R ₃ in the general formula (c1).

Here, regarding extreme ultraviolet (EUV light) exposure, leakage light (out-of-band light) generated in the ultraviolet region with a wavelength of 100 to 400 nm deteriorates surface roughness, and as a result, bridges between patterns and pattern breaks , Resolution and LWR performance tend to decrease.
However, the aromatic ring in the repeating unit (d) functions as an internal filter that can absorb the out-of-band light. Therefore, from the viewpoint of high resolution and low LWR, the resin (A) preferably contains the repeating unit (d).
Here, it is preferable that the repeating unit (d) does not have a phenolic hydroxyl group (a hydroxyl group directly bonded on an aromatic ring) from the viewpoint of obtaining high resolution.

Specific examples of the repeating unit (d) are shown below, but are not limited thereto.

The resin (A) may or may not contain the repeating unit (d), but when it is contained, the content of the repeating unit (d) is from 1 to the total repeating unit of the resin (A). The range is preferably 30 mol%, more preferably 1 to 20 mol%, and still more preferably 1 to 15 mol%. The repeating unit (d) contained in the resin (A) may contain a combination of two or more types.

The resin (A) in the present invention may have a repeating unit other than the above repeating units (a) to (d) as appropriate. As an example of such a repeating unit, a repeating unit that has an alicyclic hydrocarbon structure that does not have a polar group (for example, the acid group, hydroxyl group, and cyano group) and does not exhibit acid decomposability can be included. Thereby, the solubility of the resin can be appropriately adjusted during development using a developer containing an organic solvent. Examples of such a repeating unit include a repeating unit represented by the general formula (IV).

In general formula (IV), R ₅ represents a hydrocarbon group having at least one cyclic structure and having no polar group.
Ra represents a hydrogen atom, an alkyl group or _-CH 2 -O-Ra ₂ group. In the formula, Ra ₂ represents a hydrogen atom, an alkyl group, or an acyl group. Ra is preferably a hydrogen atom, a methyl group, a hydroxymethyl group or a trifluoromethyl group, particularly preferably a hydrogen atom or a methyl group.

The cyclic structure possessed by R ₅ includes a monocyclic hydrocarbon group and a polycyclic hydrocarbon group. Examples of the monocyclic hydrocarbon group include cycloalkenyl having 3 to 12 carbon atoms such as cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclooctyl group and the like, and cycloalkyl groups having 3 to 12 carbon atoms and cyclohexenyl group. Groups. A preferred monocyclic hydrocarbon group is a monocyclic hydrocarbon group having 3 to 7 carbon atoms, and more preferred examples include a cyclopentyl group and a cyclohexyl group.

The polycyclic hydrocarbon group includes a ring assembly hydrocarbon group and a bridged cyclic hydrocarbon group, and examples of the ring assembly hydrocarbon group include a bicyclohexyl group and a perhydronaphthalenyl group. As the bridged cyclic hydrocarbon ring, for example, bicyclic such as pinane, bornane, norpinane, norbornane, bicyclooctane ring (bicyclo [2.2.2] octane ring, bicyclo [3.2.1] octane ring, etc.) Hydrocarbon rings and tricyclic hydrocarbon rings such as homobrendane, adamantane, tricyclo [5.2.1.0 ^2,6 ] decane, tricyclo [4.3.1.1 ^2,5 ] undecane ring, tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodecane, tetracyclic hydrocarbon rings such as perhydro-1,4-methano-5,8-methanonaphthalene ring, and the like. The bridged cyclic hydrocarbon ring includes a condensed cyclic hydrocarbon ring such as perhydronaphthalene (decalin), perhydroanthracene, perhydrophenanthrene, perhydroacenaphthene, perhydrofluorene, perhydroindene, perhydroindene. A condensed ring in which a plurality of 5- to 8-membered cycloalkane rings such as a phenalene ring are condensed is also included.

Preferred examples of the bridged cyclic hydrocarbon ring include a norbornyl group, an adamantyl group, a bicyclooctanyl group, a tricyclo [5.2.1.0 ^2,6 ] decanyl group, and the like. More preferable examples of the bridged cyclic hydrocarbon ring include a norbornyl group and an adamantyl group.

These alicyclic hydrocarbon groups may have a substituent. Preferred examples of the substituent include a halogen atom, an alkyl group, a hydroxyl group substituted with a hydrogen atom, and an amino group substituted with a hydrogen atom. It is done. Preferred halogen atoms include bromine, chlorine and fluorine atoms, and preferred alkyl groups include methyl, ethyl, butyl and t-butyl groups. The alkyl group described above may further have a substituent, and examples of the substituent that may further include a halogen atom, an alkyl group, a hydroxyl group substituted with a hydrogen atom, and an amino group substituted with a hydrogen atom. The group can be mentioned.

Examples of the substituent of the hydrogen atom in the hydroxyl group and the amino group include an alkyl group, a cycloalkyl group, an aralkyl group, a substituted methyl group, a substituted ethyl group, an alkoxycarbonyl group, and an aralkyloxycarbonyl group. Preferred alkyl groups include alkyl groups having 1 to 4 carbon atoms, preferred substituted methyl groups include methoxymethyl, methoxythiomethyl, benzyloxymethyl, t-butoxymethyl, 2-methoxyethoxymethyl groups, and preferred substituted ethyl groups. 1-ethoxyethyl, 1-methyl-1-methoxyethyl, preferable acyl groups include aliphatic acyl groups having 1 to 6 carbon atoms such as formyl, acetyl, propionyl, butyryl, isobutyryl, valeryl and pivaloyl groups, alkoxycarbonyl Examples of the group include an alkoxycarbonyl group having 1 to 4 carbon atoms.

The resin (A) has an alicyclic hydrocarbon structure having no polar group, and may or may not contain a repeating unit that does not exhibit acid decomposability. The content is preferably 1 to 20 mol%, more preferably 5 to 15 mol%, based on all repeating units in the resin (A).
Specific examples of the repeating unit having an alicyclic hydrocarbon structure having no polar group and not exhibiting acid decomposability are shown below, but the present invention is not limited thereto. In the formula, Ra represents H, CH ₃ , CH ₂ OH, or CF ₃ .

The resin (A) may further contain a repeating unit represented by the following general formula (5).

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

Specific examples of the repeating unit represented by the general formula (5) are shown below, but the present invention is not limited thereto.

The content of the repeating unit represented by the general formula (5) in the resin (A) is preferably in the range of 1 to 40 mol% with respect to all the repeating units of the resin (A), and in the range of 2 to 30 mol%. Is more preferable, and the range of 5 to 25 mol% is particularly preferable.

In addition, the resin (A) may contain the following monomer components in view of the effects such as the improvement of Tg, the improvement of dry etching resistance, the above-described internal filter of out-of-band light, and the like.

In the resin (A) used in the composition of the present invention, the content molar ratio of each repeating structural unit is the resist dry etching resistance, standard developer suitability, substrate adhesion, resist profile, and general resist requirements. It is appropriately set in order to adjust the resolution, heat resistance, sensitivity, etc., which are performance.

Specific examples of the resin (A) are shown below, but the present invention is not limited thereto.

The form of the resin (A) in the present invention may be any of random type, block type, comb type, and star type.
Resin (A) is compoundable by the radical, cation, or anion polymerization of the unsaturated monomer corresponding to each structure, for example. It is also possible to obtain the desired resin by conducting a polymer reaction after polymerization using an unsaturated monomer corresponding to the precursor of each structure.
For example, as a general synthesis method, an unsaturated monomer and a polymerization initiator are dissolved in a solvent and the polymerization is performed by heating, and a solution of the unsaturated monomer and the polymerization initiator is added to the heating solvent for 1 to 10 hours. The dropping polymerization method etc. which are dropped and added over are mentioned, and the dropping polymerization method is preferable.

Examples of the solvent used for the polymerization include a solvent that can be used in preparing the actinic ray-sensitive or radiation-sensitive resin composition described below, and more preferably the composition of the present invention. Polymerization is preferably carried out using the same solvent as used in the above. Thereby, generation | occurrence | production of the particle at the time of a preservation | save can be suppressed.
The polymerization reaction is preferably performed in an inert gas atmosphere such as nitrogen or argon. As a polymerization initiator, a commercially available radical initiator (azo initiator, peroxide, etc.) is used to initiate the polymerization. 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 more preferable. Preferable initiators include azobisisobutyronitrile, azobisdimethylvaleronitrile, dimethyl 2,2′-azobis (2-methylpropionate) and the like. If necessary, the polymerization may be performed in the presence of a chain transfer agent (for example, alkyl mercaptan).

The concentration of the reaction is 5 to 70% by mass, preferably 10 to 50% by mass. The reaction temperature is usually 10 ° C to 150 ° C, preferably 30 ° C to 120 ° C, more preferably 40 ° C to 100 ° C.
The reaction time is usually 1 to 48 hours, preferably 1 to 24 hours, and more preferably 1 to 12 hours.
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 10,000 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 to 1000 parts by mass.
The temperature at the time of 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).
The polymerization reaction is preferably performed in an inert gas atmosphere such as nitrogen or argon. As a polymerization initiator, a commercially available radical initiator (azo initiator, peroxide, etc.) is used to initiate the polymerization. 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 more preferable. Preferable initiators include azobisisobutyronitrile, azobisdimethylvaleronitrile, dimethyl 2,2′-azobis (2-methylpropionate) and the like. If desired, an initiator is added or added in portions, and after completion of the reaction, it is put into a solvent and a desired polymer is recovered by a method such as powder or solid recovery. The concentration of the reaction is 5 to 50% by mass, preferably 10 to 30% by mass. The reaction temperature is usually 10 ° C. to 150 ° C., preferably 30 ° C. to 120 ° C., more preferably 60 ° C. to 100 ° C.

The molecular weight of the resin (A) in the present invention is not particularly limited, but the weight average molecular weight is preferably in the range of 1000 to 100,000, more preferably in the range of 1500 to 60000, and in the range of 2000 to 30000. It is particularly preferred. By setting the weight average molecular weight in the range of 1,000 to 100,000, the heat resistance and dry etching resistance can be prevented from being deteriorated, and the developability is deteriorated, and the film forming property is deteriorated due to an increase in viscosity. Can be prevented. Here, the weight average molecular weight of the resin indicates a molecular weight in terms of polystyrene measured by GPC (carrier: THF or N-methyl-2-pyrrolidone (NMP)).

The dispersity (Mw / Mn) is preferably 1.00 to 5.00, more preferably 1.00 to 3.50, and still more preferably 1.00 to 2.50. When the molecular weight distribution is small, the resolution and resist shape are excellent, the side walls of the resist pattern are smooth, and the roughness is excellent.

In this specification, the weight average molecular weight (Mw) and dispersity of the resin are, for example, HLC-8120 (manufactured by Tosoh Corporation), and TSKgelｇMultipore HXL-M (manufactured by Tosoh Corp., 7.8 mmID) as a column. × 30.0 cm) can be determined by using THF (tetrahydrofuran) or NMP (N-methyl-2-pyrrolidone) as the eluent.

