JP2011257613A - Actinic ray sensitive or radiation sensitive resin composition and pattern forming method using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an actinic ray sensitive or radiation sensitive resin composition which can provide a pattern having improved uniformity of coating film thickness and excellent size uniformity in the wafer surface on which the pattern has been formed by liquid immersion exposure, and a pattern forming method using the composition.SOLUTION: An actinic ray-sensitive or radiation-sensitive resin composition contains: (A) a resin which has a repeating unit represented by the following general formula (A1) and increases its dissolution rate in an alkali developer by an action of an acid; (B) a compound which generates an acid by irradiation with actinic rays or radiation; and (C) a resin which comprises a repeating unit having a lactone structure substituted by a group having a fluorine atom. (In the formula, Rrepresents a hydrogen atom, an alkyl group, a fluoroalkyl group, a halogen atom or CHOH; Rrepresents an alkylene group, a cycloalkylene group or a bivalent connecting group that is formed by combining them; n represents an integer of 0-5; if n is 2 or more, a plurality of Rmay be the same or different.)

Description

  The present invention relates to an actinic ray-sensitive or radiation-sensitive resin composition and a pattern forming method using the same. More specifically, the present invention relates to an ultra-microlithographic process applicable to a manufacturing process of a VLSI and a high-capacity microchip, a process for producing a mold for nanoimprinting, a manufacturing process of a high-density information recording medium, and other photofabrication. The present invention relates to a composition suitably used in a process, and a pattern forming method using the composition. In particular, the present invention relates to a composition suitable for exposure using an immersion projection exposure apparatus that uses far ultraviolet light having a wavelength of 300 nm or less as a light source, and a pattern forming method using the same.

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

  In addition, “exposure” means not only light irradiation with a mercury lamp, far ultraviolet rays, X-rays, EUV light, etc., but also drawing with particle beams such as electron beams and ion beams, unless otherwise specified. .

  Along with miniaturization of semiconductor elements, the wavelength of the exposure light source has been shortened and the projection lens has a high numerical aperture (high NA). With the aim of higher resolution by further shortening the wavelength, the distance between the projection lens and the sample is increased. A so-called immersion method is known in which a liquid having a refractive index (hereinafter also referred to as “immersion liquid”) is used. The liquid immersion method is effective for all pattern shapes, and can be combined with a super-resolution technique such as a phase shift method and a modified illumination method which are currently being studied.

  Since the resist for KrF excimer laser (248 nm), an image forming method called chemical amplification has been used as an image forming method for a resist in order to compensate for sensitivity reduction due to light absorption. Explaining by taking a positive chemical amplification image forming method as an example, the acid generator in the exposed part is decomposed by exposure to generate an acid by exposure, and the generated acid is reacted by a post exposure bake (PEB) reaction catalyst. Is used to change an alkali-insoluble group to an alkali-soluble group, and an exposed portion is removed by alkali development.

  The ArF excimer laser (193 nm) resist using this chemical amplification mechanism is now becoming mainstream, but when exposure is performed using a scanning immersion exposure machine, the immersion follows the movement of the lens. If the liquid does not move, the exposure speed decreases, which may affect the productivity. In the case where the immersion liquid is water, it is desirable that the resist film is hydrophobic because the water followability is good. Patent Document 1 discloses that the water followability and line edge roughness of the immersion liquid are improved by adding a specific fluorine / silicon atom-containing resin.

  On the other hand, too hydrophobizing leads to lower developability, and it is important to achieve both water followability and developability. Patent Document 2 describes a resin having a norbornene skeleton in the main chain as a resist protective film material.

  However, from the viewpoint of overall performance as a resist, it is actually difficult to find an appropriate combination of resins, photoacid generators, additives, solvents and the like to be used. In particular, when a resist pattern having a high resolution of 0.11 μm or less is required as in recent years, the resist pattern dimension uniformity in the wafer surface after development is higher than before in order to improve device characteristics. Improvement is needed. It has been found that the uniformity of the resist coating film thickness greatly affects the control of the resist pattern dimension uniformity, and improvement of the in-plane uniformity of the resist film thickness is required.

JP 2007-304545 A JP 2007-58187 A

  An object of the present invention is to provide an actinic ray-sensitive or radiation-sensitive resin capable of providing a pattern with improved uniformity of coating film thickness and excellent dimensional uniformity in a wafer surface of a pattern formed by immersion exposure It is to provide a composition and a pattern forming method using the composition.

  In one aspect, the present invention is as follows.

[1] (A) A resin containing a repeating unit represented by the following general formula (A1), which increases the dissolution rate in an alkali developer by the action of an acid, and (B) generates an acid upon irradiation with actinic rays or radiation. And a resin containing a repeating unit having a lactone structure substituted with a fluorine atom-containing group (C).

In general formula (A1),
R ₁ represents a hydrogen atom, an alkyl group, a fluorinated alkyl group, a halogen atom or CH ₂ OH.
R ₂ represents an alkylene group, a cycloalkylene group, or a divalent linking group obtained by combining them.
n represents an integer of 0 to 5.

When n is 2 or more, the plurality of R ₂ may be the same or different.

[2] The composition according to [1], wherein the resin (A) contains a repeating unit represented by the following general formula (A2).

In general formula (A2),
R ₁ c represents a hydrogen atom, a methyl group, a trifluoromethyl group, or CH ₂ OH.
R ₂ c to R ₄ c each independently represents a hydrogen atom or a hydroxyl group. However, at least one of R ₂ c to R ₄ c represents a hydroxyl group.
[3] The composition according to [1] or [2], wherein the resin (A) includes a lactone structure having a cyano group.

[4] The composition according to any one of [1] to [3], wherein the resin (A) contains a repeating unit represented by the following general formula (III).

In general formula (III):
A represents an ester bond or an amide bond.
R ₀ represents an alkylene group, a cycloalkylene group or a divalent linking group obtained by combining them, and when there are a plurality of R ₀ groups, they may be the same or different.
Z represents an ether bond, an ester bond, an amide bond, a urethane bond or a urea bond, and when there are a plurality thereof, they may be the same or different.
R ₈ represents a monovalent organic group having a lactone structure.
n is the repeating number of the structure represented by —R ₀ —Z—, and represents an integer of 1 to 5.
R ₇ represents a hydrogen atom, a halogen atom or an alkyl group.

[5] A resist film formed using the composition according to any one of [1] to [4].
[6] A pattern forming method comprising forming a film using the composition according to any one of [1] to [4], exposing the film, and developing the exposed film.
[7] The pattern forming method as described in [6], wherein the exposure is immersion exposure.

  According to the present invention, it is possible to form a pattern having excellent coating film thickness uniformity and pattern dimensional uniformity.

Hereinafter, the present invention will be described in detail.
In addition, in the description of the group (atomic group) in this specification, the description which does not describe substitution and non-substitution includes what 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).

<(A) Resin whose dissolution rate in an alkaline developer is increased by the action of an acid>
The actinic ray-sensitive or radiation-sensitive resin composition of the present invention is a resin (hereinafter also referred to as “acid-decomposable resin” or “resin (A)”) whose dissolution rate in an alkaline developer is increased by the action of an acid. contains.
Resin (A) contains the repeating unit represented by the following general formula (A1). It is important for the resin (A) to contain a repeating unit containing an alkali-soluble group represented by the general formula (A1) in order to exhibit the effects of the present invention.

In General Formula (A1), R ₁ represents a hydrogen atom, an alkyl group, a fluorinated alkyl group, a halogen atom, or CH ₂ OH. R ₂ represents an alkylene group, a cycloalkylene group, or a divalent linking group obtained by combining them. n represents an integer of 0 to 5. When n is 2 or more, the plurality of R ₂ may be the same or different.

The alkyl group for R ₁ may be linear or branched. For example, an alkyl group having 1 to 3 carbon atoms is preferable, and specific examples include a methyl group, an ethyl group, a propyl group, and an isopropyl group. . The alkyl group may have a substituent, and examples of the substituent include a fluorine atom and a hydroxyl group, and among them, a fluorine atom is preferable.
Examples of the halogen atom for R ₁ include a fluorine atom and a bromine atom, and among them, a fluorine atom is preferable.
Preferred examples of R ₁ include a hydrogen atom, a methyl group, a trifluoromethyl group, and a hydroxymethyl group.

As the alkylene group for R ₂ , for example, an alkylene group having 1 to 3 carbon atoms is preferable, and specific examples include a methylene group, an ethylene group, and a propylene group.
The cycloalkylene group for R ₂ may be monocyclic or polycyclic, and for example, a monocyclic or polycyclic cycloalkylene group having 5 to 12 carbon atoms is preferable. Specific examples of the cycloalkylene group include a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a norbornyl group, an adamantyl group, and the like.
R ₂ may be a divalent linking group in which two or more of these groups are combined.
Preferred examples of R ₂ include a methylene group, an ethylene group, a cyclohexyl group, and an adamantyl group.
n is preferably an integer of 0 to 3.

As for the content rate of the repeating unit represented by general formula (A1), 1-30 mol% is preferable with respect to all the repeating units in resin (A), More preferably, it is 1-20 mol%, More preferably, it is 1-15 mol%. It is.
Specific examples of the repeating unit represented by formula (A1) are shown below, but the present invention is not limited thereto.

The resin (A) may further contain a repeating unit other than the repeating unit represented by the general formula (A1) as a repeating unit having an alkali-soluble group.
Examples of the alkali-soluble group include a carboxyl group, a sulfonamide group, a sulfonylimide group, a bisulsulfonylimide group, and an aliphatic alcohol (for example, hexafluoroisopropanol group) substituted with an electron withdrawing group at the α-position. It is more preferable to have a repeating unit. By further containing a repeating unit having an alkali-soluble group other than the repeating unit represented by the general formula (A1), the resolution in the contact hole application is increased.

Although the specific example of the repeating unit which has an alkali-soluble group other than the repeating unit represented by general formula (A1) is shown below, this invention is not limited to this.
In specific examples, Rx represents H, CH ₃ , CH ₂ OH, or CF ₃ .

The acid-decomposable resin (A) is a group (hereinafter referred to as “acid-decomposable group”) that is decomposed by the action of an acid to generate an alkali-soluble group in the main chain or side chain of the resin, or in both the main chain and the side chain. It is preferable to have (also called).
The resin (A) is preferably insoluble or hardly soluble in an alkali developer.

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

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

A preferable group as the acid-decomposable group is a group 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 which may have a substituent, or a group represented by —CH ₂ —R ₉ . R ₉ represents a hydroxy group or a monovalent organic group, and examples thereof include an alkyl group 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. A monocyclic cycloalkyl group having 5 to 6 carbon atoms is particularly preferable.
An embodiment in which Rx ₁ is a methyl group or an ethyl group, and Rx ₂ and Rx ₃ are combined to form the cycloalkyl group described above is preferred.

  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 (A).

  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 (I) and the repeating unit represented by the general formula (II) as the repeating unit represented by the general formula (AI). More preferably.

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

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.

R represents an atomic group necessary for forming an alicyclic structure together with a carbon atom. The alicyclic structure formed by R is preferably a monocyclic alicyclic structure, and the carbon number thereof is preferably 3 to 7, 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.

As a repeating unit represented by general formula (I), the repeating unit represented by the following general formula (1-a) is mentioned, for example.

In formula, R < ₁ > and R < ₂ > are synonymous with each in General formula (1).

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

In formula (II-1),
R < ₃ > -R < ₅ > is synonymous with the thing in general formula (II).
R ₁₀ represents a substituent containing a polar group. When a plurality of R ₁₀ are present, they may be the same as or different from each other. Examples of the substituent 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. As the branched alkyl group, an isopropyl group is particularly preferable.
p represents an integer of 0 to 15. p is preferably 0 to 2, more preferably 0 or 1.

  The acid-decomposable resin is a resin containing at least one of the repeating unit represented by the general formula (I) and the repeating unit represented by the general formula (II) as the repeating unit represented by the general formula (AI). More preferably. In another embodiment, a resin containing at least two kinds of repeating units represented by the general formula (I) as the repeating unit represented by the general formula (AI) is more preferable.

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

The resin (A) preferably contains a repeating unit having a lactone structure represented by the following general formula (III).

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

Or urea bond

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

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

The alkylene group and cycloalkylene group represented by R ₀ may have a substituent.
Z is preferably an ether bond or an ester bond, and particularly preferably an ester bond.

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

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

The substituent having a lactone structure represented by R ₈ is not limited as long as it has a lactone structure, and is represented by general formulas (LC1-1) to (LC1-17) described later as specific examples. Among them, the structure represented by (LC1-4) is particularly preferable. Further, n ₂ in (LC1-1) to (LC1-17) is more preferably 2 or less.
R ₈ is preferably a monovalent organic group having an unsubstituted lactone structure or a monovalent organic group having a lactone structure having a methyl group, a cyano group or an alkoxycarbonyl group as a substituent. A monovalent organic group having a lactone structure (cyanolactone) as is more preferable.

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

The repeating unit having a lactone structure is more preferably a repeating unit represented by the following general formula (III-1).

In general formula (III-1),
R ₇ , A, R ₀ , Z, and n are as defined in the general formula (III).
R ₉ independently represents an alkyl group, a cycloalkyl group, an alkoxycarbonyl group, a cyano group, a hydroxyl group or an alkoxy group, when there are a plurality of R _{9 s} , May be formed.

X represents an alkylene group, an oxygen atom or a sulfur atom.
m is the number of substituents and represents an integer of 0 to 5. m is preferably 0 or 1.

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

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

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

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

  The content of the repeating unit represented by the general formula (III) is preferably 15 to 60 mol%, more preferably 20 to 60 mol in total with respect to all repeating units in the resin (A) when plural types are contained. %, More preferably 30 to 50 mol%.

  The resin (A) may contain a repeating unit having a lactone group in addition to the unit represented by the general formula (III).

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

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

In general formula (AII ′),
Rb ₀ represents a hydrogen atom, a halogen atom or an alkyl group having 1 to 4 carbon atoms. Preferred substituents that the alkyl group represented by Rb ₀ may have include a hydroxyl group and a halogen atom. Examples of the halogen atom for Rb ₀ include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. Preferred are a hydrogen atom, a methyl group, a hydroxymethyl group, and a trifluoromethyl group, and a hydrogen atom and a methyl group are particularly preferred.

V represents a group having a structure represented by any one of the general formulas (LC1-1) to (LC1-17).
Specific examples of the repeating unit having a lactone group other than the unit represented by the general formula (III) are shown below, but the present invention is not limited thereto.

Examples of the repeating unit having a lactone group other than the unit represented by the general formula (III) include the following repeating units. By selecting an optimal lactone group, the pattern profile and the density dependency are improved.

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

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

  In order to enhance the effect of the present invention, two or more lactone repeating units selected from general formula (III) can be used in combination. When using together, it is preferable to select and use 2 or more types from the lactone repeating unit whose n is 1 among general formula (III).

  In one embodiment, the resin (A) preferably includes a lactone structure having a cyano group. The form is not limited. For example, in the repeating unit represented by the general formula (III), the lactone structure may be substituted with a cyano group, or other than the repeating unit represented by the general formula (III). In the above-mentioned repeating unit having a lactone group, the lactone structure may be substituted with a cyano group.

  The content of the repeating unit containing a lactone structure having a cyano group is preferably 15 to 60 mol%, more preferably 20 to 50 mol%, based on the total number of repeating units in the resin (A) when a plurality of types are contained. More preferably, it is 30-50 mol%.

The resin (A) preferably has a repeating unit having a hydroxyl group or a cyano group other than the general formulas (AI) and (III). This improves the substrate adhesion and developer compatibility. The repeating unit having a hydroxyl group or a cyano group is preferably a repeating unit having an alicyclic hydrocarbon structure substituted with a hydroxyl group or a cyano group, and preferably has no acid-decomposable group. The alicyclic hydrocarbon structure in the alicyclic hydrocarbon structure substituted with a hydroxyl group or a cyano group is preferably an adamantyl group, a diamantyl group, or a norbornane group. As the alicyclic hydrocarbon structure substituted with a preferred hydroxyl group or cyano group, partial structures represented by the following general formulas (VIIa) to (VIId) are preferred.

In general formulas (VIIa) to (VIIc),
R ₂ c to R ₄ c each independently represents a hydrogen atom, a hydroxyl group or a cyano group. However, at least one of R ₂ c to R ₄ c represents a hydroxyl group or a cyano group. Preferably, one or _two members out 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.

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

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

In one aspect, the resin (A) preferably contains a repeating unit represented by the general formula (AIIa), in which at least one of R ₂ c to R ₄ c is a hydroxyl group and the remainder is a hydrogen atom. preferable.

  The content of the above repeating unit having a hydroxyl group or a cyano group is preferably 5 to 40 mol%, more preferably 5 to 30 mol%, still more preferably 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.

