JP2011048289A - Actinic ray- or radiation-sensitive resin composition and pattern forming method using the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an actinic ray- or radiation-sensitive resin composition which improves LWR, development defects and DOF and is adapted to a liquid immersion process with a line width of ≤45 nm, and a pattern forming method using the same. <P>SOLUTION: The actinic ray- or radiation-sensitive resin composition includes: (A) a resin which has a repeating unit containing a structure represented by general formula (1) and exhibits an increased solubility in an alkali developer by the action of an acid; (B) a compound (PA) which has a proton-accepting functional group, decomposes upon irradiation with actinic rays or radiation, and generates a compound with proton-accepting ability reduced or lost or with acidity changed from proton-accepting ability; and (C) a compound which generates an acid upon irradiation with actinic rays or radiation, wherein L represents a substituent having a lactone structure; when a plurality of R<SB>0</SB>s exist, the R<SB>0</SB>s each independently represent alkylene which may have a substituent, cyclic alkylene which may have a substituent or a combination of those; when a plurality of Zs exist, the Zs each independently represent an ether bond, an ester bond, an amide bond, a urethane bond or a urea bond; and n represents an integer of 1-5 indicating the number of repetitions. <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 IC, circuit boards such as liquid crystals and thermal heads, and other photofabrication processes, and the composition. The present invention relates to a pattern forming method. More specifically, the present invention relates to an actinic ray-sensitive or radiation-sensitive resin composition that is suitable when using far ultraviolet rays or electron beams of 250 nm or less as an irradiation source, and a pattern forming method using the composition. is there.

  In the present invention, “active light” or “radiation” means, for example, an emission line spectrum of a mercury lamp, far ultraviolet rays represented by excimer laser, extreme ultraviolet rays, X-rays, electron beams, and the like. In the present invention, light means actinic rays or radiation.

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), which has a small absorption in the 248 nm region. 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 resin, photoacid generator, additive, solvent and the like to be used, and the line width is 65 nm or less. In the case of forming such a fine pattern, improvement of line edge roughness performance and resolution of the line pattern has been demanded.

It has been found that the resolving power and the line edge roughness performance are improved by including a repeating unit having a specific lactone structure in the resin having the alicyclic hydrocarbon structure. For example, Patent Documents 1 and 2 describe resist compositions using a resin containing a specific lactone repeating unit in which a spacer is introduced between a polymer main chain and a lactone skeleton. In addition, Patent Document 3 uses a resist composition using a resin containing a specific lactone repeating unit having a similar spacer, thereby improving the density dependency and exposure margin in addition to resolution and line edge roughness. It is described that it is possible.
Patent Documents 4 to 6 disclose compositions characterized by a resin obtained by copolymerizing two or more lactone monomers.

  However, in the latest generation with a line width of 45 nm or less to which the immersion process is applied, the above prior art is not always sufficient, and in addition to line width roughness (LWR), depth of focus (Depth of Focus) : Further improvement of DOF) is demanded.

JP 2005-352466 A JP 2004-210917 A JP 2008-31298 A JP 2003-5375 A JP 2003-255537 A JP 2003-252933 A

  In view of the above problems in the background art, the present invention has an improved actinic ray-sensitive or radiation-sensitive resin composition that has improved LWR, development defects, and DOF, and is suitable for an immersion process with a line width of 45 nm or less, and It is an object to provide a pattern forming method used.

As a result of intensive studies to solve the above problems, the present inventors have completed the present invention shown below.
(1) (A) a resin having a repeating unit including a structure represented by the following general formula (1), and having increased solubility in an alkali developer by the action of an acid;
(B) A compound having a proton acceptor functional group and generating a compound that is decomposed by irradiation with actinic rays or radiation to decrease, disappear, or change the proton acceptor property to acidic ( PA) and (C) an actinic ray-sensitive or radiation-sensitive resin composition containing a compound that generates an acid upon irradiation with an actinic ray or radiation.

In general formula (1),
L represents a substituent having a lactone structure.
When there are a plurality of R _{0 s,} each independently represents an alkylene group that may have a substituent, a cyclic alkylene group that may have a substituent, or a combination thereof.
Z is independently an ether bond, an ester bond, an amide bond, a urethane bond or a urea bond when there are a plurality of Z.
n represents the number of repetitions and represents an integer of 1 to 5.

(2) The sensation according to (1), wherein the compound generated by decomposition of the compound (PA) upon irradiation with actinic rays or radiation is a compound represented by the following general formula (PA-1) Actinic ray-sensitive or radiation-sensitive resin composition.

In general formula (PA-1),
Q represents -SO ₃ H, -CO ₂ H or _-X 1 NHX ₂ R _f,. Here, R _f represents an alkyl group, a cycloalkyl group or an aryl group, and X ₁ and X ₂ each independently represent —SO ₂ — or —CO—.
A represents a single bond or a divalent linking group.
X represents —SO ₂ — or —CO—.
n represents 0 or 1.
B represents a single bond, an oxygen atom, or -N (Rx) Ry-. Here, Rx represents a hydrogen atom or a monovalent organic group, and Ry represents a single bond or a divalent organic group. Rx may combine with Ry to form a ring, or may combine with R to form a ring.
R represents a monovalent organic group having a proton acceptor functional group.

  (3) The acid dissociation constant (pKa) of the compound generated by decomposition of the compound (PA) upon irradiation with actinic rays or radiation satisfies -1> pKa, (1) or (2) The actinic ray-sensitive or radiation-sensitive resin composition described.

(4) The actinic ray-sensitive property according to any one of (1) to (3), wherein the compound (PA) is represented by any one of the following general formulas (4) to (6): Radiation sensitive resin composition.

In general formulas (4) to (6),
R represents a monovalent organic group having a proton acceptor functional group.
B represents a single bond, an oxygen atom, or -N (Rx) Ry-. Here, Rx represents a hydrogen atom or a monovalent organic group, and Ry represents a single bond or a divalent organic group. Rx may combine with Ry to form a ring, or may combine with R to form a ring.
X represents —SO ₂ — or —CO—.
n represents 0 or 1.
A represents a single bond or a divalent linking group.
X ₁ and X ₂ each independently represents —SO ₂ — or —CO—.
R _f represents an alkyl group, a cycloalkyl group or an aryl group.
C ⁺ represents a counter cation.
(5) The activity unit according to any one of (1) to (4), wherein the repeating unit including the structure represented by the general formula (1) is represented by the following general formula (1-1): A light-sensitive or radiation-sensitive resin composition.

In general formula (1-1),
R represents a hydrogen atom or an alkyl group which may have a substituent.
A represents -COO- or -CONH-.
L, R ₀ , Z, and n have the same meanings as in general formula (1).
(6) The actinic ray-sensitive or sensation according to (5), wherein the repeating unit represented by the general formula (1-1) is a repeating unit represented by the following general formula (1-2): Radiation resin composition.

In General Formula (1-2), R, A, R ₀ , Z, and n have the same meanings as those in General Formula (1-1).
When there are a plurality of R _{1 s} , each independently represents an alkyl group which may have a substituent, a cycloalkyl group which may have a substituent, or an ester group which may have a substituent. Or a cyano group, and when there are a plurality of them, two R _{1 's} may combine to 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.

  (7) A step of applying the actinic ray-sensitive or radiation-sensitive resin composition according to any one of (1) to (6) on a substrate to form a film, and irradiating the film with actinic rays or radiation And a pattern forming method including a step of developing with a developer.

  According to the present invention, LWR, development defects, and DOF are improved, and it is possible to provide an actinic ray-sensitive or radiation-sensitive resin composition and a pattern forming method that can be suitably used for an immersion process with a line width of 45 nm or less.

Hereinafter, the best mode for carrying out the present invention will be described.
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 does not have a substituent and what has 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).

[1] Resin (A) having a repeating unit having a structure represented by the following general formula (1) and having increased solubility in an alkali developer by the action of an acid
The resin (A) contained in the actinic ray-sensitive or radiation-sensitive resin composition of the present invention has a repeating unit including a structure represented by the following general formula (1).

In general formula (1),
L represents a substituent having a lactone structure.
When there are a plurality of R _{0 s,} each independently represents an alkylene group which may have a substituent, a cyclic alkylene group which may have a substituent, or a combination thereof.
Z is independently an ether bond, an ester bond, an amide bond, a urethane bond or a urea bond when there are a plurality of Z.
n represents the number of repetitions and represents an integer of 1 to 5.

The general formula (1) will be described in more detail.
The group represented by R ₀ is not particularly limited as long as it is a chain alkylene group or a cyclic alkylene group, but a preferable chain alkylene group is preferably a chain alkylene having 1 to 10 carbon atoms, more preferably. It is C1-C5, for example, a methylene group, ethylene group, a propylene group etc. are mentioned. Preferred cyclic alkylene is cyclic alkylene having 4 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.

Z preferably represents an ether bond, an ester bond, an amide bond or a urethane bond, and more preferably represents an ether bond or an ester bond.
n is preferably 1.
As the group represented by L, any group can be used as long as it has a lactone structure, but it is preferably a 5- to 7-membered ring lactone structure, and the bicyclo structure or spiro structure is added to the 5- to 7-membered ring lactone structure. Those in which other ring structures are condensed in a form to form are preferable. 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).

