JP5433268B2 - 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 whose properties change upon reaction with irradiation of actinic rays or radiation, and a pattern forming method using the same. More specifically, a positive photosensitive composition used in a semiconductor manufacturing process such as an IC, a circuit board such as a liquid crystal or a thermal head, a further photofabrication process, a lithographic printing plate, an acid curable composition, and the like The present invention relates to a pattern forming method using
In the present invention, “active light” or “radiation” means, for example, an emission line spectrum of a mercury lamp, far ultraviolet rays represented by excimer laser, extreme ultraviolet rays, X-rays, electron beams, and the like. In the present invention, light means actinic rays or radiation.

The chemically amplified resist generates an acid in the exposed part by irradiation with radiation such as deep ultraviolet light, and the reaction using this acid as a catalyst changes the solubility of the active radiation irradiated part and the non-irradiated part in the developer, A pattern is formed on the substrate.
When a KrF excimer laser is used as an exposure light source, it is mainly composed of a resin having a basic skeleton of poly (hydroxystyrene) that has a small absorption in the 248 nm region, so that a high-sensitivity, high-resolution and good pattern can be obtained. It is a better system than the conventional naphthoquinone diazide / novolak resin system.
On the other hand, when a further short wavelength light source, for example, ArF excimer laser (193 nm) is used as the exposure light source, the chemical amplification system is not sufficient because the aromatic compound essentially shows a large absorption in the 193 nm region. .
For this reason, various ArF excimer laser resists containing an alicyclic hydrocarbon structure have been developed. However, from the viewpoint of overall performance as a resist, it is actually difficult to find an appropriate combination of resin, photoacid generator, additive, solvent and the like to be used, and the line width is 65 nm or less. When such a fine pattern is formed, improvement in image performance such as line edge roughness performance of the line pattern and depth of focus characteristics (DOF) and improvement in storage stability of the resist solution itself have been demanded.

For example, Patent Document 1 discloses a resist composition suitable for ArF excimer laser lithography, which has particularly good line edge roughness in addition to performance such as resolution, sensitivity, and pattern shape, and can make a pattern finer in a reflow process. And a resist composition using a resin containing a specific repeating unit having an adamantane structure or a butyrolactone structure, a specific repeating unit having a norbornane lactone structure, and a specific repeating unit having an alicyclic structure.
Patent Document 2 states that a lactone structure having a monomer component of 0.5% by mass or less for a specific resin having a lactone structure is described as being suitable as a chemically amplified resist that does not generate or increase foreign matter during resist storage. The radiation sensitive resin composition containing the specific resin which has is disclosed.
In Cited Document 3, for a specific resin having a specific alicyclic structure, sensitivity, edge roughness, and profile can be improved by using a resin that is 5% or less of the total pattern area of gel permeation chromatography. It is disclosed.

  However, in the latest generation with a line width of 50 nm or less to which the immersion process is applied, further level-up is required, and in addition to line edge roughness, improvement in performance is also required for DOF and storage stability. It has been.

JP 2005-352466 A Japanese Patent No. 3969135 JP 2001-109153 A

  The problem to be solved by the present invention is an actinic ray-sensitive or radiation-sensitive resin composition having improved line edge roughness, DOF, storage stability, and the like, which are suitable for an immersion process with a line width of 50 nm or less, and the use thereof It is to provide a pattern forming method.

一般式（１）に於いて、
Ｌはラクトン構造を表す。
Ｒ _０ は、メチレン基を表す。
Ｚは、エステル結合を表す。
ｎは、繰り返し数を表し、１を表す。

一般式（１’）に於いて、Ｒｘは、水素原子、ＣＨ _３ 、ＣＦ _３ 、又はＣＨ _２ ＯＨを表す。Ｒｘａは、それぞれ炭素数１〜４のアルキル基を表す。Ｚは、極性基を含む置換基を表し、複数存在する場合は各々独立である。ｐは０または正の整数を表す。
〔２〕
（Ａ）下記一般式（１）で表される構造を含む繰り返し単位を有し、酸の作用によりアルカリ現像液に対する溶解度が増大する樹脂、（Ｂ）活性光線又は放射線の照射により酸を発生する化合物を含有し、樹脂（Ａ）中に含まれるモノマー成分が前記樹脂（Ａ）に対して１．０質量％以下であることを特徴とする感活性光線性または感放射線性樹脂組成物であって、前記化合物（Ｂ）が下記一般式（１−Ｅ）で表される化合物であることを特徴とする感活性光線性または感放射線性樹脂組成物。

一般式（１）に於いて、
Ｌはラクトン構造を表す。
Ｒ _０ は、アルキレン基、環状アルキレン基、または、これらの組み合わせを表し、複数ある場合は、同じでも異なっていてもよい。
Ｚは、エーテル結合、エステル結合、アミド結合、ウレタン結合またはウレア結合を表し、複数ある場合は、同じでも異なっていてもよい。
ｎは、繰り返し数を表し、１〜５の整数を表す。

一般式（１−Ｅ）に於いて、Ｒ _９ は水素原子、アルキル基、シクロアルキル基、アルケニル基、アシル基又は−ＳＯ _２ Ｒsを表す。Ｒsはアルキル基、シクロアルキル基又はアリール基を表す。Ｍ ^＋ は、有機対カチオンを表す。
〔３〕
前記樹脂（Ａ）が、更に下記一般式（２−２）で表される部分構造を有する繰り返し単位を有することを特徴とする〔１〕又は〔２〕に記載の感活性光線性または感放射線性樹脂組成物。

Ｒ _３ は、各々独立に、アルキル基または多環のアルキル基を表す。但し、少なくとも一つのＲ _３ が多環のアルキル基であるか、すべてアルキル基の場合、その２つが互いに結合し多環のアルキル基を形成する。
〔４〕
前記一般式（２−２）に於いて、少なくとも一つのＲ _３ が多環のアルキル基であることを特徴とする〔３〕に記載の感活性光線性または感放射線性樹脂組成物。
〔５〕
該一般式（１）の繰り返し単位が下記一般式（１−１）で表される繰り返し単位であることを特徴とする〔１〕〜〔４〕のいずれかに記載の感活性光線性または感放射線性樹脂組成物。

一般式（１−１）に於いて、
Ｒは、水素原子またはアルキル基を表す。
Ａは、−ＣＯＯ−または−ＣＯＮＨ−のいずれかの基を表す。
Ｌ、Ｒ _０ 、Ｚ、ｎは、請求項１におけるものと同義である。
〔６〕
該一般式（１−１）で表される繰り返し単位が下記一般式（１−２）で表される繰り返し単位であることを特徴とする〔５〕に記載の感活性光線性または感放射線性樹脂組成物。

一般式（１−２）に於いて、Ｒ、Ａ、Ｒ _０ 、Ｚ、ｎは、上記一般式（１−１）におけるものと同義である。
Ｒ _１ は、アルキル基、シクロアルキル基、ＲｚＣＯＯ−で表される基もしくはＲｚＯＣＯ−で表される基（Ｒｚはアルキル基もしくはシクロアルキル基を表す。）、またはシアノ基を表し、複数ある場合は、同じでも異なっていてもよく、２つのＲ _１ が結合し、環を形成していても良い。
Ｘは、アルキレン基、酸素原子または硫黄原子を表す。
ｍは、置換基数であって、０〜５の整数を表す。
〔７〕
前記一般式（１）又は（１−１）又は（１−２）で表される繰り返し単位の含有量が、樹脂（Ａ）中の全繰り返し単位に対し１０〜５５モル％であり、且つ該樹脂（Ａ）中に含まれるモノマー成分の内、以下一般式（２）で表されるモノマーが０．７質量％以下であることを特徴とする〔１〕〜〔６〕のいずれかに記載の感活性光線性または感放射線性樹脂組成物。

一般式（２）において、
Ｌはラクトン構造を表す。
Ｒ _０ は、アルキレン基、環状アルキレン基、または、これらの組み合わせを表し、複数ある場合は、同じでも異なっていてもよい。
Ｚは、エーテル結合、エステル結合、アミド結合、ウレタン結合またはウレア結合を表し、複数ある場合は、同じでも異なっていてもよい。
ｎは、繰り返し数を表し、１〜５の整数を表す。
Ｒは、水素原子またはアルキル基を表す。
Ａは、−ＣＯＯ−または−ＣＯＮＨ−のいずれかの基を表す。
〔８〕
更に（Ｃ）疎水性樹脂を含有することを特徴とする〔１〕〜〔７〕のいずれかに記載の感活性光線性または感放射線性樹脂組成物。
〔９〕
前記疎水性樹脂（Ｃ）が、下記（ｘ）〜（ｚ）の群から選ばれる基を少なくとも１つ有することを特徴とする〔８〕に記載の感活性光線性または感放射線性樹脂組成物。
（ｘ）アルカリ可溶性基、
（ｙ）アルカリ現像液の作用により分解し、アルカリ現像液中での溶解度が増大する基、
（ｚ）酸の作用により分解する基。
〔１０〕
〔１〕〜〔９〕のいずれかに記載の感活性光線性または感放射線性樹脂組成物により形成されるレジスト膜。
〔１１〕
〔１０〕に記載のレジスト膜を露光、現像する工程を含むことを特徴とするパターン形成方法。
本発明は、上記〔１〕〜〔１１〕に関するものであるが、以下、その他の事項についても記載した。 The present invention is as follows.
[1]
(A) a resin having a repeating unit containing a structure represented by the following general formula (1) and a repeating unit represented by the following general formula (1 ′), which increases the solubility in an alkali developer by the action of an acid; (B) It contains a compound that generates an acid upon irradiation with actinic rays or radiation, and the monomer component contained in the resin (A) is 1.0% by mass or less based on the resin (A). An actinic ray-sensitive or radiation-sensitive resin composition.

In general formula (1),
L represents a lactone structure.
R ₀ represents a methylene group.
Z represents an ester bond.
n represents the number of repetitions and represents 1.

In the general formula (1 ′), Rx represents a hydrogen atom, CH ₃ , CF ₃ , or CH ₂ OH. Rxa 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.
[2]
(A) A resin having a repeating unit containing the structure represented by the following general formula (1), which increases the solubility in an alkali developer by the action of an acid, and (B) generates an acid upon irradiation with actinic rays or radiation. An actinic ray-sensitive or radiation-sensitive resin composition comprising a compound, wherein the monomer component contained in the resin (A) is 1.0% by mass or less based on the resin (A). The actinic ray-sensitive or radiation-sensitive resin composition is characterized in that the compound (B) is a compound represented by the following general formula (1-E).

In general formula (1),
L represents a lactone structure.
R ₀ represents an alkylene group, a cyclic alkylene group, or a combination thereof, and when there are a plurality of R _{0 s} , they may be the same or different.
Z represents an ether bond, an ester bond, an amide bond, a urethane bond or a urea bond, and when there are a plurality thereof, they may be the same or different.
n represents the number of repetitions and represents an integer of 1 to 5.

