JP2011095635A - Active ray-sensitive or radiation-sensitive resin composition and pattern forming method using the composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an active ray-sensitive or radiation-sensitive resin composition which has improved DOF (Depth Of Focus), storage stability, resolution and pattern features and suitable even for a liquid immersion process for a line width of not more than 45 nm, and to provide a pattern forming method using the composition. <P>SOLUTION: The active ray-sensitive or radiation-sensitive resin composition contains (A) a compound generating a base by irradiation with active rays or radiation, (B) a resin having a repeating unit having a lactone structure, the solubility of which with an alkali developing solution increases by an action of an acid, and (C) a compound generating an acid by irradiation with active rays or radiation. The pattern forming method is carried out by using the above composition. <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

  The present invention relates to an actinic ray-sensitive or radiation-sensitive resin composition used in semiconductor manufacturing processes such as ICs, circuit boards such as liquid crystals and thermal heads, and other photofabrication processes, and patterns using the same. The present invention relates to a forming method. More specifically, the present invention relates to an actinic ray-sensitive or radiation-sensitive resin composition suitable for use in the case where far ultraviolet rays of 250 nm or less, an electron beam, or the like is used as an irradiation source, and a pattern forming method using the same.

The chemically amplified resist generates an acid in the exposed part by irradiation with radiation such as deep ultraviolet light, and the reaction using this acid as a catalyst changes the solubility of the active radiation irradiated part and the non-irradiated part in the developer, A pattern is formed on the substrate.
When a KrF excimer laser is used as an exposure light source, it is mainly composed of a resin having a basic skeleton of poly (hydroxystyrene) having a small absorption in the 248 nm region, so that a high sensitivity, high resolution and good pattern can be obtained. It is a better system than the conventional naphthoquinone diazide / novolak resin system.
On the other hand, when a further short wavelength light source, for example, an ArF excimer laser (193 nm) is used as an exposure light source, the above chemical amplification system is not sufficient because an aromatic compound essentially shows a large absorption in the 193 nm region. It was.
For this reason, various ArF excimer laser resists containing an alicyclic hydrocarbon structure have been developed. However, from the viewpoint of overall performance as a resist, it is actually difficult to find an appropriate combination of resins, photoacid generators, additives, solvents and the like to be used.
In Patent Document 1, a positive resist material containing a photobase generator is disclosed in order to ensure the rectangularity of the pattern and reduce the unevenness of the side wall of the pattern due to standing waves.
In the generation that forms the latest pattern with a line width of 45 nm or less to which the immersion process is applied, the prior art is not sufficient, and further improvement in depth of focus (DOF) and storage stability. Is required.

Japanese Patent Laid-Open No. 10-83079

  In view of the above problems in the background art, the present invention has good resolution and pattern shape, excellent DOF and storage stability, and a feeling suitable for an immersion process for forming a pattern with a line width of 45 nm or less. It is an object to provide an actinic ray-sensitive or radiation-sensitive resin composition and a pattern forming method using the same.

  The present invention is as follows.

(1) (A) a compound that generates a base upon irradiation with actinic rays or radiation,
(B) It has a repeating unit having a lactone structure, and contains a resin whose solubility in an alkaline developer is increased by the action of an acid, and (C) a compound that generates an acid upon irradiation with actinic rays or radiation. An actinic ray-sensitive or radiation-sensitive resin composition.

  (2) The compound (A) that generates a base upon irradiation with actinic rays or radiation has at least one partial structure represented by any one of the following general formulas (A1) to (A3). The actinic ray-sensitive or radiation-sensitive resin composition according to (1) above.

In the general formulas (A1) to (A3),
R _{1 to} R ₄ each independently represents a hydrogen atom, an alkyl group or a cycloalkyl group. R _{1 to} R ₄ may be bonded to each other to form a ring.
A ⁺ represents an ammonium cation.
X ⁻ represents a counter anion.
R represents a hydrogen atom, an alkyl group or a cycloalkyl group.

  (3) The above (1) or (2), wherein the compound (A) that generates a base upon irradiation with actinic rays or radiation is represented by any one of the following general formulas (1) to (6): Actinic ray-sensitive or radiation-sensitive resin composition as described in 1).

In general formula (1),
A ⁺ represents an ammonium cation.
X ⁻ represents a counter anion.
R represents a hydrogen atom, an alkyl group or a cycloalkyl group.
Ar represents an aryl group or a heteroaryl group.
In the general formulas (2) to (6),
R _{1 to} R ₄ each independently represents a hydrogen atom, an alkyl group or a cycloalkyl group. R _{1 to} R ₄ may be bonded to each other to form a ring.
Ar represents an aryl group or a heteroaryl group.
n represents an integer of 0 to 5.

  (4) The actinic ray-sensitive or radiation-sensitive resin composition as described in (3) above, wherein the general formula (6) is represented by the following general formula (6-1).

In general formula (6-1),
R _{1 to} R ₄ each independently represents a hydrogen atom, an alkyl group or a cycloalkyl group. R _{1 to} R ₄ may be bonded to each other to form a ring.
Z represents an atomic group forming an aryl group or a heteroaryl group.
n ₁ represents an integer of 0-4.

一般式（ＩＩＩ）中、
Ａは、エステル結合（−ＣＯＯ−で表される基）又はアミド結合（−ＣＯＮＨ−で表される基）を表す。
Ｒ_０は、複数個ある場合にはそれぞれ独立に、アルキレン基、シクロアルキレン基又はそれらを組み合わせた２価の連結基を表す。
Ｚは、複数個ある場合にはそれぞれ独立に、エーテル結合、エステル結合、アミド結合、ウレタン結合

又はウレア結合

を表す。ここで、Ｒは、水素原子、アルキル基、シクロアルキル基、アリール基を表す。
Ｒ_８は、ラクトン構造を有する１価の有機基を表す。
ｎは、−Ｒ_０−Ｚ−で表される構造の繰り返し数であり、１〜５の整数を表す。
Ｒ_７は、水素原子、ハロゲン原子又はアルキル基を表す。
（６） 更に、（Ｄ）疎水性樹脂を含有することを特徴とする上記（１）〜（５）のいずれかに記載の感活性光線性又は感放射線性樹脂組成物。 (5) The repeating units having the lactone structure contained in the resin (B) are repeating units having a lactone structure represented by the following general formula (III): The actinic ray-sensitive or radiation-sensitive resin composition according to any one of the above.

In general formula (III),
A represents an ester bond (a group represented by —COO—) or an amide bond (a group represented by —CONH—).
R ₀ independently represents an alkylene group, a cycloalkylene group or a divalent linking group obtained by combining them when there are a plurality of R ₀ .
When there are a plurality of Zs, each independently represents an ether bond, an ester bond, an amide bond, or a urethane bond.

Or urea bond

Represents. Here, R represents a hydrogen atom, an alkyl group, a cycloalkyl group, or an aryl group.
R ₈ represents a monovalent organic group having a lactone structure.
n is the repeating number of the structure represented by —R ₀ —Z—, and represents an integer of 1 to 5.
R ₇ represents a hydrogen atom, a halogen atom or an alkyl group.
(6) The actinic ray-sensitive or radiation-sensitive resin composition according to any one of (1) to (5) above, further comprising (D) a hydrophobic resin.

  (7) The actinic ray-sensitive or radiation-sensitive resin composition according to any one of (1) to (6), further comprising (E) a basic compound.

  (8) A step of forming a film with the actinic ray-sensitive or radiation-sensitive resin composition according to any one of (1) to (7) above, and exposing and developing the film. Pattern forming method.

  (9) A step of forming a film with the actinic ray-sensitive or radiation-sensitive resin composition according to any one of the above (1) to (7), and immersion exposure and development. A pattern forming method.

According to the present invention, an actinic ray-sensitive or radiation-sensitive resin composition having excellent resolution and pattern shape, excellent DOF and storage stability, and suitable for an immersion process for forming a pattern with a line width of 45 nm or less. An object and a pattern forming method using the same are provided.
The actinic ray-sensitive or radiation-sensitive resin composition in the present invention is preferably a positive chemically amplified resist composition.

Hereinafter, the present invention will be described in detail.
In addition, in the description of the group (atomic group) in this specification, the description which does not describe substitution and non-substitution includes what has a substituent with what does not have a substituent. For example, the “alkyl group” includes not only an alkyl group having no substituent (unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group).
In the present invention, “active light” or “radiation” means, for example, an emission line spectrum of a mercury lamp, far ultraviolet rays represented by an excimer laser, extreme ultraviolet rays, X-rays, electron beams and the like. In the present invention, light means actinic rays or radiation.
In addition, “exposure” in the present specification is represented not only by exposure to deep ultraviolet rays, X-rays, EUV light and the like, but also by particle beams such as electron beams and ion beams, unless otherwise specified, such as mercury lamps and excimer lasers. Drawing is also included in the exposure.

[1] (A) Compound that generates base upon irradiation with actinic ray or radiation The actinic ray-sensitive or radiation-sensitive resin composition of the present invention is a compound that generates a base upon irradiation with actinic ray or radiation (hereinafter, “ Compound (PBG) ”).
Compound (PBG) decomposes upon irradiation with actinic rays or radiation to generate a base.
The base here means a compound having a nitrogen atom having an unshared electron pair that does not contribute to π conjugation. The nitrogen atom having an unshared electron pair that does not contribute to π conjugation is, for example, a nitrogen atom having a partial structure represented by the following general formula.

  Preferred examples of the base include, for example, crown ether, azacrown ether, primary to tertiary amines, pyrrole, pyridine, imidazole, pyrazine, piperidine, piperazine and the like.

  The compound (PBG) preferably has at least one partial structure represented by any of the following general formulas (A1) to (A3).

In the general formulas (A1) to (A3),
R _{1 to} R ₄ each independently represents a hydrogen atom, an alkyl group or a cycloalkyl group. R _{1 to} R ₄ may be bonded to each other to form a ring.
A ⁺ represents an ammonium cation.
X ⁻ represents a counter anion.
R represents a hydrogen atom, an alkyl group or a cycloalkyl group.
In general formula (A3), the ammonium atom in A ⁺ is directly connected to the carbon atom to which R is bonded.

In the general formulas (A1) to (A3), R _{1 to} R ₄ and the alkyl group in R may have a substituent, and preferably a linear and branched alkyl group having 1 to 20 carbon atoms. More preferably, they are a linear and branched alkyl group having 1 to 10 carbon atoms, and may have an oxygen atom, a sulfur atom, or a nitrogen atom in the alkyl chain.
Examples of the alkyl group having a substituent include groups in which a linear or branched alkyl group is substituted with a cycloalkyl group (for example, an adamantylmethyl group, an adamantylethyl group, a cyclohexylethyl group, a camphor residue, etc.). . Examples of the group having an oxygen atom, sulfur atom or nitrogen atom in the alkyl chain include a methoxyethoxy group, an ethoxyethyl group, a methylthiomethyl group, a methylthioethyl group, and a dimethylaminomethyl group.
Further, the cycloalkyl group in R _{1 to} R ₄ and R may have a substituent, preferably a cycloalkyl group having 3 to 20 carbon atoms, more preferably a straight chain having 3 to 10 carbon atoms. A chain and a branched alkyl group, which may have an oxygen atom in the ring. Particularly preferred are a cyclohexyl group, a cyclopentyl group, a cycloheptyl group, an adamantyl group and a norbornane group, and a cyclohexyl group and a cyclopentyl group are particularly preferred among them. Examples of the group having an oxygen atom in the cycloalkyl ring include a tetrahydrofurfuryl group and a tetrahydrofurfurylmethyl group.
Preferred examples of R ₁ and R _2, if R ₁ and R ₂ are bonded to form a cyclic alkyl group, one of R ₁ and R ₂ are hydrogen atom and the other is an alkyl group, a cycloalkyl In the case of an alkyl group, when a cyclic alkyl group is formed, a case of forming a 6-membered ring or a 5-membered ring structure is particularly preferable, and any _one of R ₁ and R ₂ is a hydrogen atom, When one is an alkyl group or a cycloalkyl group, it is particularly preferred that either R ₁ or R ₂ is a hydrogen atom and the other is a cycloalkyl group.
Preferable examples of R ₃ and R ₄ include a hydrogen atom and an alkyl group, and a hydrogen atom is particularly preferable.
Each group as R _{1 to} R ₄ and R may have a substituent. Examples of the substituent include a halogen atom (fluorine atom, chlorine atom, bromine atom, etc.), hydroxy group, carboxyl group, Examples include cyano group, alkoxy group (methoxy group, ethoxy group, isopropoxy group, t-butoxy group), acetoxy group (acetyloxy group, propionyloxy group, etc.), cycloalkyl group, alkoxycarbonyl group, etc., cycloalkyl group As for the cyclic structure in the above, an alkyl group is further exemplified. The number of carbon atoms of the substituent is preferably 15 or less.

A ⁺ represents an ammonium cation, preferably an alicyclic tetraalkylammonium cation or a chain-like tetraalkylammonium cation, and particularly preferred ammonium cations include the following structures.

X ⁻ represents a counter anion, preferably a borate anion, N, N-dimethyldithiocarbamate anion, N, N-dimethylcarbamate anion, cyanate anion, trifluoromethanesulfonate anion, nonafluorobutanesulfonate anion, in particular N, N-dimethyldithiocarbamate anion and N, N-dimethylcarbamate anion are preferable.

  Examples of preferable bases generated from the partial structure represented by any one of the general formulas (A1) to (A3) include the following.

  Particularly preferred examples of the compound (PBG) include compounds represented by any one of the following general formulas (1) to (6).

In general formula (1),
A ⁺ represents an ammonium cation.
X ⁻ represents a counter anion.
R represents a hydrogen atom, an alkyl group or a cycloalkyl group.
Ar represents an aryl group or a heteroaryl group.
In the general formulas (2) to (6),
R _{1 to} R ₄ each independently represents a hydrogen atom, an alkyl group or a cycloalkyl group. R _{1 to} R ₄ may be bonded to each other to form a ring.
Ar represents an aryl group or a heteroaryl group.
n represents an integer of 0 to 5 and is preferably 1 or 2.
(NO ₂ ) _n − in the general formula (5) and (HO) _n − in the general formula (6) are n substituents (NO ₂ — or HO to the aryl group or heteroaryl group represented by Ar. -) Means.

Examples of preferable alkyl groups and cycloalkyl groups of R _{1 to} R ₄ and R in the general formulas (1) to (6) are the general formulas (A1) to (A3), R _{1 to} R ₄ and This is the same as the group described for R. Examples of preferable ammonium cations and counter anions of A ⁺ and X ⁻ are the same as the ammonium cations and counter anions described in the general formulas (A1) to (A3), A ⁺ and X ⁻ .
The aryl group for Ar preferably has 4 to 14 carbon atoms, more preferably 6 to 10 carbon atoms, and examples thereof include a phenyl group, a naphthyl group, and an anthracenyl group. The heteroaryl group for Ar is preferably It has 4 to 14 carbon atoms, more preferably 6 to 10 carbon atoms, and examples thereof include a thiophenyl group, a furanyl group, a pyridinyl group, an indole group, a pyrrole group, and a carbazole group.
Ar is preferably a phenyl group, a naphthyl group, an anthracenyl group, a thiophenyl group, a furanyl group, or a pyridinyl group, and more preferably a phenyl group or a naphthyl group.
The group as Ar and the cyclic structure in the general formulas (1) to (6) may have a substituent, and each of the groups as R _{1 to} R ₄ and R has a substituent. The substituent which may be present can be mentioned.

  Among these compounds represented by the general formulas (1) to (6), preferred compounds include those represented by the general formulas (2) to (6), and more preferably the general formulas (5) or ( The compound represented by 6) is mentioned, Especially preferably, the compound represented by the following general formula (6-1) in the compound of General formula (6) is mentioned.

In general formula (6-1),
R _{1 to} R ₄ each independently represents a hydrogen atom, an alkyl group or a cycloalkyl group. R _{1 to} R ₄ may be bonded to each other to form a ring.
Z represents an atomic group forming an aryl group or a heteroaryl group.
n ₁ represents an integer of 0-4.

Examples of preferable alkyl groups and cycloalkyl groups represented by R _{1 to} R _{4 in} the general formula (6-1) include the groups described in the general formulas (A1) to (A3) and R _{1 to} R ₄ described above. It is the same.
Preferable examples of the aryl group and heteroaryl group formed as Z are the same as the above-mentioned general formula (6), the aryl group and heteroaryl group in Ar.
n ₁ is preferably 0 to 2, and 0 is particularly preferable.
The aryl group and heteroaryl group formed as Z may have a substituent, and examples of the substituent include R _{1 to} R ₄ and substituents that each group as R may have. be able to.
The compound (PBG) may be a compound having a structure in which a plurality of the compounds (PBG) are bonded by a single bond or a linking group.

  Hereinafter, although the specific example of the compound (PBG) of this invention is shown, it is not limited to these.

The molecular weight of the compound (PBG) is generally 100 to 700, preferably 150 to 500, and more preferably 200 to 400.
As the compound (PBG), a commercially available product may be used, or a compound synthesized by a known method may be used. For example, the method described in Journal of Medicinal Chemistry, 42, 4016-4020 (1999), Journal of American Chemical Society, 113, 4303-4313 (1991), Chem. Pharm. Bull., 45, 715-718 (1997). It can be synthesized according to
The content of the compound (PBG) in the actinic ray-sensitive or radiation-sensitive resin composition is preferably 0.1 to 25% by mass based on the total solid content of the actinic ray-sensitive or radiation-sensitive resin composition. More preferably, it is 0.5-20 mass%, More preferably, it is 1.0-15 mass%.

[2] (B) Resin having a repeating unit having a lactone structure and having increased solubility in an alkaline developer by the action of an acid The actinic ray-sensitive or radiation-sensitive resin composition of the present invention is a repeating having a lactone structure A resin having a unit and increasing the solubility in an alkaline developer by the action of an acid (hereinafter also referred to as “resin (B)”) is contained.

  The repeating unit having a lactone structure contained in the resin (B) is preferably a repeating unit having a lactone structure represented by the following general formula (III).

In general formula (III),
A represents an ester bond (a group represented by —COO—) or an amide bond (a group represented by —CONH—).
R ₀ independently represents an alkylene group, a cycloalkylene group or a divalent linking group obtained by combining them when there are a plurality of R ₀ .
When there are a plurality of Zs, each independently represents an ether bond, an ester bond, an amide bond, or a urethane bond.

Or urea bond

を表す。ここで、Ｒは、水素原子、アルキル基、シクロアルキル基、アリール基を表す。

Represents. Here, R represents a hydrogen atom, an alkyl group, a cycloalkyl group, or an aryl group.

R ₈ represents a monovalent organic group having a lactone structure.
n is the repeating number of the structure represented by —R ₀ —Z—, represents an integer of 1 to 5, and is preferably 1.
R ₇ represents a hydrogen atom, a halogen atom or an alkyl group.

  Z is preferably an ether bond or an ester bond, and particularly preferably an ester bond.

The alkyl group for R ₇ is preferably an alkyl group having 1 to 4 carbon atoms, more preferably a methyl group or an ethyl group, and particularly preferably a methyl group. The alkyl group in R ₇ may be substituted. Examples of the substituent include halogen atoms such as fluorine atom, chlorine atom and bromine atom, mercapto group, hydroxy group, methoxy group, ethoxy group, isopropoxy group, Examples include alkoxy groups such as t-butoxy group and benzyloxy group, and acetoxy groups such as acetyloxy group and propionyloxy group. R ₇ is preferably a hydrogen atom, a methyl group, a trifluoromethyl group, or a hydroxymethyl group.

A preferable alkylene group in R ₀ is preferably an alkylene having 1 to 10 carbon atoms, more preferably 1 to 5 carbon atoms, and examples thereof include a methylene group, an ethylene group, and a propylene group. Preferable cycloalkylene is cycloalkylene having 1 to 20 carbon atoms, and examples thereof include cyclohexylene, cyclopentylene, norbornylene, adamantylene and the like. In order to exhibit the effect of the present invention, a chain alkylene group is more preferable, and a methylene group is particularly preferable.
The alkylene group and cycloalkylene group represented by R ₀ may have a substituent.

The monovalent organic group having a lactone structure represented by R ₈ is not limited as long as it has a lactone structure. General formulas (LC1-1) to (LC1-17) described later as specific examples And a monovalent organic group having a lactone structure represented by (LC1-4) is particularly preferable. N ₂ in (LC1-1) to (LC1-17) represents an integer of 0 to 4, but 2 or less is more preferable.
R ₈ is preferably a monovalent organic group having an unsubstituted lactone structure or a monovalent organic group having a lactone structure having a methyl group, a cyano group or an alkoxycarbonyl group as a substituent. A monovalent organic group having a lactone structure (cyanolactone) as is more preferable.

Specific examples of the repeating unit having a group having a lactone structure represented by the general formula (III) are shown below, but the present invention is not limited thereto.
In the following specific examples, R represents a hydrogen atom, an alkyl group which may have a substituent, or a halogen atom, and preferably represents a hydrogen atom, a methyl group, a hydroxymethyl group or an acetoxymethyl group.

  Among the repeating units represented by the general formula (III), a repeating unit represented by the following general formula (III-1) is more preferable.

In general formula (III-1),
R ₇ , A, R ₀ , Z, and n have the same meanings as R ₇ , A, R ₀ , Z, and n in the general formula (III).
R ₉ are each independently in the presence of two or more, an alkyl group, a cycloalkyl group, an alkoxycarbonyl group, a cyano group, a hydroxyl group or an alkoxy group. R _9, the two R ₉ are attached when a plurality, may form a ring.
X represents an alkylene group, an oxygen atom, or a sulfur atom.
m is the number of substituents and represents an integer of 0 to 5. m is preferably 0 or 1.