The lactone structure moiety 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 a preferred lactone repeating unit containing the structure represented by the general formula (1), there can be mentioned the repeating unit represented by the following (1-1).

In general formula (1-1),
R represents a hydrogen atom or an alkyl group which may have a substituent.
A represents -COO- or -CONH-.
When there are a plurality of R _{0 s,} each independently represents an alkylene group which may have a substituent, a cyclic alkylene group which may have a substituent, or a combination thereof.
Z is independently an ether bond, an ester bond, an amide bond, a urethane bond or a urea bond when there are a plurality of Z.
L represents a substituent having a lactone structure.
n represents the number of repetitions and represents an integer of 1 to 5.

General formula (1-1) will be described in more detail.
The alkyl group represented by R is preferably an alkyl group having 1 to 4 carbon atoms, more preferably a methyl group or an ethyl group, and most preferably a methyl group. Examples of the substituent that the alkyl group may have include, for example, halogen atoms such as fluorine atom, chlorine atom, bromine atom, mercapto group, hydroxy group, methoxy group, ethoxy group, isopropoxy group, t-butoxy group, and benzyl. Examples include an alkoxy group such as an oxy group, an acyl group such as an acetyl group and a propionyl group, and an acetoxy group.
Preferred ranges for R ₀ , L, Z and n are the same as described above.
More particularly preferred lactone repeating units include repeating units represented by the following general formula (1-2).

In General Formula (1-2), R, A, R ₀ , Z, and n have the same meanings as those in General Formula (1-1).
When there are a plurality of R _{1 s} , each independently represents an alkyl group which may have a substituent or a cycloalkyl group which may have a substituent, an ester group which may have a substituent, cyano Represents a group, and when there are a plurality of groups, two R ₁ may be bonded to each other to 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.

The general formula (1-2) will be described in more detail.
The preferable ranges of R, R ₀ , Z, and n are the same as those in General Formula (1-1).

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

When m is 1 or more, at least one R ₁ is preferably at least one at the α-position or β-position of the lactone carbonyl group, and particularly preferably at the α-position.
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, more preferably a methylene group.
Specific examples of the repeating unit having a group having a lactone structure represented by the general formula (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, preferably a hydrogen atom, a methyl group, a hydroxymethyl group or an acetoxymethyl group.

Among these, specific examples of the preferred repeating unit represented by formula (1-1) include the following specific examples.

The repeating unit having a lactone group usually has an optical isomer, but any optical isomer may be used.
In the present invention, the resin (A) may contain other lactone structures in addition to the lactone structure represented by the general formula (1). For example, a structure in which a hydrogen atom of a carboxylic acid group of (meth) acrylic acid is substituted with the above (LC1-1) to (LC1-17) may be included.
In the composition of the present invention, the content of the repeating unit including the structure represented by the general formula (1) is preferably 20 to 60 mol%, more preferably 30 to the total repeating units in the resin (A). ˜50 mol%.
The resin (A) used in the present invention preferably has the following repeating units in addition to the repeating unit having the structure of the general formula (1).
-Repeating unit containing acid-decomposable group 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.
The alkali-soluble group is not particularly limited as long as it is a group that dissociates and becomes an ion in an alkali developer. Preferred alkali-soluble groups include a carboxyl group, a fluorinated alcohol group (preferably hexafluoroisopropanol), and a sulfonic acid. Groups.

A preferable group as the acid-decomposable group is a group obtained by substituting the hydrogen atom of these alkali-soluble groups with a group capable of leaving with an acid.
Examples of the group leaving with an acid include -C (R ₃₆ ) (R ₃₇ ) (R ₃₈ ), -C (R ₃₆ ) (R ₃₇ ) (OR ₃₉ ), -C (R ₀₁ ) (R ₀₂ ). ) (OR ₃₉ ) and the like.
In the formula, R _{36 to} R ₃₉ each independently represents an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, or an alkenyl group. R ₃₆ and R ₃₇ may be bonded to each other to form a ring.

R _{01 and} R ₀₂ each independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group or an alkenyl group.
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 (A) 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 or a group represented by —CH ₂ —R ₉ . R ₉ represents a monovalent organic group, and examples thereof include an alkyl group having 5 or less carbon atoms and an acyl group, preferably an alkyl group having 3 or less carbon atoms, and more preferably a methyl group. Xa ₁ preferably represents a hydrogen atom, a methyl group, a trifluoromethyl group or a hydroxymethyl group.

T represents a single bond or a divalent linking group.
Rx _{1 to} Rx ₃ each independently represents an alkyl group (straight or branched) or a cycloalkyl group (monocyclic or polycyclic).
At least two of Rx _{1 to} Rx ₃ may combine to form a cycloalkyl group (monocyclic or polycyclic).

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.
The alkyl group of Rx _{1 to} Rx ₃ is preferably an alkyl group having 1 to 4 carbon atoms such as a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, or a 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 at least 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, A polycyclic cycloalkyl group such as an adamantyl group is preferred.
It is preferable that 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.

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 units 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 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 resin (A) is a resin having at least one of the repeating unit represented by the general formula (1) and the repeating unit represented by the general formula (2) as the repeating unit represented by the general formula (AI). More preferably.

In formulas (1) and (2),
R ₁ and R ₃ each independently represents a hydrogen atom, a 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.
Each R independently represents an atomic group necessary for forming an alicyclic structure with a carbon atom.
R ₁ preferably represents 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 1 to 10 carbon atoms, still more preferably 1 to 5 carbon atoms, and examples thereof include a methyl group and an ethyl group.

Each R independently represents an atomic group necessary for forming an alicyclic structure 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, more preferably 5 or 6.
R ₃ is preferably a hydrogen atom or a methyl group, 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.
The repeating unit represented by the general formula (2) is preferably a repeating unit represented by the following general formula (2-1).

In formula (2-1),
R < ₃ > -R < ₅ > is synonymous with the thing in General formula (2).
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 containing a polar group include a linear or branched alkyl group or cycloalkyl group having a hydroxyl group, a cyano group, an amino group, an alkylamide group or a sulfonamide group, and preferably a hydroxyl group. It is an alkyl group. More preferably, it is a branched alkyl group having a hydroxyl group.
p represents an integer of 0 to 15. p is preferably 0 to 2, more preferably 0 or 1.

-The repeating unit which has a hydroxyl group or a cyano group It is preferable that resin (A) has a repeating unit which has a hydroxyl group or a cyano group. 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. 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 norbornyl group. Preferred examples of the alicyclic hydrocarbon structure substituted with a hydroxyl group or a cyano group include a monohydroxyadamantyl group, a dihydroxyadamantyl group, a monohydroxydiamantyl group, a dihydroxyadamantyl group, and a norbornyl group substituted with a cyano group.
Examples of the repeating unit having the atomic group include 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 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 remaining is a hydrogen atom. In general formula (VIIa), more preferably, _two of R ₂ c to R ₄ c are hydroxyl groups and the remaining are hydrogen atoms.
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 (A).
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.

-Alkali-soluble unit Resin (A) used for the composition of this invention may have a repeating unit which has 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, 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 (A), 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 .

-Alicyclic hydrocarbon which does not have a polar group It is preferable that the resin (A) of this invention has a repeating unit which has an alicyclic hydrocarbon structure which does not have a polar group, and does not show acid-decomposability. This can reduce the elution of low molecular components from the resist film to the immersion liquid during immersion exposure. An example of such a repeating unit is a repeating unit represented by the general formula (4).

In general formula (4), 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 cyclic structure possessed by R ₅ includes a monocyclic hydrocarbon group and a polycyclic hydrocarbon group. Examples of the monocyclic hydrocarbon group include a cycloalkyl group having 3 to 12 carbon atoms and a cycloalkenyl group having 3 to 12 carbon atoms. A preferable monocyclic hydrocarbon group is a monocyclic hydrocarbon group having 3 to 7 carbon atoms.

  The polycyclic hydrocarbon group includes a ring assembly hydrocarbon group and a bridged cyclic hydrocarbon group. Examples of the bridged cyclic hydrocarbon ring include a bicyclic hydrocarbon ring, a tricyclic hydrocarbon ring, and a tetracyclic hydrocarbon ring. The bridged cyclic hydrocarbon ring also includes a condensed cyclic hydrocarbon ring (for example, a condensed ring in which a plurality of 5- to 8-membered cycloalkane rings are condensed). Preferred examples of the bridged cyclic hydrocarbon ring include a norbornyl group and an adamantyl group.

  These alicyclic 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. It is done. Preferred halogen atoms include bromine, chlorine and fluorine atoms, and preferred alkyl groups include methyl, ethyl, butyl and t-butyl groups. The above alkyl group may further have a substituent, and the substituent that 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 (A). 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 shown below, but the present invention is not limited thereto. In the formula, Ra represents H, CH ₃ , CH ₂ OH, or CF ₃ .

