JP5676021B2 - Actinic ray-sensitive or radiation-sensitive resin composition and pattern forming method using the same - Google Patents

Description

  The present invention relates to an actinic ray-sensitive or radiation-sensitive resin composition for use in a semiconductor manufacturing process such as an IC, a circuit board such as a liquid crystal or a thermal head, and other photofabrication lithography processes, and the same. The present invention relates to the pattern forming method used. In particular, the present invention relates to an actinic ray-sensitive or radiation-sensitive resin composition for immersion exposure that is suitable for exposure with an immersion projection exposure apparatus that uses far-ultraviolet light having a wavelength of 300 nm or less as a light source. The present invention relates to a pattern forming method.

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

  With the miniaturization of semiconductor elements, the exposure light source has become shorter in wavelength and the projection lens has a higher numerical aperture (high NA). Currently, an exposure machine with NA 0.84 using an ArF excimer laser having a 193 nm wavelength as a light source has been developed. ing. These can be expressed by the following equations as is generally well known.

(Resolving power) = k ₁ · (λ / NA)
(Depth of focus) = ± k ₂ · λ / NA ²
Where λ is the wavelength of the exposure light source, NA is the numerical aperture of the projection lens, and k ₁ and k ₂ are coefficients related to the process.

An exposure machine using a F ₂ excimer laser having a wavelength of 157 nm as a light source has been studied for higher resolution by further shortening the wavelength. Lens materials and resists used in the exposure apparatus for shorter wavelength have been studied. Because the materials used in the process are very limited, it is very difficult to stabilize the manufacturing cost and quality of the apparatus and materials, and the exposure apparatus and resist that have sufficient performance and stability within the required period are not in time. The possibility is coming out.

  As a technique for increasing the resolving power in an optical microscope, a so-called immersion method in which a space between a projection lens and a sample is filled with a liquid having a high refractive index (hereinafter also referred to as “immersion liquid”) has been known.

This “immersion effect” means that when λ ₀ is the wavelength of the exposure light in the air, n is the refractive index of the immersion liquid with respect to air, θ is the convergence angle of the light beam, and NA ₀ = sin θ. The above-described resolving power and depth of focus can be expressed by the following equations.

(Resolving power) = k ₁ · (λ ₀ / n) / NA ₀
(Depth of focus) = ± k ₂ · (λ ₀ / n) / NA ₀ ²
That is, the immersion effect is equivalent to using an exposure wavelength having a wavelength of 1 / n. In other words, in the case of a projection optical system with the same NA, the depth of focus can be increased n times by immersion. This 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.

Examples of apparatuses in which this effect is applied to transfer of a fine image pattern of a semiconductor element are introduced in Patent Documents 1 and 2 and the like.
Recent progress in immersion exposure technology is reported in Non-Patent Documents 1 to 3, Patent Documents 3 and 4, and the like.

In the case of using an ArF excimer laser as a light source, pure water (refractive index of 1.44 at 193 nm) is considered to be most promising as an immersion liquid in terms of handling safety, transmittance at 193 nm, and refractive index. When an F ₂ excimer laser is used as a light source, a solution containing fluorine has been studied from the balance between transmittance and refractive index at 157 nm. However, a sufficient product has not yet been seen in terms of environmental safety and refractive index. It has not been issued. From the degree of immersion effect and the degree of completeness of the resist, the immersion exposure technique is considered to be installed in the ArF exposure machine earliest.

  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 area is decomposed by exposure to generate an acid upon exposure, and the generated acid is reacted as a reaction catalyst by post exposure baking (PEB). Is used to change an alkali-insoluble group to an alkali-soluble group, and an exposed portion is removed by alkali development.

  Various compounds have also been found for acid generators which are main constituents of chemically amplified resist compositions. Patent Documents 5 and 6 disclose resist compositions containing a specific sulfonium salt compound as an acid generator. Is disclosed.

  Patent Document 7 states that, in patterning by X-ray, electron beam, and EUV exposure, polyhydroxystyrene resin and 5 to 20% by mass of acid are generated to suppress high sensitivity, high resolution, good pattern shape, and line edge roughness. A positive resist composition containing an agent is disclosed.

  However, from the viewpoint of overall performance as a resist, it is actually difficult to find an appropriate combination of resin, photoacid generator, additive, solvent, etc. to be used, and the line width is 100 nm or less. When forming such a fine pattern, the problem is that the originally designed pattern shape cannot be reproduced due to the roughness of the resist pattern side wall due to miniaturization and the focus fluctuation in normal dry exposure, and especially immersion exposure. Therefore, there is a problem that the pattern shape is likely to change, and improvements are desired.

JP-A-57-153433 JP-A-7-220990 JP-A-10-303114 International Publication No. 04/075158 Pamphlet Japanese Patent Laid-Open No. 10-232490 JP 2003-195490 A JP 2004-271629 A

Proc. SPIE, 2002, Vol. 4688, p. 11 J.Vac.Sci.Tecnol.B 17 (1999) Proc. SPIE, 2000, Vol. 3999, p. 2

  An object of the present invention is to provide an actinic ray-sensitive or radiation-sensitive resin composition that is effective in improving the roundness of a pattern and can form a pattern with a good focus margin, and a pattern using the same It is to provide a forming method.

  As a result of intensive studies to solve the above problems, the present inventors have completed the present invention shown below.

<1> (A) Resin whose solubility in an alkaline developer is increased by the action of an acid, and (B) Acid by irradiation with actinic rays or radiation represented by the following general formula (1-1) or (1-2) An actinic ray-sensitive or radiation-sensitive resin composition comprising a compound that generates a compound, wherein the resin (A) contains a repeating unit having an acid-decomposable group, and the content of the repeating unit is It is 45 to 75 mol% with respect to all repeating units in (A), and the content of compound (B) is 10 to 30% by mass based on the total solid content of the composition. An actinic ray-sensitive or radiation-sensitive resin composition.

In general formula (1-1),
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.
When there are a plurality of R _{14 s,} each independently represents an alkyl group, a cycloalkyl group, an alkoxy group, an alkylsulfonyl group, a cycloalkylsulfonyl group, an alkylcarbonyl group, an alkoxycarbonyl group, or a monocyclic or polycyclic cycloalkyl skeleton. Represents a group having
R ₁₅ each independently represents an alkyl group, a cycloalkyl group, a phenyl group, or a naphthyl group. However, the case where two R < ₁₅ > are phenyl groups simultaneously is remove | excluded. Further, two R ₁₅ may be bonded to each other to form a ring.
l represents an integer of 0-2.
r represents an integer of 0 to 8.
X ⁻ represents a non-nucleophilic anion.

In general formula (1-2),
M represents an alkyl group, a cycloalkyl group, an aryl group, or a benzyl group, and when having a ring structure, the ring structure includes an oxygen atom, a sulfur atom, an ester bond, an amide bond, or a carbon-carbon double bond. May be.
R _1c and R _2c 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, an alkoxycarbonylalkyl group, an allyl group, or a vinyl group.
R _x and R _y may combine to form a ring.
At least two of M, R _1c and R _2c may combine to form a ring, and the ring structure may contain a carbon-carbon double bond.
X ⁻ represents a non-nucleophilic anion.

  <2> The actinic ray-sensitive or radiation-sensitive resin composition according to <1>, further comprising a hydrophobic resin having at least one of a fluorine atom and a silicon atom.

  <3> The actinic ray-sensitive or radiation-sensitive resin composition according to <1> or <2>, wherein the resin (A) further contains a repeating unit containing a lactone structure.

  <4> The resin (A) contains, as a repeating unit having an acid-decomposable group, a repeating unit having an acid-decomposable group containing at least a monocyclic or polycyclic alicyclic structure, <1 The active light sensitive or radiation sensitive resin composition according to any one of <3> to <3>.

  <5> The actinic ray-sensitive or radiation-sensitive resin composition according to any one of claims 1 to 4, wherein immersion exposure is applied.

  <6> A step of forming a film using the actinic ray-sensitive or radiation-sensitive resin composition according to any one of <1> to <5>, a step of exposing the film, and a step of developing A pattern forming method comprising:

  <7> The pattern forming method according to <6>, wherein the exposure is immersion exposure.

  INDUSTRIAL APPLICABILITY According to the present invention, an actinic ray-sensitive or radiation-sensitive resin composition capable of forming a pattern having an effect of improving the roundness of a pattern and having a good focus margin, and a pattern forming method using the same It became possible to provide. The actinic ray-sensitive or radiation-sensitive resin composition of the present invention is suitable as a positive resist composition.

Hereinafter, the best mode for carrying out the present invention will be described.
In addition, in the description of the group (atomic group) in this specification, the description which does not describe substitution and non-substitution includes what does not have a substituent and what has a substituent. . For example, the “alkyl group” includes not only an alkyl group having no substituent (unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group).

  In addition, “exposure” in the present specification is represented not only by exposure to deep ultraviolet rays, X-rays, EUV light and the like, but also by particle beams such as electron beams and ion beams, unless otherwise specified, such as mercury lamps and excimer lasers. Drawing is also included in the exposure.

[1] 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 referred to as a resin whose solubility in an alkaline developer is increased by the action of an acid). "Resin (A)" or "acid-decomposable resin (A)").

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. Also called).
The resin (A) is preferably insoluble or hardly soluble in an alkali developer.