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

In general formula (IV), R ₅ represents a hydrocarbon group having at least one cyclic structure and having 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 cycloalkenyl having 3 to 12 carbon atoms such as cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclooctyl group and the like, and cycloalkyl groups having 3 to 12 carbon atoms and cyclohexenyl group. Groups. Preferable monocyclic hydrocarbon groups are monocyclic hydrocarbon groups having 3 to 7 carbon atoms, and more preferable examples include a cyclopentyl group and a cyclohexyl group.

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

Preferred examples of the bridged cyclic hydrocarbon ring include a norbornyl group, an adamantyl group, a bicyclooctanyl group, a tricyclo [5,2,1,0 ^2,6 ] decanyl group, and the like. More preferable examples of the bridged cyclic hydrocarbon ring include a norbornyl group and an adamantyl group.

  These 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 .

  Resin (A) used in the composition of the present invention has a dry etching resistance, standard developer suitability, substrate adhesion, resist profile, and resolving power, which is a general necessary characteristic of resist, in addition to the above repeating structural units. It can have various repeating structural units for the purpose of adjusting 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 composition of the present invention preferably has no aromatic group from the viewpoint of transparency to ArF light. ) Preferably has a monocyclic or polycyclic alicyclic hydrocarbon structure.
In addition, it is preferable that resin (A) does not contain a fluorine atom and a silicon atom from a compatible viewpoint with hydrophobic resin (C) 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. Moreover, the alicyclic hydrocarbon substituted by the (meth) acrylate type repeating unit 20-50 mol% which has an acid-decomposable group, the (meth) acrylate type repeating unit 20-50 mol% which has a lactone group, and a hydroxyl group or a cyano group. A copolymer containing 5 to 30 mol% of a (meth) acrylate-based repeating unit having a structure and further containing 0 to 20 mol% of another (meth) acrylate-based repeating unit is also preferred.

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

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

  The resin (A) of the present invention can be synthesized according to a conventional method (for example, radical polymerization). For example, as a general synthesis method, a monomer polymerization method in which a monomer species and an initiator are dissolved in a solvent and heating is performed, and a solution of the monomer species and the initiator is dropped into the heating solvent over 1 to 10 hours. The dropping polymerization method is added, and the dropping polymerization method is preferable. Examples of the reaction solvent include ethers such as tetrahydrofuran, 1,4-dioxane, diisopropyl ether, ketones such as methyl ethyl ketone and methyl isobutyl ketone, ester solvents such as ethyl acetate, amide solvents such as dimethylformamide and dimethylacetamide, Furthermore, the solvent which melt | dissolves the composition of this invention like the below-mentioned propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, and cyclohexanone is mentioned. More preferably, the polymerization is performed using the same solvent as the solvent used in the photosensitive composition of the present invention. Thereby, generation | occurrence | production of the particle at the time of a preservation | save can be suppressed.

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

  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 3,000 to 10,000. By setting the weight average molecular weight to 1,000 to 200,000, deterioration of heat resistance and dry etching resistance can be prevented, developability is deteriorated, and viscosity is increased, resulting in deterioration of film forming property. Can be prevented.

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

In the present invention, the blending ratio of the resin (A) in the entire composition is preferably from 30 to 99 mass%, more preferably from 60 to 95 mass%, based on the total solid content.
In addition, the resins of the present invention may be used alone or in combination.
In addition, you may use together other resin other than resin (A) of this invention in the range which does not impair the effect of this invention. Examples of the resin other than the resin (A) of the present invention include an acid-decomposable resin that may contain a repeating unit that can be contained in the resin (A), and other known acid-decomposable resins. be able to.

<(C) Resin including a repeating unit having a lactone structure substituted with a group having a fluorine atom>
The actinic ray-sensitive or radiation-sensitive resin composition of the present invention includes a resin (hereinafter referred to as “resin (C)” or “hydrophobic” including a repeating unit (c0) having a lactone structure substituted with a group having a fluorine atom. Also called “resin”.
The lactone structure which the repeating unit (c0) has is represented by the following general formula (KA-0). Here, X represents a carboxylic acid ester group (—COO—).

The lactone ring represented by the general formula (KA-0) is preferably a 5- to 7-membered lactone ring.
In addition, as in the following (KA-1-1) to (KA-1-17), a 5- to 7-membered lactone ring as a partial structure represented by the general formula (KA-0) has a bicyclo structure, a spiro It is preferred that other ring structures are condensed in a form that forms the structure.

  Regarding the peripheral ring structure to which the ring structure represented by the general formula (KA-0) may be bonded, for example, those in the following (KA-1-1) to (KA-1-17), or The thing according to can be mentioned.

As the structure containing the lactone ring structure represented by the general formula (KA-0), a structure represented by any of the following (KA-1-1) to (KA-1-17) is more preferable. The lactone structure may be directly bonded to the main chain. Preferred structures include (KA-1-1), (KA-1-4), (KA-1-5), (KA-1-6), (KA-1-13), (KA-1- 14) and (KA-1-17).

In the repeating unit (c0), the lactone ring represented by the general formula (KA-0) is substituted with a group having a fluorine atom. The form is not particularly limited as long as the fluorine atom is contained in the structure of the general formula (KA-0). For example, the substituent having a fluorine atom selected from the specific examples of the substituent Z _ka1 described later is a lactone ring (in the above (KA-1-1) to (KA-1-17), other rings In the case where the repeating unit (c0) has two or more polar conversion groups, for example, a general formula (KY-2) described later may be used. ) In which the substituent represented by R _ky5 has a fluorine atom. The lactone ring may be substituted with any group that does not contain a fluorine atom from the specific examples of the substituent Z _ka1 described later.

Examples of the repeating unit (c0) include a repeating unit represented by the general formula (K0).

In the formula, R _k1 represents a hydrogen atom, a halogen atom, a hydroxyl group, an alkyl group, a cycloalkyl group, an aryl group, or a group containing a polarity converting group.
Here, the polar converting group represents a group that decomposes by the action of an alkali developer and increases the solubility in the alkali developer. For example, carboxylic acid ester group (—COO—), acid anhydride group (—C (O) OC (O) —), acid imide group (—NHCONH—), carboxylic acid thioester group (—COS—), carbonate ester Examples include a group (—OC (O) O—), a sulfate ester group (—OSO ₂ O—), a sulfonate ester group (—SO ₂ O—), and the like.

In addition, since the ester group directly bonded to the main chain of the repeating unit, such as in acrylate, has a poor function of being decomposed by the action of the alkali developer and increasing the solubility in the alkali developer, the polar group in the present invention Is not included.
R _k2 represents a group containing a lactone structure substituted with a group having a fluorine atom. Here, examples of the lactone structure include structures represented by any of the above-mentioned (KA-1-1) to (KA-1-17).

Specific examples of the group represented by R _k2 include the following general formulas (KY-2), (KY-3), (KY-4), (KY-5), (cc), and (ca-2). ) And (cb-2).
Since the lactone structure has a carboxylic acid ester group (—COO—), it has a function as a polarity conversion group.

As in the case where R _k1 in the general formula (K0) is a polar converting group, the repeating unit (c0) may further have a polar converting group in addition to the lactone structure. The resin (C) may be a copolymer having, in addition to the repeating unit (c0), another repeating unit (c) having a polar conversion group.

  Below, the repeating unit (c0) may have a polar conversion group other than the carboxylic acid ester group constituting the lactone ring, or the resin (C) having another repeating unit (c) The polar conversion group possessed by at least one or more of the other repeating unit (c) in the case of a combination will be described.

The polar conversion group is preferably a group represented by X in the partial structure represented by the general formula (KA-1) or (KB-1).

X ′ in the general formula (KA-1) or (KB-1) is a carboxylate group: —COO—, an acid anhydride group: —C (O) OC (O) —, an acid imide group: —NHCONH— , Carboxylic acid thioester group: —COS—, carbonate ester group: —OC (O) O—, sulfate ester group: —OSO ₂ O—, sulfonate ester group: —SO ₂ O—.
Y ¹ and Y ² may be the same or different and each represents an electron-withdrawing group.

The repeating unit (c) has a group having a partial structure represented by the general formula (KA-1) or (KB-1), and thus has a preferred polarity conversion group, but the general formula (KA-1 In the case where the partial structure does not have a bond as in the case of the partial structure represented by (KB-1) when Y ¹ and Y ² are monovalent, The partial structure is a monovalent or higher valent group in which at least one arbitrary hydrogen atom in the partial structure is removed.
The partial structure represented by the general formula (KA-1) or (KB-1) is linked to the main chain of the resin (C) through a substituent at an arbitrary position.

The partial structure represented by the general formula (KA-1) is a structure that forms a ring structure together with a group as X ′.
X ′ in the general formula (KA-1) is preferably a carboxylic acid ester group (that is, when a lactone ring structure is formed as KA-1), an acid anhydride group, or a carbonate ester group. More preferably, it is a carboxylic acid ester group.

The ring structure represented by the general formula (KA-1) may have a substituent, for example, may have nka substituents Z _ka1 .

Z _ka1 independently represents an alkyl group, a cycloalkyl group, an ether group, a hydroxyl group, an amide group, an aryl group, a lactone ring group, or an electron-withdrawing group, when there are a plurality of Z _ka1 .

Z _ka1 may be linked to form a ring. Examples of the ring formed by connecting Z _{ka1 to} each other include a cycloalkyl ring and a hetero ring (a cyclic ether ring, a lactone ring, etc.).

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

The electron-withdrawing group as Z _{ka1 is the same} as the electron-withdrawing group as Y ¹ and Y ² described later represented by a halogen atom.
The electron withdrawing group may be substituted with another electron withdrawing group.

Z _ka1 is preferably an alkyl group, a cycloalkyl group, an ether group, a hydroxyl group, or an electron withdrawing group, and more preferably an alkyl group, a cycloalkyl group, or an electron withdrawing group. In addition, as an ether group, the thing substituted by the alkyl group or the cycloalkyl group, ie, the alkyl ether group, etc. are preferable. Preferred examples of the electron withdrawing group is the same as the electron-withdrawing group of Y ¹ and Y ² described later.

Examples of the halogen atom as Z _ka1 include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom, and a fluorine atom is preferable.

The alkyl group as Z _ka1 may have a substituent and may be linear or branched. As a linear alkyl group, Preferably it is C1-C30, More preferably, it is 1-20, for example, a methyl group, an ethyl group, n-propyl group, n-butyl group, sec-butyl group, t-butyl. Group, n-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, n-nonyl group, n-decanyl group and the like. As a branched alkyl group, Preferably it is C3-C30, More preferably, it is 3-20, for example, i-propyl group, i-butyl group, t-butyl group, i-pentyl group, t-pentyl group, Examples include i-hexyl group, t-hexyl group, i-heptyl group, t-heptyl group, i-octyl group, t-octyl group, i-nonyl group, t-decanoyl group and the like. C1-C4 things, such as a methyl group, an ethyl group, n-propyl group, i-propyl group, n-butyl group, i-butyl group, t-butyl group, are preferable.

The cycloalkyl group as Z _ka1 may have a substituent, may be monocyclic, polycyclic, or bridged. For example, the cycloalkyl group may have a bridged structure. The monocyclic type is preferably a cycloalkyl group having 3 to 8 carbon atoms, and examples thereof include a cyclopropyl group, a cyclopentyl group, a cyclohexyl group, a cyclobutyl group, and a cyclooctyl group. Examples of the polycyclic type include groups having a bicyclo, tricyclo, tetracyclo structure or the like having 5 or more carbon atoms, and a cycloalkyl group having 6 to 20 carbon atoms is preferable. For example, an adamantyl group, norbornyl group, isobornyl group, Examples thereof include a camphanyl group, a dicyclopentyl group, an α-pinel group, a tricyclodecanyl group, a tetocyclododecyl group, and an androstanyl group. As the cycloalkyl group, the following structure is also preferable. A part of carbon atoms in the cycloalkyl group may be substituted with a hetero atom such as an oxygen atom.

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

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

_Examples of the lactone ring group of Z _ka1 include a group in which a hydrogen atom is removed from the structure represented by any one of (KA-1-1) to (KA-1-17) described later.
Examples of the aryl group for Z _ka1 include a phenyl group and a naphthyl group.

Examples of the substituent that the alkyl group, cycloalkyl group and aryl group of Z _ka1 may further include a hydroxyl group, a halogen atom (fluorine, chlorine, bromine, iodine), a nitro group, a cyano group, the above alkyl group, a methoxy group, Alkoxy groups such as ethoxy group, hydroxyethoxy group, propoxy group, hydroxypropoxy group, n-butoxy group, isobutoxy group, sec-butoxy group and t-butoxy group, alkoxycarbonyl groups such as methoxycarbonyl group and ethoxycarbonyl group, benzyl Group, phenethyl group, aralkyl group such as cumyl group, aralkyloxy group, formyl group, acetyl group, butyryl group, benzoyl group, cyanyl group, acyl group such as valeryl group, acyloxy group such as butyryloxy group, the above alkenyl group, Vinyloxy group, propenyloxy group, allylo Shi group, and alkenyloxy groups such as butenyloxy, said aryl group, an aryloxy group such as phenoxy group, aryloxycarbonyl group such as benzoyloxy group.

  In general formula (KA-1), X ′ is a carboxylic acid ester group, and the partial structure represented by general formula (KA-1) is preferably a lactone ring, and is a 5- to 7-membered lactone ring. Is preferred.

  In addition, as in the above (KA-1-1) to (KA-1-17), a bicyclo structure is added to a 5- to 7-membered lactone ring as a partial structure represented by the general formula (KA-1). The other ring structure is preferably condensed so as to form a spiro structure.

  As for the peripheral ring structure to which the ring structure represented by the general formula (KA-1) may be bonded, for example, those in the following (KA-1-1) to (KA-1-17), or The thing according to can be mentioned.

As a structure containing a lactone ring structure represented by the general formula (KA-1), a structure represented by any one of the following (KA-1-1) to (KA-1-17) is more preferable. The lactone structure may be directly bonded to the main chain. Preferred structures include (KA-1-1), (KA-1-4), (KA-1-5), (KA-1-6), (KA-1-13), (KA-1- 14) and (KA-1-17).

  The structure containing the lactone ring structure may or may not have a substituent. Preferable substituents include those similar to the substituents that the ring structure represented by the general formula (KA-1) may have.

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

  Preferred examples of X ′ in the general formula (KB-1) include a carboxylic acid ester group (—COO—).

Y ¹ and Y ² in formula (KB-1) each independently represent an electron-withdrawing group.

The electron withdrawing group is preferably a partial structure represented by the following formula (EW). * In the formula (EW) represents a bond directly connected to (KA-1) or a bond directly connected to X ′ in (KB-1).

In formula (EW),
n _ew is the repeating number of the linking group represented by —C (R _ew1 ) (R _ew2 ) — and represents an integer of 0 or 1. When n _ew is 0, it represents a single bond, indicating that Y _ew1 is directly bonded.

Y _ew1 is a halogen atom, a cyano group, a nitrile group, a nitro group, a halo (cyclo) alkyl group represented by —C (R _f1 ) (R _f2 ) —R _f3 described later, a haloaryl group, an oxy group, or a carbonyl group. , A sulfonyl group, a sulfinyl group, and a combination thereof, and the electron-withdrawing group may have the following structure, for example. The “halo (cyclo) alkyl group” represents an alkyl group or a cycloalkyl group that is at least partially halogenated. R _ew3 and R _ew4 each independently represent an arbitrary structure. R _ew3 and R _ew4 may have any structure, and the partial structure represented by the formula (EW) may have an electron withdrawing property, and may be linked to, for example, the main chain of the resin. An alkyl group and a fluorinated alkyl group;

When Y _ew1 is a divalent or higher group, the remaining bond forms a bond with an arbitrary atom or substituent. At least one group of Y _ew1 , R _ew1 , and R _ew2 may be connected to the main chain of the resin (C) through a further substituent.

Y _ew1 is preferably a halogen atom, or a halo (cyclo) alkyl group or haloaryl group represented by —C (R _f1 ) (R _f2 ) —R _f3 .

R _ew1 and R _ew2 each independently represent an arbitrary substituent, for example, a hydrogen atom, an alkyl group, a cycloalkyl group, or an aryl group.

At least two of R _ew1 , R _ew2 and Y _ew1 may be connected to each other to form a ring.

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

R _f2 and R _f3 each independently represent a hydrogen atom, a halogen atom or an organic group, and R _f2 and R _f3 may be linked to form a ring. Examples of the organic group include an alkyl group, a cycloalkyl group, and an alkoxy group, which may be substituted with a halogen atom (preferably a fluorine atom), and more preferably R _f2 and R _f3 are (halo) It is an alkyl group. More preferably, R _f2 represents the same group as R _f1 or is linked to R _f3 to form a ring.

R _f1 and R _f3 may be linked to form a ring, and examples of the ring formed include a (halo) cycloalkyl ring and a (halo) aryl ring.

Examples of the (halo) alkyl group in R _{f1 to} R _f3 include the alkyl group in Z _ka1 described above and a structure in which this is halogenated.