<Resin (A2)>
The resin (A) has been described above. As described above, the resin (A) corresponds to the resin (A2) contained in the composition (ii).
In composition (ii), resin (A2) which is resin (A) can be used individually by 1 type or in combination of 2 or more types. The content of the resin (A2) which is the resin (A) is preferably 20 to 99% by mass, more preferably 30 to 99% by mass, and more preferably 40 to 99% based on the total solid content in the composition (ii). More preferred is mass%.

<(S) Repeating unit having a monovalent iodine atom>
Next, the repeating unit (s) will be described.
The resin (A1) contained in the composition (i) is a resin having a repeating unit (s) having a monovalent iodine atom, and preferably the resin (A) described above has a repeating unit (s). Resin. In this case, the resin (A1) is the same as the resin (A) described above except for the repeating unit (s).

More specifically, the repeating unit (s) is a repeating unit having a partial structure having a monovalent iodine atom that is not eliminated by irradiation with actinic rays or radiation. That is, the repeating unit (s) has a partial structure having a monovalent iodine atom (hereinafter also referred to as “partial structure (s1)”), but this partial structure (s1) can be obtained by irradiation with actinic rays or radiation. , A partial structure that does not desorb from the repeating unit (s). Since the partial structure (s1) having a monovalent iodine atom is not eliminated even by irradiation with actinic rays or radiation, it is considered that high sensitivity can be obtained without reducing the light absorption effect.

Here, the partial structure which decomposes | disassembles by irradiation of actinic light or a radiation is demonstrated.
In the repeating unit (s) having a monovalent iodine atom, the partial structure (s1) having a monovalent iodine atom is preferably not included in the partial structure decomposed by irradiation with actinic rays or radiation.
Examples of the partial structure that decomposes upon irradiation with actinic rays or radiation include partial structures represented by the following general formulas (I) to (III). In addition, upon irradiation with actinic rays or radiation, the S atom-S atom bond is cleaved in the general formula (I), the O atom-N atom bond is cleaved in the general formula (II), and the O atom in the general formula (III). The -N atom bond is cleaved.

In the general formulas (I) to (III),
Ar ₃ and Ar ₄ each independently represent a substituted or unsubstituted aryl group.
R ₂₀₆ , R ₂₀₇ and R ₂₀₈ represent a substituted or unsubstituted alkyl group or a substituted or unsubstituted aryl group.
A represents a substituted or unsubstituted alkylene group, a substituted or unsubstituted alkenylene group, or a substituted or unsubstituted arylene group.

In addition, the repeating unit (s) having a monovalent iodine atom may be a repeating unit having an acid-decomposable group. That is, in the repeating unit (s), it is not excluded that the partial structure (s1) having a monovalent iodine atom is a partial structure that is decomposed by the action of an acid to generate a polar group.
In this case, resin (A1) should just have only repeating unit (s), and does not need to have the repeating unit (a) which has the acid-decomposable group mentioned above. In other words, in the resin (A1) in this case, “a repeating unit having a partial structure having a monovalent iodine atom that is not eliminated by irradiation with actinic rays or radiation” is decomposed by the action of an acid to be polar. It also serves as a “repeating unit having a group for generating a group”.

Preferred examples of such a repeating unit (s) include a repeating unit represented by the following general formula (1 ').

In general formula (1 ′),
R ₁₁ , R ₁₂ and R ₁₃ each independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, a cyano group or an alkoxycarbonyl group. R ₁₃ may be bonded to Ar ₁ to form a ring. When R ₁₃ and Ar ₁ are bonded, R ₁₃ represents an alkylene group.
X ₁ represents a single bond, an alkylene group, an aromatic ring group, —O—, —S—, —CO—, —COO—, —SO ₂ NH—, —SO ₂ O—, —NR— (R represents a hydrogen atom Or an alkyl group), a divalent nitrogen-containing non-aromatic heterocyclic group, or a divalent linking group composed of a combination thereof.
Ar ₁ represents an aromatic ring group.
RI represents an iodine atom or an organic group containing at least one iodine atom.
n represents an integer of 1 or more.

In the general formula (1 ′), the alkyl group represented by R ₁₁ to R ₁₃ is preferably an optionally substituted methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, sec- Examples thereof include alkyl groups having 20 or less carbon atoms such as butyl group, hexyl group, 2-ethylhexyl group, octyl group and dodecyl group, more preferably alkyl groups having 8 or less carbon atoms, particularly preferably alkyl groups having 3 or less carbon atoms. Can be mentioned.
The alkyl group contained in the alkoxycarbonyl group is preferably the same alkyl group as the alkyl group in R ₁₁ to R ₁₃ described above.
The cycloalkyl group may be monocyclic or polycyclic. Preferred examples include a monocyclic cycloalkyl group having 3 to 10 carbon atoms such as a cyclopropyl group, a cyclopentyl group, and a cyclohexyl group, which may have a substituent.
As a halogen atom, the halogen atom except an iodine atom is mentioned, for example.

When R ₁₃ is bonded to Ar ₁ to form a ring, examples of the alkylene group 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 preferable, and an alkylene group having 1 to 2 carbon atoms is more preferable.

Examples of the alkylene group represented by X ₁ include an alkylene group having 1 to 8 carbon atoms such as a methylene group, an ethylene group, a propylene group, a butylene group, a hexylene group, and an octylene group. An alkylene group having 1 to 4 carbon atoms is exemplified. An alkylene group having 1 to 2 carbon atoms is more preferable.

The aromatic ring group represented by X ₁ is a divalent aromatic ring group, and examples thereof include a 1,4-phenylene group, a 1,3-phenylene group, a 1,2-phenylene group, and a 1,4-naphthylene group. 1,4-phenylene group is preferred.

Examples of the alkyl group represented by R in —NR— represented by X ₁ include an optionally substituted methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, sec-butyl group, hexyl group. Group, an alkyl group having 20 or less carbon atoms such as 2-ethylhexyl group, octyl group and dodecyl group, and an alkyl group having 8 or less carbon atoms is preferable.

Preferable examples of the divalent nitrogen-containing non-aromatic heterocyclic group represented by X ₁ include a group formed by removing two arbitrary hydrogen atoms from a heterocyclic ring such as pyrrole, pyrrolidine, piperidine and the like.

Of these, X ₁ is preferably a single bond, —COO—, —NR—, or a divalent linking group composed of a combination of these groups, more preferably —COO—.

The aromatic ring group represented by Ar ₁ is an (n + 1) -valent aromatic ring group.
Examples of the divalent aromatic ring group in the case where n is 1 include 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 a thiophene, furan, pyrrole, Preferred examples include aromatic ring groups containing heterocycles such as benzothiophene, benzofuran, benzopyrrole, triazine, imidazole, benzimidazole, triazole, thiadiazole, thiazole and the like.
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.
Examples of the substituent that the (n + 1) -valent aromatic ring group may have include an alkyl group, a cycloalkyl group, an aryl group, an amino group, an amide group, a ureido group, a urethane group, a hydroxyl group, a carboxyl group, and a halogen atom ( An iodine group), an alkoxy group, a thioether group, an acyl group, an acyloxy group, an alkoxycarbonyl group, a cyano group, a nitro group, and the like. The substituent preferably has 8 or less carbon atoms.
The aromatic ring group represented by Ar ₁ is preferably a phenylene group, a naphthylene group, or a group obtained by removing (n-1) arbitrary hydrogen atoms from these groups.

Examples of the organic group containing at least one iodine atom represented by RI include iodoalkyl groups such as 2-iodoethyl group and 3-iodopropyl group.
RI is preferably an iodine atom.

n represents an integer of 1 or more. The upper limit of the integer represented by n is equal to the number of substitutable hydrogen atoms in the aromatic ring group represented by Ar ₁ .
n is preferably an integer of 2 or more, and more preferably an integer of 3 or more, because of higher sensitivity and higher resolution.

Specific examples of the repeating unit (s) having a monovalent iodine atom are shown below, but the present invention is not limited to this.

In the resin (A1), only one type of the repeating unit (s) may be used, or two or more types may be used.
The content of the repeating unit (s) in the resin (A1) (the total when plural types are contained) is preferably 0.1 to 80 mol% with respect to all the repeating units in the resin (A1). 1 to 50 mol% is more preferable, and 1 to 30 mol% is still more preferable.

<Resin (A1)>
Resin (A1) which composition (i) contains can be used individually by 1 type or in combination of 2 or more types. The content of (A1) is preferably from 25 to 99 mass%, more preferably from 30 to 99 mass%, still more preferably from 40 to 99 mass%, based on the total solid content in the composition (i).

<(AD) Compound having monovalent iodine atom>
Next, the compound (AD) having a monovalent iodine atom contained in the composition (ii) will be described. Examples of the compound (AD) include (AD1) a resin having a monovalent iodine atom (hereinafter also referred to as “resin (AD1)”) and (AD2) a low molecular compound having a monovalent iodine atom (hereinafter “ Preferable examples include low molecular weight compound (AD2) ”.

<(AD1) resin having monovalent iodine atom>
Examples of the resin (AD1) having a monovalent iodine atom contained in the composition (ii) include the above-described repeating unit (s) having a monovalent iodine atom and the above-mentioned (a) acid. A resin not having a repeating unit having a degradable group is preferable.
The content of the repeating unit (s) in the resin (AD1) (when there are a plurality of types) is preferably 5 to 100 mol% with respect to all the repeating units in the resin (AD1), preferably 10 to 100 mol. % Is more preferable, and 20 to 100 mol% is still more preferable.
The resin (AD1) may have the same repeating units as those described as the repeating unit that the resin (A) may have, and the content of these repeating units in the resin (AD1) Same as (A).
In the composition (ii), the resin (AD1) can be used alone or in combination of two or more. The content of the resin (AD1) is preferably 0.1 to 50% by mass, more preferably 0.1 to 30% by mass, based on the total solid content in the composition (ii). Is more preferable.

<(AD2) Low molecular weight compound having a monovalent iodine atom>
Examples of the low molecular weight compound (AD2) having a monovalent iodine atom include a compound having a monovalent iodine atom and a molecular weight of less than 3000, preferably a compound having a molecular weight of less than 2000, and more preferably a compound having a molecular weight of less than 1500. More preferred are compounds having a molecular weight of less than 1000. As a low molecular compound (AD2) which has a monovalent iodine atom, the compound represented by the following general formula (2 ') is mentioned, for example.

In general formula (2 ′),
Ar ₂ represents an n-valent aromatic ring group.
RI represents an iodine atom or an organic group containing at least one iodine atom.
n represents an integer of 1 or more.