The acid-decomposable group preferably has a structure in which an alkali-soluble group is protected by a group that decomposes and leaves under 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 of the monovalent organic group include an alkyl group having 5 or less carbon atoms and an acyl group, preferably an alkyl group having 3 or less carbon atoms. More preferably, it is 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.
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 45 to 75 mol%, more preferably 50 to 60 mol%, based on all repeating units in the resin (A). When the ratio of the acid-decomposable group is 45 mol% or more, it is possible to sufficiently establish the collision between the generated acid and the acid-decomposable group, so that the deprotection reaction can be efficiently performed even when the amount of the generated acid changes due to focus fluctuation. This is preferable because it proceeds. However, when the acid-decomposable group exceeds 75 mol%, an excessive deprotection reaction proceeds even in a finely exposed part, so that a dissolution contrast is difficult to be obtained, which tends to be disadvantageous for resist pattern formation. On the other hand, when the acid-decomposable group is less than 45 mol%, the resolution of the resist tends to decrease because the alkali-soluble group generated by the deprotection reaction is insufficient. When the acid-decomposable group is 50 to 60 mol%, it is particularly preferable because the balance between the deprotection reaction probability and the dissolution contrast after the deprotection reaction is optimal and the resist pattern shape is good.

  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.

It is more preferable that the resin (A) has at least a repeating unit represented by the following general formula (I) as the repeating unit represented by the general formula (AI).

In formula (I),
R ₁ has the same meaning as Xa ₁ in formula (AI), and preferred specific examples are also a hydrogen atom, a methyl group, a trifluoromethyl group, or a hydroxymethyl group.
R ₂ represents a linear or branched alkyl group having 2 or more carbon atoms, preferably having 2 to 4 carbon atoms, and is an ethyl group, i-propyl group, n-propyl group, n-butyl group, sec- A butyl group is mentioned.

R represents an atomic group necessary for forming an alicyclic structure together with a carbon atom. The alicyclic structure formed by R may be a monocyclic structure or a polycyclic structure. As the monocyclic structure, a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group and the like are preferable, and as a polycyclic structure, an adamantyl group, a diamantyl group, a decahydronaphthyl group, a norbornyl group, A tricyclodecanyl group or tetracyclododecanyl is preferred.
In one embodiment, the resin (A) preferably has at least two repeating units represented by the above general formula (I) as the repeating unit represented by the general formula (AI). In another embodiment, It is preferable to have a repeating unit represented by the general formula (I) and a repeating unit represented by the following general formula (II).

In the general formula (II), R ₃ has the same meaning as Xa ₁ in the general formula (AI), and preferred specific examples are also a hydrogen atom, a methyl group, a trifluoromethyl group, or a hydroxymethyl group.
R ₄ , R ₅ and R ₆ each independently represents an alkyl group or a cycloalkyl 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.
Preferred combinations when the resin (A) uses a repeating unit having an acid-decomposable group are as follows. 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 10 to 55 mol%, more preferably 20 to 50 mol%, and more preferably 20 to 50 mol%, based on the total repeating units in the resin when a plurality of types are contained. Preferably it is 30-45 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 other than the repeating unit represented by the general formula (III) is preferably 15 to 60 mol% in total with respect to all the repeating units in the resin when more than one type is contained, more preferably Is 20 to 50 mol%, more preferably 30 to 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).

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 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 a hydroxymethyl group.
R ₂ c to R ₄ c are in the general formula (VIIa) ~ (VIIc), same meanings as R ₂ c~R ₄ c.
The content of the repeating unit having a hydroxyl group or a cyano group is preferably from 5 to 40 mol%, more preferably from 5 to 30 mol%, still more preferably from 10 to 25 mol%, based on all repeating units in the resin (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 used in the actinic ray-sensitive or radiation-sensitive resin composition of the present invention may have a repeating unit having an alkali-soluble group. Examples of the alkali-soluble group include a carboxyl group, a sulfonamide group, a sulfonylimide group, a bisulsulfonylimide group, and an aliphatic alcohol (for example, hexafluoroisopropanol group) substituted with an electron withdrawing group at the α-position. It is more preferable to have a repeating unit. By containing the repeating unit having an alkali-soluble group, the resolution in contact hole applications is increased. The repeating unit having an alkali-soluble group includes a repeating unit in which an alkali-soluble group is directly bonded to the main chain of the resin, such as a repeating unit of acrylic acid or methacrylic acid, or an alkali in the main chain of the resin through a linking group. Either a repeating unit to which a soluble group is bonded, or a polymerization initiator or chain transfer agent having an alkali-soluble group is used at the time of polymerization and introduced at the end of the polymer chain, and the linking group is monocyclic or polycyclic. It may have a cyclic hydrocarbon structure. Particularly preferred are repeating units of acrylic acid or methacrylic acid.

As for the content rate of the repeating unit which has an alkali-soluble group, 0-20 mol% is preferable with respect to all the repeating units in resin (A), More preferably, it is 3-15 mol%, More preferably, it is 5-10 mol%.
Specific examples of the repeating unit having an alkali-soluble group are shown below, but the present invention is not limited thereto.
In specific examples, Rx represents H, CH ₃ , CH ₂ OH, or CF ₃ .

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 formability (glass transition point),
(3) Alkali developability,
(4) Membrane slip (hydrophobic, alkali-soluble group selection),
(5) Adhesion of unexposed part to substrate,
(6) Dry etching resistance,
Etc. can be finely adjusted.

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

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

  In the resin (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. More preferably, the (meth) acrylate repeating unit having an acid-decomposable group is 20 to 50 mol%, the (meth) acrylate repeating unit having a lactone group is 20 to 50 mol%, and the alicyclic ring is substituted with a hydroxyl group or a cyano group. It is a copolymer containing 5 to 30 mol% of a (meth) acrylate-based repeating unit having a hydrocarbon structure and further 0 to 20 mol% of another (meth) acrylate-based repeating unit.

  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 the polymerization is performed by heating, and a solution of the monomer species and the initiator is dropped into the heating solvent over 1 to 10 hours. The dropping polymerization method is added, and the dropping polymerization method is preferable. 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 30 to 99% by mass, more preferably 60 to 95% by mass in the total solid content.
In addition, the resins of the present invention may be used alone or in combination.

[2] Compound that generates acid upon irradiation with actinic ray or radiation The composition of the present invention contains a compound that generates acid upon irradiation with actinic ray or radiation (hereinafter also referred to as “acid generator”).

  The composition of the present invention contains at least a compound represented by the following general formula (1-1) or (1-2) (hereinafter also referred to as “compound (B)”) as an acid generator. The content rate of a compound (B) is 10-30 mass% on the basis of the total solid of the composition of this invention, Preferably it is 18-30 mass%, More preferably, it is 20-26 mass%. By adding a large amount of the compound (B), there is an effect of improving the resist pattern shape.

  These compounds can maintain a high transmittance with respect to ArF light with a wavelength of 193 nm of the formed film even in the above addition amount range. For example, the transmittance with respect to light with a wavelength of 193 nm is 60% as a 100 nm film. It can be made 85% or less. The high transmittance for ArF light provides good performance in patterning with ArF light.

  The transmittance for light with a wavelength of 193 nm is, for example, by applying an actinic ray-sensitive or radiation-sensitive resin composition onto a quartz glass substrate by spin coating, and prebaking at 100 ° C. to form a film with a thickness of 100 nm. The absorbance at a wavelength of 193 nm of the film can be obtained and calculated by using an ellipsometer EPM-222 (manufactured by JA Woollam).

In the total amount of the acid generator, the compound represented by the general formula (1-1) or (1-2) is preferably contained in an amount of 50% by mass to 100% by mass, and preferably 75% by mass to 100% by mass. More preferably, the content is particularly preferably 95 to 100% by mass.

In general formula (1-1),
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.
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
R ₁₅ each independently represents an alkyl group, a cycloalkyl group, a phenyl group or a naphthyl group. However, the case where two R < ₁₅ > are phenyl groups simultaneously is remove | excluded. Two R ₁₅ may be bonded to each other to form a ring.
l represents an integer of 0-2.
r represents an integer of 0 to 8.
X ⁻ represents a non-nucleophilic anion.

In general formula (1-2),
M represents an alkyl group, a cycloalkyl group, an aryl group, or a benzyl group, and when having a ring structure, the ring structure includes an oxygen atom, a sulfur atom, an ester bond, an amide bond, or a carbon-carbon double bond. May be.
R _1c and R _2c 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, an alkoxycarbonylalkyl group, an allyl group, or a vinyl group.
R _x and R _y may combine to form a ring. Further, at least two of M, R _1c and R _2c may be bonded to form a ring, and the ring structure may contain a carbon-carbon double bond.

X ⁻ represents a non-nucleophilic anion.

In the general formula (1-1), 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, adamantyl group and the like. In particular, cyclopropyl, cyclopentyl, cyclohexyl and cyclooctyl are 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. You may have the substituent mentioned above.

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 tetracyclo decanyl ethoxy group, an adamantane methoxy group, an adamantane ethoxy group, etc. are mentioned, and a norbornyl methoxy group and a norbornyl ethoxy group are preferable. These may have the substituent mentioned above.
The alkyl group of the alkyl group of R _14, include the same specific examples as the alkyl group as R ₁₃ to R ₁₅ described above.

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

  Each of the above groups may have a substituent. Examples of the substituent include a halogen atom (for example, a fluorine atom), a hydroxyl group, a carboxyl group, a cyano group, a nitro group, an alkoxy group, an alkoxyalkyl group, an alkoxycarbonyl group. Group, alkoxycarbonyloxy group 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 methoxycarbonyloxy group, ethoxycarbonyloxy group, n-propoxycarbonyloxy group, i-propoxycarbonyloxy group, n-butoxycarbonyloxy group, t-butoxycarbonyloxy group, and cyclopentyloxy. Examples thereof include linear, branched or cyclic alkoxycarbonyloxy groups having 2 to 21 carbon atoms such as carbonyloxy group and cyclohexyloxycarbonyloxy.