Examples of the (per) halocycloalkyl group and the (per) haloaryl group in R _{f1 to} R _f3 or in the ring formed by linking R _f2 and R _f3 include, for example, the aforementioned cycloalkyl group in Z _ka1 is a halogen atom. And a perfluoroaryl group represented by -C _(n) F _(n-1) and more preferably a fluorocycloalkyl group represented by -C _(n) F _(2n-2) H Can be mentioned. Although carbon number n is not specifically limited here, the thing of 5-13 is preferable and 6 is more preferable.

The ring that may be formed by linking at least two of R _ew1 , R _ew2 and Y _ew1 preferably includes a cycloalkyl group or a heterocyclic group, and the heterocyclic group is preferably a lactone ring group. Examples of the lactone ring include structures represented by the above formulas (KA-1-1) to (KA-1-17).

  As described above, the repeating unit (c0) may have a partial structure represented by the general formula (KA-1) or a partial structure represented by the general formula (KB-1). Alternatively, the repeating unit (c0) may have both the partial structure of the general formula (KA-1) and the general formula (KB-1). In the repeating unit (c) that can be copolymerized with the repeating unit (c0), a plurality of partial structures represented by the general formula (KA-1) and a partial structure represented by the general formula (KB-1) You may have multiple or both the partial structure of general formula (KA-1) and general formula (KB-1).

In addition, part or all of the partial structure of the general formula (KA-0) or the general formula (KA-1) also serves as an electron withdrawing group as Y ¹ or Y ² in the general formula (KB-1). Also good. For example, when X in General Formula (KA-0) or X ′ in General Formula (KA-1) is a carboxylic acid ester group, the carboxylic acid ester group is Y ¹ in General Formula (KB-1) or It may function as an electron withdrawing group as Y ² .

When the polarity conversion group is decomposed by the action of an alkali developer and converted in polarity, the receding contact angle with water of the resin composition film after alkali development can be lowered.
The receding contact angle with water of the resin composition film after alkali development is preferably 50 ° or less, more preferably 40 ° or less at the temperature at the time of exposure, usually room temperature 23 ± 3 ° C. and humidity 45 ± 5%. More preferably, it is 35 ° or less, and most preferably 30 ° or less.

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

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

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

  In the present invention, it is preferable that the repeating unit (c0) further contains one or more polar conversion groups other than the lactone ring represented by the above general formula (KA-0).

When the repeating unit (c0) has at least one polar converting group other than the lactone structure substituted with a group having a fluorine atom, the repeating unit (c0) has a partial structure represented by the following general formula (KY-2). It is preferable to have. Note that the structure represented by the general formula (KY-2) is a monovalent or higher group obtained by removing at least one arbitrary hydrogen atom in the structure.

In formula (KY-2),
R _{ky6 to} R _ky10 are each independently a hydrogen atom, halogen atom, alkyl group, cycloalkyl group, carbonyl group, carbonyloxy group, oxycarbonyl group, ether group, hydroxyl group, cyano group, amide group, or aryl. Represents a group.
Two or more of R _{ky6 to} R _ky10 may be connected to each other to form a monocyclic or polycyclic structure.
R _ky5 represents an electron withdrawing group. Examples of the electron withdrawing group include the same groups as those described above for Y ¹ and Y ² , and preferably a halogen atom or a halo (cyclo (cyclo) represented by —C (R _f1 ) (R _f2 ) —R _f3. ) An alkyl group or a haloaryl group.
Specific examples of R _{ky5 to} R _ky10 include the same groups as Z _ka1 in formula (KA-1).

At least one of R _{ky5 to} R _ky10 contains a fluorine atom. Preferably, at least R _ky5 contains a fluorine atom.

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

In formula (KY-3),
Z _ka1 and nka each have the same meaning as in the general formula (KA-1). R _ky5 has the same _{meaning as} in formula (KY-2).

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

At least one of Z _ka1 and R _ky5 contains a fluorine atom. Preferably, at least R _ky5 contains a fluorine atom.

  The repeating unit (c0) is not limited as long as it is a repeating unit obtained by polymerization such as addition polymerization, condensation polymerization, addition condensation, etc., but is a repeating unit obtained by addition polymerization of a carbon-carbon double bond. Preferably there is. Examples include acrylate-based repeating units (including those having substituents at the α-position and β-position), styrene-based repeating units (including those having substituents at the α-position and β-position), vinyl ether-based repeating units, norbornene-based Repeating units, maleic acid derivatives (maleic anhydride and derivatives thereof, maleimides, etc.), and the like, acrylate-based repeating units, styrene-based repeating units, vinyl ether-based repeating units, norbornene-based repeating units An acrylate-based repeating unit, a vinyl ether-based repeating unit, and a norbornene-based repeating unit are more preferable, and an acrylate-based repeating unit is most preferable.

As a more specific structure of the repeating unit (c0), a repeating unit having the partial structure shown below is preferable.

In the general formula (KY-4),
R ₂ represents a chain or cyclic alkylene group, and when there are a plurality of R ₂ groups, they may be the same or different.
R ₃ represents a linear, branched or cyclic hydrocarbon group in which part or all of the hydrogen atoms on the constituent carbons are substituted with fluorine atoms.
R ₄ is a halogen atom, cyano group, hydroxy group, amide group, alkyl group, cycloalkyl group, alkoxy group, phenyl group, acyl group, alkoxycarbonyl group, or R—C (═O) — or R—C ( = O) A group represented by O- (R represents an alkyl group or a cycloalkyl group). If R ₄ is a plurality may be the same or different, and two or more R ₄ are attached, may form a ring.
X represents an alkylene group, an oxygen atom, or a sulfur atom.

Z and Za each independently represent a single bond, an ether bond, an ester bond, an amide bond, a urethane bond or a urea bond, and when there are a plurality of Z and Za, they may be the same or different.
* Represents a bond to the main chain or side chain of the resin.
o is the number of substituents and represents an integer of 1 to 7.
m is the number of substituents and represents an integer of 0 to 7.
n represents the number of repetitions and represents an integer of 0 to 5.
The chain alkylene group as R ₂ is preferably a linear alkylene group, preferably having 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, and more preferably 3 to 30 carbon atoms in the case of a branched alkylene group. Is 3-20. Specific examples of the chain alkylene group as R ₂ include a group obtained by removing one arbitrary hydrogen atom from the above-described specific examples of the alkyl group as Z _ka1 .

The cyclic alkylene group as R ₂ preferably has 3 to 8 carbon atoms, and specific examples thereof include a group in which one arbitrary hydrogen atom has been removed from the cycloalkyl group as Z _ka1 described above. .

The structure represented by —R ₂ —Z— is preferably a structure represented by — (CH ₂ ) ₁ —COO— (l represents an integer of 1 to 5).

The linear, branched or cyclic hydrocarbon group as R ₃ has preferably 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, and preferably 3 carbon atoms when branched. -30, more preferably 3-20, and in the case of a ring, it is 6-20. Specific examples of R ₃ include specific examples of the alkyl group and cycloalkyl group as Z _ka1 described above. Preferred carbon numbers and specific examples of the alkyl group and cycloalkyl group as R ₄ and R are the same as those described in the alkyl group and cycloalkyl group as Z _ka1 described above.

The acyl group as R ₄ is preferably one having 1 to 6 carbon atoms, and examples thereof include a formyl group, acetyl group, propionyl group, butyryl group, isobutyryl group, valeryl group, and pivaloyl group.

Examples of the alkyl moiety in the alkoxy group and alkoxycarbonyl group as R ₄ include a linear, branched or cyclic alkyl moiety, and the preferred carbon number of the alkyl moiety and specific examples thereof are those described above for Z _ka1. The same as those described in the alkyl group and cycloalkyl group.

Examples of the alkylene group as X include a chain or cyclic alkylene group, and preferred carbon numbers and specific examples thereof are the same as those described for the chain alkylene group and cyclic alkylene group as R ₂ .

More preferred is a repeating unit having a partial structure represented by formula (KY-5).

In general formula (KY-5),
R ₂ represents a chain or cyclic alkylene group, and when there are a plurality of R ₂ groups, they may be the same or different.

R ₃ represents a linear, branched or cyclic hydrocarbon group in which part or all of the hydrogen atoms on the constituent carbons are substituted with fluorine atoms.

R ₄ is a halogen atom, cyano group, hydroxy group, amide group, alkyl group, cycloalkyl group, alkoxy group, phenyl group, acyl group, alkoxycarbonyl group, or R—C (═O) — or R—C ( = O) A group represented by O- (R represents an alkyl group or a cycloalkyl group). If R ₄ is a plurality may be the same or different, and two or more R ₄ are attached, may form a ring.

  X represents an alkylene group, an oxygen atom, or a sulfur atom.

  Z represents a single bond, an ether bond, an ester bond, an amide bond, a urethane bond or a urea bond, and when there are a plurality thereof, they may be the same or different.

  * Represents a bond to the main chain or side chain of the resin.

  n represents the number of repetitions and represents an integer of 0 to 5.

  m is the number of substituents and represents an integer of 0 to 7.

The preferable range and specific examples of the carbon number in R _{2 to} R ₄ and X are the same as those described in the general formula (KY-4).

The structure represented by —R ₂ —Z— is preferably a structure represented by — (CH ₂ ) ₁ —COO— (l represents an integer of 1 to 5).

In general formulas (rf-1) and (rf-2),
X ′ represents an electron-withdrawing substituent, preferably a carbonyloxy group, an oxycarbonyl group, an alkylene group substituted with a fluorine atom, or a cycloalkylene group substituted with a fluorine atom.

  A represents a single bond or a divalent linking group represented by -C (Rx) (Ry)-. Here, Rx and Ry are each independently a hydrogen atom, a fluorine atom, an alkyl group (preferably having 1 to 6 carbon atoms and optionally substituted with a fluorine atom or the like), or a cycloalkyl group (preferably a carbon atom). And may be substituted with a fluorine atom or the like. Rx and Ry are preferably a hydrogen atom, an alkyl group, or an alkyl group substituted with a fluorine atom.

  X represents an electron withdrawing group, and preferably an fluorinated alkyl group, a fluorinated cycloalkyl group, an aryl group substituted with fluorine or a fluorinated alkyl group, an aralkyl group substituted with fluorine or a fluorinated alkyl group It is.

  * Represents a bond to the main chain or side chain of the resin. That is, it represents a bond that is bonded to the main chain of the resin through a single bond or a linking group.

  In addition, when X 'is a carbonyloxy group or an oxycarbonyl group, A is not a single bond.

The alkylene group in the alkylene group substituted with a fluorine atom as X ′ is preferably a linear alkylene group, preferably having 1 to 30 carbon atoms, more preferably 1 to 20, and preferably a branched alkylene group. It is C3-C30, More preferably, it is 3-20. Specific examples of the alkylene group include groups in which one arbitrary hydrogen atom has been removed from the specific examples of the alkyl group as Z _ka1 described above. The alkylene group substituted with a fluorine atom is preferably a perfluoroalkylene group.

The cycloalkylene group in the cycloalkylene group substituted with a fluorine atom as X ′ preferably has 3 to 8 carbon atoms, and specific examples thereof are arbitrary from the specific examples of the cycloalkyl group as Z _ka1 described above. And a group in which one hydrogen atom is removed. The cycloalkylene group substituted with a fluorine atom is preferably a perfluorocycloalkylene group.

The alkyl group in the fluorinated alkyl group as X is preferably a linear alkyl group having 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, and preferably a branched alkyl group having 3 to 30 carbon atoms. More preferably, it is 3-20. Specific examples of the alkyl group include specific examples of the alkyl group as Z _ka1 described above. The fluorinated alkyl group is preferably a perfluoroalkyl group.

The cycloalkyl group in the fluorinated cycloalkyl group as X preferably has 3 to 8 carbon atoms, and specific examples thereof include specific examples of the cycloalkyl group as Z _ka1 described above. The fluorinated cycloalkyl group is preferably a perfluorocycloalkyl group.

  The aryl group in the aryl group substituted with fluorine or a fluorinated alkyl group as X is preferably an aryl group having 6 to 12 carbon atoms, such as a phenyl group and a naphthyl group. Specific examples of the fluorinated alkyl group in the aryl group substituted with the fluorinated alkyl group are the same as those described for the fluorinated alkyl group as X.

  The aralkyl group in the aralkyl group substituted with fluorine or a fluorinated alkyl group as X is preferably an aralkyl group having 6 to 12 carbon atoms, such as benzyl group, phenethyl group, naphthylmethyl group, naphthylethyl group, naphthylbutyl. Groups and the like. Specific examples of the fluorinated alkyl group in the aralkyl group substituted with the fluorinated alkyl group are the same as those described for the fluorinated alkyl group as X.

In another embodiment, the repeating unit (c0) may be a repeating unit having the partial structure shown below.

In general formula (cc),
Z ₁ independently represents a single bond, an ether bond, an ester bond, an amide bond, a urethane bond or a urea bond, and preferably represents an ester bond, when a plurality of Z ₁ are present.

Z ₂ independently represents a chain or cyclic alkylene group, and preferably represents a C 1 or C 2 alkylene group or a C 5-10 cycloalkylene group.

Ta independently represents an alkyl group, a cycloalkyl group, an alkoxy group, a nitrile group, a hydroxyl group, an amide group, an aryl group, or an electron withdrawing group (as Y ¹ and Y ² in the general formula (KB-1)). And preferably represents an alkyl group, a cycloalkyl group, or an electron withdrawing group, and more preferably represents an electron withdrawing group. When there are a plurality of Tas, Tas may be bonded to form a ring.

L ₀ represents a single bond or an m + 1 valent hydrocarbon group (preferably having 20 or less carbon atoms), and preferably represents a single bond. The single bond as L ₀ is when m is 1. The m + 1 valent hydrocarbon group as L ₀ represents, for example, an m + 1 valent hydrocarbon group obtained by removing m-1 arbitrary hydrogen atoms from an alkylene group, a cycloalkylene group, a phenylene group, or a combination thereof. .

  L each independently represents a carbonyl group, a carbonyloxy group or an ether group.

Tc is a hydrogen atom, an alkyl group, a cycloalkyl group, a nitrile group, a hydroxyl group, an amide group, an aryl group or an electron withdrawing group (electron withdrawing as Y ¹ and Y ² in the general formula (KB-1)) It is synonymous with a sex group.

  * Represents a bond to the main chain or side chain of the resin. That is, the partial structure represented by the formula (cc) may be directly bonded to the main chain, or the partial structure represented by the formula (cc) may be bonded to the side chain of the resin. The bond to the main chain is a bond to an atom existing in the bond constituting the main chain, and the bond to the side chain is an atom existing outside the bond constituting the main chain. Is a bond to the hand.

  m represents an integer of 1 to 28, preferably an integer of 1 to 3, and more preferably 1.

  k represents an integer of 0 to 2, and is preferably 1.

q represents the number of repeating groups _(Z 2 -Z _1), represents an integer of 0 to 5, preferably 0-2.

  r represents an integer of 0 to 5.

In addition, in place of-(L) r-Tc, the -L _0- (Ta) m may be substituted.

  The case where the sugar lactone has a fluorine atom at the terminal and the case where the sugar lactone has a fluorine atom on a side chain different from the side chain on the sugar lactone side in the same repeating unit (repeating unit (c ″)) are also preferable.

The chain alkylene group as Z ₂ preferably has 1 to 30 carbon atoms, more preferably 1 to 20 in the case of a linear alkylene group, and preferably 3 to 30 carbon atoms in the case of a branched alkylene group. Is 3-20. Specific examples of the chain alkylene group as R ₂ include a group obtained by removing one arbitrary hydrogen atom from the above-described specific examples of the alkyl group as Z _ka1 .

The cyclic alkylene group as Z ₂ preferably has 3 to 8 carbon atoms, and specific examples thereof include a group in which one arbitrary hydrogen atom has been removed from the cycloalkyl group as Z _ka1 described above. .

Preferred carbon numbers and specific examples of the alkyl group and cycloalkyl group as Ta and Tc are the same as those described in the alkyl group and cycloalkyl group as Z _ka1 described above.

  The alkoxy group as Ta preferably has 1 to 8 carbon atoms, and examples thereof include a methoxy group, an ethoxy group, a propoxy group, and a butoxy group.

  The aryl group as Ta and Tc is preferably an aryl group having 6 to 12 carbon atoms, such as a phenyl group and a naphthyl group.

The preferred carbon number of the alkylene group and cycloalkylene group as L ₀ and specific examples thereof are the same as those described for the chain alkylene group and cyclic alkylene group as Z ₂ .

As a more specific structure of the repeating unit (c0), a repeating unit having the partial structure shown below is preferable.

In general formulas (ca-2) and (cb-2),
n represents an integer of 0 to 11, preferably an integer of 0 to 5, more preferably 1 or 2.

  p represents an integer of 0 to 5, preferably an integer of 0 to 3, more preferably 1 or 2.