In the general formula (1-E), R ₉ represents a hydrogen atom, an alkyl group, a cycloalkyl group, an alkenyl group, an acyl group, or —SO ₂ Rs. Rs represents an alkyl group, a cycloalkyl group or an aryl group. M ⁺ represents an organic counter cation.
[3]
The resin (A) further has a repeating unit having a partial structure represented by the following general formula (2-2): [1] or [2] Resin composition.

R ₃ each independently represents an alkyl group or a polycyclic alkyl group. However, when at least one R ₃ is a polycyclic alkyl group or all alkyl groups, the two are bonded to each other to form a polycyclic alkyl group.
[4]
The actinic ray-sensitive or radiation-sensitive resin composition according to [3], wherein in the general formula (2-2), at least one R ₃ is a polycyclic alkyl group.
[5]
The actinic ray-sensitive or sensation according to any one of [1] to [4], wherein the repeating unit of the general formula (1) is a repeating unit represented by the following general formula (1-1): Radiation resin composition.

In general formula (1-1),
R represents a hydrogen atom or an alkyl group.
A represents a group of either —COO— or —CONH—.
L, R ₀ , Z, and n are as defined in claim 1.
[6]
The actinic ray-sensitive or radiation-sensitive property according to [5], wherein the repeating unit represented by the general formula (1-1) is a repeating unit represented by the following general formula (1-2): Resin composition.

In the general formula (1-2), R, A, R ₀ , Z, and n have the same meanings as those in the general formula (1-1).
R ₁ represents an alkyl group, a cycloalkyl group, a group represented by RzCOO— or a group represented by RzOCO— (Rz represents an alkyl group or a cycloalkyl group), or a cyano group. These may be the same or different, and two R _{1 's} may be bonded to form a ring.
X represents an alkylene group, an oxygen atom or a sulfur atom.
m is the number of substituents and represents an integer of 0 to 5.
[7]
The content of the repeating unit represented by the general formula (1) or (1-1) or (1-2) is 10 to 55 mol% with respect to all the repeating units in the resin (A), and Among the monomer components contained in the resin (A), the monomer represented by the following general formula (2) is 0.7% by mass or less, and any one of [1] to [6] An actinic ray-sensitive or radiation-sensitive resin composition.

In general formula (2),
L represents a lactone structure.
R ₀ represents an alkylene group, a cyclic alkylene group, or a combination thereof, and when there are a plurality of R _{0 s} , they may be the same or different.
Z represents an ether bond, an ester bond, an amide bond, a urethane bond or a urea bond, and when there are a plurality thereof, they may be the same or different.
n represents the number of repetitions and represents an integer of 1 to 5.
R represents a hydrogen atom or an alkyl group.
A represents a group of either —COO— or —CONH—.
[8]
The actinic ray-sensitive or radiation-sensitive resin composition according to any one of [1] to [7], further comprising (C) a hydrophobic resin.
[9]
The actinic ray-sensitive or radiation-sensitive resin composition according to [8], wherein the hydrophobic resin (C) has at least one group selected from the following groups (x) to (z): .
(X) an alkali-soluble group,
(Y) a group that decomposes by the action of an alkali developer and increases the solubility in the alkali developer;
(Z) A group that decomposes by the action of an acid.
[10]
A resist film formed from the actinic ray-sensitive or radiation-sensitive resin composition according to any one of [1] to [9].
[11]
The pattern formation method characterized by including the process of exposing and developing the resist film as described in [10].
The present invention relates to the above [1] to [11], but other matters are also described below.

  (1) (A) a resin having a repeating unit containing a structure represented by the following general formula (1), which increases the solubility in an alkali developer by the action of an acid, and (B) an acid upon irradiation with actinic rays or radiation. Actinic ray-sensitive or radiation-sensitive resin composition, wherein the monomer component contained in the resin (A) is 1.0% by mass or less based on the resin (A) object.

In general formula (1),
L represents a lactone structure.
R ₀ represents an alkylene group, a cyclic alkylene group, or a combination thereof, and when there are a plurality of R _{0 s} , they may be the same or different.
Z represents an ether bond, an ester bond, an amide bond, a urethane bond or a urea bond, and when there are a plurality thereof, they may be the same or different.
n represents the number of repetitions and represents an integer of 1 to 5.

  (2) The actinic ray-sensitive or radiation-sensitive resin as described in (1) above, wherein the repeating unit of the general formula (1) is a repeating unit represented by the following general formula (1-1) Composition.

In general formula (1),
R represents a hydrogen atom or an alkyl group.
A represents a group of either —COO— or —CONH—.
L, R ₀ , Z, and n are as defined in (1) above.

  (3) The actinic ray-sensitive property as described in (2) above, wherein the repeating unit represented by the general formula (1-1) is a repeating unit represented by the following general formula (1-2): Or a radiation sensitive resin composition.

In the general formula (1-2), R, A, R ₀ , Z, and n are the same as those in the above (2).

R ₁ represents an alkyl group, a cycloalkyl group, a group represented by RzCOO— or a group represented by RzOCO— (Rz represents an alkyl group or a cycloalkyl group), or a cyano group. These may be the same or different, and two R _{1 's} may be bonded to form a ring.
X represents an alkylene group, an oxygen atom or a sulfur atom.
m is the number of substituents and represents an integer of 0 to 5.

  (4) The content of the repeating unit represented by the general formula (1) or (1-1) or (1-2) is 10 to 55 mol% with respect to all the repeating units in the resin, and Among the monomer components contained in the resin, the monomer represented by the following general formula (2) is 0.7% by mass or less, according to any one of the above (1) to (3), An actinic ray-sensitive or radiation-sensitive resin composition.

R, A, R ₀ , Z, L, and n have the same meanings as those in the general formula (1-1).

  (5) The actinic ray-sensitive or radiation-sensitive resin composition as described in any one of (1) to (4) above, further comprising (C) a hydrophobic resin.

  (6) A step of forming a film with the actinic ray-sensitive or radiation-sensitive resin composition according to any one of (1) to (5) above, and exposing and developing the film. Pattern forming method.

  The actinic ray-sensitive or radiation-sensitive resin composition of the present invention is excellent in storage stability, can provide a good pattern in which the DOF is wide and the line edge roughness is suppressed in patterning. It is suitable as a 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).
(A) Resin having a repeating unit including a structure represented by the following general formula (1) and having increased solubility in an alkali developer by the action of an acid The resin in the present invention is synthesized, for example, according to a synthesis method described later. It consists of a mixture of an oligomer and polymer component in which two or more monomer units are linked, and a raw material monomer component remaining unreacted during synthesis.

In general formula (1),
L represents a lactone structure.
R ₀ represents an alkylene group, a cyclic alkylene group, or a combination thereof, and when there are a plurality of R _{0 s} , they may be the same or different.
Z represents an ether bond, an ester bond, an amide bond, a urethane bond or a urea bond, and when there are a plurality thereof, they may be the same or different.
n represents the number of repetitions and represents an integer of 1 to 5.

The group represented by R ₀ is not particularly limited as long as it is a chain alkylene group or a cyclic alkylene group, but a preferable chain alkylene group is preferably a chain alkylene having 1 to 10 carbon atoms, more preferably. Has 1 to 5 carbon atoms, and examples thereof include a methylene group, an ethylene group, and a propylene group. Preferable cyclic alkylene is cyclic alkylene having 3 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.

  As the group represented by L, any group can be used as long as it has a lactone structure, but it is preferably a 5- to 7-membered ring lactone structure, and the bicyclo structure or spiro structure is added to the 5- to 7-membered ring lactone structure. Those in which other ring structures are condensed in a form to form are preferable. A lactone structure represented by any of the following general formulas (LC1-1) to (LC1-16) is more preferable. More preferred lactone structures are (LC1-1), (LC1-4), (LC1-5), (LC1-6), (LC1-13), and (LC1-14).

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. n2 represents an integer of 0 to 4. When n2 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.

  Among the repeating units including the structure represented by the general formula (1), the following (1-1) can be given as a preferable repeating unit.

In general formula (1-1),
R represents a hydrogen atom, a halogen atom or an alkyl group.
A represents a group of —COO— or —CONH—.
R ₀ represents an alkylene group, a cyclic alkylene group, or a combination thereof, and when there are a plurality of R _{0 s} , they may be the same or different.
Z represents an ether bond, an ester bond, an amide bond, a urethane bond or a urea bond, and when there are a plurality thereof, they may be the same or different. Z is preferably an ester bond.
L represents a lactone structure.
n represents the number of repetitions and represents an integer of 1 to 5. n is preferably 1.

The alkyl group represented by R is preferably an alkyl group having 1 to 4 carbon atoms, more preferably a methyl group or an ethyl group, and most preferably a methyl group. Examples of the substituent on R include, for example, halogen atoms such as fluorine atom, chlorine atom and bromine atom, mercapto group, hydroxy group, methoxy group, ethoxy group, isopropoxy group, t-butoxy group, benzyloxy group and other alkoxy groups. And acetoxy groups such as acetyl, propionyl and the like.
Preferred examples of R ₀ , L, and Z are the same as described above.

  More particularly preferable lactone repeating units include the following (1-2).

In general formula (1-2),
R, A, R ₀ , Z, and n are as defined above.
R ₁ represents an alkyl group, a cycloalkyl group, a group represented by RzCOO— or a group represented by RzOCO— (Rz represents an alkyl group or a cycloalkyl group), or a cyano group. These may be the same or different, and two R _{1 's} may be bonded to form a ring.
X represents an alkylene group, an oxygen atom or a sulfur atom.
m is the number of substituents and represents an integer of 0 to 5. m is preferably 0 or 1.

The group represented by R ₀ is not particularly limited as long as it is a chain alkylene group or a cyclic alkylene group, but a preferable chain alkylene group is preferably a chain alkylene having 1 to 10 carbon atoms, more preferably. Has 1 to 5 carbon atoms, and examples thereof include a methylene group, an ethylene group, and a propylene group. Preferable cyclic alkylene is cyclic alkylene having 3 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 alkyl group for R ₁ is preferably an alkyl group having 1 to 4 carbon atoms, more preferably a methyl group or an ethyl group, and most preferably a methyl group. Examples of the cycloalkyl group include cyclopropyl, cyclobutyl, cyclopentyl, and cyclohexyl groups. In the group represented by RzCOO- or the group represented by RzOCO- having an ester group, Rz represents an alkyl group (preferably having 1 to 4 carbon atoms) or a cycloalkyl group (preferably having 5 to 7 carbon atoms). .

  Examples of the group represented by RzOCO- include a methoxycarbonyl group, an ethoxycarbonyl group, an n-butoxycarbonyl group, and a t-butoxycarbonyl group. Examples of the group represented by RzCOO— include an acyloxy group, an ethylcarbonyloxy group, a propylcarbonyloxy group, a cyclohexylcarbonyloxy group, and a cyclopentylcarbonyloxy group, and an acyloxy group and an ethylcarbonyloxy group are preferable.