As a ring structure which two R ₁₅ may combine with each other, a 5-membered or 6-membered ring formed by two divalent R ₁₅ together with the sulfur atom in the general formula (1-1) Particularly preferred is a 5-membered ring (that is, a tetrahydrothiophene ring), which may be condensed with an aryl group or a cycloalkyl group. This divalent R ₁₅ may have a substituent. Examples of the substituent include a hydroxyl group, a carboxyl group, a cyano group, a nitro group, an alkoxy group, an alkoxyalkyl group, an alkoxycarbonyl group, an alkoxycarbonyloxy group, and the like. Groups and the like. R ¹⁵ in the general formula (1-1) 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.
Below, the preferable specific example of the cation in the compound represented by General formula (1-1) is shown.

  Next, general formula (1-2) will be described.

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

  The alkyl group as M may be either linear or branched, for example, an alkyl group having 1 to 20 carbon atoms, preferably a linear or branched alkyl group having 1 to 12 carbon atoms, such as methyl Group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, tert-butyl group, pentyl group, hexyl group, octyl group and 2-ethylhexyl group.

The cycloalkyl group as M is a cyclic alkyl group having 3 to 12 carbon atoms, and examples thereof include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, and a cyclodecyl group.
The aryl group as M preferably has 5 to 15 carbon atoms, and examples thereof include a phenyl group and a naphthyl group.

Each group as M may have a cycloalkyl group, an alkoxy group, a halogen atom, a phenylthio group or the like as a substituent. The cycloalkyl group and aryl group as M may further have an alkyl group as a substituent. The number of carbon atoms of the substituent is preferably 15 or less.
When M is a phenyl group, it preferably has at least one linear, branched, cyclic alkyl group, linear, branched, cyclic alkoxy group, or phenylthio group as a substituent, and more preferably carbon of the substituent. The sum of the numbers 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 alkyl group as R _1c and R _2c is, for example, an alkyl group having 1 to 12 carbon atoms, preferably a linear or branched alkyl group having 1 to 5 carbon atoms (for example, a methyl group, an ethyl group, a linear or branched group). Mention may be made of the propyl group.
The cycloalkyl group as R _1c and R _2c is, for example, a cycloalkyl group having 3 to 12 carbon atoms, and preferably includes a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclodecyl group, and the like. be able to.
Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

The aryl group as R _1c and R _2c preferably has 5 to 15 carbon atoms, and examples thereof include a phenyl group and a naphthyl group.

The ring structure formed by combining at least two of M, R _1c and R _2c is preferably a 3- to 12-membered ring, more preferably a 3- to 10-membered ring, still more preferably a 3- to 6-membered ring. The ring skeleton may have a carbon-carbon double bond.

When R _1c and R _2c are combined to form a ring, the group formed by combining R _1c and R _2c 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 _1c and R _2c may have a heteroatom such as an oxygen atom in the ring.

_Examples of the alkyl group as R _x and R _y include the same alkyl groups as R _1c and R _2c .
As the cycloalkyl group, for example, a cycloalkyl group having 3 to 8 carbon atoms is preferable, and examples thereof include a cyclopentyl group and a cyclohexyl group.

Examples of the 2-oxoalkyl group include a group having> C═O at the 2-position of the alkyl group as R _1c and R _2c .

The alkoxy group in the alkoxycarbonylalkyl group may be linear, branched or cyclic. For example, the alkoxy group having 1 to 10 carbon atoms, preferably, the linear or branched alkoxy group having 1 to 5 carbon atoms ( For example, methoxy group, ethoxy group, linear or branched propoxy group, linear or branched butoxy group, linear or branched pentoxy group), cyclic alkoxy group having 3 to 8 carbon atoms (for example, cyclopentyloxy group, cyclohexyloxy group) Can be mentioned. Moreover, about the alkyl group in an alkoxycarbonylalkyl group, a C1-C12 alkyl group, Preferably, a C1-C5 linear chain (For example, a methyl group and an ethyl group can be mentioned, for example.
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, etc.) are represented by the general formula (1-2). 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 having 4 or more carbon atoms, more preferably 6 or more, and still more preferably 8 or more.

Examples of the cation of the compound represented by formula (1-2) of the present invention include the following specific examples.

X ⁻ in the general formulas (1-1) and (1-2) represents a non-nucleophilic anion, preferably a sulfonate anion, a carboxylic acid anion, a bis (alkylsulfonyl) amide anion, tris (alkylsulfonyl) ) Methide anion, BF ₄ ⁻ , PF ₆ ⁻ , SbF ₆ ^{— and the} like, and an organic anion containing a carbon atom is preferable.
Preferable organic anions include organic anions represented by the following formula.

Rc ₁ represents an organic group.
Examples of the organic group in Rc ₁ include those having _{1 to} 30 carbon atoms, and preferably an alkyl group, an aryl group, or a plurality thereof which may have a substituent is a single bond, —O—, —CO _{2. -, - S -, - SO} 3 -, - SO 2 N (Rd 1) - can be exemplified linked group a linking group such as.
Rd ₁ represents a hydrogen atom or an alkyl group.
Rc ₃ , Rc ₄ and Rc ₅ each independently represents an organic group.
Preferred examples of the organic group for Rc ₃ , Rc ₄ , and Rc ₅ include the same organic groups as those for Rc ₁ , and most preferred is a C 1-4 perfluoroalkyl group.

Rc ₃ and Rc ₄ may be bonded to form a ring. Examples of the group formed by combining Rc ₃ and Rc ₄ include an alkylene group and an arylene group. A perfluoroalkylene group having 2 to 4 carbon atoms is preferred.
The organic group of Rc ₁ and Rc _{3 to} Rc ₅ is most preferably an alkyl group substituted at the 1-position with a fluorine atom or a fluoroalkyl group, or a phenyl group substituted with a fluorine atom or a fluoroalkyl group. By having a fluorine atom or a fluoroalkyl group, the acidity of the acid generated by light irradiation is increased and the sensitivity is improved.
Moreover, as X < ^- >, the anion represented by the following general formula (A1) can be mentioned.

  In general formula (A1), R represents a hydrogen atom or an organic group, preferably an organic group having 1 to 40 carbon atoms, more preferably an organic group having 3 to 20 carbon atoms. Most preferably, it is an organic group represented by A1a).

The organic group for R may have one or more carbon atoms. Preferably, the atom bonded to the oxygen atom in the ester bond represented by the general formula (A1) is a carbon atom, such as an alkyl group, Examples include a cycloalkyl group, an aryl group, an aralkyl group, and a group having a lactone structure, and the chain may have a hetero atom such as an oxygen atom or a sulfur atom. These may have each other as a substituent, and may have a substituent such as a hydroxyl group, an acyl group, an acyloxy group, an oxy group (═O), or a halogen atom.

In the formula (A1a), Rc represents a monocyclic or polycyclic organic group having 3 to 30 carbon atoms which may contain a cyclic ether, a cyclic thioether, a cyclic ketone, a cyclic carbonate, a lactone, or a lactam structure. Y is a hydroxyl group, a halogen atom, a cyano group, a carboxyl group, a hydrocarbon group having 1 to 10 carbon atoms, a hydroxyalkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, or an acyl having 2 to 10 carbon atoms. Group, an alkoxycarbonyl group having 2 to 10 carbon atoms, an acyloxy group having 2 to 10 carbon atoms, an alkoxyalkyl group having 2 to 10 carbon atoms, and a halogenated alkyl group having 1 to 8 carbon atoms. When m = 0 to 6 and there are a plurality of Y, they may be the same as or different from each other. n = 0 to 10.
The total number of carbon atoms constituting the R group represented by the formula (AIa) is preferably 40 or less.

n = 0 to 3 and Rc is preferably a monocyclic or polycyclic organic group having 7 to 16 carbon atoms.
Moreover, as X < ^- >, the anion corresponding to the acid represented by the following general formula (A2) can be mentioned.

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

The general formula (A2) will be described in more detail.
The alkyl group in the alkyl group substituted with the fluorine atom of Xf preferably has 1 to 10 carbon atoms, more preferably 1 to 4 carbon atoms. The alkyl group substituted with a fluorine atom of Xf is preferably a perfluoroalkyl group.
Xf is preferably a fluorine atom or a perfluoroalkyl group having 1 to 4 carbon atoms. Specifically, fluorine atom, CF ₃ , C ₂ F ₅ , C ₃ F ₇ , C ₄ F ₉ , C ₅ F ₁₁ , C ₆ F ₁₃ , C ₇ F ₅ , 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 , CH ₂ CH ₂ C ₄ F ₉ is mentioned, among which fluorine atom and CF ₃ are preferable.

The alkyl group in R ¹ and R ^{2 and} the alkyl group substituted with at least one fluorine atom are preferably those having 1 to 4 carbon atoms. More preferably, it is a C1-C4 perfluoroalkyl group. Specifically, 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 ₅ , 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 , CH ₂ CH ₂ C ₄ F _9. Among these CF ₃ are preferred.

y is preferably 0 to 4, and more preferably 0. x is preferably from 1 to 8, and preferably from 1 to 4. z is preferably 0 to 8, particularly preferably 0 to 4.
The divalent linking group of L is not particularly limited, and is —COO—, —OCO—, —CO—, —O—, —S—, —SO—, —SO ₂ —, an alkylene group, a cycloalkylene group, Alkenylene group etc. are mentioned. Of these, —COO—, —OCO—, —CO—, and —O— are preferable, and —COO— and —OCO— are more preferable.

  The group having a cyclic structure of A is not particularly limited as long as it has a cyclic structure. The group having an alicyclic group, an aryl group, or a heterocyclic structure (not only those having an aromatic attribute, but also having an aromatic attribute). For example, a tetrahydropyran ring and a lactone ring structure are also included).