The aromatic ring group represented by Ar ₂ is an n-valent aromatic ring group.
Examples of the monovalent aromatic ring group when n is 1 include an aryl group having 6 to 18 carbon atoms such as a phenyl group, a tolyl group, a naphthyl group, an anthracenyl group, a biphenyl group, and a stilbenyl group, or, for example, Preferred examples include aromatic ring groups containing heterocycles such as thiophene, furan, pyrrole, benzothiophene, benzofuran, benzopyrrole, triazine, imidazole, benzimidazole, triazole, thiadiazole, thiazole, triphenylamine.
Specific examples of the n-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 monovalent aromatic ring group. The group which can be mentioned can be mentioned suitably.
The n-valent aromatic ring group may further have a substituent.
Examples of the substituent that the n-valent aromatic ring group may have include an alkyl group, a cycloalkyl group, an aryl group, an amino group, an amide group, a ureido group, a urethane group, a hydroxyl group, a carboxyl group, and a halogen atom (iodine atom). ), An alkoxy group, a thioether group, an acyl group, an acyloxy group, an alkoxycarbonyl group, a cyano group, a nitro group, and the like. The substituent preferably has 8 or less carbon atoms.

n represents an integer of 1 or more. the upper limit value of the integer represented by n is equal to the number of replaceable hydrogen atoms in the aromatic ring group represented by Ar _2.
n is preferably an integer of 2 or more, and more preferably an integer of 3 or more.

Specific examples of the low molecular weight compound (AD2) are shown below, but the present invention is not limited thereto.

In the composition (ii), the low molecular compound (AD2) can be used alone or in combination of two or more.
The content of the low molecular weight compound (AD2) in the composition (ii) is preferably 0.1 to 50% by mass, and preferably 0.1 to 30% by mass based on the total solid content in the composition (ii). More preferred is 1 to 10% by mass.

<Common ingredients>
Next, components that can be commonly contained in the composition of the present invention (composition (i) and composition (ii)) will be described.

[1] (B) Compound that generates acid upon irradiation with actinic ray or radiation Usually, the composition of the present invention comprises a compound that generates acid upon irradiation with actinic ray or radiation (hereinafter referred to as “acid generator”, “acid”). It is also preferable to contain the generated compound (B) ”.
The acid generator is not particularly limited as long as it is a known acid generator, but upon irradiation with actinic rays or radiation, an organic acid such as sulfonic acid, bis (alkylsulfonyl) imide, or tris (alkylsulfonyl) methide is used. Compounds that generate at least either are preferred.
The compound (B) that generates an acid upon irradiation with actinic rays or radiation may be in the form of a low molecular compound or may be incorporated in a part of the polymer. Further, the form of the low molecular compound and the form incorporated in a part of the polymer may be used in combination.
When the compound (B) that generates an acid upon irradiation with actinic rays or radiation is in the form of a low molecular compound, the molecular weight is preferably 3000 or less, more preferably 2000 or less, and 1000 or less. Is more preferable.
When the compound (B) that generates an acid upon irradiation with actinic rays or radiation is in a form incorporated in a part of the polymer, the resin (A) is incorporated into a part of the resin (A) described above. You may comprise, You may incorporate in resin different from resin (A).
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 organic group as R ₂₀₁ , R ₂₀₂ and R ₂₀₃ generally has 1 to 30 carbon atoms, preferably 1 to 20 carbon atoms.
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 _{members out} 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 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. Examples include 3 to 30 cycloalkyl groups.

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 having 1 to 15 carbon atoms), an alkylsulfonyl group (preferably having 1 to 15 carbon atoms), an alkyliminosulfonyl group (preferably having 1 to 15 carbon atoms), an aryloxysulfonyl group (preferably having carbon atoms) Number 6 to 20), alkylaryloxysulfonyl group (preferably having 7 to 20 carbon atoms), 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. . Regarding the aryl group and ring structure of each group, examples of the substituent further include an alkyl group (preferably having a carbon number of 1 to 15).

As the aralkyl group in the aralkyl carboxylate anion, preferably an aralkyl group having 7 to 12 carbon atoms such as benzyl group, phenethyl group, naphthylmethyl group, naphthylethyl group, naphthylbutyl group and the like can be mentioned.

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 ⁻ ), fluorinated antimony (eg, SbF ₆ ⁻ ), and the like. .

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, perfluoro An octane sulfonate anion, a pentafluorobenzene sulfonate anion, and a 3,5-bis (trifluoromethyl) benzene sulfonate anion.

From the viewpoint of acid strength, the pKa of the generated acid is preferably −1 or less in order to improve sensitivity.

Also, as the non-nucleophilic anion, an anion represented by the following general formula (AN1) can be mentioned as a preferred embodiment.

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 preferred is a perfluoroalkyl group having 1 to 4 carbon atoms. 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 from 1 to 10, and more preferably from 1 to 5.
y is preferably 0 to 4, 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. Of 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 may be included in the resin (A). 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 having 1 to 12 carbon atoms), cyclo Alkyl group (which may be monocyclic, polycyclic or spiro ring, preferably having 3 to 20 carbon atoms), aryl group (preferably having 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 straight-chain 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 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) and the like, but are not limited thereto.

Further, when two of R ₂₀₁ to R ₂₀₃ are combined to form a ring structure, the structure represented by the following general formula (A1) is preferable.

In general formula (A1),
R ^1a to R ^13a each independently represents a hydrogen atom or a substituent.
Of R ^1a to R ^13a , 1 to 3 are preferably substituents, and any one of R ^9a to R ^13a is more preferably a substituent.
Za is a single bond or a divalent linking group.
X ⁻ has the same meaning as Z ⁻ in formula (ZI).

Specific examples of the substituent when R ^1a to R ^13a are substituents include a halogen atom, a linear, branched, and cyclic alkyl group, an alkenyl group, an alkynyl group, an aryl group, a heterocyclic group, a cyano group, and a nitro group. 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, aminocarbonylamino group, alkoxycarbonylamino group, aryloxycarbonylamino group, sulfamoylamino group, alkyl and arylsulfonylamino group, mercapto group, alkylthio group, arylthio group, heterocyclic thio group, sulfamoyl group, sulfo Group Kill 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, phosphine groups Finylamino 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), others Examples of known substituents are as follows.
When R ^1a to R ^13a are substituents, it is preferably a linear, branched or cyclic alkyl group substituted with a hydroxyl group.

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—, aminocarbonylamino group, aminosulfonylamino group and the like (n is an integer of 1 to 3).

Preferred structures when at least one of R ₂₀₁ , R ₂₀₂ and R ₂₀₃ is an organic group other than an aryl group include paragraphs 0046 to 0048 of JP-A No. 2004-233661 and JP-A No. 2003-35948. The compounds exemplified as formulas (I-1) to (I-70) in paragraphs 0040 to 0046 of the publication, US 2003/0224288 A1, and US 2003/0077540 A1 Mention may be made, for example, of cation structures such as compounds exemplified as formulas (IA-1) to (IA-54) and 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.

_Examples of the aryl group, alkyl group, and cycloalkyl group represented by R ₂₀₄ to R ₂₀₇ include the aryl group, alkyl group, and cycloalkyl group described as the aryl group, alkyl group, and cycloalkyl group represented by R ₂₀₁ to R ₂₀₃ in the aforementioned compound (ZI). It is the same as the alkyl group.
The aryl group, alkyl group, and cycloalkyl group of R ₂₀₄ to R ₂₀₇ may have a substituent. Examples of this substituent include those that the aryl group, alkyl group, and cycloalkyl group of R ₂₀₁ to R ₂₀₃ in the aforementioned compound (ZI) may have.

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 the 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. To 12 alkenylene groups (eg, ethenylene group, propenylene group, butenylene group, etc.), and as the arylene group of A, arylene groups having 6 to 10 carbon atoms (eg, phenylene group, tolylene group, naphthylene group, etc.) Each can be mentioned.

Among acid generators, particularly preferred examples are given below.

In the present invention, the compound (B) that generates the acid has a volume by irradiation with actinic rays or radiation from the viewpoint of suppressing the diffusion of the acid generated by exposure to the non-exposed portion and improving the resolution. preferably 240 Å ³ or more of a size acid compound that generates the, more preferably a compound capable of generating an acid volume of 300 Å ³ or more dimensions, generating an acid volume of 350 Å ³ or more dimensions More preferably, the compound is a compound that generates an acid having a volume of 400 ³ or more. However, from the viewpoint of sensitivity and coating solvent solubility, the volume is preferably 2000 ³ or less, and more preferably 1500 ³ or less. The volume value was determined using “WinMOPAC” manufactured by Fujitsu Limited. That is, first, the chemical structure of the acid according to each example is input, and then the most stable conformation of each acid is determined by molecular force field calculation using the MM3 method with this structure as the initial structure. By performing molecular orbital calculation using the PM3 method for these most stable conformations, the “accessible volume” of each acid can be calculated.
In the present invention, particularly preferred acid generators are exemplified below. In addition, the calculated value of the volume is appended to a part of the example (unit ^{３ 3} ). In addition, the calculated value calculated | required here is a volume value of the acid which the proton couple | bonded with the anion part.

An acid generator can be used individually by 1 type or in combination of 2 or more types.
The content of the acid generator in the composition is preferably 0.1 to 50% by mass, more preferably 0.5 to 40% by mass, and further preferably 1 to 30% by mass based on the total solid content of the composition. %.

[2] (C) Resist solvent (coating solvent)
The solvent that can be used in preparing the composition is not particularly limited as long as it is a solvent that 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.), cyclic lactone (γ-butyrolactone) Preferably 4 to 10 carbon atoms, chain or cyclic ketone (2-heptanone, cyclohexanone, etc., preferably 4 to 10 carbon atoms), alkylene carbonate (ethylene carbonate, propylene, etc.) Boneto etc.), 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 <2008> of US Patent Application Publication No. 2008 / 0248425A1.

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, 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.

[3] Basic compound The actinic ray-sensitive or radiation-sensitive resin composition of 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 that can be used is not particularly limited, for example, compounds classified into the following (1) to (7) can be used, and among them, (4) ammonium salt described later is preferable.

(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.
Examples of the compound represented by the general formula (BS-1) (description of each group, specific examples of the compound represented by the general formula (BS-1), etc.) include paragraphs of JP2013-015572A Reference can be made to the descriptions of 0471-0481, the contents of which are incorporated herein.

(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).
Examples of compounds having a preferred nitrogen-containing heterocyclic structure include, for example, guanidine, aminopyridine, aminoalkylpyridine, aminopyrrolidine, indazole, imidazole, pyrazole, pyrazine, pyrimidine, purine, imidazoline, pyrazoline, piperazine, aminomorpholine and Aminoalkylmorpholine is mentioned. 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 preferred compounds having a nitrogen-containing heterocyclic structure include, for example, 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-aminoethylpyridine, 4-aminoethylpyridine, 3-aminopyrrolidine, 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, pyrimidine, 2,4-diaminopyrimidine, 4,6 -Dihydroxypyrimidine, 2-pyrazoline, 3-pyrazoline, N-aminomorpholine and N- (2-aminoethyl) morpholine.