The alkyl group for R ₉ is preferably an alkyl group having 1 to 4 carbon atoms, more preferably a methyl group or an ethyl group, and particularly preferably a methyl group. Examples of the cycloalkyl group include cyclopropyl, cyclobutyl, cyclopentyl, and cyclohexyl groups. Examples of the alkoxycarbonyl group include a methoxycarbonyl group, an ethoxycarbonyl group, an n-butoxycarbonyl group, and a t-butoxycarbonyl group. Examples of the alkoxy group include a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, and a butoxy group. These groups may have a substituent, and examples of the substituent include an alkoxy group such as a hydroxy group, a methoxy group, and an ethoxy group, and a halogen atom such as a cyano group and a fluorine atom. R ₉ is more preferably a methyl group, a cyano group or an alkoxycarbonyl group, and even more preferably a cyano group.

  Examples of the alkylene group for X include a methylene group and an ethylene group. X is preferably an oxygen atom or a methylene group, and more preferably a methylene group.

When m is 1 or more, at least one R ₉ is preferably substituted at the α-position or β-position of the carbonyl group of the lactone, particularly preferably at the α-position.

  Specific examples of the repeating unit having a group having a lactone structure represented by formula (III-1) are shown below, but the present invention is not limited thereto. In the following specific examples, R represents a hydrogen atom, an alkyl group which may have a substituent, or a halogen atom, and preferably represents a hydrogen atom, a methyl group, a hydroxymethyl group or an acetoxymethyl group.

  The content of the repeating unit having a lactone structure including the repeating unit represented by the general formula (III) is preferably 15 to 60 mol% in total with respect to all the repeating units in the resin when more than one type is contained. Preferably it is 20-60 mol%, More preferably, it is 30-50 mol%.

The resin (B) may have a repeating unit having another lactone structure as shown below in addition to the repeating unit represented by the general formula (III).
The molar ratio of the repeating unit represented by the general formula (III) and the other repeating unit having a lactone structure is preferably 80/20 to 20/80, and more preferably 70/30 to 30/70.

  The lactone structure possessed by the repeating unit having a lactone structure is preferably a 5- to 7-membered ring lactone structure, and other ring structures are condensed to form a bicyclo structure or a spiro structure in the 5- to 7-membered ring lactone structure. Are preferred. It is more preferable to have a repeating unit having a lactone structure represented by any of the following general formulas (LC1-1) to (LC1-17). The lactone structure may be directly bonded to the main chain. Preferred lactone structures are (LC1-1), (LC1-4), (LC1-5), (LC1-6), (LC1-13), (LC1-14), and (LC1-17). By using this lactone structure, LWR and development defects are improved.

The lactone structure portion may or may not have a substituent (Rb ₂ ). Preferred substituents (Rb ₂ ) include an alkyl group having 1 to 8 carbon atoms, a cycloalkyl group having 4 to 7 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, an alkoxycarbonyl group having 1 to 8 carbon atoms, and a carboxyl group. , Halogen atom, hydroxyl group, cyano group, acid-decomposable group and the like. More preferably, they are a C1-C4 alkyl group, a cyano group, and an acid-decomposable group. n ₂ represents an integer of 0-4. 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. .

  As the repeating unit having a lactone structure other than the repeating unit represented by the general formula (III), a repeating unit represented by the following general formula (AII ′) is preferable.

In general formula (AII ′),
Rb ₀ represents a hydrogen atom, a halogen atom or an alkyl group 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, a bromine atom, and an iodine atom. Preferred are a hydrogen atom, a methyl group, a hydroxymethyl group, and a trifluoromethyl group, and a hydrogen atom and a methyl group are particularly preferred.

  V represents a group having a structure represented by any one of the general formulas (LC1-1) to (LC1-17).

  Specific examples of the repeating unit having a lactone structure other than the repeating unit represented by the general formula (III) will be given below, but the present invention is not limited thereto.

  Particularly preferred repeating units having a lactone structure other than the repeating unit represented by the general formula (III) include the following repeating units.

  The repeating unit having a lactone 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 content of the repeating unit having a lactone other than the repeating unit represented by the general formula (III) is preferably 15 to 60 mol% in total, more preferably 15 to 60 mol% with respect to all the repeating units in the resin when it contains a plurality of types. Is 20 to 50 mol%, more preferably 30 to 50 mol%.

  In order to enhance the effect of the present invention, it is also possible to use a repeating unit having two or more lactone structures selected from repeating units represented by the general formula (III). When using together, it is preferable to select and use 2 or more types from the lactone repeating unit in which n is 1 in general formula (III).

  In the chemically amplified resist composition, a resin having a repeating unit having a lactone structure and a basic compound described later may be used in combination. In that case, for example, the following lactone decomposition reaction occurs under storage conditions, particles may be generated in the resist solution, and storage stability may deteriorate. On the other hand, the compound (PBG) of the present invention has no basicity before exposure, and therefore does not induce decomposition of the lactone unit, so that no particles are generated and actinic ray sensitivity or radiation sensitivity with good storage stability. It is possible to prepare a resin composition. In the following reaction formula, R ′ represents an alkyl group, a cycloalkyl group, or an aryl group.

Resin (B) is a group that decomposes by the action of an acid on the main chain or side chain of the resin, or both of the main chain and side chain to generate an alkali-soluble group (hereinafter also referred to as “acid-decomposable group”). Have
The resin (B) is preferably insoluble or hardly soluble in an alkali developer.

The acid-decomposable group preferably has a structure protected with a group capable of decomposing and leaving an alkali-soluble group by the action of an acid.
Alkali-soluble groups include phenolic hydroxyl groups, carboxyl groups, fluorinated alcohol groups, sulfonic acid groups, sulfonamido groups, sulfonylimide groups, (alkylsulfonyl) (alkylcarbonyl) methylene groups, (alkylsulfonyl) (alkylcarbonyl) imides. 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, etc. Is mentioned.

  Preferred alkali-soluble groups include carboxyl groups, fluorinated alcohol groups (preferably hexafluoroisopropanol), and sulfonic acid groups.

A preferable group as the acid-decomposable group is a group in which the hydrogen atom of these alkali-soluble groups is substituted with a group capable of leaving with an acid.
As the acid eliminable group, there can be, for _{example, -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, R _{36 to} R ₃₉ each independently represents an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, or an alkenyl group. R ₃₆ and R ₃₇ may be bonded to each other to form a ring.

R _{01 to} R ₀₂ each independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group 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. More preferably, it is a tertiary alkyl ester group.

  The repeating unit having an acid-decomposable group that can be contained in the resin (B) is preferably a repeating unit represented by the following general formula (AI).

In general formula (AI),
Xa ₁ represents a hydrogen atom, a methyl group which may have a substituent, or a group represented by —CH ₂ —R ₉ . R ₉ represents a hydroxy group or a monovalent organic group, and examples thereof include an alkyl group or acyl group having 5 or less carbon atoms, preferably an alkyl group having 3 or less carbon atoms, and more preferably a methyl group. . Xa ₁ is preferably a hydrogen atom, a methyl group, a trifluoromethyl group or a hydroxymethyl group.
T represents a single bond or a divalent linking group.
Examples of the divalent linking group for T include an alkylene group, —COO—Rt— group, —O—Rt— group, and the like. In the formula, Rt represents an alkylene group or a cycloalkylene group.
T is preferably a single bond or a —COO—Rt— group. Rt is preferably an alkylene group having 1 to 5 carbon atoms, more preferably a —CH ₂ — group or a — (CH ₂ ) ₃ — group.
Rx _{1 to} Rx ₃ each independently represents an alkyl group (straight or branched) or a cycloalkyl group (monocyclic or polycyclic). Two of Rx _{1 to} Rx ₃ may combine to form a cycloalkyl group (monocyclic or polycyclic).
Examples of the alkyl group rx ₁ to Rx _3, methyl, ethyl, n- propyl group, an isopropyl group, n- butyl group, an isobutyl group, those having 1 to 4 carbon atoms such as t- butyl group.
Examples of the cycloalkyl group represented by Rx _{1 to} Rx ₃ include monocyclic cycloalkyl groups such as cyclopentyl group and cyclohexyl group, polycyclic cycloalkyl groups such as norbornyl group, tetracyclodecanyl group, tetracyclododecanyl group, and adamantyl group. Groups are preferred.
Examples of the cycloalkyl group formed by combining two of Rx _{1 to} Rx ₃ include a monocyclic cycloalkyl group such as a cyclopentyl group and a cyclohexyl group, a norbornyl group, a tetracyclodecanyl group, a tetracyclododecanyl group, an adamantyl group A polycyclic cycloalkyl group such as a group is preferred. A monocyclic cycloalkyl group having 5 to 6 carbon atoms is particularly preferable.
An embodiment in which Rx ₁ is a methyl group or an ethyl group, and Rx ₂ and Rx ₃ are bonded to form the above-described cycloalkyl group is preferable.
Each of the above groups may have a substituent. Examples of the substituent include an alkyl group (1 to 4 carbon atoms), a halogen atom, a hydroxyl group, an alkoxy group (1 to 4 carbon atoms), a carboxyl group, An alkoxycarbonyl group (C2-C6) etc. are mentioned, C8 or less is preferable.

  The content of the repeating unit having an acid-decomposable group as a total is preferably 20 to 70 mol%, more preferably 30 to 50 mol%, based on all repeating units in the resin.

  Although the specific example of the repeating unit which has a preferable acid-decomposable group is shown below, this invention is not limited to this.

In specific examples, Rx and Xa ₁ represent a hydrogen atom, CH ₃ , CF _3, or CH ₂ OH. Rxa and Rxb each independently represents an alkyl group having 1 to 4 carbon atoms. Z represents a substituent containing a polar group, and when there are a plurality of them, each is independent. p represents 0 or a positive integer. The substituent containing a polar group as Z and the preferred substituent thereof are the same as the substituent containing a polar group as R ₁₀ in formula (II-1) described later.

  The resin (B) has at least one of the repeating unit represented by the following general formula (I) and the repeating unit represented by the general formula (II) as the repeating unit represented by the general formula (AI). More preferably, it is a resin.

In general formulas (I) and (II),
R ₁ and R ₃ each independently represent a hydrogen atom, an optionally substituted methyl group, or a group represented by —CH ₂ —R ₉ . R ₉ represents a monovalent organic group.
R ₂ , R ₄ , R ₅ and R ₆ each independently represents an alkyl group or a cycloalkyl group.
R represents an atomic group necessary for forming an alicyclic structure together with a carbon atom.

In the general formula (I), R ₁ is preferably a hydrogen atom, a methyl group, a trifluoromethyl group or a hydroxymethyl group.
The alkyl group in R ₂ may be linear or branched, and may have a substituent.
The cycloalkyl group in R ₂ may be monocyclic or polycyclic and may have a substituent.
R ₂ is preferably an alkyl group, more preferably an alkyl group having 1 to 10 carbon atoms, still more preferably 1 to 5 carbon atoms, and particularly preferably a methyl group or an ethyl group.
R represents an atomic group necessary for forming an alicyclic structure together with a carbon atom. The alicyclic structure formed by R is preferably a monocyclic alicyclic structure, and the carbon number thereof is preferably 3 to 7, and more preferably 5 or 6.

In the general formula (II), R ₃ is preferably a hydrogen atom or a methyl group, and more preferably a methyl group.
The alkyl group in R ₄ , R ₅ , and R ₆ may be linear or branched and may have a substituent. As the alkyl group, those having 1 to 4 carbon atoms such as methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group and t-butyl group are preferable.
The cycloalkyl group in R ₄ , R ₅ and R ₆ may be monocyclic or polycyclic and may have a substituent. The cycloalkyl group is preferably a monocyclic cycloalkyl group such as a cyclopentyl group or a cyclohexyl group, or a polycyclic cycloalkyl group such as a norbornyl group, a tetracyclodecanyl group, a tetracyclododecanyl group or an adamantyl group.

  Moreover, it is preferable that the repeating unit represented by general formula (I) is a repeating unit represented by the following general formula (1-1).

In formula (1-1),
Rv ₁ and Rv ₂ each independently represents an alkyl group having 1 to 10 carbon atoms.
n represents an integer of 1 to 6.

n preferably represents 1 or 2, more preferably 1.
The alkyl group having 1 to 10 carbon atoms in Rv ₁ and Rv ₂ may be linear or branched, and may have a substituent. Examples of the substituent include a cycloalkyl group (preferably 3 to 10 carbon atoms), a halogen atom, a hydroxyl group, an alkoxy group (preferably 1 to 4 carbon atoms), a carboxyl group, and an alkoxycarbonyl group (preferably 2 to 2 carbon atoms). 6) and the like, and those having 8 or less carbon atoms are preferable.

  The repeating unit represented by the general formula (II) is preferably a repeating unit represented by the following general formula (II-1).

In general formula (II-1), R < ₃ > -R < ₅ > is synonymous with each in general formula (II).
R ₁₀ represents a substituent containing a polar group. When a plurality of R ₁₀ are present, they may be the same as or different from each other. Examples of the substituent having a polar group include a polar group itself such as a hydroxyl group, a cyano group, an amino group, an alkylamide group, or a sulfonamide group, or a linear or branched alkyl group or cycloalkyl having these polar groups. Group, and an alkyl group having a hydroxyl group is preferable. As the branched alkyl group, an isopropyl group is particularly preferable.
p represents an integer of 0 to 15. p is preferably 0 to 2, more preferably 0 or 1.

The resin (B) is a resin having at least one of the repeating unit represented by the general formula (I) and the repeating unit represented by the general formula (II) as the repeating unit represented by the general formula (AI). It is more preferable. Moreover, in another form, it is more preferable that it is resin which has at least 2 types of repeating units represented by general formula (I) as a repeating unit represented by general formula (AI).
Moreover, multiple resin (B) may be contained and each may contain a different acid-decomposable group.

In these cases, when including at least two different repeating units represented by general formula (I), when including a repeating unit represented by general formula (I) and a repeating unit represented by general formula (2), Or the case where the repeating unit represented by general formula (1-1) and the repeating unit represented by general formula (II) are included is preferable.
In the case of containing at least two types of repeating units represented by the general formula (I), for example, a combination of a repeating unit in which R ₂ is an ethyl group and a repeating unit in which the R ₂ is a methyl group in the general formula (I), and repeating units of R ₂ is an ethyl group in the general formula (I), wherein R ₂ is a combination of a repeating unit is a cycloalkyl group, R ₂ in formula (I) is formed is R a methyl or ethyl group A combination of a repeating unit in which the ring is adamantane and a repeating unit in which Rv ₂ is a methyl group or an ethyl group in formula (1-1) is preferable.
As a case where the repeating unit represented by the general formula (I) and the repeating unit represented by the general formula (II) are included, for example, R ₂ in the general formula (I) is an ethyl group repeating unit, and the general formula (II) ) In which R ₄ and R ₅ are methyl groups and R ₆ is an adamantyl group, R ₂ in general formula (I) is an ethyl group, and R ₄ and R in general formula (II) _As a combination of a repeating unit in which ₅ is a methyl group and R ₆ is a cyclohexyl group, and a repeating unit represented by the general formula (1-1) and a repeating unit represented by the general formula (II), union of the repeating units Rv ₂ is an ethyl group in the general formula _{(1-1), R 4, R} 5 in the general formula (II) is a repeating unit _{R 6} methyl groups are adamantyl group So, the repeating units of the general formula n Rv ₂ is an ethyl group in (1-1) is 2, a repeating unit _{R 6 R} 4, _{R 5} in the general formula (2) is a methyl group is cyclohexyl group And the like.

  Preferable combinations when the resin (B) uses a repeating unit having an acid-decomposable group are listed below. In the following formula, each R independently represents a hydrogen atom or a methyl group.

The resin (B) preferably has a repeating unit having a hydroxyl group or a cyano group other than the repeating unit represented by the formula (III) or (AI). This improves the substrate adhesion and developer compatibility. The repeating unit having a hydroxyl group or a cyano group is preferably a repeating unit having an alicyclic hydrocarbon structure substituted with a hydroxyl group or a cyano group, and preferably has no 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 diamantyl 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 (VIId) are preferred.

In 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 or a cyano group. Preferably, one or two of R ₂ c to R ₄ c are a hydroxyl group and the rest are hydrogen atoms. In 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 (VIId) include the repeating units represented by the following general formulas (AIIa) to (AIId).

In the general formulas (AIIa) to (AIId), R ₁ c represents a hydrogen atom, a methyl group, a trifluoromethyl group, or a hydroxymethyl group.
R ₂ c to R ₄ c are in the general formula (VIIa) ~ _(VIIc), same meanings as R 2 c~R ₄ c.

The content of the repeating unit having a hydroxyl group or a cyano group is preferably from 5 to 40 mol%, more preferably from 5 to 30 mol%, still more preferably from 10 to 25 mol%, based on all repeating units in the resin (B).

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

  The resin (B) may have a repeating unit having an alkali-soluble group. Examples of the alkali-soluble group include a carboxyl group, a sulfonamide group, a sulfonylimide group, a bisulsulfonylimide group, and an aliphatic alcohol (for example, hexafluoroisopropanol group) substituted with an electron withdrawing group at the α-position. It is more preferable to have a repeating unit. By containing the repeating unit having an alkali-soluble group, the resolution in contact hole applications is increased. The repeating unit having an alkali-soluble group includes a repeating unit in which an alkali-soluble group is directly bonded to the main chain of the resin, such as a repeating unit of acrylic acid or methacrylic acid, or an alkali in the main chain of the resin through a linking group. Either a repeating unit to which a soluble group is bonded, or a polymerization initiator or chain transfer agent having an alkali-soluble group is used at the time of polymerization and introduced at the end of the polymer chain. Both are preferable, and the linking group is monocyclic or polycyclic. It may have a cyclic hydrocarbon structure. Particularly preferred are repeating units of acrylic acid or methacrylic acid.

  As for the content rate of the repeating unit which has an alkali-soluble group, 0-20 mol% is preferable with respect to all the repeating units in resin (B), More preferably, it is 3-15 mol%, More preferably, it is 5-10 mol%.

Specific examples of the repeating unit having an alkali-soluble 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 .

  The resin (B) of the present invention can further have a repeating unit having an alicyclic hydrocarbon structure having no polar group and not exhibiting acid decomposability. Examples of such a repeating unit include a repeating unit represented by the following general formula (IV).

In general formula (IV),
R ₅ represents a hydrocarbon group having at least one cyclic structure and having neither a hydroxyl group nor a cyano group.
Ra represents a hydrogen atom, an alkyl group, or a —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 hydrocarbon group for 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. The preferred monocyclic hydrocarbon group is a monocyclic hydrocarbon group having 3 to 7 carbon atoms, more preferably a cyclopentyl group or 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 homobredan, 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, and tetracyclic hydrocarbon rings such as perhydro-1,4-methano-5,8-methanonaphthalene ring. 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 hydrocarbon groups may have a substituent, and preferred substituents include a halogen atom, an alkyl group, a hydroxyl group protected with a protecting group, an amino group protected with a protecting group, and the like. Preferred halogen atoms include bromine, chlorine and fluorine atoms, and preferred alkyl groups include methyl, ethyl, butyl and t-butyl groups. The above alkyl group may further have a substituent, and the substituent which may further have a halogen atom, an alkyl group, a hydroxyl group protected with a protecting group, an amino protected with a protecting group The group can be mentioned.
Examples of the protecting group include an alkyl group, a cycloalkyl group, an aralkyl group, a substituted methyl group, a substituted ethyl group, an alkoxycarbonyl group, and an aralkyloxycarbonyl group. Preferred alkyl groups include alkyl groups having 1 to 4 carbon atoms, preferred substituted methyl groups include methoxymethyl, methoxythiomethyl, benzyloxymethyl, t-butoxymethyl, 2-methoxyethoxymethyl groups, and preferred substituted ethyl groups. 1-ethoxyethyl, 1-methyl-1-methoxyethyl, preferred acyl groups include formyl, acetyl, propionyl, butyryl, isobutyryl, valeryl, pivaloyl groups, etc., aliphatic acyl groups having 1 to 6 carbon atoms, alkoxycarbonyl Examples of the group include an alkoxycarbonyl group having 1 to 4 carbon atoms.

  The content of the repeating unit having an alicyclic hydrocarbon structure having no polar group and not exhibiting acid decomposability is preferably 0 to 40 mol%, more preferably, based on all repeating units in the resin (B). Is 0 to 20 mol%.

Specific examples of the repeating unit having an alicyclic hydrocarbon structure having no polar group and not exhibiting acid decomposability are listed below, but the present invention is not limited thereto. In the formula, Ra represents H, CH ₃ , CH ₂ OH, or CF ₃ .

  Resin (B) adjusts dry etching resistance, standard developer suitability, substrate adhesion, profile, and resolution, heat resistance, sensitivity, etc., which are general necessary characteristics of resist, in addition to the above repeating structural units. It can have various repeating structural units for the purpose.

  Examples of such repeating structural units include, but are not limited to, repeating structural units corresponding to the following monomers.

Thereby, the performance required for the resin (B), in particular,
(1) Solubility in coating solvent,
(2) Film formability (glass transition point),
(3) Alkali developability,
(4) Membrane slip (hydrophobic, alkali-soluble group selection),
(5) Adhesion of unexposed part to substrate,
(6) Dry etching resistance,
Etc. can be finely adjusted.

As such a monomer, for example, a compound having one addition polymerizable unsaturated bond selected from acrylic acid esters, methacrylic acid esters, acrylamides, methacrylamides, allyl compounds, vinyl ethers, vinyl esters, etc. Etc.

  In addition, any addition-polymerizable unsaturated compound that can be copolymerized with monomers corresponding to the above various repeating structural units may be copolymerized.

  In the resin (B), the content molar ratio of each repeating structural unit has a dry etching resistance, standard developer suitability, substrate adhesion, profile, and resolution, heat resistance, sensitivity, etc., which are general required performances of a resist. Appropriately set for adjustment.