Other repeating units In addition to the above repeating structural units, the resin used in the composition of the present invention has dry etching resistance, standard developer suitability, substrate adhesion, resist profile, and general necessary characteristics of resist. Various repeating structural units can be included for the purpose of adjusting certain resolution, heat resistance, sensitivity, and the like.

Examples of such repeating structural units include, but are not limited to, repeating structural units corresponding to the following monomers.
Thereby, performance required for the resin used in the composition of the present invention, in particular, (1) solubility in coating solvent, (2) film-forming property (glass transition point), (3) alkali developability, (4 Fine adjustments such as () film slippage (selection of hydrophilicity / hydrophobicity, alkali-soluble group), (5) adhesion of unexposed part to substrate, (6) dry etching resistance, etc. are possible.

  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 (A) used in the composition of the present invention, the molar ratio of each repeating structural unit is the resist dry etching resistance, standard developer suitability, substrate adhesion, resist profile, and general required performance of the resist. It is appropriately set to adjust the resolving power, heat resistance, sensitivity and the like.

  When the composition of the present invention is for ArF exposure, the resin (A) used in the actinic ray-sensitive or radiation-sensitive resin composition of the present invention has an aromatic group from the viewpoint of transparency to ArF light. Preferably not.

Moreover, it is preferable that resin (A) does not contain a fluorine atom and a silicon atom from a compatible viewpoint with hydrophobic resin (HR) mentioned later.
The resin (A) 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. More preferably, the (meth) acrylate repeating unit having an acid-decomposable group is 20 to 50 mol%, the (meth) acrylate repeating unit having a lactone group is 20 to 50 mol%, and the alicyclic ring is substituted with a hydroxyl group or a cyano group. It is a copolymer containing 5 to 30 mol% of (meth) acrylate-based repeating units having a hydrocarbon structure, and further containing 0 to 20 mol% of other (meth) acrylate-based repeating units.

  The weight average molecular weight of the resin (A) 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 5,000 to 12,000. By setting the weight average molecular weight within the above range, it is possible to prevent heat resistance improvement, dry etching resistance deterioration prevention, developability deterioration, film formation deterioration due to increased viscosity, and the like.

  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 the resist shape, and the smoother the side wall of the resist pattern, the better the roughness.

As for the compounding ratio in the whole composition of resin (A) of the composition of this invention, 50-98.9 mass% is preferable in a total solid, More preferably, it is 60-99.0 mass%.
Moreover, the resin (A) of the present invention may be used alone or in combination.
The resin (A) can be synthesized and purified according to a conventional method (for example, radical polymerization). For details of the synthesis and purification method, refer to, for example, the description in Chapter 2 “Polymer Synthesis” of “5th edition Experimental Chemistry Course 26 Polymer Chemistry” published by Maruzen Co., Ltd. Regarding the purification of the resin, it is preferable to remove impurities such as unreacted monomers, oligomers and metals as much as possible from the viewpoint of reducing defects and improving resolution.

[2] A compound having a proton acceptor functional group and generating a compound that is decomposed by irradiation with actinic rays or radiation to decrease or disappear the proton acceptor, or change from proton acceptor to acidic ( PA)
The composition of the present invention comprises a compound having a proton acceptor functional group, which is decomposed by irradiation with actinic rays or radiation to decrease or disappear the proton acceptor, or change from proton acceptor to acidic. Contains a generated compound (hereinafter also referred to as compound (PA)).

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

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

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

  Proton acceptor property can be confirmed by measuring pH.

  In the present invention, the acid dissociation constant pKa of the compound generated by decomposition of the compound (PA) upon irradiation with actinic rays or radiation preferably satisfies pKa <−1, more preferably −13 <pKa <−1. And more preferably −13 <pKa <−3.

  In the present invention, the acid dissociation constant pKa represents the acid dissociation constant pKa in an aqueous solution. For example, Chemical Handbook (II) (4th revised edition, 1993, edited by the Chemical Society of Japan, Maruzen Co., Ltd.) It shows that acid strength is so large that this value is low. Specifically, the acid dissociation constant pKa in an aqueous solution can be measured by measuring an acid dissociation constant at 25 ° C. using an infinitely diluted aqueous solution, and using the following software package 1, Hammett The values based on the substituent constants and the database of known literature values can also be obtained by calculation. The values of pKa described in this specification all indicate values obtained by calculation using this software package.

Software package 1: Advanced Chemistry Development (ACD / Labs) Software V8.14 for Solaris (1994-2007 ACD / Labs)
The compound (PA) generates, for example, a compound represented by the following general formula (PA-1) as the proton adduct generated by decomposition upon irradiation with actinic rays or radiation. The compound represented by the general formula (PA-1) has an acidic group as well as a proton acceptor functional group, so that the proton acceptor property is reduced or disappeared compared to the compound (PA), or from the proton acceptor property. It is a compound that has changed to acidic.

In general formula (PA-1),
Q represents -SO ₃ H, -CO ₂ H or _-X 1 NHX ₂ R _f,. Here, R _f represents an alkyl group, a cycloalkyl group or an aryl group, and X ₁ and X ₂ each independently represent —SO ₂ — or —CO—.
A represents a single bond or a divalent linking group.
X represents —SO ₂ — or —CO—.
n represents 0 or 1.
B represents a single bond, an oxygen atom, or -N (Rx) Ry-. Rx represents a hydrogen atom or a monovalent organic group, and Ry represents a single bond or a divalent organic group. It may combine with Ry to form a ring, or may combine with R to form a ring.
R represents a monovalent organic group having a proton acceptor functional group.

General formula (PA-1) is demonstrated still in detail.
The divalent linking group in A is preferably a divalent linking group having 2 to 12 carbon atoms, and examples thereof include an alkylene group and a phenylene group. More preferably, it is an alkylene group having at least one fluorine atom, and a preferable carbon number is 2 to 6, more preferably 2 to 4. The alkylene chain may have a linking group such as an oxygen atom or a sulfur atom. The alkylene group is particularly preferably an alkylene group in which 30 to 100% of the number of hydrogen atoms are substituted with fluorine atoms, and more preferably, the carbon atom bonded to the Q site has a fluorine atom. Further, a perfluoroalkylene group is preferable, and a perfluoroethylene group, a perfluoropropylene group, and a perfluorobutylene group are more preferable.

  The monovalent organic group in Rx preferably has 1 to 30 carbon atoms, and examples thereof include an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, and an alkenyl group. These groups may further have a substituent.

  The alkyl group in Rx may have a substituent, preferably a linear or branched alkyl group having 1 to 20 carbon atoms, and has an oxygen atom, a sulfur atom, or a nitrogen atom in the alkyl chain. May be.

  Preferred examples of the divalent organic group for Ry include an alkylene group. Examples of the ring structure which Rx and Ry may be bonded to each other include a 5- to 10-membered ring containing a nitrogen atom, particularly preferably a 6-membered ring.

In addition, examples of the alkyl group having a substituent include groups in which a cycloalkyl group is substituted on a linear or branched alkyl group (for example, an adamantylmethyl group, an adamantylethyl group, a cyclohexylethyl group, a camphor residue, etc.). .
The cycloalkyl group in Rx may have a substituent, preferably a cycloalkyl group having 3 to 20 carbon atoms, and may have an oxygen atom in the ring.

The aryl group in Rx may have a substituent, and preferably an aryl group having 6 to 14 carbon atoms.
The aralkyl group in Rx may have a substituent, and preferably an aralkyl group having 7 to 20 carbon atoms.
The alkenyl group in Rx may have a substituent, and examples thereof include a group having a double bond at an arbitrary position of the alkyl group mentioned as Rx.

  The proton acceptor functional group in R is as described above, and examples thereof include azacrown ether, primary to tertiary amines, groups having a heterocyclic aromatic structure containing nitrogen such as pyridine and imidazole.

  As the organic group having such a structure, a preferable carbon number is 4 to 30, and examples thereof include an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, and an alkenyl group.

  The alkyl group, the cycloalkyl group, the aryl group, the aralkyl group, the alkyl group in the alkenyl group, the cycloalkyl group, the aryl group, the aralkyl group, and the alkenyl group in R include a proton acceptor functional group or an ammonium group. Are the same as the alkyl group, cycloalkyl group, aryl group, aralkyl group and alkenyl group mentioned above.

  Examples of the substituent that each group may have include, for example, a halogen atom, a hydroxyl group, a nitro group, a cyano group, a carboxy group, a carbonyl group, a cycloalkyl group (preferably having 3 to 10 carbon atoms), and an aryl group (preferably Has 6 to 14 carbon atoms, an alkoxy group (preferably 1 to 10 carbon atoms), an acyl group (preferably 2 to 20 carbon atoms), an acyloxy group (preferably 2 to 10 carbon atoms), an alkoxycarbonyl group (preferably C2-C20), an aminoacyl group (preferably C2-C20) etc. are mentioned. As for the cyclic structure in the aryl group, cycloalkyl group and the like, and the aminoacyl group, examples of the substituent further include an alkyl group (preferably having 1 to 20 carbon atoms).