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 to 9, and more preferably 4 to 6. Of 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. The compounds (C1-1) to (C3-3) exemplified in

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 be appropriately used, and a quaternary ammonium salt is preferable.
The cation of the ammonium salt is preferably a tetraalkylammonium cation substituted with an alkyl group having 1 to 18 carbon atoms, such as a tetramethylammonium cation, a tetraethylammonium cation, a tetra (n-propyl) ammonium cation, or a tetra (i-propyl) ammonium. Cations, tetra (n-butyl) ammonium cation, tetra (n-heptyl) ammonium cation, tetra (n-octyl) ammonium cation, dimethylhexadecylammonium cation, benzyltrimethyl cation, etc. are more preferred, and tetra (n-butyl) ammonium Cations are most preferred.
Examples of the anion of the ammonium salt include hydroxide, carboxylate, halide, sulfonate, borate, and phosphate. Of these, hydroxide or carboxylate is 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, for example, a linear or branched alkyl group having 1 to 6 carbon atoms and a cycloalkyl group having 3 to 6 carbon atoms are preferable. Specifically, for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, i-butyl, t-butyl, n-hexyl and cyclohexyl groups are preferred. 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 carboxylate may be an aliphatic carboxylate or an aromatic carboxylate, and examples thereof include acetate, lactate, bilbate, trifluoroacetate, adamantane carboxylate, hydroxyadamantane carboxylate, benzoate, naphthoate, salicylate, phthalate, phenolate, and the like. In particular, benzoate, naphthoate, phenolate and the like are preferable, and benzoate is most preferable.
In this case, tetra (n-butyl) ammonium benzoate, tetra (n-butyl) ammonium phenolate and the like are preferable as the ammonium salt.
In the case of hydroxide, this ammonium salt is a tetraalkylammonium hydroxide having 1 to 8 carbon atoms (tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetra- (n-butyl) ammonium hydroxide, etc.). Is particularly preferred.

(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 of 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 or disappearance of the proton acceptor, or an acid from the proton acceptor It may further contain a compound that generates a compound that has been changed to [hereinafter also referred to as compound (PA)].
As a compound (PA) having a proton acceptor functional group and decomposing upon irradiation with actinic rays or radiation to generate a compound whose proton acceptor property is lowered, disappeared, or changed from proton acceptor property to acidity Can be referred to the description of JP-A-2012-32762, paragraphs 0379 to 0425 (corresponding to <0386> to <0435> of the corresponding US Patent Application Publication No. 2012/0003590), the contents of which are described in this specification. Incorporated.

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.
As the guanidine compound, description in paragraphs 0374 to 0378 of JP 2012-32762 A (corresponding to <0382> to <0385> of the corresponding US Patent Application Publication No. 2012/0003590) can be referred to. Incorporated in the description.
(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 weight 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.
As the low molecular weight compound (D), description in paragraphs 0324 to 0337 of JP2012-133331A can be referred to, and the contents thereof are incorporated in the present specification.
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. The amount is usually 0.001 to 20% by mass, preferably 0.001 to 10% by mass, and more preferably 0.01 to 5% by mass based on the minute.

Other examples of basic compounds that can be used in the composition of 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. Can be mentioned.

As the basic compound, a photosensitive basic compound may be used. Examples of the photosensitive basic compound include JP-T-2003-524799 and J. Photopolym. Sci & Tech. Vol. 8, P.I. 543-553 (1995) and the like can be used.

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

These basic compounds may be used alone or in combination of two or more.

When the composition of the present invention contains a basic compound, the content thereof is preferably 0.01 to 10.0% by mass based on the total solid content of the composition, preferably 0.1 to 8%. It is more preferably 0.0% by mass, and particularly preferably 0.2 to 5.0% by mass.

The molar ratio of the basic compound to the acid 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, and still more preferably 0.1-3. The acid generator in the molar ratio is based on the total amount of the repeating unit represented by the general formula (5) of the resin and the acid generator that the resin may further contain. is there.

[4] Compound that decomposes by the action of an acid to generate an acid The actinic ray-sensitive or radiation-sensitive resin composition of the present invention further includes one or two compounds that decompose by the action of an acid to generate an acid. More than one species may be included. The acid generated from the compound that decomposes by the action of the acid to generate an acid is preferably a sulfonic acid, a methide acid, or an imido acid.

Examples of compounds that can be decomposed by the action of an acid that can be used in the present invention to generate an acid are shown below, but are not limited thereto.

The compound which decomposes | disassembles by the effect | action of the said acid and generate | occur | produces an acid can be used individually by 1 type or in combination of 2 or more types.
The content of the compound that generates an acid by being decomposed by the action of an acid is 0.1 to 40% by mass based on the total solid content of the actinic ray-sensitive or radiation-sensitive resin composition of the present invention. It is preferably 0.5 to 30% by mass, more preferably 1.0 to 20% by mass.

[5] Hydrophobic resin (HR)
The actinic ray-sensitive or radiation-sensitive resin composition of the present invention may have a hydrophobic resin (HR) separately from the resin (A).
The hydrophobic resin is preferably designed to be unevenly distributed on the surface of the resist film. However, unlike the surfactant, it is not always necessary to have a hydrophilic group in the molecule, and the polar / nonpolar substance is uniformly mixed. There is no need to contribute.
Examples of the effect of adding the hydrophobic resin include control of the static / dynamic contact angle of the resist film surface with respect to water, suppression of outgas, and the like.

The hydrophobic resin has at least one of “fluorine atom”, “silicon atom”, and “CH ₃ partial structure contained in the side chain portion of the resin” from the viewpoint of uneven distribution on the film surface. It is preferable to have two or more types.
When the hydrophobic resin contains a fluorine atom and / or a silicon atom, the fluorine atom and / or silicon atom in the hydrophobic resin may be contained in the main chain of the resin or in the side chain. It may be.

When the hydrophobic resin contains a fluorine atom, it may be a resin having an alkyl group having a fluorine atom, a cycloalkyl group having a fluorine atom, or an aryl group having a fluorine atom as a partial structure having a fluorine atom. preferable.
The alkyl group having a fluorine atom (preferably having 1 to 10 carbon atoms, more preferably 1 to 4 carbon atoms) is a linear or branched alkyl group in which at least one hydrogen atom is substituted with a fluorine atom. It may have a substituent other than.
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. .
Examples of the repeating unit having a fluorine atom or a silicon atom include those exemplified in paragraph 0519 of US2012 / 0251948A1.

Further, as described above, the hydrophobic resin preferably includes a CH ₃ partial structure in the side chain portion.
Here, the CH ₃ partial structure of the side chain portion in the hydrophobic resin (hereinafter also simply referred to as “side chain CH ₃ partial structure”) includes a CH ₃ partial structure of an ethyl group, a propyl group, or the like. Is.
On the other hand, methyl groups directly bonded to the main chain of the hydrophobic resin (for example, α-methyl groups of repeating units having a methacrylic acid structure) contribute to the uneven distribution of the surface of the hydrophobic resin due to the influence of the main chain. Since it is small, it is not included in the CH ₃ partial structure in the present invention.

More specifically, when the hydrophobic resin includes a repeating unit derived from a monomer having a polymerizable moiety having a carbon-carbon double bond, such as a repeating unit represented by the following general formula (M) In the case where R ₁₁ to R ₁₄ are CH ₃ “as is”, the CH ₃ is not included in the CH ₃ partial structure of the side chain moiety in the present invention.
Meanwhile, CH ₃ partial structure exists through some atoms from C-C backbone, and those falling under CH ₃ partial structures in the present invention. For example, when R ₁₁ is an ethyl group (CH ₂ CH ₃ ), it is assumed that it has “one” CH ₃ partial structure in the present invention.

In the general formula (M),
R ₁₁ to R ₁₄ each independently represents a side chain portion.
Examples of R ₁₁ to R _{14 in the} side chain portion include a hydrogen atom and a monovalent organic group.
Examples of the monovalent organic group for R ₁₁ to R ₁₄ include an alkyl group, a cycloalkyl group, an aryl group, an alkyloxycarbonyl group, a cycloalkyloxycarbonyl group, an aryloxycarbonyl group, an alkylaminocarbonyl group, and a cycloalkylaminocarbonyl. Group, an arylaminocarbonyl group, and the like, and these groups may further have a substituent.

The hydrophobic resin is preferably a resin having a repeating unit having a CH ₃ partial structure in the side chain portion. As such a repeating unit, the repeating unit represented by the following general formula (II) and the following general unit It is more preferable to have at least one repeating unit (x) among the repeating units represented by the formula (III).

Hereinafter, the repeating unit represented by the general formula (II) will be described in detail.

In the general formula (II), X _b1 represents a hydrogen atom, an alkyl group, a cyano group or a halogen atom, R ₂ has one or more CH ₃ partial structure represents a stable organic radical to acid. Here, the organic group which is stable to acid is more preferably an organic group other than the “acid-decomposable group” described in the resin (A).

The alkyl group of _Xb1 is preferably an alkyl group having 1 to 4 carbon atoms, and examples thereof include a methyl group, an ethyl group, a propyl group, a hydroxymethyl group, and a trifluoromethyl group, and a methyl group is preferable.
X _b1 is preferably a hydrogen atom or a methyl group.
Examples of R ₂ include an alkyl group, a cycloalkyl group, an alkenyl group, a cycloalkenyl group, an aryl group, and an aralkyl group having one or more CH ₃ partial structures. The above cycloalkyl group, alkenyl group, cycloalkenyl group, aryl group and aralkyl group may further have an alkyl group as a substituent.
R ₂ is preferably an alkyl group or an alkyl-substituted cycloalkyl group having one or more CH ₃ partial structures.
The acid-stable organic group having one or more CH ₃ partial structures as R ₂ preferably has 2 or more and 10 or less CH ₃ partial structures, and more preferably 2 or more and 8 or less.
Preferred specific examples of the repeating unit represented by the general formula (II) are shown below. Note that the present invention is not limited to this.

The repeating unit represented by the general formula (II) is preferably an acid-stable (non-acid-decomposable) repeating unit, specifically, a group other than a group that decomposes by the action of an acid to generate a polar group. A repeating unit having a group of
Hereinafter, the repeating unit represented by formula (III) will be described in detail.

In the above general formula (III), X _b2 represents a hydrogen atom, an alkyl group, a cyano group, or a halogen atom, R ₃ represents an acid-stable organic group having one or more CH ₃ partial structures, n represents an integer of 1 to 5.
The alkyl group for _Xb2 is preferably an alkyl group having 1 to 4 carbon atoms, and examples thereof include a methyl group, an ethyl group, a propyl group, a hydroxymethyl group, and a trifluoromethyl group, and a hydrogen atom is preferable.
X _b2 is preferably a hydrogen atom.
Since R ₃ is an organic group that is stable against acid, more specifically, R ₃ is preferably an organic group that does not have the “acid-decomposable group” described in the resin (A).

R ₃ includes an alkyl group having one or more CH ₃ partial structures.
The acid-stable organic group having one or more CH ₃ partial structures as R ₃ preferably has 1 or more and 10 or less CH ₃ partial structures, more preferably 1 or more and 8 or less, More preferably, it is 1 or more and 4 or less.
n represents an integer of 1 to 5, more preferably an integer of 1 to 3, and still more preferably 1 or 2.