Resin used in the actinic ray-sensitive or radiation-sensitive resin composition of the present invention from the viewpoint of transparency to ArF light when the actinic ray-sensitive or radiation-sensitive resin composition of the present invention is for ArF exposure (B) has substantially no aromatic group, for example, the ratio of the repeating unit having an aromatic group in the resin is preferably 5 mol% or less, more preferably 3 mol% or less. Specifically, it is most preferably 0 mol%, that is, it does not have an aromatic group, and preferably has a monocyclic or polycyclic alicyclic hydrocarbon structure.
In addition, it is preferable that resin (B) does not contain a fluorine atom and a silicon atom from a compatible viewpoint with the hydrophobic resin mentioned later.

The resin (B) used in the composition of the present invention is preferably one in which all of the repeating units are composed of (meth) acrylate-based repeating units. In this case, all of the repeating units are methacrylate repeating units, all of the repeating units are acrylate repeating units, or all of the repeating units are methacrylate repeating units and acrylate repeating units. Although it can be used, the acrylate-based repeating unit is preferably 50 mol% or less of the total repeating units.
Moreover, the alicyclic hydrocarbon substituted by the (meth) acrylate type repeating unit 20-50 mol% which has an acid-decomposable group, the (meth) acrylate type repeating unit 20-50 mol% which has a lactone structure, a hydroxyl group, or a cyano group A copolymer containing 5 to 30 mol% of a (meth) acrylate-based repeating unit having a structure and further containing 0 to 20 mol% of another (meth) acrylate-based repeating unit is also preferred.

  When the actinic ray-sensitive or radiation-sensitive resin composition of the present invention is irradiated with KrF excimer laser light, electron beam, X-ray, high-energy light beam (EUV, etc.) having a wavelength of 50 nm or less, the resin (B) is: Further, it preferably has a hydroxystyrene repeating unit. More preferably, it has a hydroxystyrene-based repeating unit, a hydroxystyrene-based repeating unit protected with an acid-decomposable group, and an acid-decomposable repeating unit such as a (meth) acrylic acid tertiary alkyl ester.

  Examples of the repeating unit having a preferred acid-decomposable group based on hydroxystyrene include, for example, t-butoxycarbonyloxystyrene, 1-alkoxyethoxystyrene, a repeating unit of (meth) acrylic acid tertiary alkyl ester, and the like. More preferred are repeating units of 2-alkyl-2-adamantyl (meth) acrylate and dialkyl (1-adamantyl) methyl (meth) acrylate.

The resin (B) of the present invention can be synthesized according to a conventional method (for example, radical polymerization). For example, as a general synthesis method, a monomer type and a polymerization initiator are dissolved in a solvent, and a batch polymerization method in which polymerization is performed by heating, a solution of the monomer type and the polymerization initiator is added to the heating solvent over 1 to 10 hours. Examples thereof include a dropping polymerization method which is added dropwise, and a dropping polymerization method is preferred. Examples of the reaction solvent include ethers such as tetrahydrofuran, 1,4-dioxane, diisopropyl ether, ketones such as methyl ethyl ketone and methyl isobutyl ketone, ester solvents such as ethyl acetate, amide solvents such as dimethylformamide and dimethylacetamide, Furthermore, the solvent which melt | dissolves the actinic-ray sensitive or radiation sensitive resin composition of this invention like the below-mentioned propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, and cyclohexanone is mentioned. More preferably, the polymerization is performed using the same solvent as the solvent used in the actinic ray-sensitive or radiation-sensitive resin composition of the present invention. Thereby, the generation of particles during storage can be suppressed.

  The 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 preferable. Preferred 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 from 10 ° C to 150 ° C, preferably from 30 ° C to 120 ° C, more preferably from 60 ° C to 100 ° C.

  The weight average molecular weight of the resin (B) of the present invention is preferably 1,000 to 200,000, more preferably 2,000 to 20,000, still more preferably 3, as a polystyrene conversion value by GPC method. 000 to 15,000, particularly preferably 3,000 to 10,000. By setting the weight average molecular weight to 1,000 to 200,000, deterioration of heat resistance and dry etching resistance can be prevented, and developability is deteriorated, and viscosity is increased, resulting in deterioration of film forming property. Can be prevented.

  The dispersity (molecular weight distribution) is usually 1 to 3, preferably 1 to 2.6, more preferably 1 to 2, and particularly preferably 1.4 to 2.0. The smaller the molecular weight distribution, the better the resolution and pattern shape, the smoother the side wall of the pattern, and the better the roughness.

In the present invention, the blending ratio of the resin (B) in the entire composition is preferably 30 to 99% by mass, more preferably 60 to 90% by mass in the total solid content. In addition, the resins of the present invention may be used alone or in combination.
In addition, you may use together other resin other than the resin (B) of this invention in the range which does not impair the effect of this invention. Examples of the resin other than the resin (B) of the present invention include an acid-decomposable resin that may contain a repeating unit that can be contained in the resin (B), and other known acid-decomposable resins. be able to.

[3] (C) Compound that generates acid upon irradiation with actinic ray or radiation The actinic ray-sensitive or radiation-sensitive resin composition of the present invention is a compound that generates an acid upon irradiation with actinic ray or radiation (hereinafter, “ Also referred to as “acid generator”.
As an acid generator, photo-initiator of photocation polymerization, photo-initiator of photo-radical polymerization, photo-decoloring agent of dyes, photo-discoloring agent, or irradiation with actinic ray or radiation used for micro-resist etc. Known compounds that generate acids and mixtures thereof can be appropriately selected and used.

  Examples thereof include diazonium salts, phosphonium salts, sulfonium salts, iodonium salts, imide sulfonates, oxime sulfonates, diazodisulfones, disulfones, and o-nitrobenzyl sulfonates.

Further, a group that generates an acid upon irradiation with these actinic rays or radiation, or a compound in which a compound is introduced into the main chain or side chain of the polymer, such as US Pat. No. 3,849,137, German Patent No. No. 3914407, JP-A 63-26653, JP-A 55-164824, JP-A 62-69263, JP-A 63-146038, JP-A 63-163452, The compounds described in JP-A-62-153853 and JP-A-63-146029 can be used.

  Furthermore, compounds capable of generating an acid by light described in US Pat. No. 3,779,778, European Patent 126,712, etc. can also be used.

  Preferred compounds among the acid generators include compounds represented by the following general formulas (ZI), (ZII), and (ZIII).

In the general formula (ZI),
R ₂₀₁ , R ₂₀₂ and R ₂₀₃ each independently represents an organic group.
The carbon number of the organic group as R ₂₀₁ , R ₂₀₂ and R ₂₀₃ is generally 1 to 30, preferably 1
~ 20.
Two of R _{201 to} R ₂₀₃ may be bonded to form a ring structure, and the ring may contain an oxygen atom, a sulfur atom, an ester bond, an amide bond, or a carbonyl group. The two of the group formed by bonding of the R ₂₀₁ to R _203, there can be mentioned an alkylene group (e.g., butylene, pentylene).
Z ⁻ represents a non-nucleophilic anion.

Examples of the non-nucleophilic anion as Z ⁻ include a sulfonate anion, a carboxylate anion, a sulfonylimide anion, a bis (alkylsulfonyl) imide anion, and a tris (alkylsulfonyl) methyl anion.

  A non-nucleophilic anion is an anion that has an extremely low ability to cause a nucleophilic reaction, and is an anion that can suppress degradation over time due to an intramolecular nucleophilic reaction. Thereby, the temporal stability of the actinic ray-sensitive or radiation-sensitive resin composition is improved.

  Examples of the sulfonate anion include an aliphatic sulfonate anion, an aromatic sulfonate anion, and a camphor sulfonate anion.

  Examples of the carboxylate anion include an aliphatic carboxylate anion, an aromatic carboxylate anion, and an aralkylcarboxylate anion.

The aliphatic moiety in the aliphatic sulfonate anion may be an alkyl group or a cycloalkyl group, preferably an alkyl group having 1 to 30 carbon atoms and a cycloalkyl group having 3 to 30 carbon atoms such as methyl. Group, ethyl group, propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, pentyl group, neopentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, undecyl group, dodecyl group , Tridecyl group, tetradecyl group, pentadecyl group, hexadecyl group, heptadecyl group, octadecyl group, nonadecyl group, eicosyl group, cyclopropyl group, cyclopentyl group, cyclohexyl group, adamantyl group, norbornyl group and the like.

  The aromatic group in the aromatic sulfonate 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 in the aliphatic sulfonate anion and aromatic sulfonate anion may have a substituent. Examples of the substituent of the alkyl group, cycloalkyl group, and aryl group in the aliphatic sulfonate anion and aromatic sulfonate anion include, for example, a nitro group, a halogen atom (fluorine atom, chlorine atom, bromine atom, iodine atom), carboxyl group , Hydroxyl group, amino group, cyano group, alkoxy group (preferably having 1 to 15 carbon atoms), cycloalkyl group (preferably having 3 to 15 carbon atoms), aryl group (preferably having 6 to 14 carbon atoms), alkoxycarbonyl group ( Preferably 2 to 7 carbon atoms, acyl group (preferably 2 to 12 carbon atoms), alkoxycarbonyloxy group (preferably 2 to 7 carbon atoms), alkylthio group (preferably 1 to 15 carbon atoms), alkylsulfonyl group (Preferably having 1 to 15 carbon atoms), alkyliminosulfonyl group (preferably having 2 to 15 carbon atoms), aryl Ruoxysulfonyl group (preferably having 6 to 20 carbon atoms), alkylaryloxysulfonyl group (preferably having 7 to 20 carbon atoms), cycloalkylaryloxysulfonyl group (preferably having 10 to 20 carbon atoms), alkyloxyalkyloxy group (Preferably having 5 to 20 carbon atoms), a cycloalkylalkyloxyalkyloxy group (preferably having 8 to 20 carbon atoms), and the like. About the aryl group and ring structure which each group has, an alkyl group (preferably C1-C15) can further be mentioned as a substituent.

  Examples of the aliphatic moiety in the aliphatic carboxylate anion include the same alkyl group and cycloalkyl group as in the aliphatic sulfonate anion.

  Examples of the aromatic group in the aromatic carboxylate anion include the same aryl group as in the aromatic sulfonate anion.

  The aralkyl group in the aralkyl carboxylate anion is preferably an aralkyl group having 6 to 12 carbon atoms, such as benzyl group, phenethyl group, naphthylmethyl group, naphthylethyl group, naphthylbutyl group, and the like.

  The alkyl group, cycloalkyl group, aryl group and aralkyl group in the aliphatic carboxylate anion, aromatic carboxylate anion and aralkylcarboxylate anion may have a substituent. Examples of the substituent of the alkyl group, cycloalkyl group, aryl group and aralkyl group in the aliphatic carboxylate anion, aromatic carboxylate anion and aralkylcarboxylate anion include, for example, the same halogen atom and alkyl as in the aromatic sulfonate anion Group, cycloalkyl group, alkoxy group, alkylthio group and the like.

  Examples of the sulfonylimide anion include saccharin anion.

  The alkyl group in the bis (alkylsulfonyl) imide anion and tris (alkylsulfonyl) methyl anion is preferably an alkyl group having 1 to 5 carbon atoms, such as a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, An isobutyl group, a sec-butyl group, a pentyl group, a neopentyl group, and the like can be given. 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. Alkyl groups substituted with fluorine atoms are preferred.

  Examples of other non-nucleophilic anions include fluorinated phosphorus, fluorinated boron, and fluorinated antimony.

Examples of the non-nucleophilic anion of Z ⁻ include an aliphatic sulfonate anion in which the 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. A bis (alkylsulfonyl) imide anion substituted with a fluorine atom and a tris (alkylsulfonyl) methide anion wherein an alkyl group is substituted with a fluorine atom are preferred. The non-nucleophilic anion is more preferably a perfluoroaliphatic sulfonic acid anion having 4 to 8 carbon atoms, a benzenesulfonic acid anion having a fluorine atom, still more preferably a nonafluorobutanesulfonic acid anion, a perfluorooctanesulfonic acid anion, It is a pentafluorobenzenesulfonic acid anion and 3,5-bis (trifluoromethyl) benzenesulfonic acid anion.

Examples of the organic group as R ₂₀₁ , R ₂₀₂ and R ₂₀₃ include corresponding groups in the compounds (ZI-1), (ZI-2), (ZI-3) and (ZI-4) described later. Can do.

In addition, the compound which has two or more structures represented by general formula (ZI) may be sufficient. For example, the general formula at least one of R ₂₀₁ to R ₂₀₃ of a compound represented by (ZI), the structures attached to at least one of R ₂₀₁ to R ₂₀₃ of another compound represented by formula (ZI) It may be a compound.

  More preferred (ZI) components include compounds (ZI-1), (ZI-2), (ZI-3) and (ZI-4) described below.

The compound (ZI-1) is at least one of the aryl groups R ₂₀₁ to R ₂₀₃ in formula (ZI), arylsulfonium compounds, namely, compounds containing an arylsulfonium as a cation.

In the arylsulfonium compound, all of R _{201 to} R ₂₀₃ may be an aryl group, or a part of R _{201 to} R ₂₀₃ may be an aryl group with the remaining being an alkyl group or a cycloalkyl group.

  Examples of the arylsulfonium compound include triarylsulfonium compounds, diarylalkylsulfonium compounds, aryldialkylsulfonium compounds, diarylcycloalkylsulfonium compounds, and aryldicycloalkylsulfonium compounds.

  The aryl group of the arylsulfonium compound is preferably a phenyl group or a naphthyl group, and more preferably a phenyl group. The aryl group may be an aryl group having a heterocyclic structure having an oxygen atom, a nitrogen atom, a sulfur atom or the like. Examples of the aryl group having a heterocyclic structure include a pyrrole residue (a group formed by losing one hydrogen atom from pyrrole) and a furan residue (a group formed by losing one hydrogen atom from furan). Groups), thiophene residues (groups formed by the loss of one hydrogen atom from thiophene), indole residues (groups formed by the loss of one hydrogen atom from indole), benzofuran residues ( A group formed by losing one hydrogen atom from benzofuran), a benzothiophene residue (a group formed by losing one hydrogen atom from benzothiophene), and the like. When the arylsulfonium compound has two or more aryl groups, the two or more aryl groups may be the same or different.

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

Aryl group, alkyl group of R ₂₀₁ to R _203, cycloalkyl group, an alkyl group (for example, 1 to 15 carbon atoms), a cycloalkyl group (for example, 3 to 15 carbon atoms), an aryl group (for example, 6 to 14 carbon atoms) , An alkoxy group (for example, having 1 to 15 carbon atoms), a halogen atom, a hydroxyl group, or a phenylthio group may be substituted. Preferred substituents are linear or branched alkyl groups having 1 to 12 carbon atoms, cycloalkyl groups having 3 to 12 carbon atoms, and linear, branched or cyclic alkoxy groups having 1 to 12 carbon atoms, more preferably carbon. These are an alkyl group having 1 to 4 carbon atoms and an alkoxy group having 1 to 4 carbon atoms. The substituent may be substituted with any one of the three R _{201 to} R ₂₀₃ , or may be substituted with all three. When R _{201 to} R ₂₀₃ are an aryl group, the substituent is preferably substituted at the p-position of the aryl group.

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

The organic group having no aromatic ring as R ₂₀₁ to R ₂₀₃ generally has 1 to 30 carbon atoms, preferably 1 to 20 carbon atoms.

R _{201 to} R ₂₀₃ are each independently preferably an alkyl group, a cycloalkyl group, an allyl group, or a vinyl group, more preferably a linear or branched 2-oxoalkyl group, 2-oxocycloalkyl group, alkoxy group. A carbonylmethyl group, particularly preferably a linear or branched 2-oxoalkyl group.

The alkyl group and cycloalkyl group of R ₂₀₁ to R _203, preferably a linear or branched alkyl group having 1 to 10 carbon atoms (e.g., methyl group, ethyl group, propyl group, butyl group, pentyl group), carbon Examples thereof include cycloalkyl groups of several 3 to 10 (cyclopentyl group, cyclohexyl group, norbornyl group). More preferred examples of the alkyl group include a 2-oxoalkyl group and an alkoxycarbonylmethyl group. More preferred examples of the cycloalkyl group include a 2-oxocycloalkyl group.

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

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

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

The compound (ZI-3) is a compound represented by the following general formula (ZI-3), and is a compound having a phenacylsulfonium salt structure.

In general formula (ZI-3),
M represents an alkyl group, a cycloalkyl group, an aryl group, or a benzyl group, and when having a ring structure, the ring structure includes an oxygen atom, a sulfur atom, an ester bond, an amide bond, and a carbon-carbon double bond. Also good.
In the formula, R _1c and R _2c each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, a cyano group, or an aryl group. R _1c and R _2c may combine to form a ring.
Rx and Ry each independently represents an alkyl group, a cycloalkyl group, a 2-oxoalkyl group, a 2-oxocycloalkyl group, an alkoxycarbonylalkyl group, an allyl group, or a vinyl group.
R _x and R _y may combine to form a ring. Further, at least two of M, R _1c and R _2c may be bonded to form a ring, and the ring structure may contain a carbon-carbon double bond.
X ⁻ represents a non-nucleophilic anion.

The alkyl group as M may be either linear or branched, for example, an alkyl group having 1 to 20 carbon atoms, preferably a linear or branched alkyl group having 1 to 12 carbon atoms (for example, a methyl group). , Ethyl group, linear or branched propyl group, linear or branched butyl group, linear or branched pentyl group).
Examples of the cycloalkyl group as M, R _1c , R _2c , R _x , and R _y include cyclic alkyl groups having 3 to 8 carbon atoms (for example, a cyclopentyl group and a cyclohexyl group).
The aryl group as M, R _1c and R _2c preferably has 5 to 15 carbon atoms, and examples thereof include a phenyl group and a naphthyl group.
Each group as M may have an alkyl group, a cycloalkyl group, an alkoxy group, a halogen atom, a phenylthio group or the like as a substituent. The cycloalkyl group and aryl group as M may further have an alkyl group as a substituent. The number of carbon atoms of the substituent is preferably 15 or less.
The alkyl group as R _1c and R _2c is, for example, an alkyl group having 1 to 10 carbon atoms, preferably a linear or branched alkyl group having 1 to 5 carbon atoms (for example, a methyl group, an ethyl group, a linear or branched group). Mention may be made of the propyl group.
When M is a phenyl group, it preferably has at least one linear, branched, or cyclic alkyl group, or a linear, branched, or cyclic alkoxy group as a substituent, and more preferably, the sum of the carbon number of the substituent is 2-15. Thereby, solvent solubility improves more and generation | occurrence | production of a particle is suppressed at the time of a preservation | save.
The ring structure formed by combining at least two of M, R _1c and R _2c is preferably a 3- to 10-membered ring, more preferably a 3- to 6-membered ring. The ring skeleton may have a carbon-carbon double bond.

_Examples of the alkyl group as R _x and R _y include the same alkyl groups as R _1c and R _2c .
Examples of the 2-oxoalkyl group or 2-oxocycloalkyl group include a group having> C═O at the 2-position of the alkyl group or cycloalkyl group as R _1c and R _2c .
The alkoxy group in the alkoxycarbonylmethyl group may be linear, branched or cyclic, for example, an alkoxy group having 1 to 10 carbon atoms, preferably a linear or branched alkoxy group having 1 to 5 carbon atoms ( For example, methoxy group, ethoxy group, linear or branched propoxy group, linear or branched butoxy group, linear or branched pentoxy group), cyclic alkoxy group having 3 to 8 carbon atoms (for example, cyclopentyloxy group, cyclohexyloxy group) Can be mentioned.
The allyl group is not particularly limited, but is preferably an allyl group which is unsubstituted or substituted with a monocyclic or polycyclic cycloalkyl group.
Although there is no restriction | limiting in particular as a vinyl group, It is preferable that it is a vinyl group substituted by the unsubstituted or monocyclic or polycyclic cycloalkyl group.
Examples of the group formed by combining R _x and R _y include a butylene group and a pentylene group. That is, as a ring structure that R _x and R _y may be bonded to each other, divalent R _x and R _y (for example, a methylene group, an ethylene group, a propylene group, etc.) are represented by the general formula (1-2). 5) or a 6-membered ring formed together with the sulfur atom in the above), particularly preferably a 5-membered ring (that is, a tetrahydrothiophene ring).

R _x and R _y are preferably an alkyl group having 4 or more carbon atoms, more preferably 6 or more, and still more preferably 8 or more.
Each group as Rx or Ry, and the ring structure that R _x and R _y may be bonded to each other may have a substituent. Examples of the substituent include The substituent which each group may have can be mentioned.

  Specific examples of the cation of the compound represented by the general formula (ZI-3) include the following.

  Moreover, it is preferable that it is a compound (ZI-4) represented by the following general formula (ZI-4).

In general formula (ZI-4),
R ₁₃ represents a hydrogen atom, a fluorine atom, a hydroxyl group, an alkyl group, a cycloalkyl group, an alkoxy group, an alkoxycarbonyl group, or a group having a monocyclic or polycyclic cycloalkyl skeleton. These groups may have a substituent.
When there are a plurality of R _{14 s,} each independently represents an alkyl group, a cycloalkyl group, an alkoxy group, an alkoxycarbonyl group, an alkylcarbonyl group, an alkylsulfonyl group, a cycloalkylsulfonyl group, or a monocyclic or polycyclic cycloalkyl skeleton. Represents a group having These groups may have a substituent.
R ₁₅ each independently represents an alkyl group, a cycloalkyl group or a naphthyl group. Two R ₁₅ may be bonded to each other to form a ring. These groups may have a substituent.
l represents an integer of 0-2.
r represents an integer of 0 to 8.
Z ⁻ represents a non-nucleophilic anion, and examples thereof include the same non-nucleophilic anion as Z ^{− in} formula (ZI).