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

  Examples of the aryl group include a benzene ring, a naphthalene ring, a phenanthrene ring, and an anthracene ring. Of these, naphthalene having low absorbance is preferred from the viewpoint of light absorbance at 193 nm.

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

The group having the cyclic structure may have a substituent, and the substituent may be an alkyl group (which may be linear, branched or cyclic, preferably having 1 to 12 carbon atoms), Examples include aryl groups (preferably having 6 to 14 carbon atoms), hydroxy groups, alkoxy groups, ester groups, amide groups, urethane groups, ureido groups, thioether groups, sulfonamido groups, sulfonic acid ester groups, and the like.
It is particularly preferable that the counter ion represented by X ⁻ has a structure represented by the following general formula (III).
The counter anion represented by the general formula (II) is preferably a structure represented by the following general formula (III).

In general formula (III),
A represents an oxygen atom, a nitrogen atom, or a carbon atom.
R ₂ represents a fluorine atom, an alkyl group which may have a substituent, a cycloalkyl group which may have a substituent, or an aryl group which may have a substituent.

When A is an oxygen atom, n = 1, m = 0, when A is a nitrogen atom, n + m = 2 and n = 1 or 2, m = 0 or 1, and when A is a carbon atom, n + m = 3 and n = 1-3, m = 0-2. When n is 2 or more, R ₁ may be the same or different, and R ₁ may be bonded to each other to form a ring.

The alkyl group, cycloalkyl group, and aryl group represented by R ₂ represent a chain alkyl group, a monocyclic alkyl group, a polycyclic hydrocarbon group, or a monocyclic aryl group, and the chain alkyl group, The monocyclic alkyl group, the polycyclic hydrocarbon group, and the monocyclic aryl group may have a substituent. The substituent preferably has a fluorine atom.

  The chain alkyl group may be linear or branched, and is methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, dodecyl, 2-ethylhexyl, isopropyl, sec-butyl, t-butyl, iso -Amyl etc. are mentioned.

  The alkyl group may have a substituent, and examples of the substituent include a hydroxyl group, a halogen atom (fluorine, chlorine, bromine, iodine), a nitro group, a cyano group, an amide group, a sulfonamide group, a methyl group, and an ethyl group. Group, propyl group, n-butyl group, sec-butyl group, hexyl group, 2-ethylhexyl group, alkyl group such as octyl group, methoxy group, ethoxy group, hydroxyethoxy group, propoxy group, hydroxypropoxy group, butoxy group, etc. Alkoxy groups such as methoxycarbonyl group and ethoxycarbonyl group, acyl groups such as formyl group, acetyl group and benzoyl group, acyloxy groups such as acetoxy group and butyryloxy group, and carboxy group.

  Examples of monocyclic alkyl groups include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloptyl, cyclooctyl, cyclododecanyl, cyclobenthenyl, cyclohexenyl, cyclooctadienyl, and the like, particularly cyclopropyl, cyclopentyl, cyclohexyl, Cyclooctyl is preferred.

  The monocyclic alkyl group may have a substituent, and examples of the substituent include a halogen atom (fluorine, chlorine, bromine, iodine), a nitro group, a cyano group, an amide group, a sulfonamide group, a methyl group, Alkyl group such as ethyl group, propyl group, n-butyl group, sec-butyl group, hexyl group, 2-ethylhexyl group, octyl group, methoxy group, ethoxy group, hydroxyethoxy group, propoxy group, hydroxypropoxy group, butoxy group And alkoxy groups such as methoxycarbonyl group and ethoxycarbonyl group, acyl groups such as formyl group, acetyl group and benzoyl group, acyloxy groups such as acetoxy group and butyryloxy group, and carboxy group.

Examples of polycyclic hydrocarbon groups include bicyclo [4.3.0] nonanyl, decahydronaphthalenyl, tricyclo [5.2.1.0 (2,6)] decanyl, bornyl, isobornyl, norbornyl, adamantyl, noradamantyl, 1,7 , 7-trimethyltricyclo [2.2.1.0 ^2,6 ] heptanyl, 3,7,7-trimethylbicyclo [4.1.0] heptanyl and the like, and norbornyl, adamantyl and noradamantyl are particularly preferable.

  The monocyclic aryl group means a substituted or unsubstituted phenyl group, and examples of the substituent include a hydroxyl group, a halogen atom (fluorine, chlorine, bromine, iodine), a nitro group, a cyano group, an amide group, a sulfonamide group, Alkyl group such as methyl group, ethyl group, propyl group, n-butyl group, sec-butyl group, hexyl group, 2-ethylhexyl group, octyl group, methoxy group, ethoxy group, hydroxyethoxy group, propoxy group, hydroxypropoxy group And alkoxy groups such as butoxy group, alkoxycarbonyl groups such as methoxycarbonyl group and ethoxycarbonyl group, acyl groups such as formyl group, acetyl group and benzoyl group, acyloxy groups such as acetoxy group and butyryloxy group, and carboxy group.

R ₂ preferably has an electron withdrawing group from the viewpoint of acid strength. The electron withdrawing group is not particularly limited, but cyano group, trifluoromethyl group, nitro group, carboxyl group, ketone group, acyloxy group, hydroxy group, perfluoroalkyl group, methoxy group, ethoxy group, isopropoxy group , Alkoxy groups such as t-butoxy group and benzyloxy group, halogen atoms such as fluorine atom and chlorine atom, and the like, particularly preferably having a fluorine atom. More preferably, R ₂ is a group having a fluorine atom having a molecular weight of 220 or less, and particularly R ₂ is preferably a trifluoromethyl group.

R ₃ independently represents an alkyl group which may have a substituent, a cycloalkyl group which may have a substituent, or an aryl group which may have a substituent, when there are a plurality of R _3. , R ₄ represents a hydrogen atom.
L represents a single bond or a linking group.
p1 represents an integer of 1 to 8, p2 = 1 or 2, and p3 = 0 or 1.

When p2 = 2, two R ₃ may be bonded to each other to form a ring structure, and when n = 2 or more, a plurality of R ₃ may be bonded to each other to form a ring structure.
Specific examples of the alkyl group, cycloalkyl group and aryl group represented by R ₃ include the same groups as those exemplified for each of R ₂ .
Here, R ₃ preferably has no fluorine atom from the viewpoint of low fluorine content.

L is a single bond, an oxygen atom (—O—), a sulfur atom (—S—), a nitrogen atom (> N—), a carboxyl group (—OC═O—, —CO═O—), an amide group (> NC = O—) and a sulfonamide group (> NSO ₂ —) are preferable. In particular, a p2 = 2, when two R ₃ join to form a ring together, preferably L is a linking group having an amide group, the nitrogen atom such as a sulfonamide group, two where R ₃ combine with each other to form a cyclic amine residue having a nitrogen atom on L in the ring.

  Cyclic amine residue structures include aziridine, azetidine, pyrrolidine, piperidine, hexamethyleneimine, heptamethyleneimine, piperazine, decahydroquinoline, decahydroquinoline, 8-azabicyclo [3.2.1] octane, indole, oxazolidine, thiazolidine, 2 -Azanorbornane, 7-azanorbornane, morpholine, thiamorpholine and the like may be mentioned, and these may have a substituent. Substituents include hydroxyl groups, halogen atoms (fluorine, chlorine, bromine, iodine), nitro groups, cyano groups, amide groups, sulfonamido groups, methyl groups, ethyl groups, propyl groups, n-butyl groups, sec-butyl groups. , Hexyl group, 2-ethylhexyl group, alkyl group such as octyl group, alkoxy group such as methoxy group, ethoxy group, hydroxyethoxy group, propoxy group, hydroxypropoxy group, butoxy group, alkoxy group such as methoxycarbonyl group, ethoxycarbonyl group, etc. Examples include carbonyl groups, formyl groups, acetyl groups, benzoyl groups, acyl groups such as carbonyl groups on the carbon forming the ring, acyloxy groups such as acetoxy groups and butyryloxy groups, and carboxy groups.

In the general formula (III), a site represented by the following formula:

In the above, the fluorine content represented by (mass of all fluorine atoms contained) / (mass of all atoms contained) is preferably 0.35 or less, more preferably 0.30 or less, particularly preferably 0.8. 25 or less.

Specific examples of the counter anion structure represented by the general formula (III) of the present invention include the following.

Furthermore, examples of X ⁻ include anions represented by the following general formula (A3) or (A4) described in JP-A-2005-221721.

In general formulas (A3) and (A4),
Y is an alkylene group substituted with at least one fluorine atom, preferably an alkylene group having 2 to 4 carbon atoms. An oxygen atom may be contained in the alkylene chain. A perfluoroalkylene group having 2 to 4 carbon atoms is more preferable, and a tetrafluoroethylene group, a hexafluoropropylene group, and an octafluorobutylene group are most preferable.
R in the formula (A4) represents an alkyl group or a cycloalkyl group. The alkylene chain in the alkyl group or cycloalkyl group may contain an oxygen atom.
Specific examples of the compound having an anion represented by the general formula (A3) or (A4) include those described in JP-A-2005-221721.
Examples of the compound (B) represented by the general formula (1-1) that generates an acid include the following compounds, but are not limited thereto.

Examples of the compound (B) represented by the general formula (1-2) that generates an acid include, but are not limited to, the following compounds.

  The acid generator represented by general formula (1-1) or (1-2) can be used individually by 1 type or in combination of 2 or more types. Moreover, you may use the acid generator represented by general formula (1-1) or (1-2) in combination with another acid generator.

As the acid generator, a compound represented by the following general formula (ZI), (ZII), or (ZIII) may be used in combination with the compound (B). In particular, the total amount of the acid generator represented by the general formula (1-1) or (1-2) is generally 50% by mass or less, preferably 25% by mass or less, and maintains good transmittance. More preferably, it is 10% by mass or less, more preferably 5% by mass or less.