Preferred specific examples of the repeating unit represented by the general formula (III) are given below. Note that the present invention is not limited to this.

The repeating unit represented by the general formula (III) is preferably an acid-stable (non-acid-decomposable) repeating unit, specifically, a group that decomposes by the action of an acid to generate a polar group. It is preferable that it is a repeating unit which does not have.

In the case where the hydrophobic resin contains a CH ₃ partial structure in the side chain portion, and particularly when it does not have a fluorine atom and a silicon atom, the repeating unit represented by the general formula (II) and the general formula ( The content of at least one repeating unit (x) among the repeating units represented by III) is preferably 90 mol% or more, more preferably 95 mol% or more, based on all repeating units of the hydrophobic resin. It is more preferable. Content is 100 mol% or less normally with respect to all the repeating units of hydrophobic resin.

The hydrophobic resin contains at least one repeating unit (x) among the repeating units represented by the general formula (II) and the repeating unit represented by the general formula (III) as all repeating units of the hydrophobic resin. On the other hand, the surface free energy of hydrophobic resin increases by containing 90 mol% or more. As a result, the hydrophobic resin tends to be unevenly distributed on the surface of the resist film.

In addition, the hydrophobic resin includes the following groups (x) to (z) regardless of whether (i) it contains a fluorine atom and / or a silicon atom, or (ii) contains a CH ₃ partial structure in the side chain portion. It may have at least one group selected from
(X) an acid group,
(Y) a group having a lactone structure, an acid anhydride group, or an acid imide group,
(Z) a group decomposable by the action of an acid

Examples of the acid group (x) include a phenolic hydroxyl group, a carboxylic acid group, a fluorinated alcohol group, a sulfonic acid group, a sulfonamide group, a sulfonylimide group, an (alkylsulfonyl) (alkylcarbonyl) methylene group, and an (alkylsulfonyl) (alkyl Carbonyl) imide group, bis (alkylcarbonyl) methylene group, bis (alkylcarbonyl) imide group, bis (alkylsulfonyl) methylene group, bis (alkylsulfonyl) imide group, tris (alkylcarbonyl) methylene group, tris (alkylsulfonyl) A methylene group etc. are mentioned.
Preferred acid groups include fluorinated alcohol groups (preferably hexafluoroisopropanol groups), sulfonimide groups, and bis (alkylcarbonyl) methylene groups.

The repeating unit having an acid group (x) includes a repeating unit in which an acid group is directly bonded to the main chain of the resin, such as a repeating unit of acrylic acid or methacrylic acid, or a resin having a linking group. Examples include a repeating unit in which an acid group is bonded to the main chain, and a polymerization initiator or chain transfer agent having an acid group can be introduced at the end of the polymer chain at the time of polymerization. preferable. The repeating unit having an acid group (x) may have at least one of a fluorine atom and a silicon atom.
The content of the repeating unit having an acid group (x) is preferably from 1 to 50 mol%, more preferably from 3 to 35 mol%, still more preferably from 5 to 20 mol%, based on all repeating units in the hydrophobic resin. It is.
Specific examples of the repeating unit having an acid group (x) are shown below, but the present invention is not limited thereto. In the formula, Rx represents a hydrogen atom, CH ₃ , CF ₃ , or CH ₂ OH.

As the group having a lactone structure, the acid anhydride group, or the acid imide group (y), a group having a lactone structure is particularly preferable.
The repeating unit containing these groups is a repeating unit in which this group is directly bonded to the main chain of the resin, such as a repeating unit of acrylic acid ester and methacrylic acid ester. Alternatively, this repeating unit may be a repeating unit in which this group is bonded to the main chain of the resin via a linking group. Or this repeating unit may be introduce | transduced into the terminal of resin using the polymerization initiator or chain transfer agent which has this group at the time of superposition | polymerization.
Examples of the repeating unit having a group having a lactone structure include the same repeating units as the repeating unit having a lactone structure described above in the section of the resin (A).

The content of the repeating unit having a group having a lactone structure, an acid anhydride group, or an acid imide group is preferably 1 to 100 mol% based on all repeating units in the hydrophobic resin. It is more preferably mol%, and further preferably 5 to 95 mol%.

Examples of the repeating unit having a group (z) capable of decomposing by the action of an acid in the hydrophobic resin include the same repeating units as the repeating unit having an acid-decomposable group exemplified in the resin (A). The repeating unit having a group (z) that decomposes by the action of an acid may have at least one of a fluorine atom and a silicon atom. In the hydrophobic resin, the content of the repeating unit having a group (z) that is decomposed by the action of an acid is preferably 1 to 80 mol%, more preferably 10 to 10%, based on all repeating units in the hydrophobic resin. 80 mol%, more preferably 20 to 60 mol%.

When the hydrophobic resin has a fluorine atom, the fluorine atom content is preferably 5 to 80% by mass and more preferably 10 to 80% by mass with respect to the weight average molecular weight of the hydrophobic resin. Further, the repeating unit containing a fluorine atom is preferably 10 to 100 mol%, more preferably 30 to 100 mol% in all repeating units contained in the hydrophobic resin.
When the hydrophobic resin has a silicon atom, the content of silicon atom is preferably 2 to 50% by mass, more preferably 2 to 30% by mass with respect to the weight average molecular weight of the hydrophobic resin. Further, the repeating unit containing a silicon atom is preferably 10 to 100 mol%, and more preferably 20 to 100 mol% in all repeating units contained in the hydrophobic resin.

On the other hand, in the case where the hydrophobic resin contains a CH ₃ partial structure in the side chain portion, it is also preferred that the hydrophobic resin does not substantially contain a fluorine atom and a silicon atom. The content of the repeating unit having an atom or silicon atom is preferably 5 mol% or less, more preferably 3 mol% or less, more preferably 1 mol% or less, based on all repeating units in the hydrophobic resin. More preferably, it is ideally 0 mol%, ie it does not contain fluorine and silicon atoms. Moreover, it is preferable that hydrophobic resin is substantially comprised only by the repeating unit comprised only by the atom chosen from a carbon atom, an oxygen atom, a hydrogen atom, a nitrogen atom, and a sulfur atom. More specifically, it is preferable that the repeating unit composed only of atoms selected from a carbon atom, an oxygen atom, a hydrogen atom, a nitrogen atom and a sulfur atom is 95 mol% or more in the total repeating units of the hydrophobic resin. 97 mol% or more is more preferable, 99 mol% or more is further preferable, and ideally 100 mol%.

The standard polystyrene equivalent weight average molecular weight of the hydrophobic resin is preferably 1,000 to 100,000, more preferably 1,000 to 50,000, and still more preferably 2,000 to 15,000.
Moreover, the hydrophobic resin may be used alone or in combination.
The content of the hydrophobic resin in the composition is preferably 0.01 to 10% by mass, more preferably 0.05 to 8% by mass, and more preferably 0.1 to 10% by mass with respect to the total solid content in the composition of the present invention. 7 mass% is still more preferable.

Naturally, the hydrophobic resin has a small amount of impurities such as metals, and the residual monomer or oligomer component is preferably 0.01 to 5% by mass, more preferably 0.01 to 3% by mass, 0.05 to 1% by mass is even more preferred. Thereby, a 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 5, more preferably in the range of 1 to 3, from the viewpoint of resolution, resist shape, resist pattern side wall, roughness, etc. A range of 1 to 2 is preferred.

As the hydrophobic resin, various commercially available products can be used, and can be synthesized according to a conventional method (for example, radical polymerization). 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 the polymerization is performed by heating, 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.
The reaction solvent, the polymerization initiator, the reaction conditions (temperature, concentration, etc.) and the purification method after the reaction are the same as described in the resin (A), but in the synthesis of the hydrophobic resin, the reaction concentration Is preferably 30 to 50% by mass.

As the hydrophobic resin, those described in JP 2011-248019 A, JP 2010-175859 A, and JP 2012-032544 A can also be preferably used.

[6] Surfactant The composition of the present invention may further contain a surfactant. By containing a surfactant, when an exposure light source having a wavelength of 250 nm or less, particularly 220 nm or less, is used, it is possible to form a pattern with less adhesion and development defects with good sensitivity and resolution. Become.
As the surfactant, it is particularly preferable to use a fluorine-based and / or silicon-based surfactant.

Examples of the fluorine-based and / or silicon-based surfactant include surfactants described in <0276> of US Patent Application Publication No. 2008/0248425. Also, F-top EF301 or EF303 (manufactured by Shin-Akita Kasei Co., Ltd.); Florard FC430, 431 or 4430 (manufactured by Sumitomo 3M Co., Ltd.); Megafac F171, F173, F176, F189, F113, F110, F177, F120 or R08 (manufactured by DIC Corporation); Surflon S-382, SC101, 102, 103, 104, 105 or 106 (manufactured by Asahi Glass Co., Ltd.); Troisol S-366 (manufactured by Troy Chemical Co., Ltd.); GF-300 or GF-150 (manufactured by Toa Gosei Chemical Co., Ltd.); Surflon S-393 (manufactured by Seimi Chemical Co., Ltd.); F-top EF121, EF122A, EF122B, RF122C, EF125M, EF135M, EF351, EF352, EF801, EF802 or EF601 ( ( PF636, PF656, PF6320 or PF6520 (OMNOVA); or FTX-204G, 208G, 218G, 230G, 204D, 208D, 212D, 218D or 222D (manufactured by Neos) Good. Polysiloxane polymer KP-341 (manufactured by Shin-Etsu Chemical Co., Ltd.) can also be used as a silicon surfactant.

The surfactant is a fluoroaliphatic compound produced by a telomerization method (also referred to as a telomer method) or an oligomerization method (also referred to as an oligomer method) in addition to the known surfactants as described above. You may synthesize using. Specifically, a polymer having a fluoroaliphatic group derived from this fluoroaliphatic compound may be used as a surfactant. This fluoroaliphatic compound can be synthesized, for example, by the method described in JP-A-2002-90991.

The polymer having a fluoroaliphatic group is preferably a copolymer of a monomer having a fluoroaliphatic group and at least one of (poly (oxyalkylene)) acrylate and (poly (oxyalkylene)) methacrylate. It may be distributed regularly or may be block copolymerized.
Examples of the poly (oxyalkylene) group include a poly (oxyethylene) group, a poly (oxypropylene) group, and a poly (oxybutylene) group. In addition, units having different chain length alkylene in the same chain, such as poly (block connection body of oxyethylene, oxypropylene, and oxyethylene) and poly (block connection body of oxyethylene and oxypropylene) Also good.