In the general formula (ZI-4), the alkyl group of R ₁₃ , R ₁₄ and R ₁₅ is linear or branched and preferably has 1 to 10 carbon atoms, and is preferably a methyl group, an ethyl group, n -Propyl group, i-propyl group, n-butyl group, 2-methylpropyl group, 1-methylpropyl group, t-butyl group, n-pentyl group, neopentyl group, n-hexyl group, n-heptyl group, n -An octyl group, 2-ethylhexyl group, n-nonyl group, n-decyl group etc. can be mentioned. Of these alkyl groups, a methyl group, an ethyl group, an n-butyl group, a t-butyl group, and the like are preferable.
Examples of the cycloalkyl group represented by R ₁₃ , R ₁₄ and R ₁₅ include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclododecanyl, cyclopentenyl, cyclohexenyl, cyclooctadienyl, norbornyl, tricyclo Examples include decanyl, tetracyclodecanyl, adamantyl and the like, and cyclopropyl, cyclopentyl, cyclohexyl and cyclooctyl are particularly preferable.
The alkoxy group of R ₁₃ and R ₁₄ is linear or branched and preferably has 1 to 10 carbon atoms, such as methoxy group, ethoxy group, n-propoxy group, i-propoxy group, n -Butoxy group, 2-methylpropoxy group, 1-methylpropoxy group, t-butoxy group, n-pentyloxy group, neopentyloxy group, n-hexyloxy group, n-heptyloxy group, n-octyloxy group, 2-ethylhexyloxy group, n-nonyloxy group, n-decyloxy group and the like can be mentioned. Of these alkoxy groups, a methoxy group, an ethoxy group, an n-propoxy group, an n-butoxy group, and the like are preferable.
The alkoxycarbonyl group for R ₁₃ and R ₁₄ is linear or branched and preferably has 2 to 11 carbon atoms, such as a methoxycarbonyl group, an ethoxycarbonyl group, an n-propoxycarbonyl group, i- Propoxycarbonyl group, n-butoxycarbonyl group, 2-methylpropoxycarbonyl group, 1-methylpropoxycarbonyl group, t-butoxycarbonyl group, n-pentyloxycarbonyl group, neopentyloxycarbonyl group, n-hexyloxycarbonyl group, Examples include n-heptyloxycarbonyl group, n-octyloxycarbonyl group, 2-ethylhexyloxycarbonyl group, n-nonyloxycarbonyl group, n-decyloxycarbonyl group and the like. Of these alkoxycarbonyl groups, a methoxycarbonyl group, an ethoxycarbonyl group, an n-butoxycarbonyl group, and the like are preferable.

Examples of the group having a monocyclic or polycyclic cycloalkyl skeleton of R ₁₃ and R ₁₄ include a monocyclic or polycyclic cycloalkyloxy group and an alkoxy group having a monocyclic or polycyclic cycloalkyl group. Can be mentioned. These groups may further have a substituent.
The monocyclic or polycyclic cycloalkyloxy group for R ₁₃ and R ₁₄ preferably has a total carbon number of 7 or more, more preferably a total carbon number of 7 or more and 15 or less, It is preferable to have a cycloalkyl skeleton. The monocyclic cycloalkyloxy group having 7 or more carbon atoms is cyclopropyloxy group, cyclobutyloxy group, cyclopentyloxy group, cyclohexyloxy group, cycloptyloxy group, cyclooctyloxy group, cyclododecanyloxy group, etc. Optionally substituted with methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, dodecyl, 2-ethylhexyl, isopropyl, sec-butyl, t -Alkyl group such as butyl group, iso-amyl group, hydroxyl group, halogen atom (fluorine, chlorine, bromine, iodine), nitro group, cyano group, amide group, sulfonamido group, methoxy group, ethoxy group, hydroxyethoxy group, Alkoxy groups such as propoxy group, hydroxypropoxy group, butoxy group, methoxy group Monocyclic cycloalkyloxy groups having substituents such as alkoxycarbonyl groups such as rubonyl groups, ethoxycarbonyl groups, acyl groups such as formyl groups, acetyl groups and benzoyl groups, acyloxy groups such as acetoxy groups and butyryloxy groups, and carboxy groups And the total number of carbon atoms combined with an arbitrary substituent on the cycloalkyl group is 7 or more.
Examples of the polycyclic cycloalkyloxy group having a total carbon number of 7 or more include a norbornyloxy group, a tricyclodecanyloxy group, a tetracyclodecanyloxy group, an adamantantyloxy group, and the like.

The alkoxy group having a monocyclic or polycyclic cycloalkyl skeleton of R ₁₃ and R ₁₄ preferably has a total carbon number of 7 or more, more preferably a total carbon number of 7 or more and 15 or less, An alkoxy group having a monocyclic cycloalkyl skeleton is preferable. The alkoxy group having a total of 7 or more carbon atoms and having a monocyclic cycloalkyl skeleton is methoxy, ethoxy, propoxy, butoxy, pentyloxy, hexyloxy, heptoxy, octyloxy, dodecyloxy, 2-ethylhexyloxy, isopropoxy, A monocyclic cycloalkyl group that may have the above-mentioned substituents is substituted on an alkoxy group such as sec-butoxy, t-butoxy, iso-amyloxy, etc., and the total carbon number including the substituents is 7 or more Represents things. Examples thereof include a cyclohexylmethoxy group, a cyclopentylethoxy group, a cyclohexylethoxy group, and the like, and a cyclohexylmethoxy group is preferable.
Examples of the alkoxy group having a polycyclic cycloalkyl skeleton having 7 or more carbon atoms include norbornyl methoxy group, norbornyl ethoxy group, tricyclodecanyl methoxy group, tricyclodecanyl ethoxy group, tetracyclo A decanyl methoxy group, a tetracyclodecanyl ethoxy group, an adamantane methoxy group, an adamantane ethoxy group, etc. are mentioned, and a norbornyl methoxy group, a norbornyl ethoxy group, etc. are preferable.

The alkyl group of the alkyl group of R _14, include the same specific examples as the alkyl group as R ₁₃ to R ₁₅ described above.
The alkylsulfonyl group and cycloalkylsulfonyl group of R ₁₄ are linear, branched, or cyclic, and preferably those having 1 to 10 carbon atoms, such as methanesulfonyl group, ethanesulfonyl group, n-propanesulfonyl. Group, n-butanesulfonyl group, tert-butanesulfonyl group, n-pentanesulfonyl group, neopentanesulfonyl group, n-hexanesulfonyl group, n-heptanesulfonyl group, n-octanesulfonyl group, 2-ethylhexanesulfonyl group n -Nonanesulfonyl group, n-decanesulfonyl group, cyclopentanesulfonyl group, cyclohexanesulfonyl group, etc. can be mentioned. Of these alkylsulfonyl groups and cycloalkylsulfonyl groups, a methanesulfonyl group, an ethanesulfonyl group, an n-propanesulfonyl group, an n-butanesulfonyl group, a cyclopentanesulfonyl group, a cyclohexanesulfonyl group, and the like are preferable.

Examples of the substituent that each of the above groups may have include a halogen atom (for example, a fluorine atom), a hydroxyl group, a carboxyl group, a cyano group, a nitro group, an alkoxy group, an alkoxyalkyl group, an alkoxycarbonyl group, and alkoxycarbonyloxy. Groups and the like.
Examples of the alkoxy group include methoxy group, ethoxy group, n-propoxy group, i
-Linear, branched or cyclic having 1 to 20 carbon atoms such as propoxy group, n-butoxy group, 2-methylpropoxy group, 1-methylpropoxy group, t-butoxy group, cyclopentyloxy group and cyclohexyloxy group Can be mentioned.
Examples of the alkoxyalkyl group include straight chain having 2 to 21 carbon atoms such as methoxymethyl group, ethoxymethyl group, 1-methoxyethyl group, 2-methoxyethyl group, 1-ethoxyethyl group, and 2-ethoxyethyl group. Examples thereof include a chain, branched or cyclic alkoxyalkyl group.
Examples of the alkoxycarbonyl group include methoxycarbonyl group, ethoxycarbonyl group, n-propoxycarbonyl group, i-propoxycarbonyl group, n-butoxycarbonyl group, 2-methylpropoxycarbonyl group, 1-methylpropoxycarbonyl group, t Examples thereof include linear, branched or cyclic alkoxycarbonyl groups having 2 to 21 carbon atoms such as butoxycarbonyl group, cyclopentyloxycarbonyl group, cyclohexyloxycarbonyl and the like.
Examples of the alkoxycarbonyloxy group include methoxycarbonyloxy group, ethoxycarbonyloxy group, n-propoxycarbonyloxy group, i-propoxycarbonyloxy group, n-butoxycarbonyloxy group, t-butoxycarbonyloxy group, and cyclopentyloxy. Examples thereof include linear, branched or cyclic alkoxycarbonyloxy groups having 2 to 21 carbon atoms such as carbonyloxy group and cyclohexyloxycarbonyloxy.

The ring structure which two R ₁₅ may combine with each other is a 5-membered or 6-membered ring formed by two divalent R ₁₅ together with the sulfur atom in the general formula (ZI-4). Particularly preferred is a 5-membered ring (that is, a tetrahydrothiophene ring), which may be condensed with an aryl group or a cycloalkyl group. This divalent R ₁₅ may have a substituent. Examples of the substituent include a hydroxyl group, a carboxyl group, a cyano group, a nitro group, an alkoxy group, an alkoxyalkyl group, an alkoxycarbonyl group, an alkoxycarbonyloxy group, and the like. Groups and the like. R ₁₅ in the general formula (ZI-4) is preferably a methyl group, an ethyl group, a naphthyl group, a divalent group in which two R _15s are bonded to each other to form a tetrahydrothiophene ring structure together with a sulfur atom.
The substituent that R ₁₃ and R ₁₄ may have is preferably a hydroxyl group, an alkoxy group, an alkoxycarbonyl group, or a halogen atom (particularly a fluorine atom).
l is preferably 0 or 1, and more preferably 1.
As r, 0-2 are preferable.
Specific examples of the cation of the compound represented by the general formula (ZI-4) include the following.

In the general formulas (ZII) and (ZIII),
R ₂₀₄ to R ₂₀₇ each independently represents an aryl group, an alkyl group or a cycloalkyl group.
Phenyl group and a naphthyl group are preferred as the aryl group of R ₂₀₄ to R _207, more preferably a phenyl group. Aryl group R ₂₀₄ to R ₂₀₇ represents an oxygen atom, a nitrogen atom, may be an aryl group having a heterocyclic structure having a sulfur atom and the like. Examples of the aryl group having a heterocyclic structure include a pyrrole residue (a group formed by losing one hydrogen atom from pyrrole) and a furan residue (a group formed by losing one hydrogen atom from furan). Groups), thiophene residues (groups formed by the loss of one hydrogen atom from thiophene), indole residues (groups formed by the loss of one hydrogen atom from indole), benzofuran residues ( A group formed by losing one hydrogen atom from benzofuran), a benzothiophene residue (a group formed by losing one hydrogen atom from benzothiophene), and the like.

The alkyl group and cycloalkyl group in R ₂₀₄ to R _207, preferably a linear or branched alkyl group having 1 to 10 carbon atoms (e.g., methyl group, ethyl group, propyl group, butyl group, pentyl group), carbon Examples thereof include cycloalkyl groups of several 3 to 10 (cyclopentyl group, cyclohexyl group, norbornyl group).
Aryl group, alkyl group of R ₂₀₄ to R _207, cycloalkyl groups may have a substituent. Aryl group, alkyl group of R ₂₀₄ to R _207, the cycloalkyl group substituent which may be possessed by, for example, an alkyl group (for example, 1 to 15 carbon atoms), a cycloalkyl group (for example, 3 to 15 carbon atoms ), An aryl group (eg, having 6 to 15 carbon atoms), an alkoxy group (eg, having 1 to 15 carbon atoms), a halogen atom, a hydroxyl group, and a phenylthio group.
Z ⁻ represents a non-nucleophilic anion, and examples thereof include the same as the non-nucleophilic anion of Z ^{− in} formula (ZI).

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

In general formulas (ZIV) to (ZVI),
Ar ₃ and Ar ₄ each independently represents an aryl group.
R ₂₀₈ , R ₂₀₉ and R ₂₁₀ each independently represents an alkyl group, a cycloalkyl group or an aryl group.
A represents an alkylene group, an alkenylene group or an arylene group.
Specific examples of the aryl group of Ar ₃ , Ar ₄ , R ₂₀₈ , R ₂₀₉ and R ₂₁₀ are the same as the specific examples of the aryl group as R ₂₀₁ , R ₂₀₂ and R ₂₀₃ in the general formula (ZI-1). Things 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-2), respectively. The same thing as an example can be mentioned.
The alkylene group of A is alkylene 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 to 2 carbon atoms. 12 alkenylene groups (for example, ethynylene group, propenylene group, butenylene group, etc.), and the arylene group of A is an arylene group having 6 to 10 carbon atoms (for example, phenylene group, tolylene group, naphthylene group, etc.) Can be mentioned.

Among the acid generators, compounds represented by the general formulas (ZI) to (ZIII) are more preferable.
Further, the acid generator is preferably a compound that generates an acid having one sulfonic acid group or imide group, more preferably a compound that generates monovalent perfluoroalkanesulfonic acid, or a monovalent fluorine atom or fluorine atom. A compound that generates an aromatic sulfonic acid substituted with a group that contains a monovalent fluorine atom or an imido acid that is substituted with a group containing a fluorine atom, and even more preferably, a fluorinated compound It is a sulfonium salt of a substituted alkanesulfonic acid, a fluorine-substituted benzenesulfonic acid, a fluorine-substituted imide acid or a fluorine-substituted methide acid. The acid generator that can be used is particularly preferably a fluorinated substituted alkane sulfonic acid, a fluorinated substituted benzene sulfonic acid or a fluorinated substituted imido acid whose pKa of the generated acid is pKa = -1 or less, and the sensitivity is improved. .

  Among acid generators, particularly preferred examples are given below.

  An acid generator can be used individually by 1 type or in combination of 2 or more types.

The content of the acid generator in the actinic ray-sensitive or radiation-sensitive resin composition is preferably 0.1 to 30% by mass based on the total solid content of the actinic ray-sensitive or radiation-sensitive resin composition, More preferably, it is 5-30 mass%, More preferably, it is 10-25 mass%.
When used as a positive-type actinic ray-sensitive or radiation-sensitive resin composition, the molar ratio of the acid generator to the compound (PBG) (acid generator / compound (PBG)) is 10 to 1.5, preferably 7 to 2, more preferably 5-4. When the molar ratio is larger, it is preferable from the viewpoint of image formability, and more than 10/1, that is, from the viewpoint of sensitivity and resolution, the molar ratio is preferably 2.5 or more. 300 or less is preferable from the viewpoint of suppressing the reduction in resolution due to fattening. This molar ratio is more preferably 5.0 to 200, and still more preferably 7.0 to 150.

  A combination of the compound represented by the general formula (5) or (6) as the compound (PBG) and the compound (ZI-3) or (ZI-4) as the acid generator is preferable, and represented by the general formula (6). And a combination of the compound (ZI-3) or (ZI-4) and the compound (ZI-3) or (ZI-4) is particularly preferable. preferable.

[4] Hydrophobic resin The composition according to the present invention may further contain a hydrophobic resin as described above. When a hydrophobic resin is further contained, the hydrophobic resin is unevenly distributed in the surface layer of the film formed using this composition, and the film recedes against the immersion liquid in immersion exposure using water as the immersion liquid. The corner can be improved. Thereby, the immersion liquid followability of a film | membrane can be improved.

  The hydrophobic resin typically contains fluorine atoms and / or silicon atoms. These fluorine atoms and / or silicon atoms may be contained in the main chain of the resin or may be contained in the side chain.

  In the case where the hydrophobic resin contains a fluorine atom, the resin has an alkyl group containing a fluorine atom, a cycloalkyl group containing a fluorine atom, or an aryl group containing a fluorine atom as a partial structure containing a fluorine atom. It is preferable to provide.

  The alkyl group containing a fluorine atom is a linear or branched alkyl group in which at least one hydrogen atom is substituted with a fluorine atom. The alkyl group preferably has 1 to 10 carbon atoms, and more preferably 1 to 4 carbon atoms. The alkyl group containing a fluorine atom may further have a substituent other than the fluorine atom.

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

  An aryl group containing a fluorine atom is an aryl group in which at least one hydrogen atom is substituted with a fluorine atom. Examples of the aryl group include a phenyl group and a naphthyl group. The aryl group containing a fluorine atom may further have a substituent other than the fluorine atom.

  Preferable examples of the alkyl group containing a fluorine atom, the cycloalkyl group containing a fluorine atom, and the aryl group containing a fluorine atom include groups represented by the following general formulas (F2) to (F4).

In the general formulas (F2) to (F4), R _{57 to} R ₆₈ each independently represent a hydrogen atom, a fluorine atom, or an alkyl group. However, at least one of R _{57 to} R ₆₁ represents a fluorine atom or an alkyl group in which at least one hydrogen atom is substituted with a fluorine atom. At least one of R _{62 to} R ₆₄ represents a fluorine atom or an alkyl group in which at least one hydrogen atom is substituted with a fluorine atom. At least one of R _{65 to} R ₆₈ represents a fluorine atom or an alkyl group in which at least one hydrogen atom is substituted with a fluorine atom. These alkyl groups preferably have 1 to 4 carbon atoms.

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

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

  Examples of the group represented by the general formula (F3) include trifluoromethyl group, pentafluoropropyl group, pentafluoroethyl group, heptafluorobutyl group, hexafluoroisopropyl group, heptafluoroisopropyl group, hexafluoro (2- Methyl) isopropyl group, nonafluorobutyl group, octafluoroisobutyl group, nonafluorohexyl group, nonafluoro-t-butyl group, perfluoroisopentyl group, perfluorooctyl group, perfluoro (trimethyl) hexyl group, 2,2, Examples include 3,3-tetrafluorocyclobutyl group and perfluorocyclohexyl group. Among these, a hexafluoroisopropyl group, a heptafluoroisopropyl group, a hexafluoro (2-methyl) isopropyl group, an octafluoroisobutyl group, a nonafluoro-t-butyl group or a perfluoroisopentyl group is more preferable, and a hexafluoroisopropyl group or More preferred is a heptafluoroisopropyl group.

Examples of the group represented by the general formula (F4), for _{example, -C (CF 3) 2 OH} , -C (C 2 F 5) 2 OH, -C (CF 3) (CH 3) OH, and -CH (CF ₃ ) OH. Of these, -C _{(CF 3)} 2 OH is particularly preferred.

Specific examples of the repeating unit containing a fluorine atom are shown below.
In specific examples, X ₁ represents a hydrogen atom, —CH ₃ , —F or —CF ₃ . X ₂ represents -F or -CF _3.

  When the hydrophobic resin contains a silicon atom, the resin preferably has an alkylsilyl structure or a cyclic siloxane structure as a partial structure containing a silicon atom. This allylsilyl structure is preferably a structure containing a trialkylsilyl group.

  Preferable examples of the alkylsilyl structure and the cyclic siloxane structure include groups represented by the following general formulas (CS-1) to (CS-3).

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

L < ₃ > -L < ₅ > represents a single bond or a bivalent coupling group. Examples of the divalent linking group include an alkylene group, a phenylene group, an ether group, a thioether group, a carbonyl group, an ester group, an amide group, a urethane group, a urea group, or a combination thereof.
n represents an integer of 1 to 5. n is preferably an integer of 2 to 4.

Below, the specific example of the repeating unit provided with group represented by general formula (CS-1)-(CS-3) is given. In specific examples, X ₁ represents a hydrogen atom, —CH ₃ , —F or —CF ₃ .

The hydrophobic resin may further include at least one group selected from the group consisting of the following (x) to (z).
(X) an alkali-soluble group (y) a group that decomposes by the action of an alkali developer and increases the solubility in an alkali developer (z) an acid-decomposable group

  (X) Examples of alkali-soluble groups include phenolic hydroxyl groups, carboxylic acid groups, fluorinated alcohol groups, sulfonic acid groups, sulfonamido groups, sulfonylimide groups, (alkylsulfonyl) (alkylcarbonyl) methylene groups, and (alkylsulfonyl). ) (Alkylcarbonyl) imide group, bis (alkylcarbonyl) methylene group, bis (alkylcarbonyl) imide group, bis (alkylsulfonyl) methylene group, bis (alkylsulfonyl) imide group, tris (alkylcarbonyl) methylene group, and tris (Alkylsulfonyl) methylene group may be mentioned. Preferred alkali-soluble groups include fluorinated alcohol groups, sulfonimide groups, and bis (carbonyl) methylene groups. Preferred fluorinated alcohol groups include hexafluoroisopropanol groups.

  The repeating unit having an alkali-soluble group is a repeating unit in which an alkali-soluble group is directly bonded to the main chain of the resin, such as a repeating unit by acrylic acid and methacrylic acid. Alternatively, this repeating unit may be a repeating unit in which an alkali-soluble 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 provided with the alkali-soluble group at the time of superposition | polymerization.

  The content of the repeating unit having an alkali-soluble group is preferably 1 to 50 mol%, more preferably 3 to 35 mol%, based on all repeating units in the hydrophobic resin. More preferably, it is -20 mol%.

  Specific examples of the repeating unit having an alkali-soluble group are shown below.

(Y) Examples of the group that is decomposed by the action of the alkali developer and increases the solubility in the alkali developer include a group having a lactone structure, an acid anhydride group, and an acid imide group. Of these, a group having a lactone structure is particularly preferable.

  The repeating unit containing this group 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 provided with this group at the time of superposition | polymerization.