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

Examples of Z ⁻ include a sulfonate anion (an aliphatic sulfonate anion, an aromatic sulfonate anion, a camphor sulfonate anion, etc.), a carboxylate anion (an aliphatic carboxylate anion, an aromatic carboxylate anion, an aralkyl carboxylate anion). Etc.), sulfonylimide anion, bis (alkylsulfonyl) imide anion, tris (alkylsulfonyl) methide anion and the like. Moreover, the anion as X < ^- > in the acid generator represented by the above general formula (1-1) or (1-2) may be used.

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

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

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

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

  Examples of the sulfonylimide anion include saccharin anion.

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

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

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

_Examples of the organic group for R ₂₀₁ , R ₂₀₂ and R ₂₀₃ include an aryl group (preferably having 6 to 15 carbon atoms), a linear or branched alkyl group (preferably having 1 to 10 carbon atoms), and a cycloalkyl group (having 3 carbon atoms). ~ 15 are preferred).

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

Two selected from R ₂₀₁ , R ₂₀₂ and R ₂₀₃ may be bonded via a single bond or a linking group. Examples of the linking group include an alkylene group (preferably having 1 to 3 carbon atoms), —O—, —S—, —CO—, —SO ₂ — and the like, but are not limited thereto.

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

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

Aryl group, alkyl group of R ₂₀₄ to R _207, the cycloalkyl group is the same as the aryl group described aryl group as R ₂₀₁ to R ₂₀₃ of the aforementioned alkyl group, the cycloalkyl group.

Aryl group, alkyl group of R ₂₀₄ to R _207, cycloalkyl groups may have a substituent. Examples of the substituent include those that the aryl group, alkyl group, and cycloalkyl group of R _{201 to} R ₂₀₃ may have.
Z ⁻ represents a non-nucleophilic anion, and examples thereof include the same as the non-nucleophilic anion of Z ^{− in} formula (ZI).
Examples of the acid generator further include compounds represented by the following general formulas (ZIV), (ZV), and (ZVI).

In general formulas (ZIV) to (ZVI),
Ar ₃ and Ar ₄ each independently represents an aryl group.

R ₂₀₈ , R ₂₀₉ and R ₂₁₀ each independently represents an alkyl group, a cycloalkyl group or an aryl group.
A represents an alkylene group, an alkenylene group or an arylene group.

Preferred examples of the acid generator that may be used in combination with the acid generator represented by formula (1-1) or (1-2) are given below.

[3] Hydrophobic resin The actinic ray-sensitive or radiation-sensitive resin composition of the present invention may contain a hydrophobic resin (HR).
The hydrophobic resin (HR) is preferably a resin having at least one of a fluorine atom and a silicon atom, and even if the fluorine atom or the silicon atom is present in the main chain of the resin, it is substituted with a side chain. It may be.

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

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

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

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

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

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

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

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

Specific examples of the group represented by the general formula (F4) include, for example, —C (CF ₃ ) ₂ OH, —C (C ₂ F ₅ ) ₂ OH, —C (CF ₃ ) (CH ₃ ) OH, -CH (CF ₃₎ OH and the like, -C (CF _{3) 2} OH is preferred.
Hereinafter, although the specific example of the repeating unit which has a fluorine atom is shown, this invention is not limited to this.
In specific examples, X ₁ represents a hydrogen atom, —CH ₃ , —F or —CF ₃ . X ₂ represents —F or —CF ₃ .

  The hydrophobic resin (HR) may contain a silicon atom. The partial structure having a silicon atom is preferably a resin having an alkylsilyl structure (preferably a trialkylsilyl group) or a cyclic siloxane structure.

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

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

L < ₃ > -L < ₅ > represents a single bond or a bivalent coupling group. As the divalent linking group, an alkylene group, a phenylene group, an ether group, a thioether group, a carbonyl group, an ester group, an amide group, a urethane group, or a urea group is used alone or in combination of two or more groups. A combination is mentioned.

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

Hereinafter, although the specific example of the repeating unit which has group represented by general formula (CS-1)-(CS-3) is given, this invention is not limited to this. In specific examples, X ₁ represents a hydrogen atom, —CH ₃ , —F or —CF ₃ .

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

(X) an alkali-soluble group,
(Y) 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 repeating units in which an alkali-soluble group is bonded to the chain. Furthermore, a polymerization initiator or a chain transfer agent having an alkali-soluble group can be used at the time of polymerization to be introduced at the end of the polymer chain. Is also preferable.

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

Specific examples of the repeating unit having an alkali-soluble group (x) are shown below, but the present invention is not limited thereto.

  In the hydrophobic resin (HR), examples of the repeating unit having a group (y) capable of decomposing by the action of an acid include the same repeating units having an acid-decomposable group as mentioned for the resin (A). In the hydrophobic resin (HR), the content of the repeating unit having a group (y) that is decomposed by the action of an acid is preferably 1 to 80 mol%, more preferably 10 to 10%, based on all repeating units in the polymer. 80 mol%, more preferably 20 to 60 mol%.

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

In general formula (III):
R _c31 represents a hydrogen atom, an alkyl group, or an alkyl group optionally substituted with fluorine, a cyano group, or a —CH ₂ —O—Rac ₂ group. Wherein, Rac ₂ represents a hydrogen atom, an alkyl group or an acyl group. R _c31 is preferably a hydrogen atom, a methyl group, a hydroxymethyl group or a trifluoromethyl group, particularly preferably a hydrogen atom or a methyl group.

R _c32 represents a group having an alkyl group, a cycloalkyl group, an alkenyl group, or a cycloalkenyl group. These groups may be substituted with a fluorine atom or a silicon atom.
L _c3 represents a single bond or a divalent linking group.

In general formula (III), the alkyl group represented by R _c32 is preferably a linear or branched alkyl group having 3 to 20 carbon atoms.
The cycloalkyl group is preferably a cycloalkyl group having 3 to 20 carbon atoms.
The alkenyl group is preferably an alkenyl group having 3 to 20 carbon atoms.
The cycloalkenyl group is preferably a cycloalkenyl group having 3 to 20 carbon atoms.
R _c32 is preferably an unsubstituted alkyl group or an alkyl group substituted with a fluorine atom.
The divalent linking group of L _c3 is preferably an ester group, an alkylene group (preferably having a carbon number of 1 to 5), an oxy group, a phenylene group, or an ester bond (a group represented by —COO—).
It is also preferable that the hydrophobic resin (HR) further has a repeating unit represented by the following general formula (CII-AB).

In the formula (CII-AB),
R _C11 ′ and R _C12 ′ each independently represent a hydrogen atom, a cyano group, a halogen atom or an alkyl group.
Zc ′ represents an atomic group for forming an alicyclic structure containing two bonded carbon atoms (C—C).
Specific examples of the repeating unit represented by the general formulas (III) and (CII-AB) are shown below, but the present invention is not limited thereto. In the formula, Ra represents H, CH ₃ , CH ₂ OH, CF ₃ or CN.

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

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

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

  The content of the hydrophobic resin (HR) in the composition is preferably 0.01 to 10% by mass, more preferably 0.05 to 8% by mass, based on the total solid content in the composition of the present invention. More preferably, the content is 1 to 5% by mass.

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

  As the hydrophobic resin (HR), various commercially available products can be used, or they can be synthesized according to a conventional method (for example, radical polymerization). For example, as a general synthesis method, a monomer polymerization method in which a monomer species and an initiator are dissolved in a solvent and the polymerization is performed by heating, and a solution of the monomer species and the initiator is dropped into the heating solvent over 1 to 10 hours. The dropping polymerization method is added, and the dropping polymerization method is preferable. 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 positive resist 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 examples of the initiator include azobisisobutyronitrile, azobisdimethylvaleronitrile, dimethyl 2,2′-azobis (2-methylpropionate) and the like. The concentration of the reaction is 5 to 50% by mass, preferably 30 to 50% by mass. The reaction temperature is usually 10 ° C to 150 ° C, preferably 30 ° C to 120 ° C, more preferably 60-100 ° C.

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

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

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

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

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

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

Specific examples of the hydrophobic resin (HR) are shown below. Table 1 below shows the molar ratio of the repeating units in each resin (corresponding to each repeating unit in order from the left), the weight average molecular weight, and the degree of dispersion.

  When the hydrophobic resin (HR) contains a repeating unit (c) having at least one polar conversion group that is decomposed by the action of the alkali developer and increases the solubility in the alkali developer, the reduction in development defects is particularly reduced. This is preferable. Hereinafter, the hydrophobic resin (HR) containing the repeating unit (c) is also referred to as “hydrophobic resin (C)”.

Here, the polar conversion group is a group that decomposes by the action of an alkali developer and increases the solubility in the alkali developer. For example, a lactone group, a carboxylic acid ester group (—COO—), an acid anhydride group (—C (O) OC (O) —), an acid imide group (—NHCONH—), a carboxylic acid thioester group (—COS—) , Carbonate ester group (—OC (O) O—), sulfate ester group (—OSO ₂ O—), 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.

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

In the formula, R _k1 represents a hydrogen atom, a halogen atom, a hydroxyl group, an alkyl group, a cycloalkyl group, an aryl group or a group containing a polarity converting group.
R _k2 represents an alkyl group, a cycloalkyl group, an aryl group, or a group containing a polarity converting group.

However, at least one of R _k1 and R _k2 has a polarity converting group.
In addition, as described above, the ester group directly connected to the main chain of the repeating unit represented by the general formula (K0) is not included in the polar conversion group in the present invention.
The 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 carboxylic acid ester 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 group having a partial structure is a group having a monovalent or higher group obtained by removing at least one arbitrary hydrogen atom in the partial structure. 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 with the 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 them.
Z _ka1 may be linked to form a ring. Examples of the ring formed by linking Z _{ka1 to} each other include a cycloalkyl ring and a hetero ring (such as a cyclic ether ring and a lactone ring).
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.