Each group as R ₁ may have a substituent. 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. Can do.
R ₁ is preferably a methyl group or a cyano group, and more preferably a cyano group.
Examples of the alkylene group for X include a methylene group and an ethylene group.
X is preferably a methylene group or an oxygen atom, and more preferably a methylene group.
R ₁ is preferably a substitution position represented by the following.

  Specific examples of the repeating unit having a group having a lactone structure represented by the general formula (1) are shown below, but are not limited thereto.

In the following specific examples, R and R ₁ represent a hydrogen atom, an alkyl group, or a halogen atom, preferably a hydrogen atom, a methyl group, a hydroxymethyl group, or an acetoxymethyl group.

  Among these, specific examples of preferred general formula (1) and general formula (1-1) include the following specific examples. R represents a hydrogen atom, a halogen atom or an alkyl group, preferably a hydrogen atom, a methyl group, a hydroxymethyl group or an acetoxymethyl group.

  The content of the repeating unit having the structure represented by the general formula (1) such as the repeating unit having the lactone structure represented by the general formula (1-1) is 10 to 60 mol with respect to all the repeating units in the resin. % Is preferable, 10 to 55 mol% is more preferable, and 20 to 50 mol% is particularly preferable.

  Resin (A) of this invention may contain multiple types of repeating units represented by General formula (1-1) or General formula (1-2).

  The resin (A) of the present invention preferably further contains a repeating unit represented by the following general formula (AII).

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.
Ab represents a single bond.
V represents a group having a lactone structure. Specifically, for example, it represents a group having a structure represented by any one of the general formulas (LC1-1) to (LC1-16) described above.

Among the units represented by formula (AII), particularly preferred repeating units having a lactone group include the following repeating units. In specific examples, Rx is H, CH ₃ , CH ₂
OH or CF ₃ is represented. By selecting an optimal lactone group, the pattern profile and the density dependency are improved.

  When the resin (A) of the present invention further contains a repeating unit represented by the general formula (AII), the resin (A) has a structure represented by the repeating unit represented by the general formula (AII) / the general formula (1). The copolymerization ratio (molar ratio) of the repeating units is preferably 9/1 to 1/9, more preferably 8/2 to 2/8, and particularly preferably 6/4 to 4/6.

  The resin of component (A) is a resin whose solubility in an alkaline developer is increased by the action of an acid, and decomposes into the main chain or side chain of the resin or both the main chain and the side chain by the action of an acid, It is a resin having a group that generates an alkali-soluble group (hereinafter also referred to as “acid-decomposable group”).

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.

  As the tertiary ester, a repeating unit having a partial structure represented by the following general formula can be preferably used, and more preferred repeating units include those represented by the following structure (A).

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).

In general formula (A),
Xa ₁ 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 are the same as above.

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.

  As the tertiary ester, it is preferable to use either a group represented by the following general formula (2-1) or a group represented by the general formula (2-2).

R ₂ each independently represents an alkyl group or a monocyclic cycloalkyl group. However, when at least one R ₂ is a monocyclic cycloalkyl group or all alkyl groups, the two are bonded to each other to form a monocyclic cycloalkyl group (ie, —C (R ₂ ) (R ₂ ) (R ₂ ) has at least one monocyclic cycloalkyl group).
R ₃ each independently represents an alkyl group or a polycyclic alkyl group. However, when at least one R ₃ is a polycyclic alkyl group or all alkyl groups, the two are bonded to each other to form a polycyclic alkyl group (ie, —C (R ₃ ) (R ₃ )). (R ₃ ) has at least one polycyclic cycloalkyl group.
As the alkyl group for R ₂ and R ₃ , 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, and a t-butyl group is preferable. The monocyclic cycloalkyl group represented by R ₂ is preferably a cycloalkyl group having 5 to 8 carbon atoms such as a cyclopentyl group or a cyclohexyl group, and more preferably a cyclopentyl group or a cyclohexyl group.
Examples of the polycyclic alkyl group represented by R ₃ include a norbornyl group, a tetracyclodecanyl group, a tetracyclododecanyl group, and an adamantyl group.

  In order to enhance the effect of the present invention, it is preferable to use two types of protective groups represented by the above (2-1) and (2-2) in combination.

As for content of the repeating unit which has an acid-decomposable group, 20-60 mol% is preferable with respect to all the repeating units in resin, More preferably, it is 25-55 mol%.
When the above (2-1) and (2-2) are used in combination, it is preferably 5 to 55 mol% each.

  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 the 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. Examples of the substituent containing a polar group include a hydroxyl group, a cyano group, an amino group, an alkylamide group or a sulfonamide group, or a linear or branched alkyl group or cycloalkyl group having any of these. Preferably, it is an alkyl group having a hydroxyl group. A branched alkyl group having a hydroxyl group is more preferred, and an isopropyl group having a hydroxyl group is more preferred.

  p represents 0 or a positive integer.

  The repeating unit represented by the general formula (2) is preferably a repeating unit represented by the following general formula (2-1).

In formula (2-1),
R ₃ each independently represents a hydrogen atom, a methyl group or a group represented by —CH ₂ —R ₉ .
R ₉ represents a hydroxyl group or a monovalent organic group, and examples thereof include an alkyl group having 5 or less carbon atoms and an acyl group, preferably an alkyl group having 3 or less carbon atoms, and more preferably a methyl group. R ₃ preferably represents a hydrogen atom, a methyl group, a trifluoromethyl group, or a hydroxymethyl group.
R ₄ and R ₅ each independently represents an alkyl group or a cycloalkyl group.
R ₁₀ represents a substituent containing a polar group. When a plurality of R ₁₀ are present, they may be the same as or different from each other. Examples of the substituent containing a polar group include a hydroxyl group, a cyano group, an amino group, an alkylamide group or a sulfonamide group, or a linear or branched alkyl group or cycloalkyl group having any of these. Preferably, it is an alkyl group having a hydroxyl group. More preferably, it is a branched alkyl group having a hydroxyl group.
p represents an integer of 0 to 15. p is preferably 0 to 2, more preferably 0 or 1.
R ₃ is preferably a hydrogen atom or a methyl group, more preferably a methyl group.

The alkyl group in R ₄ and R ₅ 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 and R ₅ 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.

  In particular, the following polycyclic repeating units (2-2) are preferable from the viewpoint of roughness.

  Preferred combinations when the resin (A) uses an acid-decomposable repeating unit are listed below.

  The resin of component (A) includes a repeating unit having a hydroxyl group or a cyano group (in the case where the repeating unit represented by the general formula (1-1) or (A) described above has a hydroxyl group or a cyano group) Preferably). This improves the substrate adhesion and developer compatibility. The repeating unit having a hydroxyl group or a cyano group is preferably a repeating unit having an alicyclic hydrocarbon structure substituted with a hydroxyl group or a cyano group. The alicyclic hydrocarbon structure in the alicyclic hydrocarbon structure substituted with a hydroxyl group or a cyano group is preferably an adamantyl group, a diamantyl group, or a 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 an alicyclic hydrocarbon structure substituted with a hydroxyl group or a cyano group is preferably from 5 to 40 mol%, more preferably from 5 to 30 mol%, still more preferably based on all repeating units in the resin. Is 10 to 25 mol%.

  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 of component (A) preferably has 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-attracting 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.

  The content of the repeating unit having an alkali-soluble group is preferably from 0 to 25 mol%, more preferably from 3 to 20 mol%, still more preferably from 5 to 15 mol%, based on all repeating units in the resin.

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 of component (A) may further have a repeating unit that has an alicyclic hydrocarbon structure and does not exhibit acid decomposability. This can reduce the elution of low molecular components from the resist film to the immersion liquid during immersion exposure. Examples of such a repeating unit include 1-adamantyl (meth) acrylate, diamantyl (meth) acrylate, tricyclodecanyl (meth) acrylate, and cyclohexyl (meth) acrylate repeating units.

Specific examples of the repeating unit having an alicyclic hydrocarbon structure and not exhibiting acid decomposability are listed below, but the present invention is not limited thereto. In the formula, Ra represents —H, —CH ₃ , —CH ₂ OH, or —CF ₃ .

  The content of the repeating unit having an alicyclic hydrocarbon structure and not exhibiting acid decomposability is preferably 0 to 40 mol%, more preferably 0 to 20 mol%, based on all repeating units in the resin (A). It is.

  In addition to the above repeating structural unit, the resin of component (A) includes dry etching resistance, standard developer suitability, substrate adhesion, resist profile, and general required properties of resist, such as resolution, heat resistance, and sensitivity. Various repeating structural units can be included for the purpose of adjusting the above.

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

Thereby, the performance required for the resin of component (A), 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 of component (A), the molar ratio of each repeating structural unit is the resist dry etching resistance, standard developer suitability, substrate adhesion, resist profile, and general resist performance required for resolving power and heat resistance. In order to adjust the sensitivity and the like, it is set as appropriate.

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

  Moreover, it is preferable that resin (A) does not contain a fluorine atom and a silicon atom from a compatible viewpoint with hydrophobic resin (C) mentioned later.

  The resin of component (A) 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 actinic ray-sensitive or radiation-sensitive resin 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 component (A) resin is preferably 1,000 to 200,000, more preferably 2,000 to 20,000, and still more preferably 3,000 as a polystyrene-converted value by the GPC method. ˜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 degree of dispersion (molecular weight distribution) is usually 1 to 3, preferably 1 to 2.6, more preferably 1 to 2, and particularly preferably 1.4 to 1.7. 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.

  Moreover, as for resin of (A) component of this invention, the monomer component contained in the resin is 1.0 mass% or less with respect to the said whole resin. Preferably it is 0.8 mass% or less, More preferably, it is 0.5 mass% or less. Further, an excessive purification step for completely eliminating the monomer component is not appropriate in view of production suitability, and it is preferable that the monomer component remains at 0.01% by mass or more, preferably 0.05% by mass or more. The amount of monomer components in the resin can be analyzed by high performance liquid chromatography (HPLC) of the resin. When it exceeds 1.0 mass%, the depth of focus width characteristic (DOF) is significantly deteriorated, and the allowable width due to the focus shift tends to be small at the time of resist pattern formation.

  The amount of residual monomer in the resin can be measured as follows.

  For each raw material monomer contained in the resin as a residual monomer, a calibration curve is prepared by high performance liquid chromatography (HPLC), and the corresponding resin dissolved in a solvent such as THF is subjected to HPLC measurement. The residual monomer amount is calculated from the monomer calibration curve. As HPLC conditions, for example, a 50/50 volume ratio solution of THF / buffer solution (phosphoric acid / triethylamine 0.2% by mass aqueous solution) is used as the elution solution, and the detection wavelength is 210 nm.