  Examples of the repeating unit having a group that is decomposed by the action of the alkali developer and increases the solubility in the alkali developer are the same as those having the lactone structure described above in the section of the resin (B). Can be mentioned.

  The content of the repeating unit having a group that is decomposed by the action of the alkali developer and increases the solubility in the alkali developer is 1 to 40 mol% based on all repeating units in the hydrophobic resin. Is more preferable, it is more preferable that it is 3-30 mol%, and it is still more preferable that it is 5-15 mol%.

Examples of the (z) acid-decomposable group include the same groups as those described above for the resin (B).
The content of the repeating unit having an acid-decomposable group is preferably 1 to 80 mol%, more preferably 10 to 80 mol%, based on all repeating units in the hydrophobic resin. More preferably, it is -60 mol%.

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

In general formula (III), R _c31 represents a hydrogen atom, an alkyl group, an alkyl group in which at least one hydrogen atom is substituted with a fluorine atom, a cyano group, or a —CH ₂ —O—Rac ₂ group. Here, Rac ₂ represents a hydrogen atom, an alkyl group, or an acyl group.
R _c31 is preferably a hydrogen atom, a methyl group, a hydroxymethyl group or a trifluoromethyl group, and particularly preferably a hydrogen atom or a methyl group.

R _c32 represents a group containing an alkyl group, a cycloalkyl group, an alkenyl group, a cycloalkenyl group or an aryl group. These groups may be substituted with a group having a fluorine atom and / or a silicon atom.

The alkyl group for R _c32 is preferably a linear or branched alkyl group having 3 to 20 carbon atoms.
The cycloalkyl group preferably has 3 to 20 carbon atoms.
The alkenyl group preferably has 3 to 20 carbon atoms.
The cycloalkenyl group is preferably a cycloalkenyl group having 3 to 20 carbon atoms.
The aryl group is preferably a phenyl group or naphthyl group having 6 to 20 carbon atoms, and these may have a substituent.
R _c32 is preferably an unsubstituted alkyl group or an alkyl group in which at least one hydrogen atom is substituted with a fluorine atom.

L _c3 represents a single bond or a divalent linking group. Examples of the divalent linking group include an ester group (a group represented by —COO—), an alkylene group (preferably having 1 to 5 carbon atoms), an oxy group, and a phenylene group.

  The hydrophobic resin may further contain a repeating unit represented by the following general formula (CII-AB).

In general formula (CII-AB),
R _{c11 ′} and R _{c12 ′} each independently represent a hydrogen atom, a cyano group, a halogen atom or an alkyl group. Zc ′ represents an atomic group necessary for forming an alicyclic structure together with two carbon atoms (C—C) to which R _{c11 ′} and R _{c12 ′} are bonded.

Specific examples of the repeating unit represented by the general formula (III) or (CII-AB) are given below. In specific examples, Ra represents H, CH ₃ , CH ₂ OH, CF ₃ or CN.

  Specific examples of the hydrophobic resin are given below. The following table summarizes the molar ratio of repeating units in each resin (corresponding to each repeating unit in order from the left), weight average molecular weight, and dispersity.

  The hydrophobic resin is preferably a resin containing a repeating unit having at least two polar conversion groups and containing at least one of a fluorine atom and a silicon atom. When such a resin is used as the hydrophobic resin, development defects can be further reduced. The fluorine atom may be a fluorine atom as an electron withdrawing group in the polarity conversion group, or may be another fluorine atom.

  Here, the “polarity converting group” is a group that decomposes by the action of an alkali developer and increases the solubility in the alkali developer, and includes, for example, the following general formulas (KA-1) and (KB). The portion represented by "-COO-" in -1) corresponds to this. However, ester groups that are directly bonded to the main chain of the resin (for example, ester groups in acrylates) are not included in the “polar conversion group” because they have a low ability to increase solubility by the action of an alkali developer. And

  The polarity converting group is decomposed by the action of an alkali developer, and its polarity changes. As a result, the receding contact angle between the film after alkali development and water as the immersion liquid can be further reduced.

  The receding contact angle between the film after alkali development and water is preferably 50 ° or less, more preferably 40 ° or less under the conditions of a temperature of 23 ± 3 ° C. and a humidity of 45 ± 5%, 35 More preferably, it is not more than 30 °, and most preferably not more than 30 °.

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

  When the hydrophobic resin is a resin containing a repeating unit with at least two polarity conversion groups and containing at least one of a fluorine atom and a silicon atom, the resin has at least two polarity conversions on one side chain. It preferably includes a repeating unit having both a group and at least one of a fluorine atom and a silicon atom. That is, this hydrophobic resin preferably contains a repeating unit containing at least one of a fluorine atom and a silicon atom on a side chain provided with a plurality of polarity converting groups.

  Alternatively, in this case, the hydrophobic resin comprises at least two polar conversion groups and a repeating unit not containing a fluorine atom and a silicon atom, and a repeating unit containing at least one of a fluorine atom and a silicon atom. May be included.

  Alternatively, in this case, the hydrophobic resin has at least two polarity conversion groups on one side chain, and a repeating resin containing at least one of a fluorine atom and a silicon atom on the other side chain in the same repeating unit. Units may be included. In this case, it is preferable that the side chain provided with the polarity conversion group and the side chain containing at least one of a fluorine atom and a silicon atom are in an α-position positional relationship through the carbon atom of the main chain. That is, it is preferable that these side chains have a positional relationship represented by the following formula (4). In the formula, B1 represents a side chain provided with a polarity converting group, and B2 represents a side chain containing at least one of a fluorine atom and a silicon atom.

  The side chain containing the polar conversion group preferably contains a partial structure represented by the following general formula (KA-1) or (KB-1), and is represented by the following general formula (KA-1). More preferably, the partial structure is included.

In general formula (KA-1),
Z _ka1 independently represents an alkyl group, a cycloalkyl group, an ether group, a hydroxy group, an amide group, an aryl group, a lactone ring group, or an electron-withdrawing group when nka ≧ 2. In the case of nka ≧ 2, a plurality of Z _ka1 may be bonded to each other to form a ring. Examples of this ring include cycloalkyl rings and heterocyclic rings such as cyclic ether rings and lactone rings.

  nka represents an integer of 0 to 10. nka is preferably 0 to 8, more preferably 0 to 5, still more preferably 1 to 4, and particularly preferably 1 to 3.

  Note that the structure represented by the general formula (KA-1) represents a monovalent or higher-valent substituent formed by removing at least one hydrogen atom contained in the structure.

In general formula (KB-1),
X _kb1 and X _kb2 each independently represent an electron withdrawing group.
nkb and nkb ′ each independently represents 0 or 1. Note that when nkb = nkb ′ = 0, X _kb1 and X _kb2 are directly connected to an ester group (—COO—).

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

The ring that can be formed by combining at least two of R _kb3 , R _kb4 and X _kb2 with each other preferably includes a cycloalkyl group and a heterocyclic group. As this heterocyclic group, a lactone ring group is particularly preferable. Examples of the lactone ring include those represented by the formulas (LC1-1) to (LC1-17) described for the resin (B).

In addition, when both X _kb1 and X _kb2 are monovalent substituents, the structure represented by the general formula (KB-1) is a monovalent formed by removing at least one hydrogen atom contained in the structure. The above substituents are represented.

  In the partial structure represented by the general formula (KB-1), an electron withdrawing group is present close to the ester group. Therefore, this partial structure can exhibit excellent polarity conversion ability.

Z _ka1 is preferably an alkyl group, a cycloalkyl group, an ether group, a hydroxy group or an electron withdrawing group, more preferably an alkyl group, a cycloalkyl group or an electron withdrawing group. The ether group is preferably an alkyl ether group or a cycloalkyl ether group.

The alkyl group of Z _ka1 may be linear or branched. This alkyl group may further have a substituent.
The linear alkyl group preferably has 1 to 30 carbon atoms, and more preferably 1 to 20 carbon atoms. Examples of such linear alkyl groups include methyl, ethyl, n-propyl, n-butyl, sec-butyl, t-butyl, n-pentyl, n-hexyl, and n- A heptyl group, n-octyl group, n-nonyl group, and n-decanyl group are mentioned.

  The branched alkyl group preferably has 3 to 30 carbon atoms, and more preferably 3 to 20 carbon atoms. Examples of such branched alkyl groups include i-propyl, i-butyl, t-butyl, i-pentyl, t-pentyl, i-hexyl, t-hexyl, and i-heptyl. Group, t-heptyl group, i-octyl group, t-octyl group, i-nonyl group and t-decanoyl group.

The alkyl group of Z _ka1 has 1 to 4 carbon atoms such as methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, i-butyl group and t-butyl group. Is preferred.

The cycloalkyl group of Z _ka1 may be monocyclic or polycyclic. In the latter case, the cycloalkyl group may be bridged. That is, in this case, the cycloalkyl group may have a bridged structure. A part of carbon atoms in the cycloalkyl group may be substituted with a hetero atom such as an oxygen atom.

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

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

  Examples of these cycloalkyl groups include those represented by the following formula.

  Preferred examples of the alicyclic structure include an adamantyl group, a noradamantyl group, a decalin group, a tricyclodecanyl group, a tetracyclododecanyl group, a norbornyl group, a cedrol group, a cyclohexyl group, a cycloheptyl group, a cyclo An octyl group, a cyclodecanyl group, and a cyclododecanyl group are mentioned. More preferably, an adamantyl group, a decalin group, a norbornyl group, a cedrol group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, a cyclodecanyl group, a cyclododecanyl group, and a tricyclodecanyl group are exemplified.

  These alicyclic structures may further have a substituent. Examples of the substituent include an alkyl group, a halogen atom, a hydroxyl group, an alkoxy group, a carboxy group, and an alkoxycarbonyl group.

  The alkyl group as a substituent is preferably a lower alkyl group such as a methyl group, an ethyl group, a propyl group, an isopropyl group and a butyl group, more preferably a methyl group, an ethyl group, a propyl group and an isopropyl group. .

  The alkoxy group as the substituent is preferably an alkoxy group having 1 to 4 carbon atoms such as a methoxy group, an ethoxy group, a propoxy group, and a butoxy group.

  These alkyl groups and alkoxy groups as substituents may have further substituents. As this further substituent, a hydroxyl group, a halogen atom, and an alkoxy group (preferably C1-C4) are mentioned, for example.

Examples of the aryl group for Z _ka1 include a phenyl group and a naphthyl group.

Examples of the substituent that the alkyl group, cycloalkyl group, and aryl group of Z _ka1 may further include, for example, a hydroxyl group; a halogen atom; a nitro group; a cyano group; the alkyl group described above; Alkoxy groups such as propoxy group, hydroxypropoxy group, n-butoxy group, isobutoxy group, sec-butoxy group and t-butoxy group; alkoxycarbonyl groups such as methoxycarbonyl group and ethoxycarbonyl group; benzyl group, phenethyl group and cumyl group Aralkyloxy group; Aralkyloxy group; Acyl group such as formyl group, acetyl group, butyryl group, benzoyl group, cyanamyl group and valeryl group; Acyloxy group such as butyryloxy group; Alkenyl group; Vinyloxy group, propenyloxy group, allyloxy group And butenyl An alkenyloxy group such as an oxy group; the above aryl group; an aryloxy group such as a phenoxy group; and an aryloxycarbonyl group such as a benzoyloxy group.

_Examples of the electron withdrawing group of Z _ka1 , X _kb1 , X _kb2 and R _{kb1 to} R _kb4 include a halogen atom, a cyano group, an oxy group, a carbonyl group, a carbonyloxy group, an oxycarbonyl group, a nitrile group, and a nitro group. , A sulfonyl group, a sulfinyl group, a halo (cyclo) alkyl group represented by -C (Rf1) (Rf2) -Rf3, a haloaryl group, and combinations thereof. The “halo (cyclo) alkyl group” means a (cyclo) alkyl group in which at least one hydrogen atom is substituted with a halogen atom.

Examples of the halogen atom for Z _ka1 include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. Of these, a fluorine atom is particularly preferable.

  In the halo (cyclo) alkyl group represented by —C (Rf1) (Rf2) —Rf3, Rf1 represents a halogen atom, a perhaloalkyl group, a percyclohaloalkyl group, or a perhaloaryl group. Rf1 is more preferably a fluorine atom, a perfluoroalkyl group or a perfluorocycloalkyl group, and further preferably a fluorine atom or a trifluoromethyl group.

  In the halo (cyclo) alkyl group represented by -C (Rf1) (Rf2) -Rf3, Rf2 and Rf3 each independently represent a hydrogen atom, a halogen atom or an organic group. Examples of the organic group include an alkyl group, a cycloalkyl group, and an alkoxy group. These groups may further have a substituent such as a halogen atom.

  At least two of Rf1 to Rf3 may be bonded to each other to form a ring. Examples of the ring include a cycloalkyl ring, a halocycloalkyl ring, an aryl ring, and a haloaryl ring.

Examples of the alkyl group and haloalkyl group of Rf1 to Rf3 include the alkyl group described above for Z _ka1 and a group in which at least a part of hydrogen atoms of these alkyl groups is substituted with a halogen atom.

Examples of the halocycloalkyl group and haloaryl group include groups in which at least a part of the hydrogen atoms of the cycloalkyl group and aryl group described above for Z _ka1 are substituted with a halogen atom. More preferably, the halocycloalkyl group and the haloaryl group are represented by a fluoroalkyl group represented by -C (n) F (2n-2) H and a group represented by -C (n) F (2n-1). Perfluoroaryl group to be used. Here, although there is no restriction | limiting in particular in the range of carbon number n, it is preferable that it is n = 5-13, and it is especially preferable that it is n = 6.

  More preferably, Rf2 is the same group as Rf1 or is bonded to Rf3 to form a ring.

  The electron withdrawing group is particularly preferably a halogen atom, a halo (cyclo) alkyl group or a haloaryl group. In the electron withdrawing group, a part of the fluorine atom may be substituted with an electron withdrawing group other than the fluorine atom.

  When the electron withdrawing group is a divalent or higher valent group, the remaining bond is used for bonding with an arbitrary atom or substituent. In this case, said partial structure may be couple | bonded with the principal chain of hydrophobic resin through the further substituent.

  The partial structure represented by the general formula (KA-1) is a lactone structure. This lactone structure is preferably a 5- to 7-membered ring structure, and more preferably a 5- to 7-membered lactone structure in which another ring structure is condensed in the form of forming a bicyclo structure or a spiro structure. .

  As the lactone structure in the general formula (KA-1), a lactone structure represented by any of (LC1-1) to (LC1-17) described for the resin (B) is more preferable. Among these, the structure represented by (LC1-1), (LC1-4), (LC1-5), (LC1-6), (LC1-13), (LC1-14) or (LC1-17) Is particularly preferred.

  The lactone structure usually has optical isomers, 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 thereof is preferably 90% ee or more, more preferably 95% ee or more, further preferably 98% ee or more.

  It is more preferable that the hydrophobic resin has a structure represented by the following general formula (KY-1) as a partial structure having two polarity conversion groups. Note that the structure represented by the general formula (KY-1) represents a monovalent or higher-valent substituent formed by removing at least one hydrogen atom contained in the structure.

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

R _ky2 and R _ky3 each independently represent an electron withdrawing group. Alternatively, R _ky1 and R _ky2 may be bonded to each other to form a lactone ring, and R _ky3 may be an electron withdrawing group.
As the lactone ring, the structures (LC1-1) to (LC1-17) mentioned above are preferable. Examples of the electron withdrawing group include the same groups as X _kb1 in the general formula (KB-1). This electron withdrawing group is preferably a halogen atom, a halo (cyclo) alkyl group represented by -C (Rf1) (Rf2) -Rf3, or a haloaryl group.

At least two of R _ky1 , R _ky2 and R _ky4 may be bonded to each other to form a monocyclic or polycyclic structure. R _{kb1 to} R _kb4 , nkb and nkb ′ have the same meaning as described above for the formula (KB-1). _Examples of R _ky1 and R _ky4 include the same groups as Z _ka1 in the above general formula (KA-1).

  The partial structure represented by the general formula (KY-1) is more preferably a structure represented by the following general formula (KY-2). Note that the structure represented by the general formula (KY-2) represents a monovalent or higher-valent substituent formed by removing at least one hydrogen atom contained in this structure.

In the general formula (KY-2), R _{ky6 to} R _ky10 are each independently a hydrogen atom, a halogen atom, an alkyl group, a cycloalkyl group, a carbonyl group, a carbonyloxy group, an oxycarbonyl group, an ether group, or a hydroxy group. Represents a cyano group, an amide group, or an aryl group. At least two _members out of R _{ky6 to} R _ky10 may be bonded to each other to form a ring.

R _ky5 represents an electron-withdrawing group. Examples of the electron withdrawing group include the same groups as Xkb1 in the general formula (KB-1). This electron withdrawing group is preferably a halogen atom, a halo (cyclo) alkyl group represented by -C (Rf1) (Rf2) -Rf3, or a haloaryl group.

Each of R _kb1 , R _kb2 and nkb is synonymous with that in the general formula (KB-1). _{Examples of} R _{ky5 to} R _ky10 include the same groups as Z _ka1 in the general formula (KA-1).

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

In the general formula (KY-3), each of Z _ka1 and nka has the same meaning as in the general formula (KA-1). R _ky5 has the same _meaning as in general formula (KY-2). Each of R _kb1 , R _kb2 and nkb is synonymous with that in the general formula (KB-1).

L _ky represents an alkylene group, an oxygen atom, or a sulfur atom. Examples of the alkylene group for L _ky include a methylene group and an ethylene group. L _ky is preferably an oxygen atom or a methylene group, and more preferably a methylene group.

  Rs each independently represents an alkylene group or a cycloalkylene group when ns ≧ 2. When ns ≧ 2, the plurality of Rs may be the same as or different from each other.

  Ls each independently represents a single bond, an ether bond, an ester bond, an amide bond, a urethane bond or a urea bond when ns ≧ 2. When ns ≧ 2, the plurality of Ls may be the same as or different from each other.

  ns is the number of repeating linking groups represented by-(Rs-Ls)-and represents an integer of 0 to 5.

  The hydrophobic resin preferably contains a repeating unit represented by the following general formula (K0).

In General Formula (K0), R _k1 represents a hydrogen atom, a halogen atom, a hydroxyl group, an alkyl group, a cycloalkyl group, an aryl group, or a group having a polarity converting group. R _k2 represents an alkyl group, a cycloalkyl group, an aryl group, or a group having a polarity converting group. However, the total number of polar conversion groups contained in R _k1 and R _k2 is 2 or more.
Note that, as described above, the ester group directly bonded to the main chain of the repeating unit represented by the general formula (K0) is not included in the polarity conversion group.

The repeating unit contained in the hydrophobic resin is not limited as long as it is a repeating unit obtained by polymerization such as addition polymerization, condensation polymerization, and addition condensation. However, the repeating unit obtained by addition polymerization of a carbon-carbon double bond is not limited. Preferably it is a unit.
Examples of such a repeating unit include an acrylate-based repeating unit (including a system having a substituent at the α-position and / or β-position) and a styrene-based repeating unit (a system having a substituent at the α-position and / or β-position). A vinyl ether-based repeating unit, a norbornene-based repeating unit, and a repeating unit of a maleic acid derivative (maleic anhydride, its derivative, maleimide and the like). Among these, acrylate-based repeating units, styrene-based repeating units, vinyl ether-based repeating units, or norbornene-based repeating units are more preferable, acrylate-based repeating units, vinyl ether-based repeating units, or norbornene-based repeating units are more preferable, and acrylate-based repeating units. Units are particularly preferred.

  Below, the specific example of the repeating unit provided with the at least 2 polarity conversion group is given. In specific examples, Ra represents a hydrogen atom, a fluorine atom, a methyl group or a trifluoromethyl group.

The resin containing a repeating unit having at least two polar conversion groups may further contain another repeating unit. Examples of the other repeating unit include those described above as the repeating unit that can be contained in the hydrophobic resin.
The content of the repeating unit having at least two polar conversion groups is preferably 10 to 100 mol%, more preferably 20 to 100 mol%, still more preferably based on the total repeating units of the hydrophobic resin. Is 30 to 100 mol%, particularly preferably 40 to 100 mol%.

  When the hydrophobic resin includes a repeating unit having at least two polar conversion groups and at least one of a fluorine atom and a silicon atom on one side chain, the content of the repeating unit is hydrophobic. Preferably, it is 10 to 100 mol%, more preferably 20 to 100 mol%, still more preferably 30 to 100 mol%, particularly preferably 40 to 100 mol%, based on the total repeating units of the resin. is there.

  The hydrophobic resin includes both a repeating unit having at least two polar conversion groups and not containing a fluorine atom and a silicon atom and a repeating unit containing at least one of a fluorine atom and a silicon atom. In this case, preferable contents thereof are as follows. That is, the former content is preferably 10 to 90 mol%, more preferably 15 to 85 mol%, still more preferably 20 to 80 mol%, based on all repeating units of the hydrophobic resin. Especially preferably, it is 25-75 mol%. The latter content is preferably 10 to 90 mol%, more preferably 15 to 85 mol%, still more preferably 20 to 80 mol%, based on all repeating units of the hydrophobic resin. Especially preferably, it is 25-75 mol%.

  The hydrophobic resin includes at least two polarity converting groups on one side chain, and includes a repeating unit containing at least one of a fluorine atom and a silicon atom on the other side chain in the same repeating unit. In this case, the content of the repeating unit is preferably 10 to 100 mol%, more preferably 20 to 100 mol%, still more preferably 30 to 100 mol%, and particularly preferably 40 to 100 mol%. It is.

  Below, the specific example of resin containing the repeating unit provided with the at least 2 polarity conversion group and containing at least one of the fluorine atom and the silicon atom is given. The following table summarizes the molar ratio of repeating units in each resin (corresponding to each repeating unit in order from the left), weight average molecular weight, and degree of dispersion.