  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, more preferably an alkyl group, a cycloalkyl group, or an electron withdrawing group. The ether group is preferably an ether group substituted with an alkyl group or a cycloalkyl group, that is, an alkyl ether group. The electron withdrawing group has the same meaning as described above.

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, an androstanyl group, and the following structures. 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 an adamantyl group, a noradamantyl group, a decalin group, a tricyclodecanyl group, a tetracyclododecanyl group, a norbornyl group, a cedrol group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, and a 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).

  Further, further substituents that the above group may have include hydroxyl group, halogen atom (fluorine, chlorine, bromine, iodine), nitro group, cyano group, the above alkyl group, methoxy group, ethoxy group, hydroxy group. Ethoxy group, propoxy group, hydroxypropoxy group, n-butoxy group, isobutoxy group, sec-butoxy group, alkoxy group such as t-butoxy group, alkoxycarbonyl group such as methoxycarbonyl group, ethoxycarbonyl group, benzyl group, phenethyl group Aralkyl groups such as cumyl groups, aralkyloxy groups, formyl groups, acetyl groups, butyryl groups, benzoyl groups, cyanamyl groups, acylyl groups such as valeryl groups, acyloxy groups such as butyryloxy groups, the above alkenyl groups, vinyloxy groups, propenyls Such as oxy group, allyloxy group, butenyloxy group, etc. Rukeniruokishi group, said aryl group, an aryloxy group such as phenoxy group, and an aryloxycarbonyl group such as benzoyloxy group.

  X in the general formula (KA-1) is a carboxylic acid ester group, and the partial structure represented by the general formula (KA-1) is preferably a lactone ring, and more 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-1) has a bicyclo structure, a spiro It is preferred that other ring structures are condensed in a form that forms the 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, the 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 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 number of repeating linking groups 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 represents 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 , a haloaryl group, an oxy group, a carbonyl group, a sulfonyl group Examples thereof include a group, a sulfinyl group, and a combination thereof. 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 represents 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. More preferably, R _f2 represents the same group as R _f1 or is linked to R _f3 to form a ring.

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

Examples of the (halo) alkyl group in R _{f1 to} R _f3 include 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 a ring formed by linking R _f2 and R _f3 include, for example, the above-described cycloalkyl group in Z _ka1 is a halogen atom. phased structure, more preferably _{-C (n) F (2n-} 2) fluoroalkyl group represented by H, and include perfluoro aryl group represented by _{-C (n) F (n-} 1) It is done. Although carbon number n is not specifically limited here, the thing of 5-13 is preferable and 6 is more preferable.

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

  In the repeating unit (c), a plurality of partial structures represented by the general formula (KA-1), a plurality of partial structures represented by the general formula (KB-1), or a general formula (KA- You may have both the partial structure of 1) and general formula (KB-1).

Note that part or all of the partial structure of the general formula (KA-1) may also serve as an electron withdrawing group as Y ¹ or Y ² in the general formula (KB-1). For example, when X in the general formula (KA-1) is a carboxylic acid ester group, the carboxylic acid ester group functions as an electron withdrawing group as Y ¹ or Y ² in the general formula (KB-1). There is also a possibility.

  Even if the repeating unit (c) is a repeating unit (c ′) having at least one of a fluorine atom and a silicon atom and a polarity converting group on one side chain, it has a polarity converting group, and Even a repeating unit (c *) having no fluorine atom and silicon atom has a polarity converting group on one side chain, and on a side chain different from the side chain in the same repeating unit, Although it may be a repeating unit (c ″) having at least one of a fluorine atom and a silicon atom, the resin (C) more preferably has a repeating unit (c ′) as the repeating unit (c).

In addition, when resin (C) has a repeating unit (c *), it is preferable that it is a copolymer with the repeating unit (repeating unit (c1) mentioned later) which has at least any one of a fluorine atom and a silicon atom. In the repeating unit (c ″), the side chain having a polarity converting group and the side chain having at least one of a fluorine atom and a silicon atom are bonded to the same carbon atom in the main chain. It is preferable to have a positional relationship as shown in Formula 4. In the formula, B1 represents a partial structure having a polar conversion group, and B2 represents a partial structure having at least one of a fluorine atom and a silicon atom.

In the repeating unit (c *) and the repeating unit (c ″), the polar conversion group is more preferably a partial structure represented by —COO— in the structure represented by the general formula (KA-1).
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.

  The resin (C) of the present invention is preferably a resin (C1) containing a repeating unit (c) having at least two or more polar conversion groups and having at least one of a fluorine atom and a silicon atom. .

When the repeating unit (c) has at least two polar changing groups, the repeating unit (c) preferably has a group having a partial structure having two polar changing groups 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 group having 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 those similar to Y ₁ and Y ₂ in the formula (KB-1), preferably a halogen atom or —C (R _f1 ) (R _f2 ) —R _f3 . And a halo (cyclo) alkyl group or a haloaryl group. Preferably R _ky3 halogen atom _{or,, -C (R f1) (} R f2) halo (cyclo) alkyl or haloaryl group represented by -R _f3, lactone ring linked R _ky2 and R _ky1 Or an electron withdrawing group having 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).
The structure represented by the general formula (KY-1) is more preferably a structure represented by the following general formula (KY-2). Note that the structure represented by the general formula (KY-2) is a group having a monovalent or higher group obtained by removing at least one arbitrary hydrogen atom in the structure.

In formula (KY-2),
R _{ky6 to} R _ky10 are each independently a hydrogen atom, halogen atom, alkyl group, cycloalkyl group, carbonyl group, carbonyloxy group, oxycarbonyl group, ether group, hydroxyl group, cyano group, amide group, or aryl. Represents a group.

Two or more of R _{ky6 to} R _ky10 may be connected to each other to form a monocyclic or polycyclic structure.

R _ky5 represents an electron withdrawing group. Examples of the electron withdrawing group are the same as those of Y ₁ and Y ₂ in the formula (KB-1), and preferably represented by a halogen atom or —C (R _f1 ) (R _f2 ) —R _f3. A halo (cyclo) 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).
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 is synonymous with the 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.

The repeating unit (c) 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.
The repeating unit (c) may be a repeating unit having the partial structure shown below.

In general formula (cc),
Z ₁ each 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.
Z ₂ each independently represents a chain or cyclic alkylene group, preferably an alkylene group having 1 or 2 carbon atoms or a cycloalkylene group having 5 to 10 carbon atoms.
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 Ta, 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. . when k is 2, it may form a ring by bonding to each other two L _o.

L each independently represents a carbonyl group, a carbonyloxy group or an ether group. Tc represents 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 0 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 integer of 0-5, Preferably it is 0-2.
r represents an integer of 0 to 5.
In addition, -L _0- (Ta) m may be substituted instead of-(L) r-Tc.
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 more specific structure of the repeating unit (c) is preferably a repeating unit having the partial structure shown below.

In general formulas (ca-2) and (cb-2),
Z ₁ , Z ₂ , Tc, Ta, L, q and r have the same meanings as in the general formula (cc).

Tb 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)). It is synonymous with the electron withdrawing group.

  * 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.

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

n represents an integer of 0 to 11, preferably an integer of 0 to 5, and more preferably 1 or 2.
p represents an integer of 0 to 5, preferably an integer of 0 to 3, and more preferably 1 or 2.

In general formula (2),
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 represents a halogen atom, a cyano group, a hydroxy group, an amide group, an alkyl group, a cycloalkyl group, an alkoxy group, a phenyl group, an acyl group, an alkoxycarbonyl group, or R—C (═O) — or R—C ( = O) A group represented by O- (R represents an alkyl group or a cycloalkyl group). When there are a plurality of R _{4 s} , they may be the same or different, and two or more R ₄ may be bonded to 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 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 structure represented by —R ₂ —Z— is preferably a structure represented by — (CH ₂ ) ₁ —COO— (l represents an integer of 1 to 5).
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. By containing the resin (C) / resin (CP), the resin (C) / resin (CP) is unevenly distributed in the surface layer of the film, and when the immersion medium is water, the resist film surface with respect to water when used as a film 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 resin (CP) content 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 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 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.
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).
Specific examples of the resin (CP) include (HR-1) to (HR-65) described above.

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

  The immersion liquid is 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 surface tension of the water is decreased and the surface activity is increased, so that the resist film 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 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 is desirably 18.3 MQcm or more, the TOC (organic substance concentration) is desirably 20 ppb or less, and deaeration treatment is desirably performed.

Moreover, it is possible to improve lithography performance by increasing the refractive index of the immersion liquid. From such a viewpoint, an additive for increasing 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 necessary functions for the top coat are suitability for application to the upper layer of the resist, radiation, especially transparency to 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 resist upper layer.

  From the viewpoint of 193 nm transparency, the top coat is preferably a polymer that does not contain abundant aromatics. Specifically, the polymer contains a hydrocarbon polymer, an acrylate polymer, polymethacrylic acid, polyacrylic acid, polyvinyl ether, and silicon. Examples thereof include a polymer and a fluorine-containing polymer. The aforementioned hydrophobic resin (HR) is also suitable as a top coat. From the viewpoint of contaminating the optical lens when impurities are eluted from the top coat into the immersion liquid, it is preferable that the residual monomer component of the polymer contained in the top coat is small.

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

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

  The top coat 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. Furthermore, when the immersion liquid is an organic solvent, the topcoat may be water-soluble or water-insoluble.