Tb is independently an alkyl group, a cycloalkyl group, an alkoxy group, a nitrile group, a hydroxyl group, an amide group, an aryl group, or an electron withdrawing group (as Y ¹ and Y ² in the general formula (KB-1)). It is synonymous with an electron withdrawing group, and preferably represents an alkyl group, a cycloalkyl group, or an electron withdrawing group. When there are a plurality of Tb, Tb may be bonded to form a ring.

  * Represents a bond to the main chain or side chain of the resin. That is, the partial structure represented by the formula (ca-2) or (cb-2) may be directly connected to the main chain, or the side chain of the resin may have the formula (ca-2) or (cb-2) The partial structure represented by may be combined.

Z ₁ , Z ₂ , Ta, Tc, L, *, m, q, and r are synonymous with those in the general formula (cc), and preferred ones are also the same.

In the case where the resin (C) is a copolymer containing another repeating unit (c) in addition to the repeating unit (c0), and the other repeating unit has two or more polar conversion groups, In one embodiment, the repeating unit (c) is represented by the following general formula (KY-1). Note that when the structure represented by the general formula (KY-1) does not have a bond, it is a monovalent or higher-valent group in which at least one arbitrary hydrogen atom in the structure is removed.

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

R _ky2 and R _ky3 are each independently an electron withdrawing group, or R _ky1 and R _ky2 are linked to form a lactone ring and R _ky3 is an electron withdrawing group. As the lactone ring to be formed, the structures (KA-1-1) to (KA-1-17) are preferable. Examples of the electron withdrawing group include the same groups as those described above for Y ¹ and Y ² in the formula (KB-1), and preferably a halogen atom or the aforementioned —C (R _f1 ) (R _f2 ) —R _f3. A halo (cyclo) alkyl group or a haloaryl group represented by the formula: Preferably _{R ky3} halogen atom, or the _{-C (R f1)} (R f2) is represented by the halo (cyclo) alkyl groups or haloaryl groups _{-R f3,} lactone _{R ky2} is linked to _{R ky1} An electron withdrawing group that forms a ring or has no halogen atom.

R _ky1 , R _ky2 , and R _ky4 may be connected to each other to form a monocyclic or polycyclic structure.

Specific examples of R _ky1 and R _ky4 include the same groups as Z _ka1 in formula (KA-1).

As the lactone ring formed by linking R _ky1 and R _ky2 , the structures (KA-1-1) to (KA-1-17) are preferable. Examples of the electron withdrawing group include those similar to Y ¹ and Y ² in the formula (KB-1).

Although the specific example of the repeating unit (c0) which has a polar conversion group is shown, it is not limited to these.
Ra represents a hydrogen atom, a fluorine atom, a methyl group or a trifluoromethyl group.

Specific examples of the repeating unit (c) that can be copolymerized with the repeating unit (c0) of the present invention are shown below.

  When the resin (C) is unevenly distributed on the surface layer of the film formed from the actinic ray-sensitive or radiation-sensitive resin composition of the present invention and the immersion medium is water, the receding contact angle of the film surface with respect to water is improved. In addition, the immersion water followability can be improved.

  The receding contact angle of the film is preferably 60 ° to 90 °, more preferably 65 ° or more, still more preferably 70 ° or more, particularly preferably at exposure temperature, usually room temperature 23 ± 3 ° C. and humidity 45 ± 5%. It is 75 ° or more.

  The resin (C) is unevenly distributed at the interface as described above, but unlike the surfactant, it does not necessarily have a hydrophilic group in the molecule, and contributes to uniform mixing of polar / nonpolar substances. You don't have to.

  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.

  By having fluorine atoms as the resin (C), the hydrophobicity (water followability) of the resist surface is improved and the development residue (scum) is reduced.

  The partial structure of the repeating unit having a fluorine atom is preferably a repeating unit having an alkyl group having a fluorine atom, a cycloalkyl group having a fluorine atom, or an aryl group having a fluorine atom.

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

  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 the aryl group may further have another substituent.

As the alkyl group having a fluorine atom, the cycloalkyl group having a fluorine atom, or the aryl group having a fluorine atom, a group represented by any one of the following general formulas (F2) to (F4) is preferable. However, the present invention is not limited to this.

In general formulas (F2) to (F4),
R _{57 to} R ₆₈ each independently represent a hydrogen atom, a fluorine atom, or an alkyl group (straight or branched). Provided that at least one of R _{57 to} R ₆₁ , at least one of R _{62 to} R ₆₄ and at least one of R _{65 to} R ₆₈ are a fluorine atom or an alkyl group in which at least one hydrogen atom is substituted with a fluorine atom. (Preferably having 1 to 4 carbon atoms).

R _{57 to} R ₆₁ and R _{65 to} R ₆₇ are preferably all fluorine atoms. R ₆₂ , R ₆₃ and R ₆₈ are preferably a fluoroalkyl group (preferably having 1 to 4 carbon atoms), and more preferably a perfluoroalkyl group having 1 to 4 carbon atoms. R ₆₂ and R ₆₃ may be connected to each other to form a ring. R ₆₄ is preferably a hydrogen atom.

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

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

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

  The partial structure containing a fluorine atom may be directly bonded to the main chain, and further comprises a group consisting of 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 ureylene group. Or a combination of two or more of these groups may be bonded to the main chain.

Preferred examples of the repeating unit having a fluorine atom include those shown below.

In the formula, each of R ₁₀ and R ₁₁ independently represents a hydrogen atom, a fluorine atom, or an alkyl group. The alkyl group is preferably a linear or branched alkyl group having 1 to 4 carbon atoms, and a substituent. In particular, a fluorinated alkyl group can be mentioned.

W _{3 to} W ₆ each independently represents an organic group containing at least one fluorine atom. Specific examples include the atomic groups (F2) to (F4).

In addition to these, the resin (C) may have a unit as shown below as a repeating unit having a fluorine atom.

In the formula, R _{4 to} R ₇ each independently represents a hydrogen atom, a fluorine atom, or an alkyl group. Preferably it is a C1-C4 linear or branched alkyl group, may have a substituent, and a fluorinated alkyl group can be mentioned especially. However, at least one of R _{4 to} R ₇ represents a fluorine atom. R ₄ and R ₅ or R ₆ and R ₇ may form a ring.

W ₂ represents an organic group containing at least one fluorine atom. Specific examples include the atomic groups (F2) to (F4).

L ₂ represents a single bond or a divalent linking group. Examples of the divalent linking group include a substituted or unsubstituted arylene group, a substituted or unsubstituted alkylene group, a substituted or unsubstituted cycloalkylene group, —O—, —SO ₂ —, —CO—, —N (R )-(Wherein R represents a hydrogen atom or alkyl), —NHSO ₂ — or a divalent linking group in which a plurality of these are combined.

  Q represents an alicyclic structure. The alicyclic structure may have a substituent, may be monocyclic, polycyclic, or bridged. As the monocyclic type, a cycloalkyl group having 3 to 8 carbon atoms is preferable, and examples thereof include a cyclopentyl group, a cyclohexyl group, a cyclobutyl group, and a cyclooctyl group. Examples of the polycyclic type include groups having a bicyclo, tricyclo or tetracyclo structure having 5 or more carbon atoms, and a cycloalkyl group having 6 to 20 carbon atoms is preferable, for example, an adamantyl group, norbornyl group, dicyclopentyl group. , Tricyclodecanyl group, tetocyclododecyl group and the like. A part of carbon atoms in the cycloalkyl group may be substituted with a hetero atom such as an oxygen atom.

  Next, the repeating unit containing a silicon atom will be described.

  The repeating unit containing a silicon atom preferably has 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 represent a linear or branched alkyl group (preferably having 1 to 20 carbon atoms) or a cycloalkyl group (preferably having 3 to 20 carbon atoms).

L < ₃ > -L < ₅ > represents a single bond or a bivalent coupling group. 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 group selected from the group consisting of a ureylene group or two or more groups. A combination is mentioned.
n represents an integer of 1 to 5. n is preferably an integer of 2 to 4.

  The content of the repeating unit (c0) in the resin (C) is preferably 10 to 100 mol%, more preferably 20 to 100 mol%, still more preferably 30 to the total repeating unit in the resin (C). 100 mol%, most preferably 40 to 100 mol%.

  The resin (C) may further contain a repeating unit (c1) having at least one of a fluorine atom and a silicon atom, which is different from the repeating units (c0) and (c).

  Examples of the partial structure having a fluorine atom in the repeating unit (c1) include the same ones as described above, and preferred examples include groups represented by the general formulas (F2) to (F4).

  Examples of the partial structure having a silicon atom in the repeating unit (c1) include the same ones as described above, and preferably include groups represented by the general formulas (CS-1) to (CS-3).

The repeating unit (c1) having at least either a fluorine atom or a silicon atom is preferably a (meth) acrylate-based repeating unit.
Hereinafter, although the specific example of a repeating unit (c1) is given, this invention is not limited to this. In specific examples, X ₁ represents a hydrogen atom, —CH ₃ , —F or —CF ₃ , and X ₂ represents —F or —CF ₃ .

  Furthermore, the resin (C) may have at least one group selected from the following groups (x) and (z).

(X) an alkali-soluble group,
(Z) A group that decomposes by the action of an acid.

(X) Alkali-soluble groups include phenolic hydroxyl groups, carboxylic acid groups, fluorinated alcohol groups, sulfonic acid groups, sulfonamido groups, sulfonylimide groups, (alkylsulfonyl) (alkylcarbonyl) methylene groups, (alkylsulfonyl) ( Alkylcarbonyl) imide group, bis (alkylcarbonyl) methylene group, bis (alkylcarbonyl) imide group, bis (alkylsulfonyl) methylene group, bis (alkylsulfonyl) imide group, tris (alkylcarbonyl) methylene group, tris (alkylsulfonyl) ) And a 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 a repeating unit 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 introduced at the end of the polymer chain at the time of polymerization. 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 30 mol%, based on all repeating units in the resin (C). is there.

Specific examples of the repeating unit having an alkali-soluble group (x) 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 .

  Examples of the repeating unit having a group (z) that decomposes by the action of an acid in the resin (C) are the same as the repeating unit having an acid-decomposable group listed above for the resin (A). 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 is preferably a repeating unit represented by the following general formula (CAI).

In the general formula (CAI), Xa ₁ , T, and Rx _{1 to} Rx ₃ have the same meanings as the groups in the above general formula (AI) representing the repeating unit that the resin (A) may contain.

  In the resin (C), 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%, based on all repeating units in the resin (C). It is -80 mol%, More preferably, it is 20-60 mol%. (Z) LWR can be improved by having a group that decomposes by the action of an acid.

  Resin (C) may further have other repeating units. Preferred examples of other repeating units include the following.

  (Cy1) A repeating unit having a fluorine atom and / or a silicon atom, stable to an acid, and hardly soluble or insoluble in an alkali developer.

  (Cy2) A repeating unit which does not have a fluorine atom or a silicon atom, is stable to an acid, and is hardly soluble or insoluble in an alkali developer.

  (Cy3) A repeating unit having a fluorine atom and / or a silicon atom and having a polar group other than the above (x) and (z).

  (Cy4) A repeating unit having no fluorine atom or silicon atom and having a polar group other than the above (x) and (z).

  In the repeating unit of (cy1) and (cy2), insoluble or insoluble in an alkali developer means that (cy1) and (cy2) are an alkali-soluble group or a group that generates an alkali-soluble group by the action of an acid or an alkali developer. (For example, an acid-decomposable group or a polar converting group) is not contained.

  The repeating units (cy1) and (cy2) preferably have an alicyclic hydrocarbon structure having no polar group.

  The preferred embodiments of the repeating units (cy1) to (cy4) are shown below.

The repeating units (cy1) and (cy2) are preferably repeating units represented by the following general formula (CIII).

In general formula (CIII):
R _c31 represents a hydrogen atom, an alkyl group _optionally substituted with a fluorine atom, a cyano group, or a —CH ₂ —O—Rac ₂ group. In the formula, 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, a cycloalkenyl group or an aryl group. These groups may be substituted with a group containing a silicon atom, a fluorine atom, or the like.
L _c3 represents a single bond or a divalent linking group.

In general formula (CIII), 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.
The aryl group is preferably a phenyl group or naphthyl group having 6 to 20 carbon atoms, and these may have a substituent.
R _c32 is preferably an unsubstituted alkyl group or an alkyl group substituted with a fluorine atom. The divalent linking group of L _c3 is preferably an alkylene group (preferably having 1 to 5 carbon atoms), an oxy group, a phenylene group, or an ester bond (a group represented by —COO—).
The repeating units (cy1) and (cy2) are preferably repeating units represented by the following general formula (C4) or (C5).

In general formulas (C4) and (C5),
R _c5 represents a hydrocarbon group having at least one cyclic structure and having neither a hydroxyl group nor a cyano group.

Rac represents a hydrogen atom, an alkyl group which may be substituted with a fluorine atom, a cyano group or a —CH ₂ —O—Rac ₂ group. In the formula, Rac ₂ represents a hydrogen atom, an alkyl group or an acyl group. Rac 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 _c5 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 which may further have a halogen atom, an alkyl group, a hydroxyl group protected with a protecting group, an amino protected with a protecting group The group can be mentioned.

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

R _c6 represents an alkyl group, a cycloalkyl group, an alkenyl group, a cycloalkenyl group, an alkoxycarbonyl group, or an alkylcarbonyloxy group. These groups may be substituted with a fluorine atom or a silicon atom.

The alkyl group for R _c6 is preferably a linear or branched alkyl group having 1 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.

  The alkoxycarbonyl group is preferably an alkoxycarbonyl group having 2 to 20 carbon atoms.

  The alkylcarbonyloxy group is preferably an alkylcarbonyloxy group having 2 to 20 carbon atoms.

n represents an integer of 0 to 5. When n is 2 or more, the plurality of R _c6 may be the same or different.

R _c6 is preferably an unsubstituted alkyl group or an alkyl group substituted with a fluorine atom, and particularly preferably a trifluoromethyl group or a t-butyl group.

(Cy1) and (cy2) are preferably repeating units represented by the following general formula (CII-AB).

In the formula (CII-AB),
R _c11 ′ and R _c12 ′ each independently represents a hydrogen atom, a cyano group, a halogen atom or an alkyl group.
Zc ′ represents an atomic group for forming an alicyclic structure containing two bonded carbon atoms (C—C).
The general formula (CII-AB) is more preferably the following general formula (CII-AB1) or general formula (CII-AB2).

In the formulas (CII-AB1) and (CII-AB2),
Rc ₁₃ ′ to Rc ₁₆ ′ each independently represents a hydrogen atom, a halogen atom, an alkyl group or a cycloalkyl group.
In addition, at least two members out of Rc ₁₃ ′ to Rc ₁₆ ′ may combine to form a ring.

n represents 0 or 1.
Specific examples of (cy1) and (cy2) are listed below, but the present invention is not limited to these. In the formula, Ra represents H, CH ₃ , CH ₂ OH, CF ₃ or CN.

  (Cy3) and (cy4) are preferably repeating units having a hydroxyl group or a cyano group as a polar group. This improves developer affinity. 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. As the alicyclic hydrocarbon structure substituted with a preferred hydroxyl group or cyano group, the partial structures represented by the general formulas (VIIa) to (VIId) described above for the resin (A) are preferable, and (cy3), ( As cy4), repeating units represented by the above general formulas (AIIa) to (AIId) having the partial structure are preferable.

  The content of the repeating units represented by (cy1) to (cy4) is preferably 5 to 40 mol%, more preferably 5 to 30 mol%, still more preferably 10 to 10%, based on all repeating units in the resin (C). 25 mol%.

  Resin (C) may have a plurality of repeating units represented by (cy1) to (cy4).

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

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

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

  The content of the resin (C) in the actinic ray-sensitive or radiation-sensitive resin composition is appropriately adjusted so that the receding contact angle upon exposure of the actinic ray-sensitive or radiation-sensitive resin film is within the above range. However, it is preferably 0.01 to 10% by mass, more preferably 0.1 to 10% by mass, still more preferably, based on the total solid content of the actinic ray-sensitive or radiation-sensitive resin composition. It is 0.1-9 mass%, Most preferably, it is 0.5-8 mass%.

  Resin (C) can be synthesized and purified in the same manner as resin (A), and it is natural that there are few impurities such as metals, and the residual monomer and oligomer components are 0 to 10% by mass. More preferably, 0 to 5% by mass, and still 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 3, more preferably 1 to 2, and still more preferably, in terms of resolution, resist shape, resist pattern side walls, roughness, and the like. It is in the range of 1 to 1.8, most preferably 1 to 1.5.

  As the resin (C), various commercially available products can be used, and similarly to the resin (A), the resin (C) can be synthesized according to a conventional method (for example, radical polymerization).

Specific examples of the resin (C) are shown. The table below shows the molar ratio of repeating units in each resin (corresponding to each repeating unit in order from the left), weight average molecular weight (Mw), and dispersity (Mw / Mn).