Furthermore, a copolymer of a monomer having a fluoroaliphatic group and (poly (oxyalkylene)) acrylate or methacrylate is composed of a monomer having two or more different fluoroaliphatic groups and two or more different (poly (oxyalkylene). )) It may be a ternary or higher copolymer obtained by copolymerizing acrylate or methacrylate simultaneously.
Examples of commercially available surfactants include Megafac F178, F-470, F-473, F-475, F-476, and F-472 (manufactured by DIC Corporation). Further, a copolymer of an acrylate or methacrylate having a C ₆ F ₁₃ group and (poly (oxyalkylene)) acrylate or methacrylate, an acrylate or methacrylate having a C ₆ F ₁₃ group and (poly (oxyethylene)) acrylate or methacrylate And a copolymer of (poly (oxypropylene)) acrylate or methacrylate, a copolymer of an acrylate or methacrylate having a C ₈ F ₁₇ group and (poly (oxyalkylene)) acrylate or methacrylate, and C ₈ F ₁₇ Copolymerization of a group-containing acrylate or methacrylate with (poly (oxyethylene)) acrylate or methacrylate and (poly (oxypropylene)) acrylate or methacrylate Body, and the like.

Further, surfactants other than fluorine-based and / or silicon-based surfactants described in <0280> of US Patent Application Publication No. 2008/0248425 may be used.
One of these surfactants may be used alone, or two or more thereof may be used in combination.
When the composition of the present invention contains a surfactant, the content thereof is preferably 0 to 2% by mass, more preferably 0.0001 to 2% by mass, further based on the total solid content of the composition. The amount is preferably 0.0005 to 1% by mass.

[7] Other Additives In addition to the components described above, the composition of the present invention is a dissolution inhibitor having a molecular weight of 3000 or less as described in carboxylic acid, carboxylic acid onium salt, Proceedingof SPIE, 2724, 355 (1996), etc. A 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 of the composition.

The actinic ray-sensitive or radiation-sensitive resin composition of the present invention is preferably used in a film thickness of 10 to 250 nm, more preferably in a film thickness of 20 to 200 nm, and still more preferably, from the viewpoint of improving resolution. Is used at 30-100 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 of the present invention is usually 1.0 to 10% by mass, preferably 2.0 to 5.7% by mass, more preferably 2.0. 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 mass percentage of the mass of other resist components excluding the solvent with respect to the total mass 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.

<Resist film>
The present invention also relates to an actinic ray-sensitive or radiation-sensitive film (hereinafter also referred to as a resist film) formed using the above-described composition of the present invention (composition (i) or composition (ii)). .

<Pattern formation method>
The pattern forming method of the present invention comprises:
(A) a step of forming a film (resist film) using the composition (i) or the composition (ii) described above,
(A) a step of exposing the film; and (c) a step of forming a pattern by removing an exposed portion of the exposed film using an alkali developer (alkali development step).
Is a pattern forming method having at least

Moreover, the pattern forming method of the present invention includes:
(A) a step of forming a film (resist film) using the composition (i) or the composition (ii) described above,
(A) a step of exposing the film; and (c) a step of forming a pattern by removing the exposed portion of the exposed film using a developer containing an organic solvent (organic solvent developing step).
Is a pattern forming method having at least

The exposure in the step (ii) may be immersion exposure.
The pattern forming method of the present invention preferably comprises (i) a heating step after (b) the exposure step.
The pattern forming method of the present invention may further include (e) a step of developing using an alkali developer when the developer in the step (c) is a developer containing an organic solvent. On the other hand, when the developer in the step (c) is an alkali developer, (e) it may further include a step of developing using a developer containing an organic solvent.
In the present invention, a portion with low exposure intensity is removed by the organic solvent development step, but a portion with high exposure strength is also removed by further performing the alkali development step. In this way, by the multiple development process in which development is performed a plurality of times, a pattern can be formed without dissolving only an intermediate exposure intensity region, so that a finer pattern than usual can be formed (paragraph of JP 2008-292975 A). <Mechanism similar to <0077>).
In the pattern forming method of the present invention, the order of the alkali development step and the organic solvent development step is not particularly limited, but it is more preferable to perform the alkali development before the organic solvent development step.
The pattern formation method of this invention can have (b) exposure process in multiple times.
The pattern formation method of this invention can have (d) a heating process in multiple times.

The resist film formed from the composition (i) or the composition (ii) is preferably formed on a substrate.
In the pattern forming method of the present invention, the step of forming a film on the substrate using the composition (i) or the composition (ii), the step of exposing the film, and the developing step are generally known methods. Can be performed.

The composition (i) or the composition (ii) is used for, for example, a substrate (for example, silicon / silicon dioxide coating, silicon nitride, and chromium-deposited quartz used for manufacturing precision integrated circuit elements, imprint molds, etc. It is applied on a substrate or the like using a spinner or a coater. Thereafter, this can be dried to form a resist film.

Before forming the resist film, an antireflection film may be coated on the substrate in advance.
As the antireflection film, any of an inorganic film type such as titanium, titanium dioxide, titanium nitride, chromium oxide, carbon, and amorphous silicon, and an organic film type made of a light absorber and a polymer material can be used. In addition, as the organic antireflection film, commercially available organic antireflection films such as Brewer Science DUV30 series, DUV-40 series, Shipley AR-2, AR-3 and AR-5 may be used. it can.

It is also preferable to include a preheating step (PB; Prebake) after the film formation and before the exposure step. It is also preferable to include a post-exposure heating step (PEB; Post Exposure Bake) after the exposure step and before the development step.
The heating temperature is preferably 70 to 120 ° C. for both PB and PEB, more preferably 80 to 110 ° C.
The heating time is preferably 30 to 300 seconds, more preferably 30 to 180 seconds, and still more preferably 30 to 90 seconds.
Heating can be performed by means provided in a normal exposure / developing machine, and may be performed using a hot plate or the like.
The reaction of the exposed part is promoted by baking, and the sensitivity and pattern profile are improved.
It is also preferable to include a heating step (Post Bake) after the rinsing step. The developing solution and the rinsing solution remaining between the patterns and inside the patterns are removed by baking.

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. Examples of preferable actinic rays or radiation include KrF excimer laser, ArF excimer laser, electron beam, X-ray and EUV light. More preferred are electron beam, X-ray and EUV light.

In the present invention, the substrate on which the film is formed is not particularly limited, and an inorganic substrate such as silicon, SiN, or SiO ₂ , a coated inorganic substrate such as SOG (Spin-On-Glass), a semiconductor manufacturing process such as an IC, etc. A substrate generally used in a circuit board manufacturing process such as a liquid crystal or a thermal head, and also in other photofabrication lithography processes can be used. Further, if necessary, an organic antireflection film may be formed between the film and the substrate.

When the pattern forming method of the present invention includes a step of developing using an alkali developer, examples of the alkali developer include sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, and aqueous ammonia. Inorganic amines such as ethylamine, primary amines such as n-propylamine, secondary amines such as diethylamine and di-n-butylamine, tertiary amines such as triethylamine and methyldiethylamine, dimethylethanolamine, and triethanol Alcohol amines such as amine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, tetrapentylammonium hydroxide, tetrahexyl Tetraalkylammonium hydroxide such as ammonium hydroxide, tetraoctylammonium hydroxide, ethyltrimethylammonium hydroxide, butyltrimethylammonium hydroxide, methyltriamylammonium hydroxide, dibutyldipentylammonium hydroxide, trimethylphenylammonium hydroxide, trimethylbenzyl Alkaline aqueous solutions such as quaternary ammonium salts such as ammonium hydroxide and triethylbenzylammonium hydroxide, and cyclic amines such as pyrrole and piperidine can be used.
Furthermore, an appropriate amount of alcohol or surfactant may be added to the alkaline aqueous solution.
The alkali concentration of the alkali developer is usually from 0.1 to 20% by mass.
The pH of the alkali developer is usually from 10.0 to 15.0.
In particular, an aqueous solution of 2.38% by mass of tetramethylammonium hydroxide is desirable.

As a rinsing solution in the rinsing treatment performed after alkali development, pure water can be used, and an appropriate amount of a surfactant can be added.
In addition, after the developing process or the rinsing process, a process of removing the developing solution or the rinsing liquid adhering to the pattern with a supercritical fluid can be performed.

When the pattern forming method of the present invention includes a step of developing using a developer containing an organic solvent, the developer (organic developer) in the step includes a ketone solvent, an ester solvent, and an alcohol solvent. Polar solvents such as amide solvents and ether solvents, and hydrocarbon solvents can be used.
Examples of ketone solvents include 1-octanone, 2-octanone, 1-nonanone, 2-nonanone, acetone, 2-heptanone (methyl amyl ketone), 4-heptanone, 1-hexanone, 2-hexanone, diisobutyl ketone, Examples include cyclohexanone, methylcyclohexanone, phenylacetone, methylethylketone, methylisobutylketone, acetylacetone, acetonylacetone, ionone, diacetylalcohol, acetylcarbinol, acetophenone, methylnaphthylketone, isophorone, and propylene carbonate.
Examples of ester solvents include methyl acetate, butyl acetate, ethyl acetate, isopropyl acetate, pentyl acetate, isopentyl acetate, amyl acetate, propylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, diethylene glycol monoethyl. Ether acetate, ethyl-3-ethoxypropionate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, methyl formate, ethyl formate, butyl formate, propyl formate, ethyl lactate, butyl lactate, propyl lactate, etc. Can be mentioned.
Examples of alcohol solvents include methyl alcohol, ethyl alcohol, n-propyl alcohol, isopropyl alcohol, n-butyl alcohol, sec-butyl alcohol, 4-methyl-2-pentanol, tert-butyl alcohol, isobutyl alcohol, n -Alcohols such as hexyl alcohol, n-heptyl alcohol, n-octyl alcohol, n-decanol, glycol solvents such as ethylene glycol, diethylene glycol, triethylene glycol, ethylene glycol monomethyl ether, propylene glycol monomethyl ether, ethylene glycol mono Ethyl ether, propylene glycol monoethyl ether, diethylene glycol monomethyl ether, triethylene glycol monoethyl Ether, may be mentioned glycol monoethyl ether and methoxymethyl butanol.
Examples of the ether solvent include anisole, dioxane, tetrahydrofuran and the like in addition to the glycol ether solvent.
Examples of amide solvents include N-methyl-2-pyrrolidone, N, N-dimethylacetamide, N, N-dimethylformamide, hexamethylphosphoric triamide, 1,3-dimethyl-2-imidazolidinone and the like. Can be used.
Examples of the hydrocarbon solvent include aromatic hydrocarbon solvents such as toluene and xylene, and aliphatic hydrocarbon solvents such as pentane, hexane, octane and decane.
A plurality of the above solvents may be mixed, or may be used by mixing with a solvent other than those described above or water. However, in order to fully exhibit the effects of the present invention, the water content of the developer as a whole is preferably less than 10% by mass, and more preferably substantially free of moisture.
That is, the amount of the organic solvent used relative to the organic developer is preferably 90% by mass or more and 100% by mass or less, and more preferably 95% by mass or more and 100% by mass or less with respect to the total amount of the developer. .
In particular, the organic developer is preferably a developer containing at least one organic solvent selected from the group consisting of ketone solvents, ester solvents, alcohol solvents, amide solvents and ether solvents.