The monomer component is an unreacted monomer at the time of resin production. For example, chemical purification methods such as washing with water and liquid-liquid extraction, and chemical purification methods such as these and physical purification methods such as ultrafiltration and centrifugation are used. It can be removed by a combination or the like. Of these purification methods, the reprecipitation method is preferred in which the reaction solution after the polymerization reaction is added to a poor solvent from the viewpoint of production suitability, and the powder obtained by the reprecipitation step is further added to the poor solvent. A purification method using a reslurry step in which washing is performed is more preferable.
As the poor solvent used in the reprecipitation method, a mixed solvent of heptane and ethyl acetate and a mixed solvent of methanol and water are preferable, and a ratio (volume ratio) of heptane / ethyl acetate is in the range of 6/4 to 9/1, methanol. It is particularly preferable to use / water in the range of 10/0 to 7/3.
Among the monomer components, particularly those having a large degree of performance deterioration are monomers having a group and a lactone group that are decomposed by the action of an acid to generate an alkali-soluble group, and monomers having a particularly large influence are lactone groups. Is a monomer having a lactone structure represented by the general formula (1).

  Since the monomer component having a lactone group has high polarity and generally has low solvent solubility, it tends to remain, and therefore, it is particularly necessary to control the remaining amount in the resin. Among them, the monomer component having a great influence is a monomer component represented by the following general formula (2), and the monomer represented by the general formula (2) is 0.7% by mass or less in the resin of the component (A). It is preferable that

R, A, R ₀ , Z, L, and n are as defined above.

  Specifically, the following structures are mentioned.

  The content of the repeating unit having the structure represented by the general formula (1) (preferably the repeating unit represented by the general formula (1-1) or (1-2)) is in all the repeating units in the resin. It is particularly preferable that the amount of the monomer represented by the general formula (2) is 0.7% by mass or less among the monomer components contained in the resin.

  In the actinic ray-sensitive or radiation-sensitive resin composition of the present invention, the blending amount of the component (A) resin in the entire composition is preferably 50 to 99.9% by mass in the total solid content, more preferably. It is 60-99.0 mass%.

  In the present invention, the resin of component (A) may be used alone or in combination.

(B) Compound that generates acid upon irradiation with actinic rays or radiation The actinic ray-sensitive or radiation-sensitive resin composition of the present invention (hereinafter, also simply referred to as “composition”) is irradiated with actinic rays or radiation. To contain an acid generating compound.

  Examples of such photoacid generators include photoinitiators for photocationic polymerization, photoinitiators for photoradical polymerization, photodecolorants for dyes, photochromic agents, actinic rays used in microresists, etc. Known compounds that generate an acid upon irradiation with radiation and mixtures thereof can be appropriately selected and used.

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

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

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

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

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

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

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

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

The aliphatic moiety in the aliphatic sulfonate anion may be an alkyl group or a cycloalkyl group, preferably an alkyl group having 1 to 30 carbon atoms and a cycloalkyl group having 3 to 30 carbon atoms such as methyl. Group, ethyl group, propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, pentyl group, neopentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, undecyl group, dodecyl group , Tridecyl group, tetradecyl group, pentadecyl group, hexadecyl group, heptadecyl group, octadecyl group, nonadecyl group, eicosyl group, cyclopropyl group, cyclopentyl group, cyclohexyl group, adamantyl group, norbornyl group, bornyl group and the like.
The aromatic group in the aromatic sulfonate anion is preferably an aryl group having 6 to 14 carbon atoms, such as a phenyl group, a tolyl group, and a naphthyl group.

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

Examples of the aliphatic moiety in the aliphatic carboxylate anion include the same alkyl group and cycloalkyl group as in the aliphatic sulfonate anion.
Examples of the aromatic group in the aromatic carboxylate anion include the same aryl group as in the aromatic sulfonate anion.
The aralkyl group in the aralkyl carboxylate anion is preferably an aralkyl group having 6 to 12 carbon atoms, such as benzyl group, phenethyl group, naphthylmethyl group, naphthylethyl group, naphthylbutyl group, and the like.

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

  Examples of the sulfonylimide anion include saccharin anion.

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

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

Further, the non-nucleophilic anion of Z ⁻ may have a structure represented by the following general formula (Xa) or general formula (Xb).

In general formula (Xa), 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 XI).
The organic group for R may have one or more carbon atoms, and preferably, the atom bonded to the oxygen atom in the ester bond represented by the general formula (Xa) 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.

_{- (CH 2) n -Rc- (} Y) m formula (XI)
In formula (XI), 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 1 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 (XI) is preferably 40 or less.
It is preferable that n = 0 to 3 and Rc is a monocyclic or polycyclic organic group having 7 to 16.

  In general formula (Xb), R represents a hydrogen atom or an organic group having no polycyclic skeleton, and preferably a hydrogen atom or an organic group having 1 to 40 carbon atoms having no polycyclic skeleton. More preferably, it is a C3-C20 organic group which does not have a hydrogen atom or a polycyclic skeleton. R may be different from each other or may be bonded to each other to form a ring. The organic group for R may have one or more carbon atoms. Preferably, the atom bonded to the nitrogen atom in the amide bond represented by the general formula (Xb) is a carbon atom. Examples include an alkyl group having no skeleton, 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.

  The molecular weight of the non-nucleophilic anion moiety represented by general formula (Xa) and general formula (Xb) is generally 300 to 1000, preferably 400 to 800, and more preferably 500 to 700.

Z ⁻ is also preferably an anion corresponding to an acid represented by the following general formula (Xc).

In general formula (Xc), R < ₁ > -R < ₈ > represents a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, or a hydroxyl group each independently. R ₉ represents a hydrogen atom, an alkyl group, a cycloalkyl group, an alkenyl group, an acyl group, or —SO ₂ Rs. A represents a divalent linking group containing a hetero atom or a single bond. Rs represents an alkyl group, a cycloalkyl group, or an aryl group. m1 to m4 each independently represents an integer of 0 to 12. However, m3 + m4 ≧ 1. m5 represents an integer of 1 to 3. When any one of m1 to m5 is 2 or more, a plurality of R _{1 to} R ₈ or A may be the same or different.
Here, the alkyl group, cycloalkyl group, and alkenyl group may have a fluorine atom as a substituent.
Divalent oxygen atom as the linking group containing a hetero atom of A, -CO -, - CONR - , - SO 2 NR -, - CONRCO -, - SO 2 NRCO -, - SO 2 NRSO 2 -, or -OCONR- is mentioned. Here, R represents a hydrogen atom, an alkyl group, or a cycloalkyl group.

R _{1 to} R ₈ are each independently preferably a hydrogen atom, a perfluoroalkyl group, or a fluorine atom,
A perfluoroalkyl group and a fluorine atom are more preferable. A is preferably a single bond or an oxygen atom. R ₉ is preferably an acyl group represented by —CORx. Rx represents an alkyl group, a cycloalkyl group or an aryl group, and is preferably a cycloalkyl group or an aryl group. In the general formula (Xc), the carbon atom adjacent to SO ₃ H is preferably substituted with a fluorine atom or a trifluoromethyl group.

  The compound that generates an acid having a structure represented by the general formula (Xc) is preferably a structure represented by the following general formula (1-A).

In General Formula (1-A), R _{1 to} R ₉ , A, and m1 to m5 are respectively synonymous with R _{1 to} R ₉ , A, and m1 to m5 in General Formula (Xc), and M ⁺ Represents an organic counter cation as described above, preferably an iodonium or sulfonium ion, and particularly preferably a sulfonium ion.

  The acid represented by the general formula (Xc) is more preferably a structure represented by the following general formulas (1-B) to (1-D).

In General Formulas (1-B) to (1-D), R ₉ has the same meaning as R ₉ in General Formula (Xc), and m5 represents an integer of 0 to 2.

  As a compound which generate | occur | produces the acid represented by general formula (Xc), it is especially preferable that it is a structure represented by the following general formula (1-E)-(1-G).

In formula (1-E) ~ (1 -G), R 9 and ^{M +} have the same meanings as _{R 9} and ^{M +} in the formula (1-A).

  Although the specific example of a photo-acid generator is shown below, it is not limited to these. In the following specific examples, M + represents the above organic counter cation.

Examples of the organic group as R ₂₀₁ , R ₂₀₂ and R ₂₀₃ include a compound (ZI-1) described later.
), (ZI-2) and (ZI-3).

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

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

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

In the arylsulfonium compound, all of R _{201 to} R ₂₀₃ may be an aryl group, or R ₂₀₁
Some of to R ₂₀₃ is an aryl group and the remainder may be an alkyl group or a cycloalkyl group.

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

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

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

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

  Further, as the (ZI) component, a compound (ZI-1a) having a cation represented by the following general formula (ZI-1a) is also preferable.

In general formula (ZI-1a),
R ₁₃ represents a hydrogen atom, a fluorine atom, a hydroxyl group, an alkyl group, a cycloalkyl group, an alkoxy group, or an alkoxycarbonyl group.

When a plurality of R ₁₄ are present, each independently represents an alkyl group, a cycloalkyl group, an alkoxy group, an alkylsulfonyl group, or a cycloalkylsulfonyl group.
R ₁₅ each independently represents an alkyl group or a cycloalkyl group. Two R ₁₅ may be bonded to each other to form a ring.
l represents an integer of 0-2.
r represents an integer of 0 to 10.

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

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

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

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

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

  As r, 0-2 are preferable.

Each of the above groups may have a substituent, and examples of the substituent include a hydroxyl group, a carboxyl group, a cyano group, a nitro group, an alkoxy group, an alkalkyl group, an alkoxycarbonyl group, and an alkoxycarbonyloxy group. Can be mentioned.
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 a methoxycarbonyl group, an ethoxycarbonyl group, an n-propoxycarbonyl group, an i-propoxycarbonyl group, an n-butoxycarbonyl group, a 2-methylpropoxycarbonyl group, and a 1-methylpropoxycarbonyl group. , T-butoxycarbonyl group, cyclopentyloxycarbonyl group, cyclohexyloxycarbonyl and the like, and straight chain, branched or cyclic alkoxycarbonyl groups having 2 to 21 carbon atoms.
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 carbonyl group and cyclohexyloxycarbonyl.

It is preferable that two R ¹⁵ 's are bonded to each other to form a ring structure. As the ring structure, a 5-membered or 6-membered ring together with a sulfur atom in the general formula (ZI-1a), particularly preferably Groups that form a 5-membered ring (ie, a tetrahydrothiophene ring) are desirable.
R ¹⁵ in the general formula (ZI-1a) is preferably a methyl group, an ethyl group, or a divalent group in which two R ¹⁵ are bonded to each other to form a tetrahydrothiophene ring structure together with a sulfur atom.

  Preferred specific examples of the cation represented by the general formula (ZI-1a) are shown below.

  Next, the compound (ZI-2) will be described.