  When B is -N (Rx) Ry-, R and Rx are preferably bonded to each other to form a ring. By forming the ring structure, the stability is improved, and the storage stability of the composition using the ring structure is improved. The number of carbon atoms forming the ring is preferably 4 to 20, and may be monocyclic or polycyclic, and may contain an oxygen atom, a sulfur atom, or a nitrogen atom in the ring.

  Examples of the monocyclic structure include a 4-membered ring, a 5-membered ring, a 6-membered ring, a 7-membered ring, and an 8-membered ring containing a nitrogen atom. Examples of the polycyclic structure include a structure composed of a combination of two or three or more monocyclic structures. The monocyclic structure and polycyclic structure may have a substituent, for example, a halogen atom, a hydroxyl group, a cyano group, a carboxy group, a carbonyl group, a cycloalkyl group (preferably having 3 to 10 carbon atoms), Aryl group (preferably having 6 to 14 carbon atoms), alkoxy group (preferably having 1 to 10 carbon atoms), acyl group (preferably having 2 to 15 carbon atoms), acyloxy group (preferably having 2 to 15 carbon atoms), alkoxycarbonyl A group (preferably having 2 to 15 carbon atoms), an aminoacyl group (preferably having 2 to 20 carbon atoms) and the like are preferable. As for the cyclic structure in the aryl group, cycloalkyl group and the like, examples of the substituent further include an alkyl group (preferably having a carbon number of 1 to 15). As for the aminoacyl group, examples of the substituent further include an alkyl group (preferably having a carbon number of 1 to 15).

As _{R f} in _-X 1 NHX ₂ R _f represented by Q, preferred is an alkyl group which may have a fluorine atom having 1 to 6 carbon atoms, more preferably perfluoroalkyl of 1 to 6 carbon atoms It is a group. Further, as X ₁ and X ₂ , at least one is preferably —SO ₂ —, and more preferably, both X ₁ and X ₂ are —SO ₂ —.

  Among the compounds represented by the general formula (PA-1), a compound in which the Q site is a sulfonic acid can be synthesized by using a general sulfonamidation reaction. For example, a method in which one sulfonyl halide part of a bissulfonyl halide compound is selectively reacted with an amine compound to form a sulfonamide bond, and then the other sulfonyl halide part is hydrolyzed, or a cyclic sulfonic acid anhydride is used. It can be obtained by a method of ring-opening by reacting with an amine compound.

The compound (PA) is preferably an ionic compound. The proton acceptor functional group may be contained in either the anion portion or the cation portion, but is preferably contained in the anion portion.
Preferred examples of the compound (PA) include compounds represented by the following general formulas (4) to (6).

In the general formulas (4) to (6), A, X, n, B, R, Rf, X ₁ and X ₂ have the same meanings as those in the general formula (PA-1).
C ⁺ represents a counter cation.
The counter cation is preferably an onium cation. More specifically, a sulfonium cation described as S ⁺ (R ₂₀₁ ) (R ₂₀₂ ) (R ₂₀₃ ) in the general formula (ZI) in the component (C) (acid generator) described later, in the general formula (ZII) A preferred example is the iodonium cation described as I ⁺ (R ₂₀₄ ) (R ₂₀₅ ).
Hereinafter, although the specific example of the compound (PA) of (B) component is shown, it is not limited to these.

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

In the formula, A represents a sulfur atom or an iodine atom.
m represents 1 or 2, and n represents 1 or 2. However, when A is a sulfur atom, m + n = 3, and when A is an iodine atom, m + n = 2.
R represents an aryl group.
R _N represents an aryl group substituted with a proton acceptor functional group.
X ⁻ represents a counter anion.
Specific examples of X ⁻ include the same as Z − in (ZI) of the component (C) described later.
A specific example of the aryl group of R and RN is preferably a phenyl group.

Specific examples of the proton acceptor functional group R _N are the same as those of the proton acceptor functional group described in the foregoing formula (PA-1).
In the composition of the present invention, the compounding ratio of the compound (PA) in the whole composition is preferably 0.1 to 10% by mass, more preferably 1 to 8% by mass in the total solid content.
[3] Compound (C) that generates an acid upon irradiation with actinic rays or radiation
The composition of the present invention contains a compound that generates an acid upon irradiation with actinic rays or radiation (hereinafter also referred to as “acid generator”).
The acid generator is not particularly limited as long as it is a known acid generator, and preferred examples include compounds represented by the following general formulas (ZI), (ZII), and (ZIII).

In the general formula (ZI),
R ₂₀₁ , R ₂₀₂ and R ₂₀₃ each independently represents an organic group.
The carbon number of the organic group as R ₂₀₁ , R ₂₀₂ and R ₂₀₃ is generally 1-30, 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 (an anion having an extremely low ability to cause a nucleophilic reaction).

Examples of Z ⁻ include a sulfonate anion (an aliphatic sulfonate anion, an aromatic sulfonate anion, a camphor sulfonate anion, etc.), a carboxylate anion (an aliphatic carboxylate anion, an aromatic carboxylate anion, an aralkyl carboxylate anion). Etc.), sulfonylimide anion, bis (alkylsulfonyl) imide anion, tris (alkylsulfonyl) methide anion and the like.

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

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

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

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

  Examples of the sulfonylimide anion include saccharin anion.

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

Examples of other Z ⁻ include fluorinated phosphorus, fluorinated boron, and fluorinated antimony.

Z ⁻ includes an aliphatic sulfonate anion substituted with at least α-position of sulfonic acid with a fluorine atom, an aromatic sulfonate anion substituted with a fluorine atom or a group having a fluorine atom, and an alkyl group substituted with a fluorine atom. Bis (alkylsulfonyl) imide anions and tris (alkylsulfonyl) methide anions in which the alkyl group is substituted with a fluorine atom are preferred. The non-nucleophilic anion is more preferably a perfluoroaliphatic sulfonate anion (more preferably 4 to 8 carbon atoms), a benzenesulfonate anion having a fluorine atom, still more preferably a nonafluorobutanesulfonate anion, or perfluorooctane. A sulfonate anion, a pentafluorobenzenesulfonate anion, and a 3,5-bis (trifluoromethyl) benzenesulfonate anion.

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

Where
Xf each independently represents a fluorine atom or an alkyl group substituted with at least one fluorine atom.
R ¹ and R ² each independently represents a hydrogen atom, a fluorine atom, an alkyl group, or a group selected from an alkyl group substituted with at least one fluorine atom, and R ¹ and R ² in the case where a plurality of R ¹ and R ^{2 are present.} May be the same or different.
L represents a single bond or a divalent linking group, and when there are a plurality of L, they may be the same or different.
A represents a group having a cyclic structure.
x represents an integer of 1 to 20, y represents an integer of 0 to 10, and z represents an integer of 0 to 10.

The general formula (AN1) will be described in more detail.
The alkyl group in the alkyl group substituted with the fluorine atom of Xf preferably has 1 to 10 carbon atoms, more preferably 1 to 4 carbon atoms. The alkyl group substituted with a fluorine atom of Xf is preferably a perfluoroalkyl group.
Xf is preferably a fluorine atom or a perfluoroalkyl group having 1 to 4 carbon atoms. Specifically, fluorine atom, CF ₃ , C ₂ F ₅ , C ₃ F ₇ , C ₄ F ₉ , CH ₂ CF ₃ , CH ₂ CH ₂ CF ₃ , CH ₂ C ₂ F ₅ , CH ₂ CH ₂ C ₂ F ₅ , CH ₂ C ₃ F ₇ , CH ₂ CH ₂ C ₃ F ₇ , CH ₂ C ₄ F ₉ , and CH ₂ CH ₂ C ₄ F ₉ are mentioned, among which a fluorine atom and CF ₃ are preferable.

The alkyl group in R ¹ and R ^{2 and} the alkyl group substituted with at least one fluorine atom are preferably those having 1 to 4 carbon atoms.

x is preferably 1 to 10, and more preferably 1 to 5.
y is preferably 0 to 4, and more preferably 0.
z is preferably 0 to 5, and more preferably 0 to 3.
The divalent linking group of L is not particularly limited, and is —COO—, —OCO—, —CO—, —O—, —S—, —SO—, —SO ₂ —, an alkylene group, a cycloalkylene group, Examples include alkenylene groups. Of these, —COO—, —OCO—, —CO—, —O—, and —SO ₂ — are preferable, and —COO—, —OCO—, and —SO ₂ — are more preferable.

  The group having a cyclic structure of A is not particularly limited as long as it has a cyclic structure. The group having an alicyclic group, an aryl group, or a heterocyclic structure (not only those having an aromatic attribute, but also having an aromatic attribute). And the like).

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

  Examples of the aryl group include a benzene ring, a naphthalene ring, a phenanthrene ring, and an anthracene ring.

  Examples of the group having a heterocyclic structure include a furan ring, a thiophene ring, a benzofuran ring, a benzothiophene ring, a dibenzofuran ring, a dibenzothiophene ring, a pyridine ring, and a piperidine ring. Of these, a furan ring, a thiophene ring, a pyridine ring, and a piperidine ring are preferable.