The vapor pressure of the organic developer is preferably 5 kPa or less, more preferably 3 kPa or less, and particularly preferably 2 kPa or less at 20 ° C. By setting the vapor pressure of the organic developer to 5 kPa or less, evaporation of the developer on the substrate or in the developing cup is suppressed, and the temperature uniformity in the wafer surface is improved. As a result, the dimensions in the wafer surface are uniform. Sexuality improves.
Specific examples of the developer having a vapor pressure of 5 kPa or less include 1-octanone, 2-octanone, 1-nonanone, 2-nonanone, 2-heptanone (methyl amyl ketone), 4-heptanone, 2-hexanone, Ketone solvents such as diisobutylketone, cyclohexanone, methylcyclohexanone, phenylacetone, methylisobutylketone, butyl acetate, pentyl acetate, isopentyl acetate, amyl acetate, propylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, Diethylene glycol monoethyl ether acetate, ethyl-3-ethoxypropionate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate Ester solvents such as butyl formate, propyl formate, ethyl lactate, butyl lactate, propyl lactate, n-propyl alcohol, isopropyl alcohol, n-butyl alcohol, sec-butyl alcohol, tert-butyl alcohol, isobutyl alcohol, n-hexyl alcohol Alcohol solvents such as n-heptyl alcohol, n-octyl alcohol and n-decanol, glycol solvents such as ethylene glycol, diethylene glycol and triethylene glycol, ethylene glycol monomethyl ether, propylene glycol monomethyl ether, ethylene glycol monoethyl ether , Propylene glycol monoethyl ether, diethylene glycol monomethyl ether, triethylene glycol monoethyl ether, Glycol ether solvents such as xylmethylbutanol, ether solvents such as tetrahydrofuran, amide solvents such as N-methyl-2-pyrrolidone, N, N-dimethylacetamide and N, N-dimethylformamide, and aromatics such as toluene and xylene Aliphatic hydrocarbon solvents such as aliphatic hydrocarbon solvents, octane and decane.
Specific examples of the developer having a vapor pressure of 2 kPa or less, which is a particularly preferable range, include 1-octanone, 2-octanone, 1-nonanone, 2-nonanone, 2-heptanone, 4-heptanone, 2-hexanone, Ketone solvents such as diisobutyl ketone, cyclohexanone, methylcyclohexanone, phenylacetone, butyl acetate, amyl acetate, propylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, diethylene glycol monoethyl ether acetate, ethyl-3- Ester solvents such as ethoxypropionate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, ethyl lactate, butyl lactate, propyl lactate Alcohol solvents such as n-butyl alcohol, sec-butyl alcohol, tert-butyl alcohol, isobutyl alcohol, n-hexyl alcohol, n-heptyl alcohol, n-octyl alcohol, n-decanol, ethylene glycol, diethylene glycol, triethylene glycol Glycol glycol solvents such as ethylene glycol monomethyl ether, propylene glycol monomethyl ether, ethylene glycol monoethyl ether, propylene glycol monoethyl ether, diethylene glycol monomethyl ether, triethylene glycol monoethyl ether, methoxymethyl butanol, N-methyl-2-pyrrolidone, N, N-dimethylacetamide, N, N-dimethylform Amide solvents amides, aromatic hydrocarbon solvents such as xylene, octane, aliphatic hydrocarbon solvents decane.

The organic developer may contain a basic compound. Specific examples and preferred examples of the basic compound that can be contained in the developer used in the present invention are the same as the basic compound that can be contained in the actinic ray-sensitive or radiation-sensitive resin composition described above.

An appropriate amount of a surfactant can be added to the organic developer as required.
The surfactant is not particularly limited, and for example, ionic or nonionic fluorine-based and / or silicon-based surfactants can be used. As these fluorine-based and / or silicon-based surfactants, for example, JP-A-62-36663, JP-A-61-226746, JP-A-61-226745, JP-A-62-170950 are disclosed. JP-A-63-34540, JP-A-7-230165, JP-A-8-62834, JP-A-9-54432, JP-A-9-5988, US Pat. No. 5,405,720, Mention may be made of the surfactants described in US Pat. Nos. 5,360,692, 5,529,881, 5,296,330, 5,436,098, 5,576,143, 5,294,511, and 5,824,451. Preferably, it is a nonionic surfactant. Although it does not specifically limit as a nonionic surfactant, It is still more preferable to use a fluorochemical surfactant or a silicon-type surfactant.
The amount of the surfactant used is preferably 0 to 2% by mass, more preferably 0.0001 to 2% by mass, and particularly preferably 0.0005 to 1% by mass with respect to the total amount of the developer.

As a developing method, for example, a method in which a substrate is immersed in a tank filled with a developer for a certain period of time (dip method), a method in which the developer is raised on the surface of the substrate by surface tension and is left stationary for a certain time (paddle) Method), a method of spraying the developer on the substrate surface (spray method), a method of continuously discharging the developer while scanning the developer discharge nozzle on the substrate rotating at a constant speed (dynamic dispensing method) Etc. can be applied.
When the various development methods described above include a step of discharging the developer from the developing nozzle of the developing device toward the resist film, the discharge pressure of the discharged developer (the flow rate per unit area of the discharged developer) is Preferably it is 2 mL / sec / mm ² or less, More preferably, it is 1.5 mL / sec / mm ² or less, More preferably, it is 1 mL / sec / mm ² or less. There is no particular lower limit on the flow rate, but 0.2 mL / sec / mm ² or more is preferable in consideration of throughput.
By setting the discharge pressure of the discharged developer to be in the above range, pattern defects derived from the resist residue after development can be remarkably reduced.
The details of this mechanism are not clear, but perhaps by setting the discharge pressure within the above range, the pressure applied by the developer to the resist film will decrease, and the resist film / resist pattern may be inadvertently cut or collapsed. This is considered to be suppressed.
The developer discharge pressure (mL / sec / mm ² ) is a value at the developing nozzle outlet in the developing device.

Examples of the method for adjusting the discharge pressure of the developer include a method of adjusting the discharge pressure with a pump or the like, and a method of changing the pressure by adjusting the pressure by supply from a pressurized tank.

Also, after the step of developing using a developer containing an organic solvent, a step of stopping development while replacing the organic developer with another solvent may be performed.

After the step of developing with a developer containing an organic solvent, a step of washing with a rinse solution may be included. From the viewpoint of throughput (productivity), the amount of rinse solution used, etc. It is not necessary to include the step of using and washing.

The rinsing solution used in the rinsing step after the step of developing with a developer containing an organic solvent is not particularly limited as long as the resist pattern is not dissolved, and a solution containing a general organic solvent can be used. . The rinsing liquid contains at least one organic solvent selected from the group consisting of hydrocarbon solvents (preferably decane), ketone solvents, ester solvents, alcohol solvents, amide solvents and ether solvents. It is preferable to use a rinse solution.
Specific examples of the hydrocarbon solvent, the ketone solvent, the ester solvent, the alcohol solvent, the amide solvent, and the ether solvent are the same as those described in the developer containing an organic solvent.
More preferably, it contains at least one organic solvent selected from the group consisting of ketone solvents, ester solvents, alcohol solvents, and amide solvents after the step of developing using a developer containing an organic solvent. A step of washing with a rinsing liquid is performed, more preferably, a step of washing with a rinsing liquid containing an alcohol solvent or an ester solvent is carried out, and particularly preferably, a rinsing liquid containing a monohydric alcohol is used. And, most preferably, the step of cleaning with a rinse solution containing a monohydric alcohol having 5 or more carbon atoms is performed.
Here, examples of the monohydric alcohol used in the rinsing step include linear, branched, and cyclic monohydric alcohols. Specific examples include 1-butanol, 2-butanol, and 3-methyl-1-butanol. Tert-butyl alcohol, 1-pentanol, 2-pentanol, 1-hexanol, 4-methyl-2-pentanol, 1-heptanol, 1-octanol, 2-hexanol, cyclopentanol, 2-heptanol, 2 -Octanol, 3-hexanol, 3-heptanol, 3-octanol, 4-octanol and the like can be used, and particularly preferable monohydric alcohols having 5 or more carbon atoms are 1-hexanol, 2-hexanol, 4-methyl- Use 2-pentanol, 1-pentanol, 3-methyl-1-butanol, etc. It can be.

A plurality of the above components may be mixed, or may be used by mixing with an organic solvent other than the above.

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

The vapor pressure of the rinsing solution used after the step of developing with a developer containing an organic solvent is preferably 0.05 kPa or more and 5 kPa or less, more preferably 0.1 kPa or more and 5 kPa or less at 20 ° C. 12 kPa or more and 3 kPa or less are the most preferable. By setting the vapor pressure of the rinse liquid to 0.05 kPa or more and 5 kPa or less, the temperature uniformity in the wafer surface is improved, and further, the swelling due to the penetration of the rinse solution is suppressed, and the dimensional uniformity in the wafer surface. Improves.

An appropriate amount of a surfactant can be added to the rinse solution.

In the rinsing step, the wafer that has been developed using the developer containing the organic solvent is cleaned using the rinse solution containing the organic solvent. The cleaning method is not particularly limited. For example, a method of continuing to discharge the rinse liquid onto the substrate rotating at a constant speed (rotary coating method), or immersing the substrate in a tank filled with the rinse liquid for a certain period of time. A method (dip method), a method of spraying a rinsing liquid onto the substrate surface (spray method), etc. can be applied. Among these, a cleaning process is performed by a spin coating method, and after cleaning, the substrate is rotated at a speed of 2000 rpm to 4000 rpm. It is preferable to rotate and remove the rinse liquid from the substrate. Moreover, it is also preferable to include a heating process (PostBake) after the rinsing process. The developing solution and the rinsing solution remaining between the patterns and inside the patterns are removed by baking. The heating step after the rinsing step is usually performed at 40 to 160 ° C., preferably 70 to 95 ° C., usually 10 seconds to 3 minutes, preferably 30 seconds to 90 seconds.

Note that an imprint mold may be produced using the composition of the present invention. For details, see, for example, Japanese Patent No. 4109085 and Japanese Patent Application Laid-Open No. 2008-162101.
The pattern forming method of the present invention can also be used for guide pattern formation in DSA (Directed Self-Assembly) (see, for example, ACSano Vol. 4 No. 8 Pages 4815-4823).
Further, the resist pattern formed by the above method can be used as a core material (core) of a spacer process disclosed in, for example, JP-A-3-270227 and JP-A-2013-164509.

The present invention also relates to an electronic device manufacturing method including the above-described pattern forming method of the present invention, and an electronic device manufactured by this manufacturing method.
The electronic device of the present invention is suitably mounted on electrical and electronic equipment (home appliances, OA / media related equipment, optical equipment, communication equipment, etc.).

The pattern forming method of the present invention is suitably used for semiconductor fine circuit creation such as the manufacture of VLSI and high-capacity microchips. When creating a semiconductor microcircuit, the patterned resist film is used for circuit formation and etching, and the remaining resist film portion is finally removed with a solvent or the like. Unlike so-called permanent resists, the resist film derived from the actinic ray-sensitive or radiation-sensitive resin composition of the present invention does not remain in the final product such as a microchip.