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

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

The alkyl group and cycloalkyl group of R _{201 to} R ₂₀₃ are preferably those having 1 to 1 carbon atoms.
Examples include 0 straight chain or branched alkyl groups (for example, methyl group, ethyl group, propyl group, butyl group, pentyl group) and cycloalkyl groups having 3 to 10 carbon atoms (cyclopentyl group, cyclohexyl group, norbornyl group). it can. More preferred examples of the alkyl group include a 2-oxoalkyl group and an alkoxycarbonylmethyl group. More preferred examples of the cycloalkyl group include a 2-oxocycloalkyl group.

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

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

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

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

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

Any two or more of R _{1c to} R _5c , R _6c and R _7c , and R _x and R _y may be bonded to each other to form a ring structure, and this ring structure includes an oxygen atom and a sulfur atom. , An ester bond and an amide bond may be included. Examples of the group formed by combining any two or more of R _{1c to} R _5c , R _6c and R _7c , and R _x and R _y include a butylene group and a pentylene group.

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

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

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

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

_Examples of the alkyl group and cycloalkyl group as R _x and R _y include the same alkyl group and cycloalkyl group as in R _{1c to} R _7c , such as a 2-oxoalkyl group, a 2-oxocycloalkyl group, an alkoxy group. A carbonylmethyl group is more preferred.

Examples of the 2-oxoalkyl group and 2-oxocycloalkyl group include a group having> C═O at the 2-position of the alkyl group or cycloalkyl group as R _{1c to} R _7c .

Examples of the alkoxy group in the alkoxycarbonylmethyl group include the same alkoxy groups as in R _{1c to} R _5c .

R _x and R _y are preferably an alkyl group or cycloalkyl group having 4 or more carbon atoms, more preferably 6 or more, and still more preferably 8 or more alkyl groups or cycloalkyl groups.

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

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

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

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

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

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

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

  Among the acid generators, compounds represented by the general formulas (ZI) to (ZIII) are more preferable.

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

  Among acid generators, particularly preferred examples are given below.

  As a compound (ZI-1a) which has a cation represented by the said general formula (ZI-1a), the compound shown below is mentioned, for example.

  An acid generator can be used individually by 1 type or in combination of 2 or more types. The content of the acid generator in the actinic ray-sensitive or radiation-sensitive resin composition is preferably 0.1 to 20% by mass based on the total solid content of the actinic ray-sensitive or radiation-sensitive resin composition, More preferably, it is 0.5-10 mass%, More preferably, it is 1-7 mass%.

(Immersion exposure)
The actinic ray-sensitive or radiation-sensitive resin composition of the present invention is a liquid (immersion medium) having a higher refractive index than air between the actinic ray-sensitive or radiation-sensitive film and the lens when irradiated with actinic rays or radiation. It can be used suitably also for pattern formation by immersion exposure which fills and exposes. 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.
An immersion liquid is a liquid that is transparent to the exposure wavelength and has the lowest possible temperature coefficient of refractive index so as to minimize distortion of the optical image projected onto the actinic ray-sensitive or radiation-sensitive film. In particular, when the exposure light source is an ArF excimer laser (wavelength: 193 nm), it is preferable to use water from the viewpoints of availability and ease of handling in addition to the above-described viewpoints.
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 actinic ray-sensitive or radiation-sensitive film on the wafer is not dissolved and the lower surface of the lens element is not dissolved in order to reduce the surface tension of the water and increase the surface activity. An additive (liquid) that can ignore the influence on the optical coating 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 actinic ray-sensitive or radiation-sensitive film is distorted. Is preferably distilled water. Further, pure water filtered through an ion exchange filter or the like may be used.

The electrical resistance of water is preferably 18.3 MQcm or more, and TOC (organic concentration)
Is desirably 20 ppb or less, and it is desirable to perform deaeration treatment.

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.

  In the case of exposure through an immersion medium, a hydrophobic resin (C) can be further added to the composition of the present invention as necessary. As a result, the hydrophobic resin (C) is unevenly distributed on the surface layer of the actinic ray-sensitive or radiation-sensitive film, and when the immersion medium is water, the receding contact angle of the film surface with respect to the water when the film is formed is improved. In addition, the immersion water followability can be improved. As the hydrophobic resin (C), any resin can be used as long as the receding contact angle of the surface can be improved by addition, but a resin having at least one of fluorine atom and silicon atom is preferable. The receding contact angle of the film is preferably 60 ° to 90 °, more preferably 70 ° or more.

The amount of addition can be appropriately adjusted and used so that the receding contact angle of the film falls within the above range, but is preferably 0.1 to 10% by mass, more preferably based on the total solid content of the composition. It is 0.1-5 mass%. As described above, the hydrophobic resin (C) is ubiquitous at the interface, but unlike the surfactant, it does not necessarily have a hydrophilic group in the molecule, and the polar / nonpolar substance is uniformly mixed. There is no need to contribute.
The receding contact angle is the contact angle measured when the contact line at the droplet-substrate interface recedes, and is useful for simulating the ease of droplet movement under dynamic conditions. It is generally known. In simple terms, it can be defined as the contact angle when the droplet interface recedes when the droplet discharged from the needle tip is deposited on the substrate and then sucked into the needle again. It can be measured by using a contact angle measuring method generally called an expansion / contraction method.
In the immersion exposure process, the immersion head needs to move on the wafer following the movement of the exposure head to scan the wafer at high speed to form the exposure pattern. The contact angle of the immersion liquid with respect to the film in the film becomes important, and the resist is required to follow the high-speed scanning of the exposure head without remaining droplets.

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

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

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

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

L < ₃ > -L < ₅ > represents a single bond or a bivalent coupling group. As the divalent linking group, an alkylene group, a phenylene group, an ether group, a thioether group, a carbonyl group, an ester group, an amide group, a urethane group, or a ureylene group is used alone or in combination of two or more groups. A combination is mentioned.
n represents an integer of 1 to 5.

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

Furthermore, the hydrophobic resin (C) may have at least one group selected from the following groups (x) to (z).
(X) an alkali-soluble group,
(Y) a group that decomposes by the action of an alkali developer and increases the solubility in the alkali developer;
(Z) A group that decomposes by the action of an acid.

  (X) Alkali-soluble groups include phenolic hydroxyl groups, carboxylic acid groups, fluorinated alcohol groups, sulfonic acid groups, sulfonamido groups, sulfonylimide groups, (alkylsulfonyl) (alkylcarbonyl) methylene groups, (alkylsulfonyl) ( Alkylcarbonyl) imide group, bis (alkylcarbonyl) methylene group, bis (alkylcarbonyl) imide group, bis (alkylsulfonyl) methylene group, bis (alkylsulfonyl) imide group, tris (alkylcarbonyl) methylene group, tris (alkylsulfonyl) ) And a methylene group.

  Preferred alkali-soluble groups include fluorinated alcohol groups (preferably hexafluoroisopropanol), sulfonimide groups, and bis (carbonyl) methylene groups.

Examples of the repeating unit having an alkali-soluble group (x) include a repeating unit in which an alkali-soluble group is directly bonded to the main chain of the resin, such as a repeating unit of acrylic acid or methacrylic acid, or a main group of the resin via a linking group. Examples include 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 resin. is there.

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

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

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

  The content of the repeating unit having a group (y) that increases the solubility in an alkali developer is preferably 1 to 40 mol%, more preferably 3 to 30 mol%, more preferably, based on all repeating units in the resin. Preferably it is 5-15 mol%.

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

  In the hydrophobic resin (C), examples of the repeating unit having a group (z) that is decomposed by the action of an acid are the same as the repeating unit having an acid-decomposable group exemplified in the resin of the component (A). . In the hydrophobic resin (C), the content of the repeating unit having a group (z) that is decomposed by the action of an acid is preferably 1 to 80 mol%, more preferably 10%, based on all repeating units in the resin. It is -80 mol%, More preferably, it is 20-60 mol%.

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

In general formula (III):
R ₄ represents a group having an alkyl group, a cycloalkyl group, an alkenyl group, or a cycloalkenyl group.
L ₆ represents a single bond or a divalent linking group.

In general formula (III), the alkyl group represented by R ₄ is preferably a linear or branched alkyl group having 3 to 20 carbon atoms.
The cycloalkyl group is preferably a cycloalkyl group having 3 to 20 carbon atoms.
The alkenyl group is preferably an alkenyl group having 3 to 20 carbon atoms.
The cycloalkenyl group is preferably a cycloalkenyl group having 3 to 20 carbon atoms.
The divalent linking group of L ₆ is preferably an alkylene group (preferably having 1 to 5 carbon atoms) or an oxy group.

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

  When the hydrophobic resin (C) has a silicon atom, the content of the silicon atom is preferably 2 to 50% by mass, and 2 to 30% by mass with respect to the molecular weight of the hydrophobic resin (C). Is more preferable. Moreover, it is preferable that it is 10-100 mass% in a hydrophobic resin (C), 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 (C) in terms of standard polystyrene is preferably 1,000 to 100,000, more preferably 1,000 to 50,000, and still more preferably 2,000 to 15,000. is there.

  The hydrophobic resin (C), like the resin of the component (A), naturally has few impurities such as metals, and the residual monomer or oligomer component is preferably 0 to 10% by mass, more preferably. Is more preferably 0 to 5% by mass and 0 to 1% by mass. Thereby, a composition having no change over time such as foreign matter in liquid or sensitivity is 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 1 in terms of resolution, pattern shape, pattern sidewall, roughness, and the like. It is the range of ~ 2.

  As the hydrophobic resin (C), various commercially available products can be used, and the hydrophobic resin (C) 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 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 (C) are shown below. Table 1 below shows the molar ratio of the repeating units in each resin (corresponding to each repeating unit in order from the left), the weight average molecular weight, and the degree of dispersion.

  In order to prevent the resist film from coming into direct contact with the immersion liquid between the resist film made of the actinic ray-sensitive or radiation-sensitive resin composition of the present invention and the immersion liquid, an immersion liquid hardly soluble film (hereinafter referred to as “top”). May also be provided). The functions necessary for the top coat are suitability for application to the upper layer of the resist, transparency to radiation, particularly 193 nm, and poor immersion liquid solubility. It is preferable that the top coat is not mixed with the resist and can be uniformly applied to the 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 above-mentioned hydrophobic resin (C) 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 a small penetration into the resist film is preferable. It is preferable that the peeling process can be performed with an alkali developer in that the peeling process can be performed simultaneously with the resist film development process. From the viewpoint of peeling with an alkaline developer, the topcoat is preferably acidic, but may be neutral or alkaline from the viewpoint of non-intermixability with the resist 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 an immersion liquid in an ArF excimer laser (wavelength: 193 nm), Ar
The top coat for F 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 resist film and further not mixed with the immersion liquid. From this point of view, when the immersion liquid is water, the solvent used for the top coat is preferably a water-insoluble medium that is hardly soluble in the solvent used for the positive resist composition. Furthermore, when the immersion liquid is an organic solvent, the topcoat may be water-soluble or water-insoluble.