The group having the cyclic structure may have a substituent, and the substituent may be an alkyl group (which may be linear, branched or cyclic, preferably having 1 to 12 carbon atoms), Examples include aryl groups (preferably having 6 to 14 carbon atoms), hydroxy groups, alkoxy groups, ester groups, amide groups, urethane groups, ureido groups, thioether groups, sulfonamido groups, sulfonic acid ester groups, and the like.
From the viewpoint of acid strength, the pKa of the generated acid is preferably −1 or less in order to improve sensitivity.

Examples of the organic group of R _201, R ₂₀₂ and R ₂₀₃ in formula (ZI), an aryl group (having 6 to 15 carbon atoms is preferred), a linear or branched alkyl group (having 1 to 10 carbon atoms is preferred), cyclo Examples thereof include an alkyl group (preferably having 3 to 15 carbon atoms).

Of R ₂₀₁ , R ₂₀₂ and R ₂₀₃ , at least one is preferably an aryl group, more preferably all three are aryl groups. As the aryl group, a heteroaryl group such as an indole residue, a pyrrole residue, and a thiophene residue can be used in addition to a phenyl group and a naphthyl group. These aryl groups may further have a substituent. Examples of the substituent include halogen atoms such as nitro groups and fluorine atoms, carboxyl groups, hydroxyl groups, amino groups, cyano groups, alkoxy groups (preferably having 1 to 15 carbon atoms), cycloalkyl groups (preferably having 3 to 15 carbon atoms). ), An aryl group (preferably 6 to 14 carbon atoms), an alkoxycarbonyl group (preferably 2 to 7 carbon atoms), an acyl group (preferably 2 to 12 carbon atoms), an alkoxycarbonyloxy group (preferably 2 to 2 carbon atoms). 7) and the like, but are not limited thereto.

Two selected from R ₂₀₁ , R ₂₀₂ and R ₂₀₃ may be bonded via a single bond or a linking group. Examples of the linking group include an alkylene group (preferably having 1 to 4 carbon atoms), —O—, —S—, —CO—, —SO ₂ — and the like, but are not limited thereto.

Preferred structures when at least one of R ₂₀₁ , R ₂₀₂ and R ₂₀₃ is not an aryl group include paragraphs 0047 and 0048 of JP-A-2004-233661, paragraphs 0040 to 0046 of JP-A-2003-35948, Compounds exemplified as formulas (I-1) to (I-70) in US2003 / 0224288A1, specification (IA-1) to (IA-54), formula (IB- Examples thereof include cationic structures such as compounds exemplified as 1) to (IB-24).

In particular,
(1) A structure in which at least one of R ₂₀₁ , R ₂₀₂ and R ₂₀₃ is represented by Ar—CO—X— (Ar is an aryl group which may have a substituent, and X has a substituent. The remaining two are an alkyl group or a cycloalkyl group (these alkyl groups or cycloalkyl groups may be bonded to each other to form a ring structure),
(2) At least one of R ₂₀₁ , R ₂₀₂ and R ₂₀₃ is an aryl group which may be substituted with any of a hydroxyl group, an alkoxy group and an alkyl group, and the remaining two are an alkyl group or a cycloalkyl group ( These alkyl groups or cycloalkyl groups may be bonded to each other to form a ring structure.

Furthermore, as a preferable structure when at least one of R ₂₀₁ , R ₂₀₂ and R ₂₀₃ in the general formula (ZI) is not an aryl group, a compound represented by the following general formula (ZI-A) can be given.

The compound (ZI-A) is a compound represented by the following general formula (ZI-A).

In general formula (ZI-A),
R ₁₃ represents a hydrogen atom, a fluorine atom, a hydroxyl group, an alkyl group, a cycloalkyl group, an alkoxy group, an alkylcarbonyloxy group, a cycloalkylcarbonyloxy group or an alkoxycarbonyl group.
When a plurality of R ₁₄ are present, each independently represents an alkyl group, a cycloalkyl group, an alkoxy group, an alkylsulfonyl group, or a cycloalkylsulfonyl group.
R ₁₅ each independently represents an alkyl group or a cycloalkyl group. Two R ₁₅ may be bonded to each other to form a ring.

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-A), 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 of R ₁₃ , R ₁₄ and R ₁₅ include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclododecanyl, cyclobenenyl, cyclohexenyl, cyclooctadienyl and the like. In particular, cyclopropyl, cyclopentyl, cyclohexyl and cyclooctyl are preferred.

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.

Examples of the alkylcarbonyloxy group and cycloalkylcarbonyloxy group for R ₁₃ include a methylcarbonyloxy group, an ethylcarbonyloxy group, an n-propylcarbonyloxy group, an i-propylcarbonyloxy group, an n-butylcarbonyloxy group, and 2-methyl. Propylcarbonyloxy group, 1-methylpropylcarbonyloxy group, t-butylcarbonyloxy group, n-pentylcarbonyloxy group, neopentylcarbonyloxy group, n-hexylcarbonyloxy group, n-heptylcarbonyloxy group, n-octyl Carbonyloxy group, 2-ethylhexylcarbonyloxy group, n-nonylcarbonyloxy group, n-decylcarbonyloxy group, cyclopropylcarbonyloxy group, cyclobutylcarbonyloxy group, cyclopent Examples thereof include a tilcarbonyloxy group, a cyclohexylcarbonyloxy group, a cycloheptylcarbonyloxy group, a cyclooctylcarbonyloxy group, and a decahydronaphthyl group. Of these alkylcarbonyloxy groups and cycloalkylcarbonyloxy groups, a methylcarbonyloxy group, an ethylcarbonyloxy group, an n-butylcarbonyloxy group, a cyclohexylcarbonyloxy group, and the like are preferable.

The alkoxycarbonyl group for R ₁₃ is linear or branched and preferably has 2 to 11 carbon atoms, such as a methoxycarbonyl group, an ethoxycarbonyl group, an n-propoxycarbonyl group, or an i-propoxycarbonyl group. N-butoxycarbonyl group, 2-methylpropoxycarbonyl group, 1-methylpropoxycarbonyl group, t-butoxycarbonyl group, n-pentyloxycarbonyl group, neopentyloxycarbonyl group, n-hexyloxycarbonyl group, n-heptyl Examples thereof include an oxycarbonyl group, an n-octyloxycarbonyl group, a 2-ethylhexyloxycarbonyl group, an n-nonyloxycarbonyl group, and an n-decyloxycarbonyl group. Of these alkoxycarbonyl groups, a methoxycarbonyl group, an ethoxycarbonyl group, an n-butoxycarbonyl group, and the like are preferable.

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.

l is preferably 0 or 1, and more preferably 1. As r, 0-2 are preferable.
Examples of the substituent that each group of R ₁₃ , R ₁₄ , and R ₁₅ 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, and an alkoxy group. Examples thereof include an alkyl group, an alkoxycarbonyl group, and an alkoxycarbonyloxy group.
Examples of the alkoxy group include methoxy group, ethoxy group, n-propoxy group, i-propoxy group, n-butoxy group, 2-methylpropoxy group, 1-methylpropoxy group, t-butoxy group, cyclopentyloxy group, Examples thereof include a linear, branched or cyclic alkoxy group having 1 to 20 carbon atoms such as a cyclohexyloxy group.

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.

As the ring structure that two R ₁₅ may be bonded to each other, two divalent R ₁₅ are a 5-membered or 6-membered ring together with a sulfur atom in the general formula (ZI-A), particularly Preferably a 5-membered ring (namely, tetrahydrothiophene ring) is mentioned. 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-A) is preferably a methyl group, an ethyl group, a divalent group in which two R ₁₅ are bonded to each other to form a tetrahydrothiophene ring structure together with a sulfur atom.

The alkyl group, cycloalkyl group, alkoxy group, or alkoxycarbonyl group of R _13, the alkyl group, cycloalkyl group, alkoxy group, alkylsulfonyl group, cycloalkylsulfonyl group of R ₁₄ may be substituted as described above. The substituent is preferably a hydroxyl group, an alkoxy group, an alkoxycarbonyl group, or a halogen atom (particularly a fluorine atom).
Below, the preferable specific example of the cation in the compound represented by general formula (ZI-A) is shown.

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

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

Aryl group, alkyl group of R ₂₀₄ to R _207, cycloalkyl groups may have a substituent. Examples of the substituent include those that the aryl group, alkyl group, and cycloalkyl group of R _{201 to} R ₂₀₃ in the above-described compound (ZI) may have.

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

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

In 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.
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 composition is preferably 1 to 30% by mass, more preferably 5 to 25% by mass, and still more preferably 10 to 25% by mass based on the total solid content of the composition.

[4] Basic compound The actinic ray-sensitive or radiation-sensitive composition of the present invention may contain a basic compound other than the compound (PA). 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, a compound in which at least one R in the general formula (BS-1) is an alkyl group substituted with a hydroxyl group can be mentioned as one of preferable embodiments. Specific examples of the compound include triethanolamine and N, N-dihydroxyethylaniline.

In addition, the alkyl group as R may have an oxygen atom in the alkyl chain, and an oxyalkylene chain may be formed. The oxyalkylene chain is preferably —CH ₂ CH ₂ O—. Specific examples include tris (methoxyethoxyethyl) amine and compounds exemplified in column 3, line 60 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. Examples of the phenoxy group include 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. It may have a substituent.