  When the hydrophobic resin contains a fluorine atom, the fluorine atom content is preferably 5 to 80% by mass, more preferably 10 to 80% by mass based on the molecular weight of the hydrophobic resin. . In addition, the content of the repeating unit containing a fluorine atom is preferably 10 to 100% by mass, more preferably 30 to 100% by mass, based on all repeating units of the hydrophobic resin.

  When the hydrophobic resin contains silicon atoms, the silicon atom content is preferably 2 to 50% by mass, more preferably 2 to 30% by mass, based on the molecular weight of the hydrophobic resin. . In addition, the content of the repeating unit containing a silicon atom is preferably 10 to 100% by mass, more preferably 20 to 100% by mass, based on all repeating units of the hydrophobic resin.

The weight average molecular weight of hydrophobic resin becomes like this. Preferably it is 1,000-100,000, More preferably, it is 1,000-50,000, More preferably, it is 2,000-15,000.
The degree of dispersion of the hydrophobic resin is preferably 1 to 5, more preferably 1 to 3, and still more preferably 1 to 2. This makes it possible to achieve better resolution, pattern shape, and roughness characteristics.

One type of hydrophobic resin may be used alone, or two or more types may be used in combination.
The content of the hydrophobic resin is preferably 0.01 to 10% by mass, more preferably 0.05 to 8% by mass, based on the total solid content in the composition, More preferably, it is 5 mass%.

  The hydrolysis rate of the hydrophobic resin with respect to the alkaline developer is preferably 0.001 nm / second or more, more preferably 0.01 nm / second or more, and further preferably 0.1 nm / second or more. 1 nm / second or more is particularly preferable. The hydrolysis rate of the hydrophobic resin with respect to the alkaline developer is a film obtained by forming a resin film with only a hydrophobic resin with respect to a 2.38 mass% TMAH (tetramethylammonium hydroxide) aqueous solution at 23 ° C. The rate at which the thickness decreases.

  As the hydrophobic resin, commercially available products may be used, or those synthesized according to a conventional method may be used. As a general synthesis method of this resin, for example, the same method as described above for the resin (B) can be mentioned.

  It is natural that the hydrophobic resin has few impurities such as metals, and the residual amount of the monomer and oligomer components is preferably 0 to 10% by mass, and more preferably 0 to 5% by mass. More preferably, it is 0 to 1% by mass. As a result, the amount of foreign matter in the liquid can be reduced, and changes over time such as sensitivity can be reduced.

[5] Basic compound The actinic ray-sensitive or radiation-sensitive resin composition of the present invention preferably contains a basic compound.
The basic compound is preferably a nitrogen-containing organic basic compound.
Although the compound which can be used is not specifically limited, For example, the compound classified into the following (1)-(4) is used preferably.

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

In general formula (BS-1),
Each R independently represents a hydrogen atom, an alkyl group (straight or branched), a cycloalkyl group (monocyclic or polycyclic), an aryl group, or an aralkyl group. However, not all three Rs are hydrogen atoms.
Although carbon number of the alkyl group as R is not specifically limited, Usually, 1-20, Preferably it is 1-12.
Although carbon number of the cycloalkyl group as R is not specifically limited, Usually, 3-20, Preferably it is 5-15.
Although carbon number of the aryl group as R is not specifically limited, Usually, 6-20, Preferably it is 6-10. Specific examples include a phenyl group and a naphthyl group.
Although carbon number of the aralkyl group as R is not specifically limited, Usually, 7-20, Preferably it is 7-11. Specific examples include a benzyl group.
In the alkyl group, cycloalkyl group, aryl group or aralkyl group as R, a hydrogen atom may be substituted with a substituent. Examples of the substituent include an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, a hydroxyl group, a carboxyl group, an alkoxy group, an aryloxy group, an alkylcarbonyloxy group, and an alkyloxycarbonyl group.
In the compound represented by the general formula (BS-1), it is preferable that only one of three Rs is a hydrogen atom, or all Rs are not hydrogen atoms.

Specific examples of the compound of the general formula (BS-1) include tri-n-butylamine, tri-n-pentylamine, tri-n-octylamine, tri-n-decylamine, triisodecylamine, dicyclohexylmethylamine, Tetradecylamine, pentadecylamine, hexadecylamine, octadecylamine, didecylamine, methyloctadecylamine, dimethylundecylamine, N, N-dimethyldodecylamine, methyldioctadecylamine, N, N-dibutylaniline, N, N- Examples include dihexylaniline, 2,6-diisopropylaniline, 2,4,6-tri (t-butyl) aniline.
In addition, in the general formula (BS-1), a compound in which at least one R is an alkyl group substituted with a hydroxyl group is mentioned as one of preferable embodiments. Specific examples of the compound include triethanolamine and N, N-dihydroxyethylaniline.

The alkyl group as R may have an oxygen atom in the alkyl chain, and an oxyalkylene chain may be formed. As the oxyalkylene chain, —CH ₂ CH ₂ O— is preferable. Specific examples include tris (methoxyethoxyethyl) amine and compounds exemplified in column 3, line 60 and thereafter of US Pat. No. 6,040,112.

(2) Compound having a nitrogen-containing heterocyclic structure The heterocyclic structure may or may not have aromaticity. Moreover, you may have two or more nitrogen atoms, Furthermore, you may contain hetero atoms other than nitrogen. Specifically, compounds having an imidazole structure (2-phenylbenzimidazole, 2,4,5-triphenylimidazole, etc.), compounds having a piperidine structure (N-hydroxyethylpiperidine, bis (1,2,2,6) , 6-pentamethyl-4-piperidyl) sebacate), compounds having a pyridine structure (such as 4-dimethylaminopyridine), and compounds having an antipyrine structure (such as antipyrine and hydroxyantipyrine).
A compound having two or more ring structures is also preferably used. Specific examples include 1,5-diazabicyclo [4.3.0] non-5-ene and 1,8-diazabicyclo [5.4.0] -undec-7-ene.

(3) Amine compound having a phenoxy group An amine compound having a phenoxy group has a phenoxy group at the terminal opposite to the nitrogen atom of the alkyl group of 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 carboxyl 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.
More preferably, it is a compound having at least one oxyalkylene chain between the phenoxy group and the nitrogen atom. The number of oxyalkylene chains in one molecule is preferably 3-9, more preferably 4-6. Among the oxyalkylene chains, —CH ₂ CH ₂ O— is preferable.
Specific examples include 2- [2- {2- (2,2-dimethoxy-phenoxyethoxy) ethyl} -bis- (2-methoxyethyl)]-amine and US Patent Application Publication No. 2007 / 0224539A1. The compounds (C1-1) to (C3-3) exemplified in paragraph [0066] of the above.

(4) Ammonium salt Ammonium salts are also used as appropriate. Preferred is hydroxide or carboxylate. More specifically, tetraalkylammonium hydroxide represented by tetrabutylammonium hydroxide is preferable.

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

A basic compound is used individually or in combination of 2 or more types.
The usage-amount of a basic compound is 0.001-10 mass% normally on the basis of solid content of a composition, Preferably it is 0.01-5 mass%.
The molar ratio of compound (PBG) / basic compound is preferably 100/1 to 5/1, more preferably 80/1 to 10/1, and particularly preferably 60/1 to 20/1.
The molar ratio of acid generator / basic compound is preferably 2.5 to 300. That is, the molar ratio is preferably 2.5 or more from the viewpoints of sensitivity and resolution, and is preferably 300 or less from the viewpoint of suppressing the reduction in resolution due to pattern thickening over time until post-exposure heat treatment. This molar ratio is more preferably 5.0 to 200, and still more preferably 7.0 to 150.

[6] Low molecular weight compound having a group capable of leaving by the action of an acid The composition of the present invention contains a low molecular weight compound having a group capable of leaving by the action of an acid (hereinafter also referred to as “compound (D)”). can do. The group capable of leaving by the action of an acid is not particularly limited, but is preferably an acetal group, a carbonate group, a carbamate group, a tertiary ester group, a tertiary hydroxyl group, or a hemiaminal ether group, and a carbamate group or a hemiaminal ether group. It is particularly preferred.
The molecular weight range of the low molecular weight compound having a group capable of leaving by the action of an acid is preferably 100 to 1000, more preferably 100 to 700, and particularly preferably 100 to 500.

  When the low molecular weight compound having a group capable of leaving by the action of an acid has a tertiary ester structure, it is particularly preferably a carboxylic acid ester or an unsaturated carboxylic acid ester represented by the following general formula (1a).

In the general formula (1a), R ¹ independently represents a monovalent alicyclic hydrocarbon group (preferably having 4 to 20 carbon atoms) or a derivative thereof, or an alkyl group (preferably having 1 to 4 carbon atoms). And at least one of R ¹ is the alicyclic hydrocarbon group or a derivative thereof, or any two R ¹ are bonded to each other, and each of them is bonded to a carbon atom to which the divalent alicyclic ring is bonded. Form a hydrocarbon group (preferably having 4 to 20 carbon atoms) or a derivative thereof, and the remaining R ¹ is an alkyl group (preferably having 1 to 4 carbon atoms) or a monovalent alicyclic hydrocarbon group (preferably Represents a carbon number of 4 to 20) or a derivative thereof.
X independently represents a hydrogen atom or a hydroxy group, and at least one is a hydroxy group.
A represents a single bond or a divalent linking group, preferably a single bond or a group represented by -D-COO-, and D represents an alkylene group (preferably having 1 to 4 carbon atoms).

  In the general formula (1a), examples of the divalent linking group of A include a methylene group, a methylenecarbonyl group, a methylenecarbonyloxy group, an ethylene group, an ethylenecarbonyl group, an ethylenecarbonyloxy group, a propylene group, a propylenecarbonyl group, A propylene carbonyloxy group etc. are mentioned. Particularly preferred is a methylenecarbonyloxy group.

In the general formula (1a), a monovalent alicyclic hydrocarbon group of R ¹ (preferably having 4 to 20 carbon atoms) and a divalent alicyclic group formed by bonding any two R ¹ to each other. Examples of the hydrocarbon group (preferably having 4 to 20 carbon atoms) are derived from, for example, norbornane, tricyclodecane, tetracyclododecane, adamantane, cycloalkanes such as cyclobutane, cyclopentane, cyclohexane, cycloheptane, and cyclooctane. A group consisting of an alicyclic ring; a group consisting of these alicyclic rings is, for example, a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, a 2-methylpropyl group, 1 -The group etc. which were substituted by 1 or more types of C1-C4 alkyl groups and cycloalkyl groups, such as a methylpropyl group and t-butyl group, etc. are mentioned. Among these alicyclic hydrocarbon groups, a group consisting of an alicyclic ring derived from norbornane, tricyclodecane, tetracyclododecane, adamantane, cyclopentane or cyclohexane, or a group consisting of these alicyclic rings is described above. A group substituted with an alkyl group is preferred.

  Examples of the alicyclic hydrocarbon group derivative include hydroxyl group; carboxyl group; oxo group (ie, ═O group); hydroxymethyl group, 1-hydroxyethyl group, 2-hydroxyethyl group, 1-hydroxy. A hydroxyalkyl group having 1 to 4 carbon atoms such as propyl group, 2-hydroxypropyl group, 3-hydroxypropyl group, 1-hydroxybutyl group, 2-hydroxybutyl group, 3-hydroxybutyl group, 4-hydroxybutyl group; C1-C4 alkoxyl groups such as methoxy group, ethoxy group, n-propoxy group, i-propoxy group, n-butoxy group, 2-methylpropoxy group, 1-methylpropoxy group, t-butoxy group; cyano group A cyano group having 2 to 5 carbon atoms such as a cyanomethyl group, a 2-cyanoethyl group, a 3-cyanopropyl group, a 4-cyanobutyl group; It can include a group having a substituent such as Kill group one or more, or 1 or more. Of these substituents, a hydroxyl group, a carboxyl group, a hydroxymethyl group, a cyano group, a cyanomethyl group, and the like are preferable.

Examples of the alkyl group for R ¹ include a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, a 2-methylpropyl group, a 1-methylpropyl group, and a t-butyl group. The C1-C4 alkyl group of these can be mentioned. Of these alkyl groups, a methyl group, an ethyl group, an n-propyl group, and an i-propyl group are preferable.

  Preferable specific examples include the following compounds.

When the low molecular weight compound is an unsaturated carboxylic acid ester, a (meth) acrylic acid ester is particularly preferable. Specific examples of the (meth) acrylic acid tertiary ester having a tertiary alkyl group as a group capable of leaving by the action of an acid are shown below, but are not limited thereto.

(D) The low molecular compound having a group capable of leaving by the action of an acid may be a commercially available compound or a compound synthesized by a known method.
As the compound (D), an amine derivative having a group capable of leaving by the action of an acid on the nitrogen atom is preferable.

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

In general formula (d-1),
R ′ each independently represents a hydrogen atom, a linear, branched or cyclic alkyl group, an aryl group, an aralkyl group, or an alkoxyalkyl group. R ′ may be bonded to each other to form a ring.
R ′ is preferably a linear or branched alkyl group, cycloalkyl group, or aryl group. More preferably, it is a linear or branched alkyl group or cycloalkyl group.
The specific structure of such a group is shown below.

The compound (D) can also be constituted by arbitrarily combining the basic compound and the structure represented by the general formula (d-1).
The compound (D) particularly preferably has a structure represented by the following general formula (A).
The compound (D) may correspond to the basic compound as long as it is a low molecular compound having a group capable of leaving by the action of an acid.

In the general formula (A), Ra independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group or an aralkyl group. When n = 2, the two Ras may be the same or different, and the two Ras are bonded to each other to form a heterocyclic hydrocarbon group (preferably having a carbon number of 20 or less) or a derivative thereof. It may be.
Rb independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group or an aralkyl group. At least two Rb's may combine to form an alicyclic hydrocarbon group, an aromatic hydrocarbon group, a heterocyclic hydrocarbon group or a derivative thereof.
n represents an integer of 0 to 2, m represents an integer of 1 to 3, and n + m = 3.

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

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

Specifically shown in the present invention are particularly preferred examples: Nt-butoxycarbonyldi-n-octylamine, Nt-butoxycarbonyldi-n-nonylamine, Nt-butoxycarbonyldi-n-decylamine, Nt-butoxycarbonyldicyclohexylamine, Nt-butoxycarbonyl-1-adamantylamine, Nt-butoxycarbonyl-2-adamantylamine, Nt-butoxycarbonyl-N-methyl-1-adamantylamine, ( S)-(−)-1- (t-butoxycarbonyl) -2-pyrrolidinemethanol, (R)-(+)-1- (t-butoxycarbonyl) -2-pyrrolidinemethanol, Nt-butoxycarbonyl- 4-hydroxypiperidine, Nt-butoxycarbonylpyrrolidine, Nt-butoxy Rubonylmorpholine, Nt-butoxycarbonylpiperazine, N, N-di-t-butoxycarbonyl-1-adamantylamine, N, N-di-t-butoxycarbonyl-N-methyl-1-adamantylamine, Nt -Butoxycarbonyl-4,4'-diaminodiphenylmethane, N, N'-di-t-butoxycarbonylhexamethylenediamine, N, N, N'N'-tetra-t-butoxycarbonylhexamethylenediamine, N, N ' -Di-t-butoxycarbonyl-1,7-diaminoheptane, N, N'-di-t-butoxycarbonyl-1,8-diaminooctane, N, N'-di-t-butoxycarbonyl-1,9- Diaminononane, N, N′-di-t-butoxycarbonyl-1,10-diaminodecane, N, N′-di-t-butoxycarbonyl 1,12-diaminododecane, N, N′-di-t-butoxycarbonyl-4,4′-diaminodiphenylmethane, Nt-butoxycarbonylbenzimidazole, Nt-butoxycarbonyl-2-methylbenzimidazole, N -T-butoxycarbonyl-2-phenylbenzimidazole etc. are mentioned.

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

  The compound represented by the general formula (A) can be easily synthesized from a commercially available amine by a method described in Protective Groups in Organic Synthesis Fourth Edition. As the most general method, there is a method obtained by reacting a dicarbonate or haloformate with a commercially available amine. In the formula, X represents a halogen atom.

  In the present invention, the low molecular weight compound having a group capable of leaving by the action of an acid can be used alone or in combination of two or more.

  In the present invention, the amount of the low molecular compound having a group capable of leaving by the action of an acid is usually 0.001 to 20% by mass, preferably based on the total solid content of the composition combined with the basic compound. Is 0.001 to 10 mass%, more preferably 0.01 to 5 mass%.

  The composition ratio of the low molecular weight compound having a group capable of leaving by the action of an acid generator and an acid is as follows: acid generator / [low molecular weight compound having a group capable of leaving by the action of an acid + the basic compound + The compound (PBG)] (molar ratio) is preferably 1.0 to 100. That is, the molar ratio is preferably 1.0 or more from the viewpoint of sensitivity and resolution, and is preferably 100 or less from the viewpoint of suppressing the reduction in resolution due to pattern thickening over time until post-exposure heat treatment. The acid generator / [low molecular compound having a group capable of leaving by the action of an acid + the basic compound + the compound (PBG)] (molar ratio) is more preferably 2.0 to 75, still more preferably 3. 0-50.

[7] Surfactant The composition of the present invention may further contain a surfactant. When contained, the surfactant is preferably a fluorine-based and / or silicon-based surfactant.
Surfactants corresponding to these include Megafac F176, Megafac R08 manufactured by Dainippon Ink and Chemicals, PF656, PF6320 manufactured by OMNOVA, Troisol S-366 manufactured by Troy Chemical, Sumitomo 3M Examples include Fluorad FC430 manufactured by Co., Ltd., polysiloxane polymer KP-341 manufactured by Shin-Etsu Chemical Co., Ltd., and the like.
Further, other surfactants other than fluorine-based and / or silicon-based surfactants can also be used. More specific examples include polyoxyethylene alkyl ethers and polyoxyethylene alkyl aryl ethers.

  In addition, known surfactants can be used as appropriate. Examples of the surfactant that can be used include surfactants described in [0273] et seq. Of US Patent Application Publication No. 2008 / 0248425A1.

Surfactants may be used alone or in combination of two or more.
The amount of the surfactant used is preferably 0 to 2% by mass, more preferably 0.0001 to 2% by mass, based on the total solid content (total amount excluding the solvent) of the actinic ray-sensitive or radiation-sensitive resin composition. %, Particularly preferably 0.0005 to 1% by mass.
On the other hand, it is also preferable that the addition amount of the surfactant is 10 ppm or less or not contained. This increases the uneven distribution of the surface of the hydrophobic resin, thereby making the surface of the film formed from the actinic ray-sensitive or radiation-sensitive resin composition more hydrophobic and following water during immersion exposure. Can be improved.

[8] Solvent The solvent that can be used in preparing the actinic ray-sensitive or radiation-sensitive resin composition of the present invention is not particularly limited as long as it dissolves each component. For example, an alkylene glycol monoalkyl ether Carboxylate (such as propylene glycol monomethyl ether acetate), alkylene glycol monoalkyl ether (such as propylene glycol monomethyl ether), lactic acid alkyl ester (such as ethyl lactate and methyl lactate), cyclic lactone (such as γ-butyrolactone), preferably 4 to 4 carbon atoms 10), chain or cyclic ketones (2-heptanone, cyclohexanone, etc., preferably 4 to 10 carbon atoms), alkylene carbonates (ethylene carbonate, propylene carbonate, etc.), alkyl carboxylates (such as butyl acetate). Alkyl acetate is preferred), and the like alkoxy alkyl acetates (ethyl ethoxypropionate). Other usable solvents include, for example, the solvents described in US Patent Application Publication No. 2008 / 0248425A1 after [0244].

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

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

[9] Substance that decomposes by the action of an acid to produce an acid stronger than a carboxylic acid The composition of the present invention decomposes by the action of an acid to produce an acid that is stronger than a carboxylic acid (hereinafter referred to as “acid growth”). May also be included).
The acid produced from the acid proliferating agent is preferably one having a high acid strength. Specifically, the acid dissociation constant (pKa) is preferably 3 or less, more preferably 2 or less. The acid generated from the acid proliferating agent is preferably sulfonic acid.
Examples of the acid proliferating agent include International Publication No. 95/29968, International Publication No. 98/24000, JP-A-8-305262, JP-A-9-34106, JP-A-8-248561, JP-A-8-503082, US Pat. No. 5,445,917, JP-T-8-503081, US Pat. No. 5,534,393, US Pat. No. 5,395,736, US Pat. No. 5,741,630, US Pat. No. 5,334,489, US Pat. No. 5,582,956, US Pat. No. 5,578,424, US Pat. No. 5,453,345, US Pat. No. 5,445,917, European patent No. 665,960, European Patent No. 757,628, European Patent No. 665,961, US Pat. No. 5,667,943, Japanese Patent Laid-Open No. 10-1508, Japanese Patent Laid-Open No. 10-282642, Japanese Patent Laid-Open No. 9- No. 12498, JP-2000-62337, may be used in combination of the acid proliferation agent described in JP 2005-17730 like one, or two or more.

  Specifically, compounds represented by the following general formulas (1) to (6) are preferable.