  Resin (C) can be used individually by 1 type or in combination of 2 or more types.

  Moreover, it is preferable to use it combining with resin (CP) which has at least any one of a fluorine atom or a silicon atom different from resin (C).

(CP) Resin having at least one of fluorine atom and silicon atom The actinic ray-sensitive or radiation-sensitive resin composition of the present invention contains at least one of fluorine atom and silicon atom separately from the resin (C). You may further contain resin (CP) which has. When the resin (C) and the resin (CP) are contained, the resin (C) and the resin (CP) are unevenly distributed in the film surface layer, and when the immersion medium is water, the resist film surface with respect to water when the film is formed The receding contact angle can be improved, and the immersion water followability can be improved. The receding contact angle of the film is preferably 60 ° to 90 °, more preferably 70 ° or more. The content of the resin (CP) can be appropriately adjusted and used so that the receding contact angle of the film falls within the above range, but 0.01% based on the total solid content of the actinic ray-sensitive or radiation-sensitive resin composition It is preferable that it is -10 mass%, More preferably, it is 0.01-5 mass%, More preferably, it is 0.01-4 mass%, Most preferably, it is 0.01-3 mass%.

  The resin (CP) is unevenly distributed at the interface as described above, but unlike the surfactant, it does not necessarily have a hydrophilic group in the molecule, and contributes to uniform mixing of polar / nonpolar substances. You don't have to.

  The fluorine atom or silicon atom in the resin (CP) having at least one of a fluorine atom and a silicon atom may be present in the main chain of the resin or may be substituted with a side chain.

  The resin (CP) 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 the aryl group 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 preferably include groups represented by the general formulas (F2) to (F4) in the resin (C). However, the present invention is not limited to this.

  In this invention, it is preferable that group represented by general formula (F2)-(F4) is contained in a (meth) acrylate type repeating unit.

  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.

  The resin (CP) 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 general formulas (CS-1) to (CS-3) in the resin (C).

  Furthermore, the resin (CP) may further have at least one group selected from the following groups (x) and (z).

(X) an alkali-soluble group,
(Z) A group that decomposes by the action of an acid.

  Specific examples of these groups include the same groups as those in the resin (C).

  Examples of the repeating unit having a group (z) that decomposes by the action of an acid in the resin (CP) are the same as the repeating unit having an acid-decomposable group listed above for the resin (A). The content of the repeating unit having a group (z) that decomposes by the action of an acid in the resin (CP) is preferably from 1 to 80 mol%, more preferably 10%, based on all repeating units in the resin (CP). It is -80 mol%, More preferably, it is 20-60 mol%.

  The resin (CP) may further have a repeating unit represented by the general formula (CIII) in the resin (C).

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

  When resin (CP) has a silicon atom, it is preferable that the content rate of a silicon atom is 2-50 mass% with respect to the molecular weight of resin (CP), and it is more preferable that it is 2-30 mass%. Moreover, it is preferable that the repeating unit containing a silicon atom is 10-100 mass% with respect to all the repeating units of resin (CP), and it is more preferable that it is 20-100 mass%.

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

  The resin (CP) can be synthesized and purified in the same manner as the resin (A). Naturally, the residual monomer and oligomer components are 0 to 10% by mass with less impurities such as metals. More preferably, 0 to 5% by mass, and still more preferably 0 to 1% by mass. As a result, an actinic ray-sensitive or radiation-sensitive resin composition that does not change over time such as foreign matter in liquid or sensitivity can be obtained. The molecular weight distribution (Mw / Mn, also referred to as dispersity) is preferably in the range of 1 to 3, more preferably 1 to 2, and still more preferably, in terms of resolution, resist shape, resist pattern side walls, roughness, and the like. It is in the range of 1 to 1.8, most preferably 1 to 1.5.

  As the resin (CP), various commercially available products can be used, and as with the resin (A), the resin (CP) can be purified and synthesized according to a conventional method (for example, radical polymerization). Specifically, it can be synthesized in the same manner as the resin (C).

Specific examples of the resin (CP) having at least one of a fluorine atom and a silicon atom are shown below. The table below shows the molar ratio of repeating units in each resin (corresponding to each repeating unit in order from the left), weight average molecular weight (Mw), and dispersity (Mw / Mn).

  About the film | membrane formed from the actinic-ray sensitive or radiation sensitive resin composition of this invention, the liquid (immersion medium) with a refractive index higher than air is satisfy | filled between a film | membrane and a lens at the time of irradiation of actinic light or a radiation. Exposure (immersion exposure) may be performed. Thereby, resolution can be improved. As the immersion medium to be used, any liquid can be used as long as it has a higher refractive index than air, but pure water is preferred.

  The immersion liquid used for the immersion exposure will be described below.

  The immersion liquid is preferably a liquid that is transparent to the exposure wavelength and has a refractive index temperature coefficient as small as possible so as to minimize distortion of the optical image projected onto the resist film. Is an ArF excimer laser (wavelength; 193 nm), it is preferable to use water from the viewpoints of availability and ease of handling in addition to the above-mentioned viewpoints.

  Further, a medium having a refractive index of 1.5 or more can be used in that the refractive index can be further improved. This medium may be an aqueous solution or an organic solvent.

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

  The electrical resistance of water as the immersion liquid is preferably 18.3 MQcm or more, the TOC (organic substance concentration) is preferably 20 ppb or less, and deaeration treatment is preferably performed.

Moreover, it is possible to improve lithography performance by increasing the refractive index of the immersion liquid. From such a viewpoint, an additive that increases the refractive index may be added to water, or heavy water (D ₂ O) may be used instead of water.

  An immersion liquid poorly soluble film (hereinafter also referred to as “topcoat”) may be provided between the film of the composition of the present invention and the immersion liquid so that the film does not directly contact the immersion liquid. Good. The functions necessary for the top coat are suitability for application to the upper layer of the resist, transparency to radiation, particularly 193 nm, and poor immersion liquid solubility. It is preferable that the top coat is not mixed with the resist and can be uniformly applied to the upper layer of the resist.

  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 above-mentioned hydrophobic resins (C) and (CP) are also suitable as a top coat. From the viewpoint of contaminating the optical lens when impurities are eluted from the top coat into the immersion liquid, it is preferable that the residual monomer component of the polymer contained in the top coat is small.

  When peeling the top coat, a developer may be used, or a separate release agent may be used. As the release agent, a solvent having low penetration into the film is preferable. In terms of being able to perform the peeling process simultaneously with the film development process, it is preferable that the peeling process can be performed with an alkaline developer. The top coat is preferably acidic from the viewpoint of peeling with an alkali developer, but may be neutral or alkaline from the viewpoint of non-intermixability with the film.

  The resolution is improved when there is no difference in refractive index between the top coat and the immersion liquid. In the case of using water as the immersion liquid in an ArF excimer laser (wavelength: 193 nm), the top coat for ArF immersion exposure is preferably close to the refractive index of the immersion liquid. From the viewpoint of making the refractive index close to the immersion liquid, it is preferable to have fluorine atoms in the topcoat. A thin film is more preferable from the viewpoint of transparency and refractive index.

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

<Compound that generates acid upon irradiation with actinic ray 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” or “photoacid generator”).
As an acid generator, photo-initiator of photocation polymerization, photo-initiator of photo-radical polymerization, photo-decoloring agent of dyes, photo-discoloring agent, or irradiation with actinic ray or radiation used for micro-resist etc. Known compounds that generate acids and mixtures thereof can be appropriately selected and used.

  Examples of the acid generator include diazonium salts, phosphonium salts, sulfonium salts, iodonium salts, imide sulfonates, oxime sulfonates, diazodisulfones, disulfones, and o-nitrobenzyl sulfonates.

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

Furthermore, compounds capable of generating an acid by light described in US Pat. No. 3,779,778, European Patent 126,712, etc. can also be used.
Preferred compounds among the acid generators include compounds represented by the following general formulas (ZI), (ZII), and (ZIII).

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

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

  A non-nucleophilic anion is an anion that has an extremely low ability to cause a nucleophilic reaction, and is an anion that can suppress degradation over time due to an intramolecular nucleophilic reaction. This improves the temporal stability of the resist.

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

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

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

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

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

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

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

Examples of the sulfonylimide anion include saccharin anion.
The alkyl group in the bis (alkylsulfonyl) imide anion and tris (alkylsulfonyl) methyl anion is preferably an alkyl group having 1 to 5 carbon atoms, such as a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, An isobutyl group, a sec-butyl group, a pentyl group, a neopentyl group, and the like can be given. Examples of substituents for these alkyl groups include halogen atoms, alkyl groups substituted with halogen atoms, alkoxy groups, alkylthio groups, alkyloxysulfonyl groups, aryloxysulfonyl groups, cycloalkylaryloxysulfonyl groups, and the like. Alkyl groups substituted with fluorine atoms are preferred.

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

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

Moreover, it is preferable that the non-nucleophilic anion of Z ⁻ is represented by the following general formula (LD1), for example.

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 group selected from the group consisting of a hydrogen atom, a fluorine atom, an alkyl group, and an alkyl group substituted with at least one fluorine atom.
L each independently represents a single bond or a divalent linking group.
Cy represents a group having a cyclic structure.
x represents an integer of 1 to 20.
y represents an integer of 0 to 10.
z represents an integer of 0 to 10.
Xf represents a fluorine atom or an alkyl group substituted with at least one fluorine atom. The alkyl group preferably has 1 to 10 carbon atoms, more preferably 1 to 4 carbon atoms. The alkyl group substituted with at least one fluorine atom is preferably a perfluoroalkyl group.

Xf is preferably a fluorine atom or a perfluoroalkyl group having 1 to 4 carbon atoms. More specifically, Xf is a fluorine atom, CF ₃ , C ₂ F ₅ , C ₃ F ₇ , C ₄ F ₉ , C ₅ F ₁₁ , C ₆ F ₁₃ , C ₇ F ₁₅ , C ₈ F ₁₇ , _{CH 2 CF 3, CH 2 CH} 2 CF 3, CH 2 C 2 F 5, CH 2 CH 2 C 2 F 5, CH 2 C 3 F 7, CH 2 CH 2 C 3 F 7, CH 2 C 4 F 9 Or CH ₂ CH ₂ C ₄ F ₉ is preferred.

R ₁ and R ₂ are each independently a group selected from the group consisting of a hydrogen atom, a fluorine atom, an alkyl group, and an alkyl group substituted with at least one fluorine atom. The alkyl group and the alkyl group in the alkyl group substituted with at least one fluorine atom are preferably those having 1 to 4 carbon atoms. More preferably, it is a C1-C4 perfluoroalkyl group. Specifically, for example, CF ₃ , C ₂ F ₅ , C ₃ F ₇ , C ₄ F ₉ , C ₅ F ₁₁ , C ₆ F ₁₃ , C ₇ F ₁₅ , C ₈ F ₁₇ , CH ₂ CF ₃ , _{CH 2 CH 2 CF 3, CH} 2 C 2 F 5, CH 2 CH 2 C 2 F 5, CH 2 C 3 F 7, CH 2 CH 2 C 3 F 7, CH 2 C 4 F 9, and _CH 2 CH ₂ C ₄ F ₉ is mentioned, and CF ₃ is particularly preferable.

L represents a single bond or a divalent linking group. Examples of the divalent linking group include —COO—, —OCO—, —CONH—, —CO—, —O—, —S—, —SO—, —SO ₂ —, an alkylene group, and a cycloalkylene group. And alkenylene groups. Among these, —COO—, —OCO—, —CONH—, —CO—, —O—, or —SO ₂ — is preferable, and —COO—, —OCO—, —CONH—, or —SO ₂ — is more preferable. preferable.

  Cy represents a group having a cyclic structure. Examples of the group having a cyclic structure include an alicyclic group, an aryl group, and a group having a heterocyclic structure.

  The alicyclic group may be monocyclic or polycyclic. Examples of the monocyclic alicyclic group include monocyclic cycloalkyl groups such as a cyclopentyl group, a cyclohexyl group, and a cyclooctyl group. Examples of the polycyclic alicyclic group include polycyclic cycloalkyl groups such as a norbornyl group, a tricyclodecanyl group, a tetracyclodecanyl group, a tetracyclododecanyl group, and an adamantyl group. 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, and an adamantyl group, is a PEB (post-exposure heating) step. From the viewpoints of suppressing diffusibility in the film and improving MEEF (Mask Error Enhancement Factor).

  The aryl group may be monocyclic or polycyclic. Examples of the aryl group include a phenyl group, a naphthyl group, a phenanthryl group, and an anthryl group. Among these, a naphthyl group having a relatively low light absorbance at 193 nm is preferable.

  The group having a heterocyclic structure may be monocyclic or polycyclic, but the polycyclic can suppress acid diffusion more. Further, the group having a heterocyclic structure may have aromaticity or may not have aromaticity. Examples of the heterocyclic ring having aromaticity include a furan ring, a thiophene ring, a benzofuran ring, a benzothiophene ring, a dibenzofuran ring, a dibenzothiophene ring, and a pyridine ring. Examples of the heterocyclic ring not having aromaticity include a tetrahydropyran ring, a lactone ring, and a decahydroisoquinoline ring. As the heterocyclic ring in the group having a heterocyclic structure, a furan ring, a thiophene ring, a pyridine ring, or a decahydroisoquinoline ring is particularly preferable.

  The group having the cyclic structure may have a substituent. Examples of the substituent include an alkyl group, a cycloalkyl group, an aryl group, a hydroxy group, an alkoxy group, an ester group, an amide group, a urethane group, a ureido group, a thioether group, a sulfonamide group, and a sulfonic acid ester group. It is done. The alkyl group may be linear or branched. The alkyl group preferably has 1 to 12 carbon atoms. The cycloalkyl group may be monocyclic or polycyclic. The cycloalkyl group preferably has 3 to 12 carbon atoms. The aryl group preferably has 6 to 14 carbon atoms.

x is preferably 1 to 8, more preferably 1 to 4, and particularly preferably 1. y is preferably 0 to 4, and more preferably 0. z is preferably 0 to 8, particularly preferably 0 to 4.
Moreover, it is also preferable that the non-nucleophilic anion of Z ⁻ is represented by the following general formula (LD2), for example.

In General Formula (LD2), Xf, R ₁ , R ₂ , L, Cy, x, y, and z have the same meanings as in General Formula (LD1). Rf is a group containing a fluorine atom.

Examples of the group containing a fluorine atom represented by Rf include an alkyl group having at least one fluorine atom, a cycloalkyl group having at least one fluorine atom, and an aryl group having at least one fluorine atom. .
These alkyl group, cycloalkyl group and aryl group may be substituted with a fluorine atom, or may be substituted with another substituent containing a fluorine atom. When Rf is a cycloalkyl group having at least one fluorine atom or an aryl group having at least one fluorine atom, other substituents containing a fluorine atom include, for example, alkyl substituted with at least one fluorine atom. Groups.
Further, these alkyl group, cycloalkyl group and aryl group may be further substituted with a substituent not containing a fluorine atom. As this substituent, the thing which does not contain a fluorine atom among what was demonstrated about Cy previously can be mentioned, for example.

  Examples of the alkyl group having at least one fluorine atom represented by Rf include those described above as the alkyl group substituted with at least one fluorine atom represented by Xf. Examples of the cycloalkyl group having at least one fluorine atom represented by Rf include a perfluorocyclopentyl group and a perfluorocyclohexyl group. Examples of the aryl group having at least one fluorine atom represented by Rf include a perfluorophenyl group.

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

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

More preferred (ZI) components include compounds (ZI-1), (ZI-2), (ZI-3) and (ZI-4) described below.
The compound (ZI-1) is an arylsulfonium compound in which at least one of R _{201 to} R _{203 in} the general formula (ZI) is an aryl group, that is, a compound having arylsulfonium as a cation.

In the arylsulfonium compound, all of R _{201 to} R ₂₀₃ may be an aryl group, or a part of R _{201 to} R ₂₀₃ may be an aryl group, and the rest may be an alkyl group or a cycloalkyl group.
Examples of the arylsulfonium compound include triarylsulfonium compounds, diarylalkylsulfonium compounds, aryldialkylsulfonium compounds, diarylcycloalkylsulfonium compounds, and aryldicycloalkylsulfonium compounds.

  The aryl group of the arylsulfonium compound is preferably a phenyl group or a naphthyl group, and more preferably a phenyl group. The aryl group may be an aryl group having a heterocyclic structure having an oxygen atom, a nitrogen atom, a sulfur atom or the like. Examples of the heterocyclic structure include pyrrole, furan, thiophene, indole, benzofuran, benzothiophene, and the like. When the arylsulfonium compound has two or more aryl groups, the two or more aryl groups may be the same or different.