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 paragraph [0066] of US2007 / 0224539A1. And compounds (C1-1) to (C3-3) exemplified in the above.

(4) Ammonium salt derived from any of the compounds (1) to (3) Ammonium salts are also used as appropriate. Preferred is hydroxide or carboxylate. More specifically, tetraalkylammonium hydroxide represented by tetrabutylammonium hydroxide is preferable.

  The compounds synthesized in the examples of JP 2002-363146 A, the compounds described in paragraph 0108 of JP 2007-298869 A, and the like can also be used.

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 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.

[5] Surfactant The composition of the present invention preferably further contains a surfactant. As the surfactant, fluorine-based and / or silicon-based surfactants are preferable.
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 US 2008/0248425 A1 after [0273].
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, and particularly preferably 0.0005 to 1% by mass with respect to the total solid content of the composition.

[6] Solvent The solvent that can be used in preparing the composition is not particularly limited as long as it dissolves each component. For example, alkylene glycol monoalkyl ether carboxylate (such as propylene glycol monomethyl ether acetate), alkylene Glycol monoalkyl ether (such as propylene glycol monomethyl ether), alkyl lactate ester (such as ethyl lactate, methyl lactate), cyclic lactone (such as γ-butyrolactone, preferably 4 to 10 carbon atoms), chain or cyclic ketone (2- Heptanone, cyclohexanone, etc., preferably 4 to 10 carbon atoms, alkylene carbonate (ethylene carbonate, propylene carbonate, etc.), alkyl carboxylate (preferably alkyl acetate such as butyl acetate), alkoxy And alkyl acetate (ethyl ethoxypropionate) and the like. Examples of other usable solvents include those described in US 2008/0248425 A1 [0244] and thereafter.

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.

[7] 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.

[Pattern formation method]
The composition of the present invention is used by dissolving the above components in a solvent, filtering the solution, and applying the solution to a support. The filter is preferably made of polytetrafluoroethylene, polyethylene, or nylon having a pore size of 0.1 μm or less, more preferably 0.05 μm or less, and still more preferably 0.03 μm or less.
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 alkaline 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 can be used, and an appropriate amount of a surfactant can be added.

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.

Exposure (immersion exposure) may be performed by filling a liquid (immersion medium) having a higher refractive index than air between the film and the lens during irradiation with actinic rays or radiation. Thereby, resolution can be improved. The immersion medium used is preferably water. Water is also suitable in terms of a small temperature coefficient of refractive index, ease of availability, and ease of handling.
A medium having a refractive index of 1.5 or more can also be used in that the refractive index can be improved. This medium may be an aqueous solution or an organic solvent.

  When water is used as the immersion liquid, an additive for the purpose of improving the refractive index may be added in a small proportion. Examples of additives are detailed in Chapter 12 of CMC publication “Processes and Materials for Immersion Lithography”. On the other hand, the presence of impurities that are opaque to 193 nm light and impurities whose refractive index is significantly different from that of water causes distortion of the optical image projected on the film, and therefore, distilled water is preferred as the water to be used. Further, pure water purified with an ion exchange filter or the like may be used. The electric resistance of pure 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.

  When exposing the film | membrane which consists of a composition of this invention through an immersion medium, hydrophobic resin (HR) can be further added as needed. As a result, when the hydrophobic resin (HR) is unevenly distributed on the surface of the resist film and the immersion medium is water, the receding contact angle of the resist film surface with respect to water when the resist film is formed is improved, and the immersion water followability is improved. Can be made. As the hydrophobic resin (HR), any resin can be used as long as the receding contact angle of the surface can be improved by addition, but a resin having at least one of fluorine atom and silicon atom is preferable. The receding contact angle of the resist film is preferably 60 ° to 90 °, more preferably 70 ° or more. The amount added can be adjusted as appropriate so that the receding contact angle of the resist film falls within the above range, but is preferably 0.1 to 10% by mass, more preferably based on the total solid content of the composition. It is 0.1-5 mass%. Hydrophobic resin (HR) is ubiquitous at the interface as described above, but unlike a surfactant, it does not necessarily have a hydrophilic group in the molecule, and polar / nonpolar substances are mixed uniformly. There is no need to contribute.

  The receding contact angle is a contact angle measured when the contact line at the droplet-substrate interface recedes, and is useful for estimating the ease of movement of the droplet in a dynamic state. Are 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. In this case, the contact angle of the immersion liquid with respect to the resist film is important, and the resist is required to follow the high-speed scanning of the exposure head without remaining droplets.

  The fluorine atom or silicon atom in the hydrophobic resin (HR) may be contained in the main chain of the resin or may be substituted on the side chain.

  The hydrophobic resin (HR) is preferably a resin having an alkyl group having a fluorine atom, a cycloalkyl group having a fluorine atom, or an aryl group having a fluorine atom as a partial structure having a fluorine atom.

  The alkyl group having a fluorine atom (preferably having 1 to 10 carbon atoms, more preferably 1 to 4 carbon atoms) is a linear or branched alkyl group in which at least one hydrogen atom is substituted with a fluorine atom, It may have a substituent.

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

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

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

In general formulas (F2) to (F4),
R _{57 to} R ₆₈ each independently represents a hydrogen atom, a fluorine atom or an alkyl group. However, at least one of R _{57 to} R ₆₁ , R _{62 to} R ₆₄ and R _{65 to} R ₆₈ is a fluorine atom or an alkyl group in which at least one hydrogen atom is substituted with a fluorine atom (preferably having a carbon number of 1 ~ 4). R _{57 to} R ₆₁ and R _{65 to} R ₆₇ are preferably all fluorine atoms. R ₆₂ , R ₆₃ and R ₆₈ are preferably an alkyl group (preferably having 1 to 4 carbon atoms) in which at least one hydrogen atom is substituted with a fluorine atom, and preferably a perfluoroalkyl group having 1 to 4 carbon atoms. Further preferred. R ₆₂ and R ₆₃ may be connected to each other to form a ring.

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

  Specific examples of the group represented by the general formula (F3) include trifluoromethyl group, pentafluoropropyl group, pentafluoroethyl group, heptafluorobutyl group, hexafluoroisopropyl group, heptafluoroisopropyl group, hexafluoro (2 -Methyl) isopropyl group, nonafluorobutyl group, octafluoroisobutyl group, nonafluorohexyl group, nonafluoro-t-butyl group, perfluoroisopentyl group, perfluorooctyl group, perfluoro (trimethyl) hexyl group, 2,2 1,3,3-tetrafluorocyclobutyl group, perfluorocyclohexyl group and the like. Hexafluoroisopropyl group, heptafluoroisopropyl group, hexafluoro (2-methyl) isopropyl group, octafluoroisobutyl group, nonafluoro-t-butyl group and perfluoroisopentyl group are preferable, and hexafluoroisopropyl group and heptafluoroisopropyl group are preferable. Further preferred.

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

Hereinafter, although the specific example of the repeating unit which has a fluorine atom is shown, this invention is not limited to this.
In specific examples, X ₁ represents a hydrogen atom, —CH ₃ , —F or —CF ₃ .
X ₂ represents —F or —CF ₃ .
Specific examples include repeating units having fluorine atoms, which are contained in the resins (HR-1) to (HR-65) described later.

The hydrophobic resin (HR) is preferably a resin having an alkylsilyl structure (preferably a trialkylsilyl group) or a cyclic siloxane structure as a partial structure having a silicon atom.
Specific examples of the alkylsilyl structure or 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 (preferably having 1 to 20 carbon atoms) or a cycloalkyl group (preferably having 3 to 20 carbon atoms).
L < ₃ > -L < ₅ > represents a single bond or a bivalent coupling group. As the divalent linking group, an alkylene group, a phenylene group, an ether group, a thioether group, a carbonyl group, an ester group, an amide group, a urethane group, or a urea group is used alone or in combination of two or more groups. A combination is mentioned.
n represents an integer of 1 to 5.

  Hereinafter, although the specific example of the repeating unit which has group represented by general formula (CS-1)-(CS-3) is given, this invention is not limited to this. In addition, as a specific example, the repeating unit which has a silicon atom contained in resin (HR-1)-(HR-65) mentioned later is also mentioned.

In specific examples, X ₁ represents a hydrogen atom, —CH ₃ , —F or —CF ₃ .

  Furthermore, the hydrophobic resin (HR) may have at least one group selected from the following groups (x) to (z).

(X) Alkali-soluble group (y) Group that decomposes by the action of an alkali developer and increases the solubility in the alkali developer (z) Group that decomposes by the action of an acid (x) The alkali-soluble group includes phenolic Hydroxyl group, carboxylic acid group, fluorinated alcohol group, sulfonic acid group, sulfonamide group, sulfonylimide group, (alkylsulfonyl) (alkylcarbonyl) methylene group, (alkylsulfonyl) (alkylcarbonyl) imide group, bis (alkylcarbonyl) Examples include a methylene group, a bis (alkylcarbonyl) imide group, a bis (alkylsulfonyl) methylene group, a bis (alkylsulfonyl) imide group, a tris (alkylcarbonyl) methylene group, and a tris (alkylsulfonyl) methylene group. Preferred alkali-soluble groups include fluorinated alcohol groups (preferably hexafluoroisopropanol), sulfonimide groups, and bis (carbonyl) methylene groups.