In the general formulas (1) to (6),
R represents an alkyl group, a cycloalkyl group, an aryl group, or an aralkyl group.
R ₀ represents a group capable of leaving by the action of an acid.
R ₁ represents an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, an alkoxy group, or an aryloxy group.
R ₂ represents an alkyl group or an aralkyl group.
R ₃ represents an alkyl group, a cycloalkyl group, an aryl group or an aralkyl group.
R ₄ and R ₅ each independently represents an alkyl group, and R ₄ and R ₅ may be bonded to each other to form a ring.
R ₆ represents a hydrogen atom or an alkyl group.
R ₇ represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group or an aralkyl group.
R ₈ represents an alkyl group, a cycloalkyl group, an aryl group or an aralkyl group.
R ₉ represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group or an aralkyl group.
R ₉ may combine with R ₇ to form a ring.
R ₁₀ represents an alkyl group, a cycloalkyl group, an alkoxy group, an aryl group, an aralkyl group, an aryloxy group or an alkenyloxy group.
R ₁₁ represents an alkyl group, a cycloalkyl group, an alkoxy group, an aryl group, an aralkyl group, an aryloxy group or an alkenyl group.
R ₁₀ and R ₁₁ may combine with each other to form a ring.
R ₁₂ represents an alkyl group, a cycloalkyl group, an aryl group, an alkenyl group, an alkenyl group, or a cyclic imide group.

In the general formulas (1) to (6), examples of the alkyl group include an alkyl group having 1 to 8 carbon atoms, specifically a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, An octyl group etc. are mentioned.
Examples of the cycloalkyl group include cycloalkyl groups having 4 to 10 carbon atoms, and specifically include cyclopropyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, adamantyl group, boronyl group, isobornyl group, tricyclo group. Examples include decanyl group, dicyclopentenyl group, nobornane epoxy group, menthyl group, isomenthyl group, neomenthyl group, tetracyclododecanyl group and the like.

Examples of the aryl group include aryl groups having 6 to 14 carbon atoms, and specific examples include a phenyl group, a naphthyl group, and a tolyl group.
Examples of the aralkyl group include aralkyl groups having 7 to 20 carbon atoms, and specific examples include a benzyl group, a phenethyl group, and a naphthylethyl group.
As an alkoxy group, a C1-C8 alkoxy group is mentioned, Specifically, a methoxy group, an ethoxy group, a propoxy group, a butoxy group etc. are mentioned.
Examples of the alkenyl group include alkenyl groups having 2 to 6 carbon atoms, and specific examples include a vinyl group, a propenyl group, an allyl group, a butenyl group, a pentenyl group, a hexenyl group, and a cyclohexenyl group.

Examples of the aryloxy group include an aryloxy group having 6 to 14 carbon atoms, and specific examples include a phenoxy group and a naphthoxy group.
Examples of the alkenyloxy group include alkenyloxy groups having 2 to 8 carbon atoms, and specific examples include a vinyloxy group and an allyloxy group.

  Each of the above substituents may further have a substituent, and examples of the substituent include the following. That is, halogen atoms such as Cl, Br, and F, -CN group, -OH group, alkyl group having 1 to 4 carbon atoms, cycloalkyl group having 3 to 8 carbon atoms, and alkoxy group having 1 to 4 carbon atoms , Acylamino groups such as acetylamino group, aralkyl groups such as benzyl group and phenethyl group, allyloxyalkyl groups such as phenoxyethyl group, alkoxycarbonyl groups having 2 to 5 carbon atoms, acyloxy groups having 2 to 5 carbon atoms, etc. Can be mentioned. And the range of a substituent is not limited to these.

Examples of the ring formed by combining R ₄ and R ₅ with each other include a 1,3-dioxolane ring and a 1,3-dioxane ring.
Examples of the ring formed by combining R ₇ and R ₉ with each other include a cyclopentyl ring and a cyclohexyl ring.
Examples of the ring formed by combining R ₁₀ and R ₁₁ with each other include a 3-oxocyclohexenyl ring and a 3-oxoindenyl ring which may contain an oxygen atom in the ring.
Examples of the group capable of leaving by the action of an acid of Ro include tertiary alkyl groups such as t-butyl group and t-amyl group, isobornyl group, 1-ethoxyethyl group, 1-butoxyethyl group, 1-isobutoxy group. 1-alkoxyethyl groups such as ethyl group, 1-cyclohexyloxyethyl group, alkoxymethyl groups such as 1-methoxymethyl group, 1-ethoxymethyl group, tetrahydropyranyl group, tetrahydrofuranyl group, trialkylsilyl group, 3- Examples thereof include an oxocyclohexyl group.

Preferred examples of each of R, R ₀ and R _{1 to} R ₁₁ include the following.
R: methyl group, ethyl group, propyl group, butyl group, octyl group, trifluoromethyl group, nonafluorobutyl group, heptadecafluorooctyl group, 2,2,2-trifluoroethyl group, phenyl group, pentafluorophenyl Group, methoxyphenyl group, toluyl group, mesityl group, fluorophenyl group, naphthyl group, cyclohexyl group, camphor group.
_R0 : t-butyl group, methoxymethyl group, ethoxymethyl group, 1-ethoxyethyl group, tetrahydropyranyl group.
R ₁ ; methyl group, ethyl group, propyl group, cyclopropyl group, cyclopentyl group, cyclohexyl group, phenyl group, naphthyl group, benzyl group, phenethyl group, methoxy group, ethoxy group, propoxy group, phenoxy group, naphthoxy group.
R ₂ : methyl group, ethyl group, propyl group, butyl group, benzyl group.
R ₃ : methyl group, ethyl group, propyl group, cyclopropyl group, cyclopentyl group, cyclohexyl group, phenyl group, naphthyl group, benzyl group, phenethyl group, naphthylmethyl group.
R ₄ , R ₅ : Methyl group, ethyl group, propyl group, those bonded to each other to form an ethylene group or a propylene group.
R ₆ : hydrogen atom, methyl group, ethyl group.

R ₇ , R ₉ ; hydrogen atom, methyl group, ethyl group, propyl group, butyl group, pentyl group, cyclopropyl group, cyclopentyl group, cyclohexyl group, phenyl group, naphthyl group, benzyl group, phenethyl group, bonded to each other Forming a cyclopentyl ring or a cyclohexyl ring.
R ₈ ; methyl group, ethyl group, isopropyl group, t-butyl group, neopentyl group, cyclohexyl group, phenyl group, benzyl group.
R ₁₀ : methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, cyclopropyl group, cyclopentyl group, cyclohexyl group, methoxy group, ethoxy group, phenyl group, naphthyl group, benzyl group, phenoxy group, naphthoxy Group formed by forming a 3-oxocyclohexenyl ring or a 3-oxoindenyl ring, which may be bonded to each other to contain an oxygen atom.
R ₁₁ : methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, cyclopropyl group, cyclopentyl group, cyclohexyl group, methoxy group, ethoxy group, phenyl group, naphthyl group, benzyl group, phenoxy group, naphthoxy A group formed by forming a 3-oxocyclohexenyl ring or a 3-oxoindenyl ring, which may be bonded to each other to contain an oxygen atom.

In the general formula (6), when R ₁₂ represents an alkyl group, examples of the alkyl group include linear and branched alkyl groups having 1 to 20 carbon atoms. Specific examples thereof include methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, undecyl group, dodecyl group, tridecyl group, hexadecyl group, octadecyl group. , Eicosyl group, isopropyl group, isobutyl group, s-butyl group, t-butyl group, isopentyl group, neopentyl group, 1-methylbutyl group, isohexyl group, 2-ethylhexyl group, 2-methylhexyl group and the like. . Among these, a linear alkyl group having 1 to 12 carbon atoms and a branched alkyl group having 3 to 12 carbon atoms are more preferable.
When R ₁₂ represents a cycloalkyl group, examples of the cycloalkyl group include cycloalkyl groups having 3 to 20 carbon atoms. Specific examples thereof include a cyclohexyl group, a cyclopentyl group, and a 2-norbornyl group. In these, a C5-C10 cycloalkyl group is more preferable.

When R ₁₂ represents a substituted alkyl group or a substituted cycloalkyl group, a monovalent nonmetallic atomic group other than hydrogen is used as the substituent. Preferred examples include halogen atoms (—F, —Br, — Cl, -I), hydroxyl group, alkoxy group, aryloxy group, mercapto group, alkylthio group, arylthio group, alkyldithio group, aryldithio group, amino group, N-alkylamino group, N, N-dialkylamino group, N- Arylamino group, N, N-diarylamino group, N-alkyl-N-arylamino group, acyloxy group, carbamoyloxy group, N-alkylcarbamoyloxy group, N-arylcarbamoyloxy group, N, N-dialkylcarbamoyloxy Group, N, N-diarylcarbamoyloxy group, N-alkyl-N-arylcarbamo Iroxy group, alkylsulfoxy group, arylsulfoxy group, acylthio group, acylamino group, N-alkylacylamino group, N-arylacylamino group, ureido group, N'-alkylureido group, N ', N'-dialkyl Ureido group, N'-arylureido group, N ', N'-diarylureido group, N'-alkyl-N'-arylureido group, N-alkylureido group, N-arylureido group, N'-alkyl-N -Alkylureido group, N'-alkyl-N-arylureido group, N ', N'-dialkyl-N-alkylureido group, N', N'-dialkyl-N-arylureido group, N'-aryl-N -Alkylureido group, N'-aryl-N-arylureido group, N ', N'-diaryl-N-alkylureido N ′, N′-diaryl-N-arylureido group, N′-alkyl-N′-aryl-N-alkylureido group, N′-alkyl-N′-aryl-N-arylureido group, alkoxycarbonylamino Group, aryloxycarbonylamino group, N-alkyl-N-alkoxycarbonylamino group, N-alkyl-N-aryloxycarbonylamino group, N-aryl-N-alkoxycarbonylamino group, N-aryl-N-aryloxy Carbonylamino group, formyl group, acyl group, carboxyl group, alkoxycarbonyl group, aryloxycarbonyl group, carbamoyl group, N-alkylcarbamoyl group, N, N-dialkylcarbamoyl group, N-arylcarbamoyl group, N, N-diaryl Carbamoyl group, N-alkyl-N Arylcarbamoyl group, an alkylsulfinyl group, an arylsulfinyl group, an alkylsulfonyl group, an arylsulfonyl group, a sulfo group (-SO 3 _H) and its conjugated base group (hereinafter referred to as sulfonato group), alkoxy sulfonyl group, aryloxy sulfonyl group Sulfinamoyl group, N-alkylsulfinamoyl group, N, N-dialkylsulfinamoyl group, N-arylsulfinamoyl group, N, N-diarylsulfinamoyl group, N-alkyl-N-arylsulfinamoyl Group, sulfamoyl group, N-alkylsulfamoyl group, N, N-dialkylsulfamoyl group, N-arylsulfamoyl group, N, N-diarylsulfamoyl group, N-alkyl-N-arylsulfa Moyl group, phosphono group (—PO ₃ H ₂ ) And conjugated base groups thereof (hereinafter referred to as phosphonate groups), dialkyl phosphono groups (—PO ₃ (alkyl) ₂ ), diaryl phosphono groups (—PO ₃ (aryl) ₂ ), alkylaryl phosphono groups (— PO ₃ (alkyl) (aryl)), monoalkyl phosphono group _(-PO 3 H (alkyl)) and its conjugated base group (hereinafter referred to as alkyl phosphonophenyl group), monoaryl phosphono group _(-PO 3 H (Aryl)) and its conjugate base group (hereinafter referred to as arylphosphonate group), phosphonooxy group (—OPO ₃ H ₂ ) and its conjugate base group (hereinafter referred to as phosphonateoxy group), dialkylphosphono oxy group _{(-OPO 3 (alkyl) 2)} , diaryl phosphonooxy group _(-OPO 3 _{(aryl) 2)} Alkylaryl phosphonooxy group _(-OPO 3 (alkyl) (aryl)), monoalkyl phosphonooxy group _(-OPO 3 H (alkyl)) and its conjugated base group (hereinafter referred to as alkyl phosphonophenyl group), And monoarylphosphonooxy group (—OPO ³ H (aryl)) and its conjugate base group (hereinafter referred to as arylphosphonateoxy group), cyano group, nitro group, aryl group, alkenyl group, alkynyl group and the like. .

Specific examples of the alkyl group in these substituents include the aforementioned alkyl groups, and specific examples of the aryl group include a phenyl group, a biphenyl group, a naphthyl group, a tolyl group, a xylyl group, a mesityl group, a cumenyl group, Chlorophenyl group, bromophenyl group, chloromethylphenyl group, hydroxyphenyl group, methoxyphenyl group, ethoxyphenyl group, phenoxyphenyl group, acetoxyphenyl group, benzoyloxyphenyl group, methylthiophenyl group, phenylthiophenyl group, methylaminophenyl Group, dimethylaminophenyl group, acetylaminophenyl group, carboxyphenyl group, methoxycarbonylphenyl group, ethoxyphenylcarbonyl group, phenoxycarbonylphenyl group, N-phenylcarbamoylphenyl group, phenyl group, Anofeniru group, sulfophenyl group, sulfonatophenyl group, phosphonophenyl phenyl group, and a phosphonophenyl phenyl group. Examples of the alkenyl group include vinyl group, 1-propenyl group, 1-butenyl group, cinnamyl group, 2-chloro-1-ethenyl group and the like. Examples of alkynyl group include ethynyl group, 1- A propynyl group, a 1-butynyl group, a trimethylsilylethynyl group, etc. are mentioned. Examples of R ₁₃ in the acyl group (R ₁₃ CO—) include hydrogen and the above alkyl group, cycloalkyl group, and aryl group.

  Among these substituents, more preferred are a halogen atom (—F, —Br, —Cl, —I), alkoxy group, aryloxy group, alkylthio group, arylthio group, N-alkylamino group, N, N -Dialkylamino group, acyloxy group, N-alkylcarbamoyloxy group, N-arylcarbamoyloxy group, acylamino group, formyl group, acyl group, carboxyl group, alkoxycarbonyl group, aryloxycarbonyl group, carbamoyl group, N-alkylcarbamoyl group Group, N, N-dialkylcarbamoyl group, N-arylcarbamoyl group, N-alkyl-N-arylcarbamoyl group, sulfo group, sulfonate group, sulfamoyl group, N-alkylsulfamoyl group, N, N-dialkylsulfa group Moyl group, N-aryl sulf Moyl group, N-alkyl-N-arylsulfamoyl group, phosphono group, phosphonate group, dialkyl phosphono group, diaryl phosphono group, monoalkyl phosphono group, alkyl phosphonate group, monoaryl phosphono group, aryl phosphine group Examples include an onato group, a phosphonooxy group, a phosphonateoxy group, an aryl group, and an alkenyl group.

  On the other hand, examples of the alkylene group in the substituted alkyl group include a divalent organic residue except for any one of the hydrogen atoms on the alkyl group having 1 to 20 carbon atoms, preferably A linear alkylene group having 1 to 12 carbon atoms, a branched chain having 3 to 12 carbon atoms, and a cyclic alkylene group having 5 to 10 carbon atoms can be exemplified. Preferable specific examples of the substituted alkyl group obtained by combining the substituent and the alkylene group include chloromethyl group, bromomethyl group, 2-chloroethyl group, trifluoromethyl group, methoxymethyl group, methoxyethoxyethyl group, allyl group. Oxymethyl group, phenoxymethyl group, methylthiomethyl group, tolylthiomethyl group, ethylaminoethyl group, diethylaminopropyl group, morpholinopropyl group, acetyloxymethyl group, benzoyloxymethyl group, N-cyclohexylcarbamoyloxyethyl group, N- Phenylcarbamoyloxyethyl group, acetylaminoethyl group, N-methylbenzoylaminopropyl group, 2-oxoethyl group, 2-oxopropyl group, carboxypropyl group, methoxycarbonylethyl group, allyloxy Rubonylbutyl group, chlorophenoxycarbonylmethyl group, carbamoylmethyl group, N-methylcarbamoylethyl group, N, N-dipropylcarbamoylmethyl group, N- (methoxyphenyl) carbamoylethyl group, N-methyl-N- (sulfophenyl) ) Carbamoylmethyl group, sulfobutyl group, sulfonatobutyl group, sulfamoylbutyl group, N-ethylsulfamoylmethyl group, N, N-dipropylsulfamoylpropyl group, N-tolylsulfamoylpropyl group, N-methyl- N- (phosphonophenyl) sulfamoyloctyl group, phosphonobutyl group, phosphonatohexyl group, diethylphosphonobutyl group, diphenylphosphonopropyl group, methylphosphonobutyl group, methylphosphonatobutyl group, tolylphosphono F Sil group, tolylphosphonatohexyl group, phosphonooxypropyl group, phosphonatooxybutyl group, benzyl group, phenethyl group, α-methylbenzyl group, 1-methyl-1-phenylethyl group, p-methylbenzyl group, cinnamyl Group, allyl group, 1-propenylmethyl group, 2-butenyl group, 2-methylallyl group, 2-methylpropenylmethyl group, 2-propynyl group, 2-butynyl group, 3-butynyl group and the like.

When R ₁₂ represents an aryl group, examples of the aryl group include those in which 1 to 3 benzene rings form a condensed ring, and those in which a benzene ring and a 5-membered unsaturated ring form a condensed ring. Specific examples include a phenyl group, a naphthyl group, an anthryl group, a phenanthryl group, an indenyl group, an acenaphthenyl group, a fluorenyl group, and the like. Among these, a phenyl group and a naphthyl group are more preferable. The aryl group includes a heterocyclic (hetero) aryl group in addition to the carbocyclic aryl group. Examples of the heterocyclic aryl group include those having 3 to 20 carbon atoms and 1 to 5 hetero atoms such as a pyridyl group, a furyl group, and other quinolyl groups condensed with a benzene ring, a benzofuryl group, a thioxanthone group, and a carbazole group. Used.

When R ₁₂ represents a substituted aryl group, as the substituted aryl group, those having a monovalent non-metallic atomic group excluding hydrogen as a substituent on the ring-forming carbon atom of the aforementioned aryl group are used. Examples of preferable substituents include those shown as the substituents in the aforementioned alkyl group and cycloalkyl group.

  Preferred examples of such a substituted aryl group include biphenyl group, tolyl group, xylyl group, mesityl group, cumenyl group, chlorophenyl group, bromophenyl group, fluorophenyl group, chloromethylphenyl group, trifluoromethylphenyl group. Hydroxyphenyl group, methoxyphenyl group, methoxyethoxyphenyl group, allyloxyphenyl group, phenoxyphenyl group, methylthiophenyl group, tolylthiophenyl group, ethylaminophenyl group, diethylaminophenyl group, morpholinophenyl group, acetyloxyphenyl group, Benzoyloxyphenyl group, N-cyclohexylcarbamoyloxyphenyl group, N-phenylcarbamoyloxyphenyl group, acetylaminophenyl group, N-methylbenzoylaminophenyl group, carbo Cyphenyl group, methoxycarbonylphenyl group, allyloxycarbonylphenyl group, chlorophenoxycarbonylphenyl group, carbamoylphenyl group, N-methylcarbamoylphenyl group, N, N-dipropylcarbamoylphenyl group, N- (methoxyphenyl) carbamoylphenyl group N-methyl-N- (sulfophenyl) carbamoylphenyl group, sulfophenyl group, sulfonatophenyl group, sulfamoylphenyl group, N-ethylsulfamoylphenyl group, N, N-dipropylsulfamoylphenyl group, N-tolylsulfamoylphenyl group, N-methyl-N- (phosphonophenyl) sulfamoylphenyl group, phosphonophenyl group, phosphonatophenyl group, diethylphosphonophenyl group, diphenylphosphono Enyl group, methylphosphonophenyl group, methylphosphonatophenyl group, tolylphosphonophenyl group, tolylphosphonatophenyl group, allyl group, 1-propenylmethyl group, 2-butenyl group, 2-methylallylphenyl group, 2- Examples thereof include a methylpropenylphenyl group, a 2-propynylphenyl group, a 2-butynylphenyl group, and a 3-butynylphenyl group.

When R ₁₂ represents an alkenyl group, a substituted alkenyl group [—C (R ₁₄ ) ═C (R ₁₅ ) (R ₁₆ )], an alkynyl group, or a substituted alkynyl group [—C≡C (R ₁₇ )] As R _{14 to} R ₁₇ , a monovalent nonmetallic atomic group can be used. Preferable examples of R _{14 to} R ₁₇ include a hydrogen atom, a halogen atom, an alkyl group, a substituted alkyl group, an aryl group, and a substituted aryl group. Specific examples thereof include those shown as the above examples. More preferable substituents for R _{14 to} R ₁₇ include a hydrogen atom, a halogen atom, and a linear, branched, or cyclic alkyl group having 1 to 10 carbon atoms. Specific examples of the alkenyl group, substituted alkenyl group, alkynyl group and substituted alkynyl group include vinyl group, 1-butenyl group, 1-pentenyl group, 1-hexenyl group, 1-octenyl group, 1-methyl-1-propenyl group. 2-methyl-1-propenyl group, 2-methyl-1-butenyl group, 2-phenyl-1-ethenyl group, 2-chloro-1-ethenyl group, ethynyl group, propynyl group, phenylethyl group, etc. Can do.

When R ₁₂ represents a cyclic imide group, as the cyclic imide, those having 4 to 20 carbon atoms such as succinic acid imide, phthalic acid imide, cyclohexane dicarboxylic acid imide, norbornene dicarboxylic acid imide can be used.
Specific examples of the compounds represented by the general formulas (1) to (6) include, for example, compounds exemplified after [0215] of JP-A-2008-209889.

  The content of the acid proliferating agent in the actinic ray-sensitive or radiation-sensitive resin composition is preferably 0 to 30% by mass, more preferably based on the total solid content of the actinic ray-sensitive or radiation-sensitive resin composition. Is 0.1 to 30% by mass, more preferably 0.5 to 20% by mass.

[10] Other components In addition to the components described above, the composition of the present invention includes a carboxylic acid onium salt, a dissolution inhibiting compound having a molecular weight of 3000 or less, a dye, and the like described in Proceeding of SPIE, 2724, 355 (1996). A plasticizer, a photosensitizer, a light absorber and the like can be appropriately contained.