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

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

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

The organic group having no aromatic ring as R ₂₀₁ to R ₂₀₃ generally has 1 to 30 carbon atoms, preferably 1 to 20 carbon atoms.
R _{201 to} R ₂₀₃ are each independently preferably an alkyl group, a cycloalkyl group, an allyl group, or a vinyl group, more preferably a linear or branched 2-oxoalkyl group, 2-oxocycloalkyl group, alkoxy group. A carbonylmethyl group, particularly preferably a linear or branched 2-oxoalkyl group.

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

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

The alkoxy group in the alkoxycarbonylmethyl group is preferably an alkoxy group having 1 to 5 carbon atoms (methoxy group, ethoxy group, propoxy group, butoxy group, pentoxy group).
R _{201 to} R ₂₀₃ may be further substituted with a halogen atom, an alkoxy group (for example, having 1 to 5 carbon atoms), a hydroxyl group, a cyano group, or a nitro group.

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

In general formula (ZI-3),
R _{1c to} R _5c each independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, an alkoxy group, a halogen atom or a phenylthio group.
R _6c and R _7c each independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, a cyano group or an aryl group.
R _x and R _y each independently represents an alkyl group, a cycloalkyl group, a 2-oxoalkyl group, a 2-oxocycloalkyl group, an alkoxycarbonylalkyl group, an allyl group, or a vinyl group.

Any two or more of R _{1c to} R _5c , R _6c and R _7c , and R _x and R _y may be bonded to each other to form a ring structure, and this ring structure includes an oxygen atom and a sulfur atom. , An ester bond and an amide bond may be included. Examples of the group formed by combining any two or more of R _{1c to} R _5c , R _6c and R _7c , and R _x and R _y include a butylene group and a pentylene group.
Zc ⁻ represents a non-nucleophilic anion, and examples thereof include the same non-nucleophilic anion as Z ⁻ in the general formula (ZI).

The alkyl group as R _{1c to} R _7c may be either linear or branched, for example, an alkyl group having 1 to 20 carbon atoms, preferably a linear or branched alkyl group having 1 to 12 carbon atoms ( Examples thereof include a methyl group, an ethyl group, a linear or branched propyl group, a linear or branched butyl group, and a linear or branched pentyl group. Examples of the cycloalkyl group include cyclohexane having 3 to 8 carbon atoms. An alkyl group (for example, a cyclopentyl group, a cyclohexyl group) can be mentioned.

The alkoxy group as R _{1c to} R _{5c may} be linear, branched or cyclic, for example, an alkoxy group having 1 to 10 carbon atoms, preferably a linear or branched alkoxy group having 1 to 5 carbon atoms. (For example, methoxy group, ethoxy group, linear or branched propoxy group, linear or branched butoxy group, linear or branched pentoxy group), C3-C8 cyclic alkoxy group (for example, cyclopentyloxy group, cyclohexyloxy group) ).

Preferably, any of R _{1c to} R _5c is a linear or branched alkyl group, a cycloalkyl group, or a linear, branched or cyclic alkoxy group, and more preferably the sum of the carbon number of R _{1c to} R _5c. Is 2-15. Thereby, solvent solubility improves more and generation | occurrence | production of a particle is suppressed at the time of a preservation | save.

The aryl group as R _6c and R _7c preferably has 5 to 15 carbon atoms, and examples thereof include a phenyl group and a naphthyl group.

When R _6c and R _7c are combined to form a ring, the group formed by combining R _6c and R _7c is preferably an alkylene group having 2 to 10 carbon atoms, such as ethylene group, propylene Group, butylene group, pentylene group, hexylene group and the like. The ring formed by combining R _6c and R _7c may have a hetero atom such as an oxygen atom in the ring.
_Examples of the alkyl group and cycloalkyl group as R _x and R _y include the same alkyl group and cycloalkyl group as in R _{1c to} R _7c .

Examples of the 2-oxoalkyl group and 2-oxocycloalkyl group include a group having> C═O at the 2-position of the alkyl group or cycloalkyl group as R _{1c to} R _7c .
Examples of the alkoxy group in the alkoxycarbonylalkyl group include the same alkoxy groups as in R _{1c to} R _5c , and examples of the alkyl group include an alkyl group having 1 to 12 carbon atoms, preferably 1 to 1 carbon atom. 5 straight chain (for example, methyl group and ethyl group).

The allyl group is not particularly limited, but is preferably an allyl group which is unsubstituted or substituted with a monocyclic or polycyclic cycloalkyl group.
Although there is no restriction | limiting in particular as a vinyl group, It is preferable that it is a vinyl group substituted by the unsubstituted or monocyclic or polycyclic cycloalkyl group.

As the ring structure that R _x and R _y may be bonded to each other, divalent R _x and R _y (for example, a methylene group, an ethylene group, a propylene group, and the like) are represented by the general formula (ZI-3). A 5-membered or 6-membered ring formed with a sulfur atom, particularly preferably a 5-membered ring (that is, a tetrahydrothiophene ring).

R _x and R _y are preferably an alkyl group or cycloalkyl group having 4 or more carbon atoms, more preferably 6 or more, and still more preferably 8 or more alkyl groups or cycloalkyl groups.
Specific examples of the cation moiety of compound (ZI-3) are shown below.

The compound (ZI-4) is a compound represented by the following general formula (ZI-4).

In general formula (ZI-4),
R ₁₃ represents a hydrogen atom, a fluorine atom, a hydroxyl group, an alkyl group, a cycloalkyl group, an alkoxy group, an alkoxycarbonyl group, or a group having a monocyclic or polycyclic cycloalkyl skeleton. These groups may have a substituent.

When there are a plurality of R _{14 s,} each independently represents an alkyl group, a cycloalkyl group, an alkoxy group, an alkoxycarbonyl group, an alkylcarbonyl group, an alkylsulfonyl group, a cycloalkylsulfonyl group, or a monocyclic or polycyclic cycloalkyl skeleton. Represents a group having These groups may have a substituent.

R ₁₅ each independently represents an alkyl group, a cycloalkyl group or a naphthyl group. Two R ₁₅ may be bonded to each other to form a ring. These groups may have a substituent.
l represents an integer of 0-2.
r represents an integer of 0 to 8.
Z ^- represents a non-nucleophilic anion, in the general formula (ZI) Z ^- and include the same non-nucleophilic anion.

In the general formula (ZI-4), the alkyl group of R ₁₃ , R ₁₄ and R ₁₅ is linear or branched and preferably has 1 to 10 carbon atoms, and is preferably a methyl group, an ethyl group, n -Propyl group, i-propyl group, n-butyl group, 2-methylpropyl group, 1-methylpropyl group, t-butyl group, n-pentyl group, neopentyl group, n-hexyl group, n-heptyl group, n -An octyl group, 2-ethylhexyl group, n-nonyl group, n-decyl group etc. can be mentioned. Of these alkyl groups, a methyl group, an ethyl group, an n-butyl group, a t-butyl group, and the like are preferable.

Examples of the cycloalkyl group represented by R ₁₃ , R ₁₄ and R ₁₅ include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclododecanyl, cyclopentenyl, cyclohexenyl, cyclooctadienyl, norbornyl, tricyclo Examples include decanyl, tetracyclodecanyl, adamantyl and the like, and cyclopropyl, cyclopentyl, cyclohexyl and cyclooctyl are particularly preferable.

The alkoxy group of R ₁₃ and R ₁₄ is linear or branched and preferably has 1 to 10 carbon atoms, such as methoxy group, ethoxy group, n-propoxy group, i-propoxy group, n -Butoxy group, 2-methylpropoxy group, 1-methylpropoxy group, t-butoxy group, n-pentyloxy group, neopentyloxy group, n-hexyloxy group, n-heptyloxy group, n-octyloxy group, 2-ethylhexyloxy group, n-nonyloxy group, n-decyloxy group and the like can be mentioned. Of these alkoxy groups, a methoxy group, an ethoxy group, an n-propoxy group, an n-butoxy group, and the like are preferable.

The alkoxycarbonyl group for R ₁₃ and R ₁₄ is linear or branched and preferably has 2 to 11 carbon atoms, such as a methoxycarbonyl group, an ethoxycarbonyl group, an n-propoxycarbonyl group, i- Propoxycarbonyl group, n-butoxycarbonyl group, 2-methylpropoxycarbonyl group, 1-methylpropoxycarbonyl group, t-butoxycarbonyl group, n-pentyloxycarbonyl group, neopentyloxycarbonyl group, n-hexyloxycarbonyl group, Examples include n-heptyloxycarbonyl group, n-octyloxycarbonyl group, 2-ethylhexyloxycarbonyl group, n-nonyloxycarbonyl group, n-decyloxycarbonyl group and the like. Of these alkoxycarbonyl groups, a methoxycarbonyl group, an ethoxycarbonyl group, an n-butoxycarbonyl group, and the like are preferable.

Examples of the group having a monocyclic or polycyclic cycloalkyl skeleton of R ₁₃ and R ₁₄ include a monocyclic or polycyclic cycloalkyloxy group and an alkoxy group having a monocyclic or polycyclic cycloalkyl group. Can be mentioned. These groups may further have a substituent.

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

  Examples of the polycyclic cycloalkyloxy group having a total carbon number of 7 or more include a norbornyloxy group, a tricyclodecanyloxy group, a tetracyclodecanyloxy group, an adamantantyloxy group, and the like.

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

  Examples of the alkoxy group having a polycyclic cycloalkyl skeleton having 7 or more carbon atoms include norbornyl methoxy group, norbornyl ethoxy group, tricyclodecanyl methoxy group, tricyclodecanyl ethoxy group, tetracyclo A decanyl methoxy group, a tetracyclodecanyl ethoxy group, an adamantane methoxy group, an adamantane ethoxy group, etc. are mentioned, and a norbornyl methoxy group, a norbornyl ethoxy group, etc. are preferable.

The alkyl group of the alkyl group of R _14, include the same specific examples as the alkyl group as R ₁₃ to R ₁₅ described above.

The alkylsulfonyl group and cycloalkylsulfonyl group of R ₁₄ are linear, branched, or cyclic, and preferably those having 1 to 10 carbon atoms, such as methanesulfonyl group, ethanesulfonyl group, n-propanesulfonyl. Group, n-butanesulfonyl group, tert-butanesulfonyl group, n-pentanesulfonyl group, neopentanesulfonyl group, n-hexanesulfonyl group, n-heptanesulfonyl group, n-octanesulfonyl group, 2-ethylhexanesulfonyl group, Examples thereof include an n-nonanesulfonyl group, an n-decanesulfonyl group, a cyclopentanesulfonyl group, and a cyclohexanesulfonyl group. Of these alkylsulfonyl groups and cycloalkylsulfonyl groups, a methanesulfonyl group, an ethanesulfonyl group, an n-propanesulfonyl group, an n-butanesulfonyl group, a cyclopentanesulfonyl group, a cyclohexanesulfonyl group, and the like are preferable.

  Examples of the substituent that each of the above groups may have include a halogen atom (for example, a fluorine atom), a hydroxyl group, a carboxy group, a cyano group, a nitro group, an alkoxy group, an alkoxyalkyl group, an alkoxycarbonyl group, and alkoxycarbonyloxy. Groups and the like.

  Examples of the alkoxy group include methoxy group, ethoxy group, n-propoxy group, i-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 a methoxycarbonyloxy group, an ethoxycarbonyloxy group, an n-propoxycarbonyloxy group, an i-propoxycarbonyloxy group, an n-butoxycarbonyloxy group, a t-butoxycarbonyloxy group, and a cyclopentyloxy group. Examples thereof include linear, branched or cyclic alkoxycarbonyloxy groups having 2 to 21 carbon atoms such as carbonyloxy group and cyclohexyloxycarbonyloxy.

The ring structure which two R ₁₅ may combine with each other is a 5-membered or 6-membered ring formed by two divalent R ₁₅ together with the sulfur atom in the general formula (ZI-4). Particularly preferred is a 5-membered ring (that is, a tetrahydrothiophene ring), which may be condensed with an aryl group or a cycloalkyl group. The divalent R ₁₅ may have a substituent. Examples of the substituent include a hydroxyl group, a carboxy group, a cyano group, a nitro group, an alkoxy group, an alkoxyalkyl group, an alkoxycarbonyl group, an alkoxycarbonyloxy group, and the like. Groups and the like. R ₁₅ in the general formula (ZI-4) is preferably a methyl group, an ethyl group, a naphthyl group, a divalent group in which two R _15s are bonded to each other to form a tetrahydrothiophene ring structure together with a sulfur atom.

The substituent that R ₁₃ and R ₁₄ may have is preferably a hydroxyl group, an alkoxy group, an alkoxycarbonyl group, or a halogen atom (particularly a fluorine atom).
l is preferably 0 or 1, and more preferably 1.
As r, 0-2 are preferable.
Specific examples of the cation moiety of compound (ZI-4) are given below.

Next, the general formulas (ZII) and (ZIII) will be described.
In formula (ZII), (ZIII), R 204 ~R 207 each independently represents an aryl group, an alkyl group or a cycloalkyl group.
Phenyl group and a naphthyl group are preferred as the aryl group of R ₂₀₄ to R _207, more preferably a phenyl group. Aryl group R ₂₀₄ to R ₂₀₇ represents an oxygen atom, a nitrogen atom, may be an aryl group having a heterocyclic structure having a sulfur atom and the like. Examples of the heterocyclic structure include pyrrole, furan, thiophene, indole, benzofuran, benzothiophene, and the like.

The alkyl group and cycloalkyl group in R ₂₀₄ to R _207, preferably a linear or branched alkyl group having 1 to 10 carbon atoms (e.g., methyl group, ethyl group, propyl group, butyl group, pentyl group), carbon Examples thereof include cycloalkyl groups of several 3 to 10 (cyclopentyl group, cyclohexyl group, norbornyl group).

Aryl group, alkyl group of R ₂₀₄ to R _207, cycloalkyl groups may have a substituent. Aryl group, alkyl group of R ₂₀₄ to R _207, the cycloalkyl group substituent which may be possessed by, for example, an alkyl group (for example, 1 to 15 carbon atoms), a cycloalkyl group (for example, 3 to 15 carbon atoms ), An aryl group (for example, having 6 to 15 carbon atoms), an alkoxy group (for example, having 1 to 15 carbon atoms), a halogen atom, a hydroxyl group, and a phenylthio group.

Z ⁻ represents a non-nucleophilic anion, and examples thereof include the same as the non-nucleophilic anion of Z ^{− in} formula (ZI).
Examples of the acid generator further include compounds represented by the following general formulas (ZIV), (ZV), and (ZVI).

In general formulas (ZIV) to (ZVI),
Ar ₃ and Ar ₄ each independently represents an aryl group.
R ₂₀₈ , R ₂₀₉ and R ₂₁₀ each independently represents an alkyl group, a cycloalkyl group or an aryl group.
A represents an alkylene group, an alkenylene group or an arylene group.

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

Among acid generators, particularly preferred examples are given below.

An acid generator can be used individually by 1 type or in combination of 2 or more types.
The content of the acid generator is preferably 0.1 to 30% by mass, more preferably 0.5 to 25% by mass, still more preferably 3 to 20% by mass, particularly preferably based on the total solid content of the composition. Is 3 to 15% by mass.

  When the acid generator is represented by the general formula (ZI-3) or (ZI-4), the content is preferably 5 to 20% by mass based on the total solid content of the composition. 8-20 mass% is more preferable, 10-20 mass% is still more preferable, and 10-15 mass% is especially preferable.

<Basic compound>
The composition of the present invention preferably contains a basic compound in order to reduce the change in performance over time from exposure to heating.
Preferred examples of the basic compound include compounds having structures represented by the following formulas (A) to (E).

In general formulas (A) and (E),
R ²⁰⁰ , R ²⁰¹ and R ²⁰² may be the same or different, and are a hydrogen atom, an alkyl group (preferably having 1 to 20 carbon atoms), a cycloalkyl group (preferably having 3 to 20 carbon atoms) or an aryl group (having a carbon number). 6-20), wherein R ²⁰¹ and R ²⁰² may combine with each other to form a ring. R ²⁰³ , R ²⁰⁴ , R ²⁰⁵ and R ²⁰⁶ may be the same or different and each represents an alkyl group having 1 to 20 carbon atoms.

About the said alkyl group, as an alkyl group which has a substituent, a C1-C20 aminoalkyl group, a C1-C20 hydroxyalkyl group, or a C1-C20 cyanoalkyl group is preferable.
The alkyl groups in the general formulas (A) and (E) are more preferably unsubstituted.

  Preferred compounds include guanidine, aminopyrrolidine, pyrazole, pyrazoline, piperazine, aminomorpholine, aminoalkylmorpholine, piperidine and the like, and more preferred compounds include imidazole structure, diazabicyclo structure, onium hydroxide structure, onium carboxylate Examples thereof include a compound having a structure, a trialkylamine structure, an aniline structure or a pyridine structure, an alkylamine derivative having a hydroxyl group and / or an ether bond, and an aniline derivative having a hydroxyl group and / or an ether bond.