  Examples of the repeating unit having an alkali-soluble group (x) include 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 a main group of the resin via a linking group. Examples include repeating units in which an alkali-soluble group is bonded to the chain. Furthermore, a polymerization initiator or a chain transfer agent having an alkali-soluble group can be used at the time of polymerization to be introduced at the end of the polymer chain. Is also preferable.

  The content of the repeating unit having an alkali-soluble group (x) is preferably from 1 to 50 mol%, more preferably from 3 to 35 mol%, still more preferably from 5 to 20 mol%, based on all repeating units in the polymer.

Specific examples of the repeating unit having an alkali-soluble group (x) are shown below, but the present invention is not limited thereto. Specific examples also include a repeating unit having an alkali-soluble group (x) contained in the resins (HR-1) to (HR-65) described later.
In the specific examples shown below, Rx represents any of H, CH ₃ , CF ₃ , and CH ₂ OH.

  (Y) Examples of the group that decomposes by the action of an alkali developer and increases the solubility in the alkali developer include a group having a lactone structure, an acid anhydride group, an acid imide group, and the like, and preferably a lactone A group having a structure.

  As the repeating unit having a group (y) that is decomposed by the action of an alkali developer and increases the solubility in the alkali developer, an alkali is added to the main chain of the resin, such as a repeating unit of an acrylate ester or a methacrylate ester. A polymerization initiator having a repeating unit to which a group (y) that decomposes by the action of the developer and increases the solubility in an alkali developer is bonded, or a group (y) that increases the solubility in an alkali developer And a chain transfer agent used at the time of polymerization are preferably introduced at the end of the polymer chain.

  The content of the repeating unit having a group (y) whose solubility in an alkali developer is increased is preferably 1 to 40 mol%, more preferably 3 to 30 mol%, still more preferably based on all repeating units in the polymer. 5 to 15 mol%.

  Specific examples of the repeating unit having a group (y) that increases the solubility in an alkali developer include the same repeating units as those having a lactone structure exemplified for the resin of the component (A).

In the hydrophobic resin (HR), examples of the repeating unit having a group (z) that is decomposed by the action of an acid are the same as the repeating unit having an acid-decomposable group listed for the resin of the component (A). . In the hydrophobic resin (HR), the content of the repeating unit having a group (z) that is decomposed by the action of an acid is preferably 1 to 80 mol%, more preferably 10 to 10%, based on all repeating units in the polymer. 80 mol%, more preferably 20 to 60 mol%.
The hydrophobic resin (HR) may further have a repeating unit represented by the following general formula (III).

In general formula (III):
R _c31 represents a hydrogen atom, an alkyl group, or an alkyl group optionally substituted with fluorine, a cyano group, or a —CH ₂ —O—Rac ₂ group. Wherein, 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, particularly preferably a hydrogen atom or a methyl group.
R _c32 represents a group having an alkyl group, a cycloalkyl group, an alkenyl group, or a cycloalkenyl group. These groups may be substituted with a fluorine atom or a silicon atom.
L _c3 represents a single bond or a divalent linking group.

In general formula (III), the alkyl group represented by R _c32 is preferably a linear or branched alkyl group having 3 to 20 carbon atoms.
The cycloalkyl group is preferably a cycloalkyl group having 3 to 20 carbon atoms.
The alkenyl group is preferably an alkenyl group having 3 to 20 carbon atoms.
The cycloalkenyl group is preferably a cycloalkenyl group having 3 to 20 carbon atoms.
R _c32 is preferably an unsubstituted alkyl group or an alkyl group substituted with a fluorine atom.
The divalent linking group of L _c3 is preferably an ester group, an alkylene group (preferably having a carbon number of 1 to 5), an oxy group, a phenylene group, or an ester bond (a group represented by —COO—).
When the hydrophobic resin (HR) has a fluorine atom, the content of the fluorine atom is preferably 5 to 80 mol%, preferably 10 to 80 mol% with respect to the molecular weight of the hydrophobic resin (HR). Is more preferable. Moreover, it is preferable that the repeating unit containing a fluorine atom is 10-100 mol% in all the repeating units of hydrophobic resin (HR), and it is more preferable that it is 30-100 mass%.

  When the hydrophobic resin (HR) has a silicon atom, the content of the silicon atom is preferably 2 to 50 mol%, preferably 2 to 30 mol% with respect to the molecular weight of the hydrophobic resin (HR). Is more preferable. Moreover, it is preferable that it is 10-100 mass% in all the repeating units of hydrophobic resin (HR), and, as for the repeating unit containing a silicon atom, it is more preferable that it is 20-100 mass%.

  The weight average molecular weight of the hydrophobic resin (HR) in terms of standard polystyrene is preferably 1,000 to 100,000, more preferably 1,000 to 50,000, and even more preferably 2,000 to 15,000. is there.

  The hydrophobic resin (HR), like the resin of the component (A), naturally has few impurities such as metals, and it is preferable that the residual monomer and oligomer components are as close to 0 as possible. Specifically, it is preferably 0 to 10% by mass, more preferably 0 to 5% by mass, and even more preferably 0 to 1% by mass. Thereby, a resist having no change over time such as foreign matter in liquid or sensitivity can be obtained. The molecular weight distribution (Mw / Mn, also referred to as dispersity) is preferably in the range of 1 to 5, more preferably 1 to 3, and still more preferably from the viewpoints of resolution, resist shape, resist pattern sidewall, roughness, and the like. It is the range of 1-2.

As the hydrophobic resin (HR), various commercially available products can be used, and can be synthesized and purified according to a conventional method (for example, radical polymerization). For the detailed synthesis and purification method, refer to the method described in the above-mentioned resist main resin and the description in Chapter 2 “Polymer Synthesis” of “5th edition Experimental Chemistry Course 26 Polymer Chemistry” published by Maruzen Co., Ltd. I want.
Specific examples of the hydrophobic resin (HR) are shown below. Table 1 below shows the molar ratio of the repeating units in each resin (corresponding to each repeating unit in order from the left), the weight average molecular weight, and the degree of dispersion.

In order to prevent the film from coming into direct contact with the immersion liquid between the film made of the actinic ray-sensitive or radiation-sensitive resin composition of the present invention and the immersion liquid, the immersion liquid hardly soluble film (hereinafter referred to as “top”). May also be provided).
The performance required for the top coat and how to use it are explained in Chapter 7 of "Category and process of immersion lithography" published by CMMC.
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. Commercially available top coat materials can also be used as appropriate.

EXAMPLES Hereinafter, although an Example demonstrates this invention, this invention is not limited to this.
<Synthesis of Resin (A)>
Synthesis Example 1 (Synthesis of Resin (1))
Under a nitrogen stream, 25.5 g of cyclohexanone was placed in a three-necked flask and heated to 80 ° C. To this, the following monomers were added in order from the left: 6.04 g, 1.25 g, 2.71 g, 2.60 g, polymerization initiator V601 (manufactured by Wako Pure Chemicals, 0.798 g, 7.0 mol% with respect to the monomer), 46 g of cyclohexanone. The solution dissolved in was added dropwise over 6 hours. After completion of dropping, the reaction was further carried out at 80 ° C. for 2 hours. The reaction solution was allowed to cool and then added dropwise to a mixed solution of 420 g of hexane / 180 g of ethyl acetate over 20 minutes. The precipitated powder was collected by filtration and dried to obtain 10 g of polymer (1). The weight average molecular weight of the obtained polymer (1) was 9570 in terms of standard polystyrene, and the dispersity (Mw / Mn) was 1.7.

The other resins (2) to (15) described later were synthesized in the same manner as the resin (1).
<Synthesis of Compound (PA)>
Synthesis Example 2 (Synthesis of Compound (PA-a))
Under a nitrogen stream, a mixture of 5.0 g (15.8 mmol) of 1,1,2,2,3,3-hexafluoropropane-1,3-disulfonyldifluoride and 50 mL of THF was ice-cooled, and 1-methyl was added thereto. A mixed solution of 1.66 g (16.6 mmol) of piperazine, 10 mL of triethylamine and 50 mL of THF was added dropwise over 60 minutes. The mixture was stirred for 1 hour under ice cooling, and further stirred at room temperature for 1 hour. The organic layer was washed successively with water, a saturated aqueous ammonium chloride solution and water, and the organic layer was dried over sodium sulfate. The solvent was concentrated, 2.36 g (15.8 mmol) of trifluoromethanesulfonamide and 10 mL of triethylamine were added to the residue, transferred to a pressure-resistant glass tube, and stirred in a sealed tube at 100 ° C. for 20 hours. 100 mL of chloroform was added, the organic layer was washed with water, and the organic layer was dried over sodium sulfate to obtain a brown oil. Methanol 25mL and 1.5N-HCl 60mL were made neutral to this, and the depositing white solid was filtered, and 5.65g of the following compound (PA-a) was obtained.
Other compounds (PA-b) to (PA-j) were synthesized in the same manner.