[11] Pattern Forming Method The composition of the present invention is used by dissolving the above-described components in a solvent, filtering the solution, and coating the support. The filter is preferably made of polytetrafluoroethylene, polyethylene or nylon having a pore size of 0.1 microns or less, more preferably 0.05 microns or less, and still more preferably 0.03 microns or less.
The concentration of the total solid content in the composition of the present invention is generally 2 to 10% by mass, preferably 3 to 5% by mass.

The composition is applied by a suitable application method, such as a spinner, onto a substrate (eg, silicon / silicon dioxide coating) as used in the manufacture of integrated circuit devices. Thereafter, it is dried to form a photosensitive film.
The film is irradiated with actinic rays or radiation through a predetermined mask, preferably baked (heated), developed and rinsed. Thereby, a good pattern can be obtained. Note that in electron beam irradiation, drawing (direct drawing) without using a mask is common.

Although it does not specifically limit as actinic light or a radiation, For example, they are a KrF excimer laser, ArF excimer laser, EUV light, an electron beam, etc., ArF excimer laser, EUV light, and an electron beam are preferable.

As the alkali developer in the development step, a quaternary ammonium salt typified by tetramethylammonium hydroxide is usually used, but other alkalis such as inorganic alkalis, primary to tertiary amines, alcohol amines and cyclic amines are also used. An aqueous solution can also be used.
Furthermore, an appropriate amount of alcohol or surfactant may be added to the alkaline developer.
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.
As the rinsing liquid, pure water is preferable, and an appropriate amount of a surfactant can be added and used.

Before forming the photosensitive 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 DUV30 series, DUV-40 series manufactured by Brewer Science, AR-2, AR-3, AR-5 manufactured by Shipley, etc. may be used. it can.

  The film comprising the actinic ray-sensitive or radiation-sensitive resin composition of the present invention is filled with a liquid (immersion medium) having a higher refractive index than air between the film and the lens when irradiated with actinic rays or radiation. Exposure (immersion exposure) may be performed. Thereby, resolution can be improved. As the immersion medium to be used, any liquid can be used as long as it has a higher refractive index than air, but pure water is preferred.

The immersion liquid used for the immersion exposure will be described below.
The immersion liquid is transparent to the exposure wavelength and has a refractive index so as to minimize distortion of the optical image projected onto the film formed from the actinic ray-sensitive or radiation-sensitive resin composition. A liquid having a temperature coefficient as small as possible is preferable. In particular, in the case where the exposure light source is an ArF excimer laser (wavelength: 193 nm), in addition to the above-mentioned viewpoints, water is easy to obtain and easy to handle. Is preferably used.
Further, a medium having a refractive index of 1.5 or more can be used in that the refractive index can be further improved. This medium may be an aqueous solution or an organic solvent.

  When water is used as the immersion liquid, the film formed from the actinic ray-sensitive or radiation-sensitive resin composition on the wafer is not dissolved in order to reduce the surface tension of the water and increase the surface activity. In addition, an additive (liquid) that can ignore the influence on the optical coating on the lower surface of the lens element may be added in a small proportion. The additive is preferably an aliphatic alcohol having a refractive index substantially equal to that of water, and specifically includes methyl alcohol, ethyl alcohol, isopropyl alcohol and the like. By adding an alcohol having a refractive index substantially equal to that of water, even if the alcohol component in water evaporates and the content concentration changes, an advantage that the change in the refractive index of the entire liquid can be made extremely small can be obtained. On the other hand, when an opaque substance or impurities whose refractive index is significantly different from that of water are mixed with 193 nm light, the optical image projected on the film is distorted. Therefore, distilled water is preferable as the water to be used. Further, pure water filtered through an ion exchange filter or the like may be used.

The electrical resistance of water is desirably 18.3 MQcm or more, the TOC (organic substance concentration) is desirably 20 ppb or less, and deaeration treatment is desirably performed.
Moreover, it is possible to improve lithography performance by increasing the refractive index of the immersion liquid. From such a viewpoint, an additive that increases the refractive index may be added to water, or heavy water (D ₂ O) may be used instead of water.

When exposing the film | membrane which consists of a composition of this invention through an immersion medium, hydrophobic resin can be added as needed. Thereby, when the hydrophobic resin is unevenly distributed on the surface layer of the membrane and the immersion medium is water, the receding contact angle of the membrane surface with respect to water when the membrane is formed can be improved, and the immersion water followability can be improved. By adding the hydrophobic resin, the receding contact angle of the surface is improved. The receding contact angle of the film is preferably 60 ° to 90 °, more preferably 70 ° or more. The hydrophobic resin is unevenly distributed at the interface as described above, but unlike the surfactant, it does not necessarily have a hydrophilic group in the molecule and contributes to uniform mixing of polar / nonpolar substances. It is not necessary.
The receding contact angle is a contact angle measured when the contact line at the droplet-substrate interface recedes, and is useful for simulating the ease of movement of the droplet in a dynamic state. It is generally known. In simple terms, it can be defined as the contact angle when the droplet interface recedes when the droplet discharged from the needle tip is deposited on the substrate and then sucked into the needle again. It can be measured by using a contact angle measuring method generally called an expansion / contraction method.
In the immersion exposure process, the immersion head needs to move on the wafer following the movement of the exposure head to scan the wafer at high speed to form the exposure pattern. The contact angle of the immersion liquid to the film formed from the actinic ray-sensitive or radiation-sensitive resin composition is important, and there is a need for the ability to follow the high-speed scanning of the exposure head without remaining droplets. It is done.

An immersion liquid poorly soluble film (hereinafter also referred to as “topcoat”) may be provided between the film of the composition of the present invention and the immersion liquid so that the film does not directly contact the immersion liquid. Good. The functions necessary for the top coat are suitability for application to the upper layer of a film formed from an actinic ray-sensitive or radiation-sensitive resin composition, transparency to radiation, particularly 193 nm, and poor immersion liquid solubility. It is preferable that the top coat is not mixed with the film and can be uniformly applied to the upper layer of the film.
From the viewpoint of 193 nm transparency, the top coat is preferably a polymer that does not contain abundant aromatics. Specifically, the polymer contains a hydrocarbon polymer, an acrylate polymer, polymethacrylic acid, polyacrylic acid, polyvinyl ether, and silicon. Examples thereof include a polymer and a fluorine-containing polymer. The aforementioned hydrophobic resin (HR) is also suitable as a top coat. From the viewpoint of contaminating the optical lens when impurities are eluted from the top coat into the immersion liquid, it is preferable that the residual monomer component of the polymer contained in the top coat is small.

When peeling the top coat, a developer may be used, or a separate release agent may be used. As the release agent, a solvent having low penetration into the film is preferable. In terms of being able to perform the peeling process simultaneously with the film development process, it is preferable that the peeling process can be performed with an alkaline developer. The top coat is preferably acidic from the viewpoint of peeling with an alkali developer, but may be neutral or alkaline from the viewpoint of non-intermixability with the film.
The resolution is improved when there is no difference in refractive index between the top coat and the immersion liquid. In the case of using water as the immersion liquid in an ArF excimer laser (wavelength: 193 nm), the top coat for ArF immersion exposure is preferably close to the refractive index of the immersion liquid. From the viewpoint of making the refractive index close to the immersion liquid, it is preferable to have fluorine atoms in the topcoat. A thin film is more preferable from the viewpoint of transparency and refractive index.

  The topcoat is preferably not mixed with the membrane and further not mixed with the immersion liquid. From this point of view, when the immersion liquid is water, the solvent used for the top coat is preferably a water-insoluble medium that is hardly soluble in the solvent used for the composition of the present invention. Further, when the immersion liquid is an organic solvent, the topcoat may be water-soluble or water-insoluble.

EXAMPLES Hereinafter, although an Example demonstrates this invention still in detail, the content of this invention is not limited by this.

[Synthesis Example of Resin (D)]
Under a nitrogen stream, 8 g of propylene glycol methyl ether acetate and 2 g of propylene glycol methyl ether were placed in a three-necked flask and heated to 85 ° C. To this, 5.50 g of monomer A, 0.95 g of monomer B, 2.19 g of monomer C, 1.57 g of monomer D, polymerization initiator (dimethyl-2,2′-azobis (2-methylpropionate (V-601): Wako Pure Chemical) (Manufactured) A solution prepared by dissolving 0.553 g in 16 g of propylene glycol methyl ether acetate and 4 g of propylene glycol methyl ether was added dropwise over 6 hours, and further reacted for 2 hours at 85 ° C. After allowing the reaction liquid to cool. The mixture was dropped into a heptane / ethyl acetate mixed solution (240 g / 160 g) over 20 minutes, and the precipitated powder was collected by filtration and dried to obtain 8.0 g of the desired resin (used in Example 1). The weight average molecular weight was 8500 in terms of standard polystyrene, and the dispersity (Mw / Mn) was 1.55.

  Other resins such as Resins A to C and Resins E to I were synthesized using the same method.

  For the compound (PBG), Journal of Medicinal Chemistry, 42, 4016-4020 (1999), Journal of American Chemical Society, 113, 4303-4313 (1991), Chem. Pharm. Bull., 45, 715-718 (1997) ).

<Synthesis of hydrophobic resin K-216>
(Synthesis of raw material monomer (monomer 4 below))
The following compound (1) was synthesized by the method described in International Publication No. 07/037213 pamphlet.
150.00 g of water was added to 35.00 g of compound (1), and 27.30 g of NaOH was further added. The mixture was stirred for 9 hours under heating and reflux conditions. Hydrochloric acid was added to make it acidic, and the mixture was extracted with ethyl acetate. The organic layers were combined and concentrated to obtain 36.90 g of compound (2) (yield 93%).
¹ H-NMR (400 MHz in (CD ₃ ) ₂ CO): σ (ppm) = 1.56-1.59 (1H), 1.68-1.72 (1H), 2.13-2.15 (1H), 2.13-2.47 (2H), 3.49 -3.51 (1H), 3.68 (1H), 4.45-4.46 (1H)
200 ml of CHCl ₃ was added to 20.00 g of compound (2), 50.90 g of 1,1,1,3,3,3-hexafluoroisopropyl alcohol and 30.00 g of 4-dimethylaminopyridine were further added and stirred. To the solution, 22.00 g of 1-ethyl-3- (3-dimethylaminopropyl) carbodiimide hydrochloride was added and stirred for 3 hours. The reaction solution was added to 500 ml of 1N HCl to stop the reaction. Add 1N HCl to the organic layer
And then with water, and the organic layer was concentrated to obtain 30.00 g of compound (3) (
Yield 85%).
¹ H-NMR (400 MHz in (CD ₃ ) ₂ CO): σ (ppm) = 1.62 (1H), 1.91-1.95 (1H), 2.21-2.24 (1H),
2.45-2.53 (2H), 3.61-3.63 (1H), 3.76 (1H), 4.32-4.58 (1H), 6.46-6.53 (1H)
300.00 g of toluene was added to 15.00 g of compound (3), 3.70 g of methacrylic acid and 4.20 g of p-toluenesulfonic acid monohydrate were added, and the mixture was refluxed for 15 hours while removing generated water by azeotropic distillation. The reaction solution was concentrated, and the concentrate was purified by column chromatography to obtain 11.70 g of compound (4) (yield 65%).
¹ H-NMR (400 MHz in (CD ₃ ) ₂ CO): σ (ppm) = 1.76-1.79 (1H), 1.93 (3H), 2.16-2.22 (2H),
2.57-2.61 (1H), 2.76-2.81 (1H), 3.73-3.74 (1H), 4.73 (1H), 4.84-4.86 (1H), 5.69-5.70 (1H), 6.12 (1H), 6.50-6.56 (1H )

(Synthesis of hydrophobic resin K-216)
Under a nitrogen stream, 7.7 g of MEK was placed in a three-necked flask and heated to 75 ° C. The monomer 4 (20.5 g), t-butylstyrene (2.5 g), polymerization initiator V-601 (manufactured by Wako Pure Chemical Industries, Ltd.) 0.345 g, dodecanethiol 0.304 g were added to MEK 30.9 g. The solution dissolved in was added dropwise over 6 hours. After completion of the dropwise addition, the reaction was further carried out at 75 ° C. for 2 hours. The reaction solution was allowed to cool and then added dropwise to a mixed solution of 400 g of heptane / 100 g of ethyl acetate, and the precipitated powder was collected by filtration and dried to obtain Resin (K-216) (19.5 g).
The weight average molecular weight of the obtained resin was 7500 in terms of standard polystyrene, and the dispersity (Mw / Mn) was 1.6.
Other hydrophobic resins were synthesized in the same manner.

<Preparation of actinic ray-sensitive or radiation-sensitive resin composition>
The components shown in Table 1 below are dissolved in a solvent, and a solution having a solid content concentration of 4% by mass is prepared for each of the components. A product was prepared. The actinic ray-sensitive or radiation-sensitive resin composition was evaluated by the following method, and the results are shown in Table 1.
About each component in Table 1, the ratio at the time of using multiple is a mass ratio.
In Table 1, when the actinic ray-sensitive or radiation-sensitive resin composition contains a hydrophobic resin, the addition form is marked as “addition”. When the actinic ray-sensitive or radiation-sensitive resin composition does not contain a hydrophobic resin (HR) and a topcoat protective film containing a hydrophobic resin is formed on the upper layer after forming a film, Labeled “Topcoat”.

<Evaluation>
(Exposure condition 1: ArF immersion exposure)
Examples 14 to 40, Comparative Example 1 and Reference Example 1
An organic antireflection film ARC29SR (manufactured by Nissan Chemical Industries, Ltd.) was applied on a silicon wafer, and baked at 205 ° C. for 60 seconds to form an antireflection film having a thickness of 98 nm. The actinic ray-sensitive or radiation-sensitive resin composition prepared thereon was applied and baked at 130 ° C. for 60 seconds to form a film having a thickness of 120 nm. In the case of using a top coat, a 3% by mass solution in which a hydrophobic resin is further dissolved in decane / octanol (mass ratio 9/1) is applied on the film obtained above and baked at 85 ° C. for 60 seconds. A top coat layer having a thickness of 50 nm was formed. An ArF excimer laser immersion scanner (XTML1700i, NA1.20, C-Quad, outer sigma 0.981, inner sigma 0.895, XY deflection manufactured by ASML) was used, and a 6% halftone mask with 45 nm 1: 1 line and space pattern. Exposed through. Ultra pure water was used as the immersion liquid. After heating at 130 ° C. for 60 seconds, the film was developed with an aqueous tetramethylammonium hydroxide solution (2.38 mass%) for 30 seconds, rinsed with pure water, and then spin-dried to form a pattern.

(Exposure condition 2: ArF dry exposure)
Examples 1 to 13 and Comparative Example 2
An organic antireflection film ARC29A (Nissan Chemical Co., Ltd.) was applied on a silicon wafer and baked at 205 ° C. for 60 seconds to form an antireflection film having a thickness of 78 nm. The actinic ray-sensitive or radiation-sensitive resin composition prepared thereon was applied and baked at 130 ° C. for 60 seconds to form a film having a thickness of 120 nm. This was exposed using an ArF excimer laser scanner (PAS5500 / 1100, manufactured by ASML, NA0.75, Dipole, σo / σi = 0.89 / 0.65) through a 6% halftone mask with a 75 nm 1: 1 line and space pattern. After heating at 130 ° C. for 60 seconds, the film was developed with an aqueous tetramethylammonium hydroxide solution (2.38 mass%) for 30 seconds, rinsed with pure water, and then spin-dried to obtain a pattern.

(DOF evaluation)
In exposure condition 1, the depth of focus at which the line width of 45 nm ± 10% was reproduced was measured as DOF (μm). In the case of exposure condition 2, the depth of focus at which the line width of 75 nm ± 10% was reproduced was measured as DOF (μm). A larger value is desirable because the tolerance for defocus is large.

(Pattern shape evaluation)
About the pattern (dry: 75 nm, immersion: 45 nm) created by the above-mentioned evaluation, the cross-sectional shape of the pattern was observed with the scanning microscope (S9380 by Hitachi, Ltd.). A rectangular pattern shape indicates better performance.

(Resolution)
With respect to the pattern (dry: 75 nm, immersion: 45 nm) created in the above evaluation, the presence or absence of pattern resolution was observed with a scanning microscope (S9380, manufactured by Hitachi, Ltd.). In the case of dry exposure, the case where the pattern shape of 75 nm is resolved, and in the case of immersion exposure, indicates that the performance is good.

(Particle evaluation)
For the actinic ray-sensitive or radiation-sensitive resin composition prepared above, the number of particles in the solution immediately after preparation (particle initial value) and the number of particles in the solution after standing at 4 ° C. for 1 week (particles after aging) Number) was counted with a particle counter manufactured by Rion.
The number of particles increased calculated by (number of particles after time) − (initial particle value) was calculated. Here, particles having a particle diameter of 0.25 μm or more contained in 1 mL of the solution were counted. Since an increase in particles indicates a deterioration in storage stability, a smaller number indicates a better performance.

  The abbreviations in Table 1 represent those shown in the above specific examples or the following.

  [Compound (PBG)]

  [Acid generator]

  [Resin (B)]

[Basic compounds]
TPSA: triphenylsulfonium acetate DIA: 2,6-diisopropylaniline TEA: triethanolamine DBA: N, N-dibutylaniline PBI: 2-phenylbenzimidazole TMEA: tris (methoxyethoxyethyl) amine PEA: N-phenyldiethanolamine

[Surfactant]
W-1: MegaFuck F176 (Dainippon Ink Chemical Co., Ltd.) (Fluorine)
W-2: Megafuck R08 (Dainippon Ink Chemical Co., Ltd.) (fluorine and silicon)
W-3: Polysiloxane polymer KP-341 (manufactured by Shin-Etsu Chemical Co., Ltd.) (silicon-based)
W-4: Troisol S-366 (manufactured by Troy Chemical Co., Ltd.)

〔solvent〕
S1: Propylene glycol monomethyl ether acetate (PGMEA; 1-methoxy-2-acetoxypropane)
S2: 2-Heptanone S3: Cyclohexanone S4: γ-Butyrolactone S5: Propylene glycol monomethyl ether (PGME; 1-methoxy-2-propanol)
S6: Ethyl lactate S7: Propylene carbonate

  As shown in Table 1, it was confirmed that the compositions of the present invention were excellent in DOF performance and storage stability as well as the pattern shape and resolution as compared with the compositions shown in the comparative examples. .

Claims (9)

(A) a compound that generates a base upon irradiation with actinic rays or radiation,
(B) It has a repeating unit having a lactone structure, and contains a resin whose solubility in an alkaline developer is increased by the action of an acid, and (C) a compound that generates an acid upon irradiation with actinic rays or radiation. An actinic ray-sensitive or radiation-sensitive resin composition. 2. The compound (A) that generates a base upon irradiation with actinic rays or radiation has at least one partial structure represented by any one of the following general formulas (A1) to (A3). The actinic ray-sensitive or radiation-sensitive resin composition described in 1.

In the general formulas (A1) to (A3),
R _{1 to} R ₄ each independently represents a hydrogen atom, an alkyl group or a cycloalkyl group. R _{1 to} R ₄ may be bonded to each other to form a ring.
A ⁺ represents an ammonium cation.
X ⁻ represents a counter anion.
R represents a hydrogen atom, an alkyl group or a cycloalkyl group. The activity-sensitive compound according to claim 1 or 2, wherein the compound (A) that generates a base upon irradiation with actinic rays or radiation is represented by any one of the following general formulas (1) to (6). A light-sensitive or radiation-sensitive resin composition.

In general formula (1),
A ⁺ represents an ammonium cation.
X ⁻ represents a counter anion.
R represents a hydrogen atom, an alkyl group or a cycloalkyl group.
Ar represents an aryl group or a heteroaryl group.
In the general formulas (2) to (6),
R _{1 to} R ₄ each independently represents a hydrogen atom, an alkyl group or a cycloalkyl group. R _{1 to} R ₄ may be bonded to each other to form a ring.
Ar represents an aryl group or a heteroaryl group.
n represents an integer of 0 to 5. The actinic ray-sensitive or radiation-sensitive resin composition according to claim 3, wherein the general formula (6) is represented by the following general formula (6-1).

In general formula (6-1),
R _{1 to} R ₄ each independently represents a hydrogen atom, an alkyl group or a cycloalkyl group. R _{1 to} R ₄ may be bonded to each other to form a ring.
Z represents an atomic group forming an aryl group or a heteroaryl group.
n ₁ represents an integer of 0-4. The feeling according to any one of claims 1 to 4, wherein the repeating unit having a lactone structure contained in the resin (B) is a repeating unit having a lactone structure represented by the following general formula (III). Actinic ray-sensitive or radiation-sensitive resin composition.

In general formula (III),
A represents an ester bond (a group represented by —COO—) or an amide bond (a group represented by —CONH—).
R ₀ independently represents an alkylene group, a cycloalkylene group or a divalent linking group obtained by combining them when there are a plurality of R ₀ .
When there are a plurality of Zs, each independently represents an ether bond, an ester bond, an amide bond, or a urethane bond.

Or urea bond

Represents. Here, R represents a hydrogen atom, an alkyl group, a cycloalkyl group, or an aryl group.
R ₈ represents a monovalent organic group having a lactone structure.
n is the repeating number of the structure represented by —R ₀ —Z—, and represents an integer of 1 to 5.
R ₇ represents a hydrogen atom, a halogen atom or an alkyl group.   Furthermore, (D) hydrophobic resin is contained, The actinic-ray-sensitive or radiation-sensitive resin composition in any one of Claims 1-5 characterized by the above-mentioned.   The actinic ray-sensitive or radiation-sensitive resin composition according to claim 1, further comprising (E) a basic compound.   A pattern forming method comprising the steps of: forming a film with the actinic ray-sensitive or radiation-sensitive resin composition according to claim 1; and exposing and developing the film.   A pattern forming method comprising a step of forming a film with the actinic ray-sensitive or radiation-sensitive resin composition according to claim 1, and subjecting the film to immersion exposure and development.