  Examples of the compound having an imidazole structure include imidazole, 2,4,5-triphenylimidazole, benzimidazole, and 2-phenylbenzimidazole. Examples of the compound having a diazabicyclo structure include 1,4-diazabicyclo [2,2,2] octane, 1,5-diazabicyclo [4,3,0] non-5-ene, and 1,8-diazabicyclo [5,4,0. ] Undecar 7-ene etc. are mentioned. Examples of the compound having an onium hydroxide structure include tetrabutylammonium hydroxide, triarylsulfonium hydroxide, phenacylsulfonium hydroxide, sulfonium hydroxide having a 2-oxoalkyl group, specifically, triphenylsulfonium hydroxide, tris ( and t-butylphenyl) sulfonium hydroxide, bis (t-butylphenyl) iodonium hydroxide, phenacylthiophenium hydroxide, 2-oxopropylthiophenium hydroxide, and the like. As the compound having an onium carboxylate structure, an anion portion of the compound having an onium hydroxide structure is converted to a carboxylate, and examples thereof include acetate, adamantane-1-carboxylate, and perfluoroalkylcarboxylate. Examples of the compound having a trialkylamine structure include tri (n-butyl) amine and tri (n-octyl) amine. Examples of the aniline compound include 2,6-diisopropylaniline, N, N-dimethylaniline, N, N-dibutylaniline, N, N-dihexylaniline and the like. Examples of the alkylamine derivative having a hydroxyl group and / or an ether bond include ethanolamine, diethanolamine, triethanolamine, N-phenyldiethanolamine, and tris (methoxyethoxyethyl) amine. Examples of aniline derivatives having a hydroxyl group and / or an ether bond include N, N-bis (hydroxyethyl) aniline.

  Preferred examples of the basic compound further include an amine compound having a phenoxy group, an ammonium salt compound having a phenoxy group, an amine compound having a sulfonic acid ester group, and an ammonium salt compound having a sulfonic acid ester group.

The amine compound having a phenoxy group, the ammonium salt compound having a phenoxy group, the amine compound having a sulfonate group, and the ammonium salt compound having a sulfonate group have at least one alkyl group bonded to a nitrogen atom. Is preferred. The alkyl chain preferably has an oxygen atom and an oxyalkylene group is formed. The number of oxyalkylene groups is one or more in the molecule, preferably 3 to 9, and more preferably 4 to 6. -CH ₂ CH ₂ O Among the oxyalkylene group _{-, - CH (CH 3)} CH 2 O- or -CH ₂ CH ₂ CH ₂ O- structure is preferred.

Specific examples of the amine compound having a phenoxy group, an ammonium salt compound having a phenoxy group, an amine compound having a sulfonic acid ester group, and an ammonium salt compound having a sulfonic acid ester group include US Patent Application Publication No. 2007/0224539. The compounds (C1-1) to (C3-3) exemplified in [0066] are not limited thereto.
These basic compounds are used alone or in combination of two or more.
The content rate of a basic compound is 0.001-10 mass% normally based on the total solid of the composition of this invention, Preferably it is 0.01-5 mass%.
The content ratio of the acid generator and the basic compound in the composition is preferably acid generator / basic compound (molar ratio) = 2.5 to 300. In other words, the molar ratio is preferably 2.5 or more from the viewpoint of sensitivity and resolution, and is preferably 300 or less from the viewpoint of suppressing the reduction in resolution due to the thickening of the resist pattern over time until post-exposure heat treatment. The acid generator / basic compound (molar ratio) is more preferably 5.0 to 200, still more preferably 7.0 to 150.

<Low molecular compound having a group capable of leaving by the action of an acid and increasing basicity by the elimination>
The composition of the present invention contains a low molecular compound (hereinafter, also referred to as “low molecular compound (D)”) having a group capable of leaving by the action of an acid and increasing the basicity due to the elimination. It is preferable.
The group capable of leaving by the action of an acid is not particularly limited, but is preferably an acetal group, a carbonate group, a carbamate group, a tertiary ester group, a tertiary hydroxyl group, or a hemiaminal ether group, and a carbamate group or a hemiaminal ether group. It is particularly preferred.

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

As the compound (D), an amine derivative having a group capable of leaving by the action of an acid on the nitrogen atom is preferable.
Compound (D) may have a carbamate group having a protecting group on the nitrogen atom. The protecting group constituting the carbamate group can be represented by the following general formula (d-1).

In general formula (d-1),
R ′ each independently represents a hydrogen atom, a linear or branched alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, or an alkoxyalkyl group. R ′ may be bonded to each other to form a ring.
R ′ is preferably a linear or branched alkyl group, cycloalkyl group, or aryl group. More preferably, it is a linear or branched alkyl group or cycloalkyl group.
The low molecular compound (D) can also be constituted by arbitrarily combining the above basic compound and the structure represented by the general formula (d-1).
It is particularly preferable that the low molecular compound (D) has a structure represented by the following general formula (A).
The low molecular compound (D) may correspond to the above basic compound as long as it is a low molecular compound having a group capable of leaving by the action of an acid.

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

Rb independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, or an alkoxyalkyl group. However, in -C (Rb) (Rb) (Rb), when one or more Rb is a hydrogen atom, at least one of the remaining Rb is a cyclopropyl group, a 1-alkoxyalkyl group or an aryl group.
At least two Rb may be bonded to form an alicyclic hydrocarbon group, an aromatic hydrocarbon group, a heterocyclic hydrocarbon group or a derivative thereof.
n represents an integer of 0 to 2, m represents an integer of 1 to 3, and n + m = 3.

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

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

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

Although the particularly preferable low molecular compound (D) in the present invention is specifically shown, the present invention is not limited thereto.

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

In the present invention, the low molecular weight compound (D) can be used alone or in combination of two or more.
In the present invention, the content of the low molecular weight compound (D) is usually 0.001 to 20% by mass, preferably 0.001 to 10%, based on the total solid content of the composition combined with the basic compound described above. It is 0.01 mass%, More preferably, it is 0.01-5 mass%.

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

<Solvent>
Solvents that can be used in preparing the composition of the present invention by dissolving the above-described components include, for example, alkylene glycol monoalkyl ether carboxylate, alkylene glycol monoalkyl ether, alkyl lactate ester, and alkyl alkoxypropionate. And organic solvents such as cyclic lactones (preferably having 4 to 10 carbon atoms), monoketone compounds which may contain rings (preferably having 4 to 10 carbon atoms), alkylene carbonates, alkyl alkoxyacetates and alkyl pyruvates. it can.

  Examples of the alkylene glycol monoalkyl ether carboxylate include propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, propylene glycol monobutyl ether acetate, propylene glycol monomethyl ether propionate, propylene glycol monoethyl Preferred examples include ether propionate, ethylene glycol monomethyl ether acetate, and ethylene glycol monoethyl ether acetate.

  Preferred examples of the alkylene glycol monoalkyl ether include propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, ethylene glycol monomethyl ether, and ethylene glycol monoethyl ether.

Preferred examples of the alkyl lactate include methyl lactate, ethyl lactate, propyl lactate and butyl lactate.
Preferable examples of the alkyl alkoxypropionate include ethyl 3-ethoxypropionate, methyl 3-methoxypropionate, methyl 3-ethoxypropionate, and ethyl 3-methoxypropionate.
Examples of cyclic lactones include β-propiolactone, β-butyrolactone, γ-butyrolactone, α-methyl-γ-butyrolactone, β-methyl-γ-butyrolactone, γ-valerolactone, γ-caprolactone, and γ-octano. Preferred are iclactone and α-hydroxy-γ-butyrolactone.

  Examples of the monoketone compound which may contain a ring include 2-butanone, 3-methylbutanone, pinacolone, 2-pentanone, 3-pentanone, 3-methyl-2-pentanone, 4-methyl-2-pentanone, 2 -Methyl-3-pentanone, 4,4-dimethyl-2-pentanone, 2,4-dimethyl-3-pentanone, 2,2,4,4-tetramethyl-3-pentanone, 2-hexanone, 3-hexanone, 5-methyl-3-hexanone, 2-heptanone, 3-heptanone, 4-heptanone, 2-methyl-3-heptanone, 5-methyl-3-heptanone, 2,6-dimethyl-4-heptanone, 2-octanone, 3-octanone, 2-nonanone, 3-nonanone, 5-nonanone, 2-decanone, 3-decanone, 4-decanone, 5-hexen-2-one 3-penten-2-one, cyclopentanone, 2-methylcyclopentanone, 3-methylcyclopentanone, 2,2-dimethylcyclopentanone, 2,4,4-trimethylcyclopentanone, cyclohexanone, 3- Methylcyclohexanone, 4-methylcyclohexanone, 4-ethylcyclohexanone, 2,2-dimethylcyclohexanone, 2,6-dimethylcyclohexanone, 2,2,6-trimethylcyclohexanone, cycloheptanone, 2-methylcycloheptanone, 3-methyl Preferred is cycloheptanone.

Preferred examples of the alkylene carbonate include propylene carbonate, vinylene carbonate, ethylene carbonate, and butylene carbonate.
Examples of the alkyl alkoxyacetate include 2-methoxyethyl acetate, 2-ethoxyethyl acetate, 2- (2-ethoxyethoxy) ethyl acetate, 3-methoxy-3-methylbutyl acetate, and 1-methoxy-acetate. 2-propyl is preferred.
Preferred examples of the alkyl pyruvate include methyl pyruvate, ethyl pyruvate, and propyl pyruvate.

As a solvent which can be preferably used, a solvent having a boiling point of 130 ° C. or higher under normal temperature and normal pressure can be mentioned. Specifically, cyclopentanone, γ-butyrolactone, cyclohexanone, ethyl lactate, ethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, ethyl 3-ethoxypropionate, ethyl pyruvate, 2-ethoxyethyl acetate, acetic acid -2- (2-ethoxyethoxy) ethyl and propylene carbonate are mentioned.
In the present invention, the above solvents may be used alone or in combination of two or more.

In this invention, you may use the mixed solvent which mixed the solvent which contains a hydroxyl group in a structure, and the solvent which does not contain a hydroxyl group as an organic solvent.
As the solvent containing a hydroxyl group and the solvent not containing a hydroxyl group, the above-mentioned exemplary compounds can be selected as appropriate, but as the solvent containing a hydroxyl group, alkylene glycol monoalkyl ether, alkyl lactate, etc. are preferable, propylene glycol monomethyl ether, More preferred is ethyl lactate. Further, as the solvent not containing a hydroxyl group, alkylene glycol monoalkyl ether acetate, alkyl alkoxypropionate, monoketone compound which may contain a ring, cyclic lactone, alkyl acetate and the like are preferable, and among these, propylene glycol monomethyl ether Acetate, ethyl ethoxypropionate, 2-heptanone, γ-butyrolactone, cyclohexanone and butyl acetate are particularly preferred, and propylene glycol monomethyl ether acetate, ethyl ethoxypropionate and 2-heptanone are most preferred.

The mixing ratio (mass) of the solvent containing a hydroxyl group and the solvent not containing a hydroxyl group is 1/99 to 99/1, preferably 10/90 to 90/10, more preferably 20/80 to 60/40. . A mixed solvent containing 50% by mass or more of a solvent not containing a hydroxyl group is particularly preferred from the viewpoint of coating uniformity.
The solvent is preferably a mixed solvent of two or more containing propylene glycol monomethyl ether acetate.

<Surfactant>
The actinic ray-sensitive or radiation-sensitive resin composition may further contain a surfactant. When it contains, it contains either fluorine-based and / or silicon-based surfactant (fluorine-based surfactant, silicon-based surfactant, surfactant having both fluorine atom and silicon atom), or two or more kinds It is preferable to do.

  When the composition of the present invention contains the above-described surfactant, it is possible to provide a resist pattern with less adhesion and development defects with good sensitivity and resolution when using an exposure light source of 250 nm or less, particularly 220 nm or less. It becomes.

  Examples of the fluorine-based and / or silicon-based surfactant include surfactants described in [0276] of US Patent Application Publication No. 2008/0248425. For example, Ftop EF301, EF303, (Shin-Akita Kasei Co., Ltd.) )), FLORARD FC430, 431, 4430 (manufactured by Sumitomo 3M Co., Ltd.), Megafac F171, F173, F176, F189, F113, F110, F177, F120, R08 (manufactured by Dainippon Ink & Chemicals, Inc.), Surflon S-382, SC101, 102, 103, 104, 105, 106 (manufactured by Asahi Glass Co., Ltd.), Troisol S-366 (manufactured by Troy Chemical Co., Ltd.), GF-300, GF-150 (Toagosei Chemical Co., Ltd.) ), Surflon S-393 (manufactured by Seimi Chemical Co., Ltd.), F-top EF121, EF122A EF122B, RF122C, EF125M, EF135M, EF351, EF352, EF801, EF802, EF601 (manufactured by Gemco), PF636, PF656, PF6320, PF6520 (manufactured by OMNOVA), FTX-204G, 208G, 218G230G 208D, 212D, 218D, 222D (manufactured by Neos Co., Ltd.) and the like. Polysiloxane polymer KP-341 (manufactured by Shin-Etsu Chemical Co., Ltd.) can also be used as a silicon-based surfactant.

  In addition to the known surfactants described above, surfactants are derived from fluoroaliphatic compounds produced by the telomerization method (also referred to as the telomer method) or the oligomerization method (also referred to as the oligomer method). A surfactant using a polymer having a fluoroaliphatic group can be used. The fluoroaliphatic compound can be synthesized by the method described in JP-A-2002-90991.

  As the polymer having a fluoroaliphatic group, a copolymer of a monomer having a fluoroaliphatic group and (poly (oxyalkylene)) acrylate and / or (poly (oxyalkylene)) methacrylate is preferable and distributed irregularly. Or may be block copolymerized. Examples of the poly (oxyalkylene) group include a poly (oxyethylene) group, a poly (oxypropylene) group, a poly (oxybutylene) group, and the like, and a poly (oxyethylene, oxypropylene, and oxyethylene group). A unit having different chain lengths in the same chain length, such as a block link) or poly (block link of oxyethylene and oxypropylene) may be used. Furthermore, a copolymer of a monomer having a fluoroaliphatic group and (poly (oxyalkylene)) acrylate (or methacrylate) is not only a binary copolymer but also a monomer having two or more different fluoroaliphatic groups, Further, it may be a ternary or higher copolymer obtained by simultaneously copolymerizing two or more different (poly (oxyalkylene)) acrylates (or methacrylates).

For example, as a commercially available surfactant, Megafac F178, F-470, F-473, F-475, F-476, F-472 (manufactured by Dainippon Ink & Chemicals, Inc.), C ₆ F ₁₃ group Copolymer of acrylate (or methacrylate) and (poly (oxyalkylene)) acrylate (or methacrylate), acrylate (or methacrylate) and (poly (oxyethylene)) acrylate (or methacrylate) having C ₃ F ₇ groups And a copolymer of (poly (oxypropylene)) acrylate (or methacrylate).

In the present invention, surfactants other than fluorine-based and / or silicon-based surfactants described in [0280] of US Patent Application Publication No. 2008/0248425 can also be used.
These surfactants may be used alone or in several combinations.
The content of the surfactant is preferably 0 to 2% by mass, more preferably 0.0001 to 2% by mass with respect to the total solid content (total amount excluding the solvent) of the actinic ray-sensitive or radiation-sensitive resin composition. %, Particularly preferably 0.0005 to 1% by mass.

<Carboxylic acid onium salt>
The composition of the present invention may contain a carboxylic acid onium salt. As the carboxylic acid onium salt, an iodonium salt and a sulfonium salt are preferable. As the anion moiety, a linear, branched, monocyclic or polycyclic alkylcarboxylic acid anion having 1 to 30 carbon atoms is preferable. More preferably, an anion of a carboxylic acid in which some or all of these alkyl groups are fluorine-substituted is preferable. The alkyl chain may contain an oxygen atom. This ensures transparency with respect to light of 220 nm or less, improves sensitivity and resolution, and improves density dependency and exposure margin.

  Fluoro-substituted carboxylic acid anions include fluoroacetic acid, difluoroacetic acid, trifluoroacetic acid, pentafluoropropionic acid, heptafluorobutyric acid, nonafluoropentanoic acid, perfluorododecanoic acid, perfluorotridecanoic acid, perfluorocyclohexanecarboxylic acid, 2 , 2-bistrifluoromethylpropionic acid anion and the like.

  The content of the carboxylic acid onium salt in the composition is generally 0.1 to 20% by mass, preferably 0.5 to 10% by mass, more preferably 1 to 7%, based on the total solid content of the composition. % By mass.

<Dissolution-inhibiting compound having a molecular weight of 3000 or less, which is decomposed by the action of an acid to increase the solubility in an alkaline developer>
The composition of the present invention may contain a dissolution-inhibiting compound having a molecular weight of 3000 or less (hereinafter also referred to as “dissolution-inhibiting compound”) that is decomposed by the action of an acid to increase the solubility in an alkaline developer. . The dissolution inhibiting compound contains an acid-decomposable group, such as a cholic acid derivative containing an acid-decomposable group described in Proceeding of SPIE, 2724,355 (1996), in order not to lower the permeability of 220 nm or less. Preferred are alicyclic or aliphatic compounds. Examples of the acid-decomposable group and alicyclic structure are the same as those described for the resin (A).