Solvents Solvents that can be used in preparing the composition of the present invention by dissolving the above components include, for example, alkylene glycol monoalkyl ether carboxylate, alkylene glycol monoalkyl ether, alkyl lactate ester, alkoxypropionic acid. List organic solvents such as alkyl, cyclic lactone (preferably having 4 to 10 carbon atoms), monoketone compounds (preferably having 4 to 10 carbon atoms) which may contain a ring, alkylene carbonate, alkyl alkoxyacetate and alkyl pyruvate. Can do.

  Examples of the alkylene glycol monoalkyl ether carboxylate include propylene glycol monomethyl ether acetate (PGMEA: 1-methoxy-2-acetoxypropane), propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, propylene glycol monobutyl ether acetate, Preferred are propylene glycol monomethyl ether propionate, propylene glycol monoethyl ether propionate, ethylene glycol monomethyl ether acetate, and ethylene glycol monoethyl ether acetate.

Examples of the alkylene glycol monoalkyl ether include propylene glycol monomethyl ether (PGME: 1-methoxy-2-propanol), propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, ethylene glycol monomethyl ether, ethylene glycol Preferred is 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 the cyclic lactone include β-propiolactone, β-butyrolactone, γ-butyrolactone, α-methyl-γ-butyrolactone, β-methyl-γ-butyrolactone, γ-valerolactone, γ-caprolactone, and γ-octano. Preferred are iclactone and α-hydroxy-γ-butyrolactone.

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

  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.

  Examples of the solvent containing a hydroxyl group include ethylene glycol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, propylene glycol, propylene glycol monomethyl ether, propylene glycol monoethyl ether, ethyl lactate, and the like. Particularly preferred are propylene glycol monomethyl ether and ethyl lactate.

  Examples of the solvent not containing a hydroxyl group include propylene glycol monomethyl ether acetate, ethyl ethoxypropionate, 2-heptanone, γ-butyrolactone, cyclohexanone, butyl acetate, N-methylpyrrolidone, N, N-dimethylacetamide, dimethyl sulfoxide and the like. 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. 2-heptanone is 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.

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) to (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.
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.
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.
The alkyl groups in these general formulas (A) to (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.

As the amine compound, a primary, secondary or tertiary amine compound can be used, and an amine compound in which at least one alkyl group is bonded to a nitrogen atom is preferable. The amine compound is more preferably a tertiary amine compound. As long as at least one alkyl group (preferably having 1 to 20 carbon atoms) is bonded to a nitrogen atom, the amine compound has an cycloalkyl group (preferably having 3 to 20 carbon atoms) or an aryl group (preferably having 3 to 20 carbon atoms). Preferably C6-C12) may be bonded to a nitrogen atom. The amine compound preferably has an oxygen atom in the alkyl chain 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. Among the oxyalkylene groups, an oxyethylene group (—CH ₂ CH ₂ O—) or an oxypropylene group (—CH (CH ₃ ) CH ₂ O— or —CH ₂ CH ₂ CH ₂ O—) is preferable, and more preferably oxy Ethylene group.

As the ammonium salt compound, a primary, secondary, tertiary, or quaternary ammonium salt compound can be used, and an ammonium salt compound in which at least one alkyl group is bonded to a nitrogen atom is preferable. As long as at least one alkyl group (preferably having 1 to 20 carbon atoms) is bonded to a nitrogen atom, the ammonium salt compound has a cycloalkyl group (preferably having 3 to 20 carbon atoms) or an aryl group in addition to the alkyl group. (Preferably having 6 to 12 carbon atoms) may be bonded to a nitrogen atom. The ammonium salt compound preferably has an oxygen atom in the alkyl chain 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. Among the oxyalkylene groups, an oxyethylene group (—CH ₂ CH ₂ O—) or an oxypropylene group (—CH (CH ₃ ) CH ₂ O— or —CH ₂ CH ₂ CH ₂ O—) is preferable, and more preferably oxy Ethylene group. Examples of the anion of the ammonium salt compound include halogen atoms, sulfonates, borates, and phosphates. Among them, halogen atoms and sulfonates are preferable. As the halogen atom, chloride, bromide, and iodide are particularly preferable. As the sulfonate, an organic sulfonate having 1 to 20 carbon atoms is particularly preferable. Examples of the organic sulfonate include alkyl sulfonates having 1 to 20 carbon atoms and aryl sulfonates. The alkyl group of the alkyl sulfonate may have a substituent, and examples of the substituent include fluorine, chlorine, bromine, alkoxy groups, acyl groups, and aryl groups. Specific examples of the alkyl sulfonate include methane sulfonate, ethane sulfonate, butane sulfonate, hexane sulfonate, octane sulfonate, benzyl sulfonate, trifluoromethane sulfonate, pentafluoroethane sulfonate, and nonafluorobutane sulfonate. Examples of the aryl group of the aryl sulfonate include a benzene ring, a naphthalene ring, and an anthracene ring. The benzene ring, naphthalene ring and anthracene ring may have a substituent, and the substituent is preferably a linear or branched alkyl group having 1 to 6 carbon atoms or a cycloalkyl group having 3 to 6 carbon atoms. Specific examples of the linear or branched alkyl group and cycloalkyl group include methyl, ethyl, n-propyl, isopropyl, n-butyl, i-butyl, t-butyl, n-hexyl, cyclohexyl and the like. Examples of the other substituent include an alkoxy group having 1 to 6 carbon atoms, a halogen atom, cyano, nitro, an acyl group, and an acyloxy group.

  The amine compound having a phenoxy group and the ammonium salt compound having a phenoxy group are those having a phenoxy group at the terminal opposite to the nitrogen atom of the alkyl group of the amine compound or ammonium salt compound. The phenoxy group may have a substituent. Examples of the substituent of the phenoxy group include an alkyl group, an alkoxy group, a halogen atom, a cyano group, a nitro group, a carboxyl group, a carboxylic acid ester group, a sulfonic acid ester group, an aryl group, an aralkyl group, an acyloxy group, and an aryloxy group. Etc. The substitution position of the substituent may be any of the 2-6 positions. The number of substituents may be any in the range of 1 to 5.

It is preferable to have at least one oxyalkylene group between the phenoxy group and the nitrogen atom. The number of oxyalkylene groups is one or more in the molecule, preferably 3 to 9, and more preferably 4 to 6. Among the oxyalkylene groups, an oxyethylene group (—CH ₂ CH ₂ O—) or an oxypropylene group (—CH (CH ₃ ) CH ₂ O— or —CH ₂ CH ₂ CH ₂ O—) is preferable, and more preferably oxy Ethylene group.

  In the amine compound having a sulfonic acid ester group and the ammonium salt compound having a sulfonic acid ester group, the sulfonic acid ester group may be any of alkyl sulfonic acid ester, cycloalkyl group sulfonic acid ester, and aryl sulfonic acid ester. In the case of an alkyl sulfonate ester, the alkyl group has 1 to 20 carbon atoms, in the case of a cycloalkyl sulfonate ester, the cycloalkyl group has 3 to 20 carbon atoms, and in the case of an aryl sulfonate ester, the aryl group has 6 carbon atoms. ~ 12 are preferred. Alkyl sulfonic acid ester, cycloalkyl sulfonic acid ester, and aryl sulfonic acid ester may have a substituent. Examples of the substituent include a halogen atom, a cyano group, a nitro group, a carboxyl group, a carboxylic acid ester group, and a sulfonic acid. An ester group is preferred.

It is preferable to have at least one oxyalkylene group between the sulfonate group and the nitrogen atom. The number of oxyalkylene groups is one or more in the molecule, preferably 3 to 9, and more preferably 4 to 6. Among the oxyalkylene groups, an oxyethylene group (—CH ₂ CH ₂ O—) or an oxypropylene group (—CH (CH ₃ ) CH ₂ O— or —CH ₂ CH ₂ CH ₂ O—) is preferable, and more preferably oxy Ethylene group.

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 the composition of this invention, 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. That is, the molar ratio is preferably 2.5 or more from the viewpoints of sensitivity and resolution, and is preferably 300 or less from the viewpoint of suppressing the reduction in resolution due to pattern thickening over time until post-exposure heat treatment. The acid generator / basic compound (molar ratio) is more preferably 5.0 to 200, still more preferably 7.0 to 150.

Surfactant The actinic ray-sensitive or radiation-sensitive resin composition preferably further contains a surfactant, and a fluorine-based and / or silicon-based surfactant (fluorine-based surfactant, silicon-based surfactant, It is more preferable to contain either one or two or more surfactants having both fluorine atoms and silicon atoms.

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

  Examples of the fluorine-based and / or silicon-based surfactant include surfactants described in [0276] of US Patent Application Publication No. 2008/0248425. For example, Ftop EF301, EF303, (Shin-Akita Kasei Co., Ltd.) )), FLORARD FC430, 431, 4430 (manufactured by Sumitomo 3M), MegaFuck F171, F173, F176, F189, F113, F110, F177, F120, R08 (Dainippon Ink Chemical Co., Ltd.), Surflon S-382, SC101, 102, 103, 104, 105, 106 (manufactured by Asahi Glass Co., Ltd.), Troisol S-366 (manufactured by Troy Chemical Co., Ltd.), GF-300, GF-150 (Toagosei Chemical Co., Ltd.) ), Surflon S-393 (manufactured by Seimi Chemical Co., Ltd.), F-top EF121, EF122A EF122B, RF122C, EF125M, EF135M, EF351, 352, EF801, EF802, EF601 (manufactured by Gemco), PF636, PF656, PF6320, PF6520 (manufactured by OMNOVA), FTX-204G, 208G, 218G, 230G 208D, 212D, 218D, 222D (manufactured by Neos Co., Ltd.) and the like. Polysiloxane polymer KP-341 (manufactured by Shin-Etsu Chemical Co., Ltd.) can also be used as a silicon-based surfactant.

  In addition to the known surfactants described above, 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 the method described in JP-A-2002-90991.

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

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

In the present invention, surfactants other than fluorine-based and / or silicon-based surfactants described in [0280] of US Patent Application Publication No. 2008/0248425 can also be used.
These surfactants may be used alone or in several combinations.

  The amount of the surfactant used is preferably 0.0001 to 2% by mass, more preferably 0.001 to 1% by mass, based on the total amount of the actinic ray-sensitive or radiation-sensitive resin composition (excluding the solvent). is there.

Carboxylic acid onium salt The composition in this invention may contain carboxylic acid onium salt. Examples of the carboxylic acid onium salt include a carboxylic acid sulfonium salt, a carboxylic acid iodonium salt, and a carboxylic acid ammonium salt. In particular, as the carboxylic acid onium salt, an iodonium salt and a sulfonium salt are preferable. Furthermore, it is preferable that the carboxylate residue of the carboxylic acid onium salt of the present invention does not contain an aromatic group or a carbon-carbon double bond. As a particularly preferable 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.