<Preparation of actinic ray-sensitive or radiation-sensitive resin composition>
The components shown in Table 2 below are dissolved in a solvent, and a solution with a solid content of 4% by mass is prepared for each, and this is filtered through a polyethylene filter having a pore size of 0.05 μm, and an actinic ray-sensitive or radiation-sensitive resin composition. 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 3.
About each component in a table | surface, ratio when using multiple is mass ratio.
In Table 2, when the actinic ray-sensitive or radiation-sensitive resin composition contains a hydrophobic resin (HR), its usage form is marked as “addition”. On the other hand, the actinic ray-sensitive or radiation-sensitive resin composition does not contain a hydrophobic resin (HR), and after forming a film, a top coat protective film containing a hydrophobic resin (HR) is formed thereon. In this case, the addition form was labeled “TC”.

  Hereinafter, abbreviations in the table are shown.

[Resin (A)]

[Compound PA]

[Photoacid generator]

[Basic compounds]
DIA: 2,6-diisopropylaniline PEA: N-phenyldiethanolamine TMEA: tris (methoxyethoxyethyl) amine TBAH: tetrabutylammonium hydroxide DBA: N, N-dibutylaniline [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: Troisol S-336 (manufactured by Troy Chemical Co., Ltd.)
W-4: PF656 (OMNOVA, fluorine system)
W-5: PF6320 (OMNOVA, fluorine system)
〔solvent〕
A1: Propylene glycol monomethyl ether acetate A2: Cyclohexanone A3: γ-butyrolactone B1: Propylene glycol monomethyl ether B2: Ethyl lactate (Exposure condition 1: ArF immersion exposure) Examples 1-4, 6-9, 14-16, comparison Examples 1-2
An organic antireflection film ARC29A (manufactured by Nissan Chemical Industries, Ltd.) was applied onto 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 obtained by further dissolving a resin for top coat in decane / octanol (9/1 mass ratio) is applied on the film obtained above, and at 85 ° C. for 60 seconds. Baking was performed to form a 50 nm thick top coat layer. The obtained wafer was exposed through a 6% halftone mask with a 45 nm 1: 1 line and space pattern using an ArF excimer laser immersion scanner (XT1700i, NA 1.2 manufactured by ASML). 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% by mass) for 30 seconds, rinsed with pure water, and then spin-dried to form a pattern.

(Exposure condition 2: ArF dry exposure) Examples 5 and 10-13
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 resist film having a thickness of 120 nm. Using the obtained wafer ArF excimer laser scanner (manufactured by ASML, PAS5500 / 1100, NA0.75), exposure was performed through a 6% halftone mask of 75 nm 1: 1 line and space pattern. Thereafter, heating was performed at 130 ° C. for 60 seconds, followed by development with an aqueous tetramethylammonium hydroxide solution (2.38 mass%) for 30 seconds, rinsing with pure water, and spin drying to obtain a resist pattern.

[LWR evaluation]
In the case of exposure condition 1, 50 lines were measured for a 45 nm 1/1 (line and space) pattern, and the 3σ value was calculated as LWR.
In the case of the exposure condition 2, 50 lines were measured for a 75 nm 1/1 (line and space) pattern line, and the 3σ value was calculated as LWR.
[DOF evaluation]
In the exposure condition 1, a depth of focus that reproduces a line width of 45 n ± 10% was observed. In the case of exposure condition 2, the depth of focus that reproduces a line width of 75 nm ± 10% was observed. A larger value is desirable because the tolerance for defocus is large.

[Defect (development defect) evaluation]
The prepared actinic ray-sensitive or radiation-sensitive resin composition solution was directly applied onto an 8-inch silicon wafer subjected to hexamethyldisilazane (HMDS) treatment using a spinner, and was heated at 105 ° C. for 90 seconds on a hot plate. By pre-baking (PAB) and drying, a resist film having a thickness of 220 nm was formed.
Next, an ArF excimer laser (193 nm) is selectively passed through a mask pattern (binary) using an ArF exposure apparatus NSR-S306 (manufactured by Nikon Corporation; NA (numerical aperture) = 0.78, σ = 0.30). Irradiated.
Then, PEB treatment at 110 ° C. for 90 seconds, paddle development with a 2.38 mass% tetramethylammonium hydroxide aqueous solution at 23 ° C. for 60 seconds, conditions of 1000 rotations for 1 second, and then 500 rotations for 15 seconds ( A rinsing solution was added dropwise under a forced condition such that defects are more likely to occur, and dried to form a resist pattern.
In addition, a dense hole pattern (a pattern in which hole patterns with a diameter of 300 nm are arranged at intervals of 300 nm) was formed as the pattern.
Next, the surface defect observation apparatus KLA2351 (product name) manufactured by KLA Tencor was used to measure the number of defects in the wafer.
The same evaluation was performed once again, and the average value of the number of defects on the two wafers was obtained.

  From Table 3, the pattern formed using the actinic ray-sensitive or radiation-sensitive resin composition of the present invention is excellent in LWR, development characteristics and DOF, and suitable for ArF immersion exposure process as well as dry exposure process. It was found that it can be used.

Claims (7)

(A) a resin having a repeating unit containing a structure represented by the following general formula (1), and having increased solubility in an alkali developer by the action of an acid;
(B) A compound having a proton acceptor functional group and generating a compound that is decomposed by irradiation with actinic rays or radiation to decrease, disappear, or change the proton acceptor property to acidic ( PA) and (C) an actinic ray-sensitive or radiation-sensitive resin composition containing a compound that generates an acid upon irradiation with an actinic ray or radiation.

In general formula (1),
L represents a substituent having a lactone structure.
When there are a plurality of R _{0 s,} each independently represents an alkylene group that may have a substituent, a cyclic alkylene group that may have a substituent, or a combination thereof.
Z is independently an ether bond, an ester bond, an amide bond, a urethane bond or a urea bond when there are a plurality of Z.
n represents the number of repetitions and represents an integer of 1 to 5. The actinic ray-sensitive composition according to claim 1, wherein the compound generated by decomposition of the compound (PA) upon irradiation with actinic rays or radiation is a compound represented by the following general formula (PA-1). Or a radiation sensitive resin composition.

In general formula (PA-1),
Q represents -SO ₃ H, -CO ₂ H or _-X 1 NHX ₂ R _f,. Here, R _f represents an alkyl group, a cycloalkyl group or an aryl group, and X ₁ and X ₂ each independently represent —SO ₂ — or —CO—.
A represents a single bond or a divalent linking group.
X represents —SO ₂ — or —CO—.
n represents 0 or 1.
B represents a single bond, an oxygen atom, or -N (Rx) Ry-. Here, Rx represents a hydrogen atom or a monovalent organic group, and Ry represents a single bond or a divalent organic group. Rx may combine with Ry to form a ring, or may combine with R to form a ring.
R represents a monovalent organic group having a proton acceptor functional group.   The active light ray according to claim 1 or 2, wherein the acid dissociation constant (pKa) of the compound generated by decomposition of the compound (PA) upon irradiation with actinic light or radiation satisfies -1> pKa. Or radiation sensitive resin composition. The actinic ray-sensitive or radiation-sensitive resin composition according to any one of claims 1 to 3, wherein the compound (PA) is represented by any one of the following general formulas (4) to (6): object.

In general formulas (4) to (6),
R represents a monovalent organic group having a proton acceptor functional group.
B represents a single bond, an oxygen atom, or -N (Rx) Ry-. Here, Rx represents a hydrogen atom or a monovalent organic group, and Ry represents a single bond or a divalent organic group. Rx may combine with Ry to form a ring, or may combine with R to form a ring.
X represents —SO ₂ — or —CO—.
n represents 0 or 1.
A represents a single bond or a divalent linking group.
X ₁ and X ₂ each independently represents —SO ₂ — or —CO—.
R _f represents an alkyl group, a cycloalkyl group or an aryl group.
C ⁺ represents a counter cation. The actinic ray-sensitive or radiation-sensitive composition according to any one of claims 1 to 4, wherein the repeating unit including the structure represented by the general formula (1) is represented by the following general formula (1-1). Resin composition.

In general formula (1-1),
R represents a hydrogen atom or an alkyl group which may have a substituent.
A represents -COO- or -CONH-.
L, R ₀ , Z, and n have the same meanings as in general formula (1). 6. The actinic ray-sensitive or radiation-sensitive resin according to claim 5, wherein the repeating unit represented by the general formula (1-1) is a repeating unit represented by the following general formula (1-2). Composition.

In General Formula (1-2), R, A, R ₀ , Z, and n have the same meanings as those in General Formula (1-1).
When there are a plurality of R _{1 s} , each independently represents an alkyl group which may have a substituent, a cycloalkyl group which may have a substituent, or an ester group which may have a substituent. Or a cyano group, and when there are a plurality of them, two R _{1 's} may combine to 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. A step of coating the substrate with the actinic ray-sensitive or radiation-sensitive resin composition according to claim 1 to form a film, a step of irradiating the film with actinic rays or radiation, and development A pattern forming method including a step of developing with a liquid.