  When the composition of the present invention is exposed with a KrF excimer laser or irradiated with an electron beam, the dissolution inhibiting compound contains a structure in which the phenolic hydroxyl group of the phenol compound is substituted with an acid-decomposable group. preferable. As a phenol compound, what contains 1-9 phenol frame | skeleton is preferable, More preferably, it contains 2-6 pieces.

The addition amount of the dissolution inhibiting compound is preferably 3 to 50% by mass, more preferably 5 to 40% by mass, based on the total solid content of the actinic ray-sensitive or radiation-sensitive resin composition.
Specific examples of the dissolution inhibiting compound are shown below, but the present invention is not limited thereto.

<Other additives>
If necessary, the composition of the present invention further contains a dye, a plasticizer, a photosensitizer, a light absorber, and a compound that promotes solubility in a developer (for example, a phenol compound having a molecular weight of 1000 or less, a carboxyl group). Alicyclic or aliphatic compound) or the like.

  Such a phenol compound having a molecular weight of 1000 or less is disclosed in, for example, JP-A-4-1222938, JP-A-2-28531, US Pat. No. 4,916,210, European Patent 219294, and the like. It can be easily synthesized by those skilled in the art with reference to the method described.

  Specific examples of alicyclic or aliphatic compounds having a carboxyl group include carboxylic acid derivatives having a steroid structure such as cholic acid, deoxycholic acid, lithocholic acid, adamantane carboxylic acid derivatives, adamantane dicarboxylic acid, cyclohexane carboxylic acid, cyclohexane Examples thereof include, but are not limited to, dicarboxylic acids.

<Pattern formation method>
The composition of the present invention is preferably used in a film thickness of 30 to 250 nm, more preferably in a film thickness of 30 to 200 nm, from the viewpoint of improving resolution. By setting the solid content concentration in the actinic ray-sensitive or radiation-sensitive resin composition to an appropriate range to have an appropriate viscosity, and improving the coating property and film forming property, such a film thickness is obtained. Can do.

  The total solid concentration in the composition of the present invention is generally 1 to 10% by mass, more preferably 1 to 8.0% by mass, and still more preferably 1.0 to 6.0% by mass.

  The composition of the present invention is used by dissolving the above-described components in a predetermined organic solvent, preferably the mixed solvent, filtering the solution, and applying the solution on a predetermined support as follows. The pore size of the filter used for filter filtration is preferably 0.1 μm or less, more preferably 0.05 μm or less, and still more preferably 0.03 μm or less made of polytetrafluoroethylene, polyethylene, or nylon.

For example, an actinic ray-sensitive or radiation-sensitive resin composition is applied to a substrate (eg, silicon / silicon dioxide coating) used for manufacturing a precision integrated circuit element by an appropriate application method such as a spinner or a coater. Dry to form a 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.

Examples of the actinic ray or radiation include infrared light, visible light, ultraviolet light, far ultraviolet light, extreme ultraviolet light, X-ray, electron beam, etc., preferably 250 nm or less, more preferably 220 nm or less, particularly Preferably, far ultraviolet light having a wavelength of 1 to 200 nm, specifically KrF excimer laser (248 nm), ArF excimer laser (193 nm), F ₂ excimer laser (157 nm), X-ray, electron beam, etc., ArF excimer Laser, F ₂ excimer laser, EUV (13 nm), and electron beam are preferable.

Before forming the film, an antireflection film may be previously coated on the substrate.
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.

As the alkaline developer in the development step, a quaternary ammonium salt typified by tetramethylammonium hydroxide is usually used. In addition, inorganic alkali, primary amine, secondary amine, tertiary amine, alcohol amine are also used. An aqueous alkali solution such as a cyclic amine can also be used.
Furthermore, alcohols and surfactants can be added in appropriate amounts 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.
Furthermore, alcohols and surfactants can be added in appropriate amounts to the alkaline aqueous solution.
As the rinsing liquid, pure water can be used, and an appropriate amount of a surfactant can be added.

  Further, after the development process or the rinsing process, a process of removing the developer or the rinsing liquid adhering to the pattern with a supercritical fluid can be performed.

  Liquid immersion exposure may be performed on the film formed using the composition according to the present invention. That is, irradiation with actinic rays or radiation may be performed in a state where a liquid having a higher refractive index than air is filled between the film and the lens. Thereby, it becomes possible to further improve the resolution.

The immersion liquid used for the immersion exposure will be described below.
The immersion liquid is preferably a liquid that is transparent to the exposure wavelength and has a refractive index temperature coefficient as small as possible so as to minimize distortion of the optical image projected onto the resist film. In particular, when the exposure light source is an ArF excimer laser (wavelength: 193 nm), it is preferable to use water from the viewpoints of availability and ease of handling in addition to the above-described viewpoints.
In addition, a medium having a refractive index of 1.5 or more can be used in order to further shorten the wavelength. This medium may be an aqueous solution or an organic solvent.

  When water is used as the immersion liquid, the surface tension of the water is decreased and the surface activity is increased, so that the resist layer on the wafer is not dissolved and the influence on the optical coating on the lower surface of the lens element can be ignored. An additive (liquid) may be added in a small proportion.

  The additive is preferably an aliphatic alcohol having a refractive index substantially equal to that of water, and specific examples include methyl alcohol, ethyl alcohol, and isopropyl alcohol. By adding an alcohol having a refractive index substantially equal to that of water, even if the alcohol component in water evaporates and the concentration of the content changes, the refractive index change of the entire liquid can be made extremely small. On the other hand, when an opaque substance or impurities whose refractive index is significantly different from that of water are mixed with respect to 193 nm light, the optical image projected on the resist is distorted. Therefore, distilled water is preferable as the water to be used. Further, pure water filtered through an ion exchange filter or the like may be used.

  The electrical resistance of the water used as the immersion liquid is preferably 18.3 MQcm or more, the TOC (organic substance concentration) is preferably 20 ppb or less, and it is desirable that deaeration treatment is performed.

Moreover, it is possible to improve lithography performance by increasing the refractive index of the immersion liquid. From such a viewpoint, an additive for improving the refractive index may be added to water, and heavy water (D ₂ O) may be used instead of water.

  An immersion liquid poorly soluble film (hereinafter also referred to as “top coat”) may be provided between the resist film and the immersion liquid in order to avoid contact between the resist film and the immersion liquid. Functions necessary for the top coat include suitability for coating on the resist layer, transparency to radiation, particularly radiation having a wavelength of 193 nm, and poor immersion liquid solubility. As the top coat, it is preferable to use a top coat that is not mixed with the resist and can be applied uniformly on the resist layer.

  From the viewpoint of transparency at 193 nm, the topcoat is preferably a polymer that does not contain aromatics. Examples of such polymers include hydrocarbon polymers, acrylic ester polymers, polymethacrylic acid, polyacrylic acid, polyvinyl ether, silicon-containing polymers, and fluorine-containing polymers. The hydrophobic resin described above is also suitable as a top coat. When impurities are eluted from the top coat into the immersion liquid, the optical lens is contaminated. Therefore, it is preferable that the residual monomer component of the polymer contained in the top coat is small.

  When peeling the top coat, a developer may be used, or a separate release agent may be used. As the release agent, a solvent having a small penetration into the resist is preferable. It is preferable that the peeling process can be performed with an alkali developer in that the peeling process can be performed simultaneously with the resist development process. The top coat is preferably acidic from the viewpoint of peeling with an alkali developer, but may be neutral or alkaline from the viewpoint of non-intermixability with the resist.

  There is preferably no or small difference in refractive index between the top coat and the immersion liquid. In this case, the resolution can be improved. When the exposure light source is an ArF excimer laser (wavelength: 193 nm), it is preferable to use water as the immersion liquid. Therefore, the top coat for ArF immersion exposure is close to the refractive index of water (1.44). preferable.

  Moreover, it is preferable that a topcoat is a thin film from a viewpoint of transparency and a refractive index. The top coat is preferably not mixed with the resist film and further not mixed with the immersion liquid. From this point of view, when the immersion liquid is water, the solvent used for the top coat is preferably a water-insoluble medium that is hardly soluble in the solvent used for the composition of the present invention. Further, when the immersion liquid is an organic solvent, the top coat may be water-soluble or water-insoluble.

  As the alkaline developer in the development step, an aqueous solution of a quaternary ammonium salt typified by tetramethylammonium hydroxide is usually used, but an inorganic alkali, primary amine, secondary amine, tertiary amine, alcohol amine, and cyclic amine are used. Other alkaline aqueous solutions such as amines can also be used. An appropriate amount of alcohols and / 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. Moreover, you may perform the process which removes the developing solution or rinse liquid adhering on a pattern with a supercritical fluid after a development process or a rinse process.

EXAMPLES Hereinafter, although an Example demonstrates this invention still in detail, the content of this invention is not limited by this.
<Synthesis of Resin (A)>
Synthesis Example 1 Synthesis of Resin 1 Monomer 1, monomer 2, monomer 3 and monomer 4 shown in the table below were charged in a ratio (molar ratio) of 40/10/40/10, dissolved in cyclohexanone, and a solid content concentration of 15 450 g of a mass% solution was prepared. To this solution, 1 mol% of a polymerization initiator V-60 manufactured by Wako Pure Chemical Industries, Ltd. was added dropwise to 50 g of cyclohexanone heated to 100 ° C. in a nitrogen atmosphere over 6 hours. The reaction liquid was stirred for 2 hours after completion | finish of dripping. After completion of the reaction, the reaction solution was cooled to room temperature, crystallized in 5 L of methanol, and the precipitated white powder was collected by filtration to recover the target resin 1.

The polymer composition ratio determined from NMR was 40/10/40/10. Moreover, the weight average molecular weight (Mw) of standard polystyrene conversion calculated | required by GPC measurement was 8400, and dispersion degree (Mw / Mn) was 1.66.
Other acid-decomposable resins were synthesized in the same manner.

Table 7 shows the structure of the acid-decomposable resin used in each example described later. In Table 7, the monomer units shown on the left are defined as monomer 1, monomer 2, monomer 3, monomer 4 and monomer 5, and the composition ratio of repeating units derived from each monomer in the acid-decomposable resin, acid-decomposable resin The weight average molecular weight and the degree of dispersion are shown in the same table.

<Synthesis of hydrophobic resin (C)>
Synthesis Example 2 Synthesis of Resin 3 (C-7) The two components shown in 3 were charged at a ratio (molar ratio) of 90/10 and dissolved in propylene glycol monomethyl ether acetate (PGMEA) to prepare 450 g of a solution having a solid content concentration of 15% by mass. 1 mol% of Wako Pure Chemical Co., Ltd. polymerization initiator V-60 was added to this solution, and this was added dropwise to 50 g of PGMEA heated to 100 ° C. in a nitrogen atmosphere over 6 hours. The reaction liquid was stirred for 2 hours after completion | finish of dripping. After completion of the reaction, the reaction solution was cooled to room temperature, crystallized in 5 L of methanol, and the precipitated white powder was collected by filtration to recover the target resin 3 (C-7).
The polymer composition ratio determined from NMR was 90/10. Moreover, the weight average molecular weight (Mw) of standard polystyrene conversion calculated | required by GPC measurement was 8000, and dispersion degree (Mw / Mn) was 1.4.
Other hydrophobic resins were synthesized in the same manner.

Table 8 shows the structure of the hydrophobic resin used. The composition ratio (corresponding in order from the left in the structural formula in Table 8), weight average molecular weight, and degree of dispersion are shown in the same table.

<Preparation of resist composition>
The components shown in Table 9 below were dissolved in a solvent, and a solution with a solid content of 4% by mass was prepared for each, and this was filtered through a polyethylene filter having a pore size of 0.1 μm to prepare a positive resist composition. The prepared positive resist composition was evaluated by the following method, and the results are shown in the same table.
<Evaluation of pattern dimension uniformity>
An organic antireflection film ARC29A (Nissan Chemical Co., Ltd.) was applied on a 300 mm silicon wafer and baked at 205 ° C. for 60 seconds to form an antireflection film having a thickness of 78 nm. The positive resist composition prepared thereon was applied and heated and dried on a hot plate at 120 ° C. for 60 seconds to form a resist film having a thickness of 100 nm.
The obtained resist film was exposed through a 6% halftone mask of 45 nm 1: 1 line and space pattern using an ArF excimer laser immersion scanner (XT1700i, NA 1.20 manufactured by ASML). Ultra pure water was used as the immersion liquid. Thereafter, it was heated on a hot plate at 110 ° C. for 60 seconds. Further, the resist film was developed with an aqueous 2.38 mass% tetramethylammonium hydroxide solution at 23 ° C. for 60 seconds, rinsed with pure water for 40 seconds, and then dried to obtain a resist pattern.

  In observing the 45 nm line and space pattern resolved at the optimum exposure, 100 points were observed in the wafer surface from the top of the pattern using Hitachi measurement SEM: S9380, and the standard deviation (3σ) was calculated. A smaller value indicates better pattern dimension uniformity.

<Evaluation of coating uniformity>
An organic antireflection film ARC29A (Nissan Chemical Co., Ltd.) was applied on a 300 mm silicon wafer and baked at 205 ° C. for 60 seconds to form an antireflection film having a thickness of 78 nm. The positive resist composition prepared thereon was applied and heated and dried on a hot plate at 120 ° C. for 60 seconds to form a resist film having a thickness of 100 nm. The obtained resist film was measured at 550 points in the wafer plane by VM-3110 (Dainippon Screen Mfg. Co., Ltd.), and the standard deviation (3σ) was calculated. A smaller value indicates better film thickness uniformity.

The compounds used in addition to the resin (A) and the resin (C) are shown below.
[Photoacid generator]
Of the specific examples listed above, those listed in Table 9 were used.
[Basic compounds]
N-1: N, N-dibutylaniline N-2: 2,6-diisopropylaniline N-3: tri-n-octylamine
[Surfactant]
W-1: Troisol S-366 (manufactured by Troy Chemical Co., Ltd.)
W-2: PF6320 (manufactured by OMNOVA, fluorine-based)
W-3: Polysiloxane polymer KP-341 (manufactured by Shin-Etsu Chemical Co., Ltd.)
(Silicon)
〔solvent〕
SL-1: Propylene glycol monomethyl ether acetate (PGMEA)
SL-2: Ethyl lactate SL-3: Propylene glycol monomethyl ether SL-4: 2-heptanone SL-5: Cyclohexanone

Claims (7)

(A) a resin containing a repeating unit represented by the following general formula (A1), which increases the dissolution rate in an alkaline developer by the action of an acid, (B) a compound that generates an acid upon irradiation with active light or radiation, And (C) an actinic ray-sensitive or radiation-sensitive resin composition comprising a resin containing a repeating unit having a lactone structure substituted with a group having a fluorine atom.

In general formula (A1),
R ₁ represents a hydrogen atom, an alkyl group, a fluorinated alkyl group, a halogen atom or CH ₂ OH.
R ₂ represents an alkylene group, a cycloalkylene group, or a divalent linking group obtained by combining them.
n represents an integer of 0 to 5.
When n is 2 or more, the plurality of R ₂ may be the same or different. Resin (A) contains the repeating unit represented by the following general formula (A2), The composition of Claim 1 characterized by the above-mentioned.

In general formula (A2),
R ₁ c represents a hydrogen atom, a methyl group, a trifluoromethyl group, or CH ₂ OH.
R ₂ c to R ₄ c each independently represents a hydrogen atom or a hydroxyl group. However, at least one of R ₂ c to R ₄ c represents a hydroxyl group.   Resin (A) contains the lactone structure which has a cyano group, The composition of Claim 1 or 2 characterized by the above-mentioned. Resin (A) contains the repeating unit represented by the following general formula (III), The composition in any one of Claims 1-3 characterized by the above-mentioned.

In general formula (III):
A represents an ester bond or an amide bond.
R ₀ represents an alkylene group, a cycloalkylene group or a divalent linking group obtained by combining them, and when there are a plurality of R ₀ groups, they may be the same or different.
Z represents an ether bond, an ester bond, an amide bond, a urethane bond or a urea bond, and when there are a plurality thereof, they may be the same or different.
R ₈ represents a monovalent organic group having a lactone structure.
n is the repeating number of the structure represented by —R ₀ —Z—, and represents an integer of 1 to 5.
R ₇ represents a hydrogen atom, a halogen atom or an alkyl group.   The resist film formed using the composition in any one of Claims 1-4.   The pattern formation method including forming a film | membrane using the composition in any one of Claims 1-4, exposing this film | membrane, and developing the exposed film | membrane.   The pattern forming method according to claim 6, wherein the exposure is immersion exposure.