[4] Solvent Examples of the solvent that can be used in preparing the positive resist composition by dissolving the above components include, for example, alkylene glycol monoalkyl ether carboxylate, alkylene glycol monoalkyl ether, alkyl lactate ester, Organic solvents such as alkyl alkoxypropionates, cyclic lactones (preferably having 4 to 10 carbon atoms), monoketone compounds that may contain rings (preferably having 4 to 10 carbon atoms), alkylene carbonates, alkyl alkoxyacetates, alkyl pyruvates, etc. Can be mentioned.

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, -Penten-2-one, cyclopentanone, 2-methylcyclopentanone, 3-methylcyclopentanone, 2,2-dimethylcyclopentanone, 2,4,4-trimethylcyclopentanone, cyclohexanone, 3-methyl Cyclohexanone, 4-methylcyclohexanone, 4-ethylcyclohexanone, 2,2-dimethylcyclohexanone, 2,6-dimethylcyclohexanone, 2,2,6-trimethylcyclohexanone, cycloheptanone, 2-methylcycloheptanone, 3-methylcyclo A preferred example is heptanone.

  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.

[5] 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, the ammonium salt compound having a phenoxy group, the amine compound having a sulfonic acid ester group, and the ammonium salt compound having a sulfonic acid ester group are exemplified in [0066] of US2007 / 0224539A. Examples thereof include, but are not limited to, compounds (C1-1) to (C3-3).

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

  The usage-amount of a basic compound is 0.001-10 mass% normally on the basis of the total solid of a composition, Preferably it is 0.01-5 mass%.

  The use 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.

[6] Surfactant The composition of the present invention 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 positive resist composition of the present invention contains the surfactant, it is possible to provide a resist pattern with good sensitivity and resolution and with less adhesion and development defects.

  Examples of commercially available surfactants that can be used include EFTOP EF301 and EF303 (manufactured by Shin-Akita Kasei Co., Ltd.), Florard FC430, 431 and 4430 (manufactured by Sumitomo 3M Co., Ltd.), MegaFuck F171, F173, F176 and 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 (manufactured by Toa Gosei Chemical Co., Ltd.), Surflon S-393 (manufactured by Seimi Chemical Co., Ltd.), F-top EF121, EF122A, EF122B, RF122C, EF125M , EF135M, EF351, EF352, EF801, EF802, F601 (manufactured by Gemco), PF636, PF656, PF6320, PF6520 (manufactured by OMNOVA), FTX-204G, 208G, 218G, 230G, 204D, 208D, 212D, 218D, 222D (manufactured by Neos) Fluorine type surfactant or silicon type surfactant can be mentioned. 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, the surfactant is derived from a fluoroaliphatic compound produced by a telomerization method (also called telomer method) or an oligomerization method (also called oligomer method). A surfactant using a polymer having a fluoroaliphatic group can be used. The fluoroaliphatic compound can be synthesized by a method described in the vicinity of [0015] to [0018] of JP-A-2002-90991. The polymer having a fluoroaliphatic group may be a copolymer of a monomer having a fluoroaliphatic group and (poly (oxyalkylene)) acrylate and / or (poly (oxyalkylene)) methacrylate.

As commercially available surfactants corresponding to the above, Megafac F178, F-470, F-473, F-475, F-476, F-472 (manufactured by Dainippon Ink & Chemicals, Inc.) can be exemplified. . Further, a copolymer of an acrylate (or methacrylate) having a C ₆ F ₁₃ group and (poly (oxyalkylene)) acrylate (or methacrylate), an acrylate (or methacrylate) having a C ₃ F ₇ group and (poly (oxy) And a copolymer of (ethylene)) acrylate (or methacrylate) and (poly (oxypropylene)) acrylate (or methacrylate).

  In the present invention, other surfactants other than fluorine-based and / or silicon-based surfactants can also be used. Specifically, polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether and polyoxyethylene stearyl ether, polyoxyethylene alkyl aryl ethers such as polyoxyethylene octylphenol ether and polyoxyethylene nonylphenol ether, polyoxyethylene Polyoxypropylene block copolymers, sorbitan monolaurate, sorbitan monopalmitate, sorbitan fatty acid esters such as sorbitan monostearate, sorbitan tristearate, polyoxyethylene sorbitan monolaurate, polyoxyethylene sorbitan monopalmitate , Polyoxyethylene sorbitan monostearate, polyoxyethylene sorbitan trioleate, polyoxyethylene It can be mentioned nonionic surfactants such as polyoxyethylene sorbitan fatty acid esters such as sorbitan tristearate.

  These surfactants may be used alone or in several combinations.

  The amount of the surfactant used is preferably 0 to 2% by mass, more preferably 0.0001 to 2% by mass, based on the total solid content (total amount excluding the solvent) of the actinic ray-sensitive or radiation-sensitive resin composition. %, Particularly preferably 0.0005 to 1% by mass.

[7] 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.

Fluorine-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% by mass, based on the total solid content of the composition. %.

[8] Dissolution-inhibiting compound having a molecular weight of 3000 or less that decomposes by the action of an acid to increase the solubility in an alkaline developer Acid that decomposes by the action of an acid to increase the solubility in an alkaline developer to have a molecular weight of 3000 or less As a dissolution inhibiting compound (hereinafter also referred to as “dissolution inhibiting compound”), a cholic acid containing an acid-decomposable group described in Proceeding of SPIE, 2724,355 (1996) is used in order not to lower the permeability of 220 nm or less. Alicyclic or aliphatic compounds containing acid-decomposable groups such as derivatives are preferred. 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 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.

[9] Other additives In the composition of the present invention, a dye, a plasticizer, a photosensitizer, a light absorber, and a compound that promotes solubility in a developer (for example, a molecular weight of 1000 or less) are added to the composition of the present invention as necessary. A phenol compound, an alicyclic compound having a carboxyl group, or an aliphatic compound).

  Such phenolic compounds having a molecular weight of 1000 or less can be obtained by referring to, for example, the methods described in JP-A-4-1222938, JP-A-2-28531, US Pat. No. 4,916,210, European Patent 219294, etc. It can be easily synthesized by those skilled in the art.

  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 Forming Method The composition of the present invention is preferably used at a film thickness of 30 to 250 nm, more preferably at 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, it is possible to obtain such a film thickness by improving the coating property and film forming property. it can.

  The total solid concentration in the actinic ray-sensitive or radiation-sensitive resin composition 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 on a substrate (eg, silicon / silicon dioxide coating) used for the manufacture of precision integrated circuit elements by a suitable application method such as a spinner or coater, and dried. Then, a film is formed.
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.

  EXAMPLES Hereinafter, although an Example demonstrates this invention further more concretely, this invention is not limited to a following example.

Synthesis Example 1 (Synthesis of Resin (1))
Under a nitrogen stream, 8.8 g of cyclohexanone was placed in a three-necked flask and heated to 80 ° C. To this, 8.5 g of norbornane lactone methacrylate, 2.2 g of hydroxyadamantyl methacrylate, 9.0 g of 2-cyclohexylisopropyl methacrylate, and a polymerization initiator V-60 (manufactured by Wako Pure Chemical Industries, Ltd.) at 13 mol% with respect to the monomers. Was dissolved in 79 g of cyclohexanone dropwise over 6 hours. After completion of dropping, the reaction was further carried out at 80 ° C. for 2 hours. The reaction solution is allowed to cool and then added dropwise to a mixed solution of 900 m of methanol / 100 ml of water over 20 minutes. The precipitated powder is collected by filtration and dried, and then a white powder solid polymer compound having a structure shown below (resin ( 18 g of 1)) was obtained. The weight average molecular weight (Mw) of the obtained resin (1) was 10000 in GPC in terms of polystyrene, and the dispersity (Mw / Mn) was 1.8.
Similarly, a resin (14) was synthesized from the other resin (2) shown below.

The structure of the acid-decomposable resin (A) used in the examples and comparative examples is shown below. The following table shows the molar ratio of repeating units in each resin (in order from the left in the structural formula), weight average molecular weight (Mw), and dispersity (Mw / Mn).

Synthesis Example 2 (Synthesis of acid generator PAG-1)
The following PAG-1 was synthesized according to the following synthesis route.

[Synthesis of Compound 1]
After 20 g of bromomethylcyclohexane and 12.5 g of 1-naphthol were dissolved in 300 g of NMP in a three-necked flask, 12 g of potassium carbonate and 14 g of potassium iodide were added and heated at 120 ° C. for 8 hours. 300 g of water was added to the reaction solution, extraction was performed 3 times with 100 g of hexane, the obtained organic layers were combined, washed once with 100 g of 1N aqueous sodium hydroxide, once with 100 g of water, and once with 100 g of Brine, and then concentrated. 13 g of Compound 1 was obtained.
[Synthesis of Compound 2]
Compound 2 was synthesized with reference to the method described in JP-A-2005-266799.

[Synthesis of PAG-1]
13.1 g of Compound 1 was dissolved in 65 g of Eaton reagent in a three-necked flask, and then 5.7 g of tetramethylene sulfoxide was added dropwise with stirring, followed by further stirring for 3 hours. The reaction solution was poured into 240 g of water, and then 25 g of compound 2 and 50 g of chloroform were added. After the organic layer was separated, the aqueous layer was further extracted twice with 50 g of chloroform. The obtained organic layers were combined, washed twice with water and concentrated. The obtained composition organism was recrystallized using 20 g of ethyl acetate to obtain 22 g of PAG1.
PAG-2 and 4-7 were also prepared in the same manner as PAG-1. PAG-3 and PAG-8 were prepared by a known method.

The structure of the acid generator used in the examples and comparative examples is shown below.