  These carboxylic acid onium salts can be synthesized by reacting sulfonium hydroxide, iodonium hydroxide, ammonium hydroxide and carboxylic acid with silver oxide in a suitable solvent.

  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. %.

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 alkali developer. 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 alkali developer. (Hereinafter also referred to as “dissolution-inhibiting compound”), since it does not lower the permeability of 220 nm or less, like cholic acid derivatives containing acid-decomposable groups described in Proceeding of SPIE, 2724,355 (1996). An alicyclic or aliphatic compound containing an acid-decomposable group is preferred. Examples of the acid-decomposable group and alicyclic structure are the same as those described for the component (A) resin.

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

The molecular weight of the dissolution inhibiting compound in the present invention is 3000 or less, preferably 300 to 3000, and more preferably 500 to 2500.
The addition amount of the dissolution inhibiting compound is preferably 3 to 50% by mass, more preferably 5 to 40% by mass, based on the total solid content of the composition of the present invention.

  Specific examples of the dissolution inhibiting compound are shown below, but the present invention is not limited thereto.

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 phenol compound having a molecular weight of 1000 or less) are included in the composition of the present invention. , An alicyclic or aliphatic compound having a carboxyl group) and the like.

  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. Such a film thickness can be obtained by setting the solid content concentration in the composition to an appropriate range to give an appropriate viscosity and improving the coating property and film forming property.

  The total solid concentration in the 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 microns or less, more preferably 0.05 microns or less, and even more preferably 0.03 microns or less made of polytetrafluoroethylene, polyethylene, or nylon.

For example, the composition of the present invention is coated on a substrate (eg, silicon / silicon dioxide coating) used for the manufacture of precision integrated circuit elements by a suitable coating method such as a spinner or coater, and dried to form a film. Form.
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 the film is formed, an antireflection film may be coated on the substrate in advance.
As the antireflection film, any of an inorganic film type such as titanium, titanium dioxide, titanium nitride, chromium oxide, carbon, and amorphous silicon, and an organic film type made of a light absorber and a polymer material can be used. In addition, as the organic antireflection film, commercially available organic antireflection films such as DUV30 series, DUV-40 series manufactured by Brewer Science, AR-2, AR-3, AR-5 manufactured by Shipley, etc. may be used. it can.

In the development step, an alkaline developer is used as follows. Examples of the alkaline developer include inorganic alkalis such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, and aqueous ammonia, primary amines such as ethylamine and n-propylamine, diethylamine, di- Secondary amines such as n-butylamine, tertiary amines such as triethylamine and methyldiethylamine, alcohol amines such as dimethylethanolamine and triethanolamine, quaternary ammonium such as tetramethylammonium hydroxide and tetraethylammonium hydroxide Alkaline aqueous solutions such as salts, cyclic amines such as pyrrole and pihelidine can 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, this invention is not limited to this. In addition, Example 3, 9 and 11 shall be read as a reference example.

Synthesis Example 1 (Synthesis of polymer (1))
Under a nitrogen stream, 25.5 g of cyclohexanone was placed in a three-necked flask and heated to 80 ° C. A solution prepared by dissolving 6.04 g, 1.25 g, 2.71 g, 2.60 g of the following compounds in order from the left and polymerization initiator V-601 (manufactured by Wako Pure Chemical Industries, Ltd., 0.798 g) in 46 g of cyclohexanone was added for 6 hours. It was dripped over. After completion of dropping, the reaction was further carried out at 80 ° C. for 2 hours. The reaction solution was allowed to cool and then added dropwise over 20 minutes to a mixed solution of 420 g of hexane / 180 g of ethyl acetate, and the precipitated powder was collected by filtration. Furthermore, reslurry washing was performed with 350 g of hexane / 150 g of ethyl acetate, followed by drying to obtain 10 g of polymer (1). The weight average molecular weight of the obtained polymer (1) was 9570 in terms of standard polystyrene, and the dispersity (Mw / Mn) was 1.7. The residual monomer amount in the resin was 0.36% by mass (from the left monomer, 0.24% by mass, 0.04% by mass, 0.01% by mass, 0.07% by mass) with respect to the total amount of the resin.

The amount of residual monomer in the resin was measured as follows.
A calibration curve is prepared by high performance liquid chromatography (HPLC) for each raw material monomer contained in the resin as the residual monomer, and the HPLC measurement is performed on the corresponding resin dissolved in THF, and the obtained peak area and the calibration of each monomer. The amount of residual monomer was calculated from the line.
In HPLC, a 50/50 volume ratio solution of THF / buffer solution (phosphoric acid / triethylamine 0.2 mass% aqueous solution) was used as the elution solution, and the detection wavelength was 210 nm.

It measured similarly about subsequent resin.
Synthesis Example 2 (Synthesis of polymer (2))
Under a nitrogen stream, 25.5 g of cyclohexanone was placed in a three-necked flask and heated to 80 ° C. A solution prepared by dissolving 6.04 g, 1.25 g, 2.71 g, 2.60 g of the following compounds in order from the left and polymerization initiator V-601 (manufactured by Wako Pure Chemical Industries, Ltd., 0.798 g) in 46 g of cyclohexanone was added for 6 hours. It was dripped over. After completion of dropping, the reaction was further carried out at 80 ° C. for 2 hours. The reaction mixture was allowed to cool and then added dropwise to a mixture of 500 g of hexane / 100 g of ethyl acetate over 20 minutes, and the precipitated powder was collected by filtration. Further, the slurry was washed with 475 g of hexane / 25 g of ethyl acetate and dried to obtain 10 g of polymer (2). The weight average molecular weight of the obtained polymer (2) was 9340 in terms of standard polystyrene, and the dispersity (Mw / Mn) was 1.8. The residual monomer amount in the resin was 0.94% by mass (0.81%, 0.05%, 0.02%, 0.06% by mass from the left monomer) based on the total amount of the resin.

Synthesis Example 3 (Synthesis of polymer (3))
Under a nitrogen stream, 25.5 g of 1,4-dioxane was placed in a three-necked flask and heated to 80 ° C. In this order, 5.08 g, 1.45 g, 1.01 g, 8.41 g, 4.51 g, polymerization initiator V-601 (manufactured by Wako Pure Chemical Industries, Ltd., 0.821 g) in order from the left to 6 g of 1,4-dioxane. The dissolved solution was added dropwise over 6 hours. After completion of dropping, the reaction was further carried out at 80 ° C. for 2 hours. The reaction solution was allowed to cool and then added dropwise to a mixed solution of 150 g of methanol / 35 g of ion exchange water over 20 minutes, and the precipitated powder was collected by filtration. Further, the filtrate was put into a solution of 85 g of methanol and filtered after stirring. The obtained filtrate was put into the same liquid and the operation of stirring and filtering was further performed three times. Subsequent drying gave 9.5 g of polymer (3). The weight average molecular weight of the obtained polymer (3) was 8200 in terms of standard polystyrene, and the dispersity (Mw / Mn) was 1.6. The residual monomer amount in the resin was 0.38% by mass (from the left monomer, 0.15%, 0.07%, 0.03%, 0.01%, 0.12% by mass) from the total amount of the resin.

Synthesis Example 4 (Synthesis of polymer (4))
Under a nitrogen stream, 25.5 g of 2-butanone was placed in a three-necked flask and heated to 80 ° C. 6.17 g, 1.30 g, 5.01 g and the polymerization initiator V-601 (manufactured by Wako Pure Chemical Industries, 0.798 g, 7.0 mol% with respect to the monomer) are dissolved in 46 g of 2-butanone in order from the left. The solution was added dropwise over 3 hours. After completion of dropping, the reaction was further carried out at 80 ° C. for 3 hours. The reaction solution was allowed to cool and then added dropwise to 200 g of methanol over 20 minutes, and the precipitated powder was collected by filtration. Further, the filtrate was put into a solution of 85 g of methanol and filtered after stirring. The obtained filtrate was put into the same liquid, and the operation of stirring and filtering was further performed twice to obtain 9.5 g of polymer (4). The weight average molecular weight of the obtained polymer (4) was 9210 in terms of standard polystyrene, and the dispersity (Mw / Mn) was 1.6. Further, the residual monomer amount in the resin was 0.65% by mass (from the left monomer, 0.45% by mass, 0.06% by mass, and 0.14% by mass) with respect to the total amount of the resin.

Synthesis Example 5 (Synthesis of polymer (7))
Under a nitrogen stream, 25.5 g of 2-butanone was placed in a three-necked flask and heated to 80 ° C. A solution prepared by dissolving 7.30 g, 1.67 g, 3.87 g of the following compounds in this order from the left and polymerization initiator V-601 (manufactured by Wako Pure Chemical Industries, Ltd., 0.765 g) in 46 g of 2-butanone over 4 hours was added thereto. And dripped. After completion of dropping, the reaction was further carried out at 80 ° C. for 2 hours. The reaction solution was allowed to cool and then added dropwise to 150 g of methanol over 20 minutes, and the precipitated powder was collected by filtration. Further, the slurry was washed with 90 g of methanol / 10 g of water and dried to obtain 9.8 g of polymer (7). The weight average molecular weight of the obtained polymer (7) was 7980 in terms of standard polystyrene, and the dispersity (Mw / Mn) was 1.6. Further, the residual monomer amount in the resin was 0.52% by mass (from the left monomer, 0.32% by mass, 0.05% by mass, and 0.15% by mass) with respect to the total amount of the resin.

  Further, the following resin of the present invention was synthesized in the same manner as in Synthesis Example 1.

Comparative Example 1 (Synthesis of polymer (R1))
Under a nitrogen stream, 25.5 g of 1,4-dioxane was placed in a three-necked flask and heated to 80 ° C. In this order, 5.08 g, 1.45 g, 1.01 g, 8.41 g, 4.51 g, polymerization initiator V-601 (manufactured by Wako Pure Chemical Industries, Ltd., 0.821 g) in order from the left to 6 g of 1,4-dioxane. The dissolved solution was added dropwise over 6 hours. After completion of dropping, the reaction was further carried out at 80 ° C. for 2 hours. The reaction solution was allowed to cool and then poured into a mixed solution of 540 g of hexane / 60 g of ethyl acetate, followed by stirring and filtration. The obtained filtrate was put into the same liquid and stirred and filtered once more. After drying, 15.3 g of polymer (R1) was obtained. The weight average molecular weight of the obtained polymer (R1) was 8100 in terms of standard polystyrene, and the dispersity (Mw / Mn) was 1.8. Further, the residual monomer amount in the resin was 1.24% by mass (from the left monomer, 0.92% by mass, 0.04% by mass, 0.06% by mass, 0.08% by mass, 0.14% by mass) with respect to the total amount of the resin.