Hereinafter, the present invention will be described more specifically with reference to examples, but the present invention is not limited to the following examples.

<Synthesis Example 1: Synthesis of Resin (P-1)>
5.0 g of the compound represented by the following formula (1), 14.3 g of the compound represented by the following formula (2), 25.0 g of a 50 mass% cyclohexanone solution of p-hydroxystyrene and a polymerization initiator V-601 (sum) 4.0 g (manufactured by Kojun Pharmaceutical Co., Ltd.) was dissolved in 76.3 g of cyclohexanone. In a reaction vessel, 15.3 g of cyclohexanone was placed, and the solution prepared above at 85 ° C. was added dropwise 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 obtained reaction solution was added dropwise to 1300 g of a mixed solution of heptane / ethyl acetate (9/1 (mass ratio)) to reprecipitate the polymer. By filtering the precipitate, 28.8 g of Resin (P-1) was obtained.

Hereinafter, resins (P-2) to (P-16) are synthesized using the same method as the synthesis of resin (P-1) except that the monomers used in the synthesis of resin (P-1) are changed. Synthesized. The structure, weight average molecular weight (Mw) and dispersity (Mw / Mn) of the synthesized polymers (resins (P-2) to (P-16)) are shown below. Moreover, the composition ratio of each repeating unit of the following polymer structure was shown by molar ratio.

Hereinafter, the used acid generator is shown.

Hereinafter, the used low molecular weight compounds are shown.

Basic compound TBAH: Tetrabutylammonium hydroxide TBAB: Tetrabutylammonium benzoate TOA: Tri (n-octyl) amine TPI: 2,4,5-triphenylimidazole

Solvent S1: PGMEA (bp = 146 ° C.)
S2: PGME (bp = 120 ° C.)
S3: cyclohexanone (bp = 157 ° C.)
S4: γ-butyrolactone

Surfactant W-1: Megafax R08 (manufactured by DIC Corporation; 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., Ltd .; fluorine-based)
W-4: PF6320 (manufactured by OMNOVA; fluorine-based)

Developer / Rinse G-1: Butyl acetate G-2: 2-Heptanone G-3: Anisole G-4: 4-Methyl-2-pentanol G-5: 1-Hexanol G-6: Decane

[Examples 1-1 to 1-20, Comparative Examples 1-1 to 1-4 (EUV exposure (alkali development))]
(1) Preparation and coating of actinic ray-sensitive or radiation-sensitive resin composition A resin composition having the composition shown in the table below is microfiltered with a membrane filter having a pore size of 0.05 μm, and actinic ray-sensitive Or the radiation sensitive resin composition (resist composition) (solid content concentration: 1.5 mass%) was obtained.
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 100 ° C. for 60 seconds. It dried on the hotplate and obtained the resist film with a film thickness of 50 nm.

(2) EUV exposure and development On a wafer having the resist film obtained in (1) above, an EUV exposure apparatus (Micro Exposure Tool, manufactured by Exitech, NA 0.3, Quadrupole, outer sigma 0.68, inner sigma 0.36) ) And pattern exposure was performed using an exposure mask (line / space = 1/1). After pattern exposure, the wafer was heated on a hot plate at 110 ° C. for 60 seconds and then immersed in an aqueous 2.38 mass% tetramethylammonium hydroxide (TMAH) solution for 60 seconds. Next, the wafer was rinsed with water for 30 seconds and dried to obtain a wafer having a 1: 1 line and space pattern resist pattern with a line width of 50 nm.

(3) Evaluation of resist pattern Using a scanning electron microscope (S-9380II manufactured by Hitachi, Ltd.), the sensitivity and resolution of the obtained resist pattern were evaluated by the following methods. The results are shown in the table below.

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

(3-2) Resolution In the above Eop, the minimum line width of the separated (1: 1) line and space pattern was defined as the resolution. The smaller this value, the better the performance.

As can be seen from Table 1, Examples 1-1 to 1-20 have higher sensitivity and higher resolution than Comparative Examples 1-1 to 1-4 in which the composition of the present invention is not used. I was able to be satisfied at the same time.
In Comparative Example 1-3, since the low molecular compound M-3, which is a crosslinking agent, crosslinks with the polar group, the exposed area was not removed even with alkali development, and a desired pattern was not obtained.

[Examples 2-1 to 2-20, Comparative Examples 2-1 to 2-4 (EUV exposure (organic solvent development))]
The composition is changed as shown in the table below, and development is performed with the organic developer described in the table below instead of the alkaline aqueous solution (TMAH; 2.38 mass% tetramethylammonium hydroxide aqueous solution), and the water is replaced with water. An actinic ray-sensitive or radiation-sensitive resin composition was prepared and a pattern was formed in the same manner as in Example 1-1 except that rinsing was performed using the rinsing liquid described in the following table. In the table below, rinsing is not performed in the examples where “None” is described in the column of the rinsing liquid.

Evaluation of resist pattern Using a scanning electron microscope (S-9380II manufactured by Hitachi, Ltd.), the obtained resist patterns were the same as in Examples 1-1 to 1-20 and Comparative Examples 1-1 to 1-4. The sensitivity and resolving power were evaluated by the above method. The results are shown in the table below.

As can be seen from Table 2 above, Examples 2-1 to 2-20 have higher sensitivity and higher resolution than Comparative Examples 2-1 to 2-4 that do not use the composition of the present invention. I was able to be satisfied at the same time.
In Comparative Example 2-3, since the low molecular compound M-3, which is a cross-linking agent, crosslinks with a polar group, the exposed area is removed when an organic solvent is developed, and a desired pattern cannot be obtained. It was.

Claims

The step of forming a film using the actinic ray-sensitive or radiation-sensitive resin composition (i) or (ii) below, the step of exposing the film, and the exposure using an alkali developer The pattern formation method which has the process of removing the exposure part of a film | membrane and forming a pattern.
(I) A resin having a repeating unit having a group that decomposes by the action of an acid to generate a polar group, and a repeating unit containing a partial structure having a monovalent iodine atom that is not eliminated by irradiation with actinic rays or radiation ( An actinic ray-sensitive or radiation-sensitive resin composition containing A1) (ii) a resin (A2) having a repeating unit having a group that is decomposed by the action of an acid to generate a polar group, and a monovalent iodine atom Actinic ray-sensitive or radiation-sensitive resin composition containing compound (AD) having
Using the actinic ray-sensitive or radiation-sensitive resin composition that is the following (i) or (ii), a step of forming a film, a step of exposing the film, and a developer containing an organic solvent, A pattern forming method including a step of forming a pattern by removing an unexposed portion of an exposed film.
(I) A resin having a repeating unit having a group that decomposes by the action of an acid to generate a polar group, and a repeating unit containing a partial structure having a monovalent iodine atom that is not eliminated by irradiation with actinic rays or radiation ( An actinic ray-sensitive or radiation-sensitive resin composition containing A1) (ii) a resin (A2) having a repeating unit having a group that is decomposed by the action of an acid to generate a polar group, and a monovalent iodine atom Actinic ray-sensitive or radiation-sensitive resin composition containing compound (AD) having
The pattern forming method according to claim 1 or 2, wherein the actinic ray-sensitive or radiation-sensitive resin composition is the actinic ray-sensitive or radiation-sensitive resin composition (i).
The content of the resin (A1) is 25 to 99% by mass based on the total solid content in the actinic ray-sensitive or radiation-sensitive resin composition (i). 2. The pattern forming method according to claim 1.
The pattern forming method according to any one of claims 1 to 4, wherein the resin (A1) contains a repeating unit represented by the following general formula (1 ').

In general formula (1 ′),
R 11 , R 12 and R 13 each independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, a cyano group or an alkoxycarbonyl group. R 13 may be bonded to Ar 1 to form a ring. When R 13 and Ar 1 are bonded, R 13 represents an alkylene group.
X 1 represents a single bond, an alkylene group, aromatic ring group, -O -, - S -, - CO -, - COO -, - SO 2 NH -, - SO 2 O -, - NR-, 2 divalent nitrogen It represents a divalent linking group comprising a non-aromatic heterocyclic group or a combination thereof. R represents a hydrogen atom or an alkyl group.
Ar 1 represents an aromatic ring group.
RI represents an iodine atom or an organic group containing at least one iodine atom.
n represents an integer of 1 or more.
The pattern formation method according to claim 5, wherein RI in the general formula (1 ') is an iodine atom.
The pattern forming method according to claim 5 or 6, wherein n in the general formula (1 ') is an integer of 2 or more.
The pattern forming method according to any one of claims 5 to 7, wherein X 1 in the general formula (1 ') is -COO-.
The pattern formation according to any one of claims 1 to 8, wherein the actinic ray-sensitive or radiation-sensitive resin composition further contains a compound (B) that generates an acid upon irradiation with actinic rays or radiation. Method.
The pattern forming method according to any one of claims 3 to 8, wherein the resin (A1) has a repeating unit having a group capable of generating an acid upon irradiation with an actinic ray or radiation.
The pattern forming method according to any one of claims 1 to 10, wherein the exposure is exposure with EUV light.
An electronic device manufacturing method including the pattern forming method according to any one of claims 1 to 11.
An electronic device manufactured by the electronic device manufacturing method according to claim 12.
A step of forming a film using the actinic ray-sensitive or radiation-sensitive resin composition, a step of exposing the film, and using an alkaline developer, the exposed portion of the exposed film is removed to form a pattern. An actinic ray-sensitive or radiation-sensitive resin composition that is used in a pattern forming method including a forming step and is the following (i) or (ii).
(I) A resin having a repeating unit having a group that decomposes by the action of an acid to generate a polar group, and a repeating unit containing a partial structure having a monovalent iodine atom that is not eliminated by irradiation with actinic rays or radiation ( An actinic ray-sensitive or radiation-sensitive resin composition containing A1) (ii) a resin (A2) having a repeating unit having a group that is decomposed by the action of an acid to generate a polar group, and a monovalent iodine atom Actinic ray-sensitive or radiation-sensitive resin composition containing compound (AD) having
A step of forming a film using an actinic ray-sensitive or radiation-sensitive resin composition, a step of exposing the film, and a developer containing an organic solvent are used to remove unexposed portions of the exposed film. An actinic ray-sensitive or radiation-sensitive resin composition that is used in a pattern forming method including a step of forming a pattern and is the following (i) or (ii).
(I) A resin having a repeating unit having a group that decomposes by the action of an acid to generate a polar group, and a repeating unit containing a partial structure having a monovalent iodine atom that is not eliminated by irradiation with actinic rays or radiation ( An actinic ray-sensitive or radiation-sensitive resin composition containing A1) (ii) a resin (A2) having a repeating unit having a group that is decomposed by the action of an acid to generate a polar group, and a monovalent iodine atom Actinic ray-sensitive or radiation-sensitive resin composition containing compound (AD) having
A resist film formed from the actinic ray-sensitive or radiation-sensitive resin composition according to claim 14 or 15.