<Synthesis of hydrophobic resin>
Synthesis Example 3 Synthesis of Hydrophobic Resin C-7 Monomers corresponding to the following repeating units were charged at a ratio (molar ratio) of 90/10, respectively, and dissolved in PGMEA to prepare 450 g of a solution having a solid content concentration of 15% by mass. 1 mol% of Wako Pure Chemicals polymerization initiator V-60 was added to this solution, and this was dripped at 50 g of PGMEA heated at 100 degreeC over 6 hours in nitrogen atmosphere. 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 product, Resin C-7.

  The polymer composition ratio determined from NMR was 90/10. Moreover, the weight average molecular weight of standard polystyrene conversion calculated | required by GPC measurement was 8000, and dispersion degree 1.40.

In the same manner as in the above Synthesis Example 3, the resin C-8, C-94, HR-9, HR-26, HR-47 and HR-50 are shown in Tables 1 and 2 above, and the composition ratios and weights. Each resin having an average molecular weight (Mw) and a dispersity (Mw / Mn) was synthesized.

<Resist preparation>
The components shown in the following table were dissolved in a solvent, and a solution with a solid content concentration 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 table.

In Table 4, the positive resist composition does not contain a hydrophobic resin (HR), and after forming a film, a top coat protective film containing a hydrophobic resin (HR) is formed thereon. , The addition form was labeled as “TC form”.

<Image performance test>
[Exposure conditions: ArF immersion exposure]
An organic antireflection film ARC29A (manufactured by Nissan Chemical Industries, Ltd.) was applied onto a silicon wafer and baked at 205 ° C. for 60 seconds to form an antireflection film having a thickness of 98 nm. A positive resist composition prepared thereon was applied and baked at 120 ° C. for 60 seconds to form a resist film having a thickness of 100 nm. The obtained wafer was exposed using an ArF excimer laser immersion scanner (XT1700i, NA 1.20 manufactured by ASML) through a 6% halftone mask having a contact hole pattern of 130 nm pitch. Ultra pure water was used as the immersion liquid. Thereafter, the mixture was heated at 100 ° C. for 60 seconds, developed with an aqueous tetramethylammonium hydroxide solution (2.38 mass%) for 30 seconds, rinsed with pure water, and spin-dried to obtain a resist pattern.

  In Table 3, the positive resist composition does not contain the hydrophobic resin (C), and after forming the resist film, a top coat protective film containing the hydrophobic resin (HR) is formed on the upper layer. In this case, the addition form of the hydrophobic resin (C) was set to “blank”, and the usage form of the top coat was described in Table 3 separately. At that time, after forming the photosensitive film, the following operation was performed.

<Formation method of top coat>
A hydrophobic resin (HR) was dissolved in a solvent on the photosensitive film and applied by a spin coater, and the wafer was heated and dried at 115 ° C. for 60 seconds to form a 0.05 μm top coat layer. At this time, the top coat application unevenness was observed, and it was confirmed that it was uniformly applied without application unevenness.

[Roundness evaluation]
The roundness of the contact hole pattern with a diameter of 65 nm was observed with a scanning electron microscope (Hitachi S-9380II), and the average diameter of the contact hole pattern was taken as a reference line, and the distance from it was measured with a length measurement SEM 144. The points were measured, the standard deviation was obtained, and 3σ was calculated, the smaller the value, the better the performance.

[Focus margin evaluation]
When the focus at the time of exposure is shifted up and down by 0.1 μm with respect to the optimum exposure amount for forming the contact hole pattern with a diameter of 65 nm obtained above, the line width falls within the range of ± 10% from the target line width of 65 nm. The maximum value of the defocus in a range that does not enter and does not involve pattern shape deterioration was defined as the focus margin. The larger the value, the greater the tolerance for defocus.

[Basic compounds]
N-1: N, N-dibutylaniline N-2: N, N-dihexylaniline N-3: 2,6-diisopropylaniline N-4: tri-n-octylamine N-5: N, N-dihydroxyethyl Aniline N-6: 2,4,5-triphenylimidazole N-7: Tris (methoxyethoxyethyl) amine [Surfactant]
W-1: Megafac F176 (Dainippon Ink Chemical Co., Ltd., fluorine-based)
W-2: Megafuck R08 (Dainippon Ink Chemical Co., Ltd., fluorine and silicon)
W-3: Polysiloxane polymer KP-341 (manufactured by Shin-Etsu Chemical Co., Ltd., silicon-based)
W-4: Troisol S-366 (manufactured by Troy Chemical Co., Ltd.)
W-5: PF656 (manufactured by OMNOVA, fluorine-based)
W-6: PF6320 (manufactured by OMNOVA, fluorine-based)
〔solvent〕
SL-1: Cyclohexanone SL-2: Propylene glycol monomethyl ether acetate (PGMEA)
SL-3: Ethyl lactate SL-4: Propylene glycol monomethyl ether (PGME)
SL-5: γ-butyrolactone SL-6: propylene carbonate SL-7: 2-ethylbutanol SL-8: perfluorobutyltetrahydrofuran [Hydrophobic resin (HR)]

  From Table 3, it was found that the resist pattern formed using the positive resist composition of the present invention has excellent performance in roundness and focus margin.

Claims (14)

(A) A resin whose solubility in an alkali developer increases by the action of an acid, and at least (B) a compound represented by the following general formula (1-1) as a compound that generates an acid upon irradiation with actinic rays or radiation a sensitive or radiation-sensitive resin composition comprising the repeating units of the resin (a) has an acid-decomposable group, based on all repeating units in the resin (a) of 45～75Mol% The content of the compound (B) is 10 to 30 based on the total solid content of the composition. An actinic ray-sensitive or radiation-sensitive resin composition characterized by being in mass%.
In general formula (1-1),
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.
When there are a plurality of R _{14 s,} each independently represents an alkyl group, a cycloalkyl group, an alkoxy group, an alkylsulfonyl group, a cycloalkylsulfonyl group, an alkylcarbonyl group, an alkoxycarbonyl group, or a monocyclic or polycyclic cycloalkyl skeleton. Represents a group having
R ₁₅ each independently represents an alkyl group, a cycloalkyl group, a phenyl group, or a naphthyl group. However, the case where two R < ₁₅ > are phenyl groups simultaneously is remove | excluded. Further, two R ₁₅ may be bonded to each other to form a ring.
l represents an integer of 0-2.
r represents an integer of 0 to 8.
X ⁻ represents a non-nucleophilic anion represented by the general formula (A2).
Where
Xf each independently represents a fluorine atom or an alkyl group substituted with at least one fluorine atom.
R ₁ and R ₂ each independently represents a hydrogen atom, a fluorine atom, an alkyl group, or a group selected from an alkyl group substituted with at least one fluorine atom, and R ₁ and R ₂ in the case where a plurality of R ₁ and R _{2 are present.} May be the same or different.
L represents a single bond or a divalent linking group, and when there are a plurality of L, they may be the same or different.
A represents a group having a cyclic structure.
x represents an integer of 1 to 20, y represents an integer of 0 to 10, and z represents an integer of 0 to 10.
Where
R 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.
R ₂ represents a linear or branched alkyl group having 2 or more carbon atoms.
R represents an atomic group necessary for forming an alicyclic structure together with a carbon atom. The alicyclic structure formed by R may be a monocyclic structure or a polycyclic structure.   The actinic ray-sensitive or radiation-sensitive resin composition according to claim 1, further comprising a hydrophobic resin having at least one of a fluorine atom and a silicon atom.   The actinic ray-sensitive or radiation-sensitive resin composition according to claim 1 or 2, wherein the resin (A) further contains a repeating unit containing a lactone structure. The actinic ray-sensitive or radiation-sensitive property according to claim 3, wherein the resin (A) contains at least a repeating unit represented by the following general formula (III) as a repeating unit containing a lactone structure. Resin composition.
Where
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 content of the repeating unit having an acid-decomposable group contained in the resin (A) is 50 to 60 mol% with respect to all the repeating units in the resin (A). The actinic ray-sensitive or radiation-sensitive resin composition according to any one of the above. The resin (A) further contains a repeating unit represented by the following general formula (II) as a repeating unit having an acid-decomposable group, according to any one of claims 1 to 5. An actinic ray-sensitive or radiation-sensitive resin composition.
In general formula (II),
R ₃ 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.
R ₄ , R ₅ and R ₆ each independently represents an alkyl group or a cycloalkyl group. The resin (A) contains at least two repeating units represented by the general formula (I) as the repeating unit having an acid-decomposable group, according to any one of claims 1 to 6. The actinic ray-sensitive or radiation-sensitive resin composition described. The content of the repeating unit represented by the general formula (I) is 45 to 75 mol% with respect to all repeating units in the resin (A), according to any one of claims 1 to 7 , The actinic ray-sensitive or radiation-sensitive resin composition described. 9. The actinic ray-sensitive or radiation-sensitive property according to any one of claims 1 to 8, wherein the alicyclic structure formed by R in the general formula (I) together with a carbon atom is a monocycle. Resin composition. The compound (B) represented by the general formula (1-1) is contained in a proportion of 50 to 100% by mass with respect to the total amount of the compound that generates an acid upon irradiation with actinic rays or radiation. Item 10. The actinic ray-sensitive or radiation-sensitive resin composition according to any one of Items 1 to 9 . The content of compound (B), based on the total solids of the composition, the actinic ray-sensitive or according to claims 1, wherein in any one of 10 to be 18 to 30 wt% Radiation sensitive resin composition. Wherein the liquid immersion exposure is applied, the actinic ray-sensitive or radiation-sensitive resin composition according to any one of claims 1 to 11. It includes a step of forming a film using the actinic ray-sensitive or radiation-sensitive resin composition according to any one of claims 1 to 11 , a step of exposing the film, and a step of developing. Pattern forming method. The pattern forming method according to claim 13 , wherein the exposure is immersion exposure.