Comparative Example 2 (Synthesis of polymer (R2))
Under a nitrogen stream, 25.5 g of 2-butanone was placed in a three-necked flask and heated to 80 ° C. 6.17 g, 5.01 g, 1.37 g and the polymerization initiator V-601 (manufactured by Wako Pure Chemical Industries, 0.798 g, 7.0 mol% with respect to the monomer) were dissolved in 46 g of 2-butanone in order from the left. The solution was added dropwise over 3 hours. After completion of dropping, the reaction was further carried out at 80 ° C. for 3 hours. The reaction solution was allowed to cool, then, poured into a mixture of hexane 540 g / ethyl acetate 60 g, and filtered after stirring. The obtained filtrate was put into the same liquid and stirred and filtered once more. Further, the filtrate was put into a solution of 85 g of methanol and filtered after stirring. After drying, 9.5 g of polymer (R2) was obtained. The weight average molecular weight of the obtained polymer (R2) was 8560 in terms of standard polystyrene, and the dispersity (Mw / Mn) was 1.8. Further, the amount of residual monomer in the resin was 1.36% by mass (from the left monomer, 0.95% by mass, 0.13% by mass, 0.28% by mass) with respect to the total amount of the resin.

Comparative Example 3
Only the monomer component was changed, and the resin of Comparative Example 3 was synthesized in the same manner as in Synthesis Example 1.

Comparative Example 4
Under a nitrogen stream, 25.5 g of cyclohexanone was placed in a three-necked flask and heated to 80 ° C. A solution prepared by dissolving 5.44 g, 1.30 g, 3.01 g, 2.89 g, polymerization initiator V-601 (manufactured by Wako Pure Chemical Industries, Ltd., 0.798 g) in 46 g of cyclohexanone in this order for 6 hours It was dripped over. After completion of dropping, the reaction was further carried out at 80 ° C. for 2 hours. The reaction solution was allowed to cool and then added dropwise to a mixed solution of 540 g of hexane / 60 g of ethyl acetate over 20 minutes, and the precipitated powder was collected by filtration and dried to obtain 10 g of polymer (R4). The weight average molecular weight of the obtained polymer (R4) was 9390 in terms of standard polystyrene, and the dispersity (Mw / Mn) was 1.8. The amount of residual monomer in the resin was 1.52% by mass (0.85%, 0.18%, 0.17%, 0.32% by mass from the left monomer) based on the total amount of the resin.

<Preparation of actinic ray-sensitive or radiation-sensitive resin composition>
A resist solution was prepared from a solution in which the components shown in Table 1 below were dissolved in a solvent, and this was filtered through a polyethylene filter having a pore size of 0.05 μm to prepare an actinic ray-sensitive or radiation-sensitive resin composition. The prepared actinic ray-sensitive or radiation-sensitive resin composition was evaluated by the following method, and the results are shown in Table 2. About each component in Table 1, the ratio at the time of using multiple is a mass ratio.

  In Table 1, when the actinic ray-sensitive or radiation-sensitive resin composition contains the hydrophobic resin (C), the addition form is indicated as “addition”. When the actinic ray-sensitive or radiation-sensitive resin composition does not contain the hydrophobic resin (C), and after forming a film, a top coat protective film containing the hydrophobic resin (C) is formed on the upper layer, The addition form was labeled “TC”.

  Hereinafter, abbreviations in the table are shown.

[Photoacid generator]
PAG-1:

[Basic compounds]
DIA: 2,6-Diisopropylaniline TBAH: Tetrabutylammonium hydroxide TMEA: Tris (methoxyethoxyethyl) amine PEA: N-phenyldiethanolamine [Surfactant]
W-1: MegaFuck F176 (Dainippon Ink Chemical Co., Ltd.) (Fluorine)
W-2: Megafuck R08 (Dainippon Ink Chemical Co., Ltd.) (fluorine and silicon)
W-3: Troisol S-366 (manufactured by Troy Chemical Co., Ltd.)
W-4: PF656 (manufactured by OMNOVA, fluorine-based)
W-5: PF6320 (manufactured by OMNOVA, fluorine-based)
〔solvent〕
A1: Propylene glycol monomethyl ether acetate (PGMEA)
A2: γ-butyrolactone B1: Propylene glycol monomethyl ether (PGME)

(Exposure conditions 1: Examples 1 to 9, Comparative examples 1 to 4: ArF immersion exposure)
An organic antireflection film ARC29SR (manufactured by Nissan Chemical Industries, Ltd.) was applied on a silicon wafer, and baked at 205 ° C. for 60 seconds to form an antireflection film having a thickness of 95 nm. The actinic ray-sensitive or radiation-sensitive resin composition prepared thereon was applied, and baked at 85 ° C. for 60 seconds to form a film with a thickness of 100 nm. In the case of using a top coat, a 3% by mass solution obtained by further dissolving a resin for top coat in decane / octanol (9/1 mass ratio) is applied on the resist film obtained above, and at 85 ° C., 60 ° C. Baking was performed for 2 seconds to form a top coat layer having a thickness of 50 nm. The obtained wafer was subjected to an ArF excimer laser immersion scanner (XT-1700Fi manufactured by ASML, NA 1.20, σo / σi = 0.94 / 0.74), 6% halftone of a 1/1 line and space pattern with a line width of 50 nm. Exposed through a mask. Ultra pure water was used as the immersion liquid. After heating at 90 ° C. for 60 seconds, the film was developed with an aqueous tetramethylammonium hydroxide solution (2.38 mass%) for 30 seconds, rinsed with pure water, and then spin-dried to form a pattern.

(LWR (Line Width Roughness) measurement)
A line having a 1/1 (line and space) pattern with a line width of 50 nm was measured at 50 points, and its 3σ value (nm) was calculated.

(DOF evaluation)
The depth of focus at which the line width of 50 nm ± 10% was reproduced at the optimum exposure dose was observed. A larger value is desirable because the tolerance for defocus is large.

(Exposure condition 2: Examples 10 to 15: ArFDry exposure)
An organic antireflection film ARC29A (Nissan Chemical Co., Ltd.) was applied on a silicon wafer and baked at 205 ° C. for 60 seconds to form an antireflection film having a thickness of 78 nm. The actinic ray-sensitive or radiation-sensitive resin composition prepared thereon was applied, and baked at 130 ° C. for 60 seconds to form a film having a thickness of 120 nm. Using the obtained wafer ArF excimer laser scanner (PAS5500 / 1100, manufactured by ASML, NA0.75), the film was exposed through a 6% halftone mask having a line width of 75 nm and a 1: 1 line and space pattern. Thereafter, heating was performed at 90 ° C. for 60 seconds, followed by development with an aqueous tetramethylammonium hydroxide solution (2.38% by mass) for 30 seconds, rinsing with pure water, and spin drying to obtain a pattern. (LWR (Line Width Roughness) measurement)
The length of a 1/1 (line and space) pattern having a line width of 75 nm was measured at 50 points, and the 3σ value (nm) was calculated.

(DOF evaluation)
The depth of focus at which the line width of 75 nm ± 10% was reproduced at the optimum exposure dose was observed. A larger value is desirable because the tolerance for defocus is large.

(Storage stability evaluation)
For storage stability evaluation, samples were stored at 5 ° C. for 30 days, and the total number of foreign matters having a size of 0.25 μm to 1.0 μm before and after storage was measured using a Rion Co., Ltd. particle counter KL-20A and a flow rate of 10 ml / min. Measurement was performed under analysis conditions. The number of foreign matters before and after storage under the above conditions was expressed as a ratio (number after aging / number before aging). The smaller the value, the smaller the change over time, and the better the storage stability.

  It can be seen that the composition of the present invention is excellent in all of LWR, DOF, and storage stability.

Claims (11)

(A) a resin having a repeating unit containing a structure represented by the following general formula (1) and a repeating unit represented by the following general formula (1 ′), which increases the solubility in an alkali developer by the action of an acid; (B) It contains a compound that generates an acid upon irradiation with actinic rays or radiation, and the monomer component contained in the resin (A) is 1.0% by mass or less based on the resin (A). An actinic ray-sensitive or radiation-sensitive resin composition.

In general formula (1),
L represents a lactone structure.
R ₀ represents a methylene group .
Z is, to table a an ester binding.
n represents the number of repetitions and represents 1 .

In the general formula (1 ′), Rx represents a hydrogen atom, CH ₃ , CF ₃ , or CH ₂ OH. Rxa 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. (A) A resin having a repeating unit containing the structure represented by the following general formula (1), which increases the solubility in an alkali developer by the action of an acid, and (B) generates an acid upon irradiation with actinic rays or radiation. An actinic ray-sensitive or radiation-sensitive resin composition comprising a compound, wherein the monomer component contained in the resin (A) is 1.0% by mass or less based on the resin (A). The actinic ray-sensitive or radiation-sensitive resin composition is characterized in that the compound (B) is a compound represented by the following general formula (1-E).

In general formula (1),
L represents a lactone structure.
R ₀ Represents an alkylene group, a cyclic alkylene group, or a combination thereof, and when there are a plurality of these, they may be the same or different.
Z represents an ether bond, an ester bond, an amide bond, a urethane bond or a urea bond, and when there are a plurality thereof, they may be the same or different.
n represents the number of repetitions and represents an integer of 1 to 5.

In the general formula (1-E), R ₉ Is a hydrogen atom, alkyl group, cycloalkyl group, alkenyl group, acyl group or -SO ₂ Rs is represented. Rs represents an alkyl group, a cycloalkyl group or an aryl group. M ⁺ Represents an organic counter cation. The actinic ray-sensitive or radiation-sensitive resin according to claim 1 or 2, wherein the resin (A) further has a repeating unit having a partial structure represented by the following general formula (2-2). Composition.

R ₃ Each independently represents an alkyl group or a polycyclic alkyl group. However, at least one R ₃ Are a polycyclic alkyl group or all alkyl groups, the two are bonded to each other to form a polycyclic alkyl group. In the general formula (2-2), at least one R ₃ The actinic ray-sensitive or radiation-sensitive resin composition according to claim 3, wherein is a polycyclic alkyl group. The actinic ray-sensitive or radiation-sensitive property according to any one of claims 1 to 4, wherein the repeating unit of the general formula (1) is a repeating unit represented by the following general formula (1-1). Resin composition.

In general formula (1-1),
R represents a hydrogen atom or an alkyl group.
A represents a group of either —COO— or —CONH—.
L, R ₀ , Z, and n are as defined in claim 1. The actinic-ray- or radiation according to claim 5, repeating units represented by the one general formula (1-1) is characterized in that it is a repeating unit represented by the following general formula (1-2) Resin composition.

In the general formula ( 1-2 ), R, A, R ₀ , Z, and n have the same meanings as those in the general formula (1-1) .
R ₁ represents an alkyl group, a cycloalkyl group, a group represented by RzCOO— or a group represented by RzOCO— (Rz represents an alkyl group or a cycloalkyl group), or a cyano group. These may be the same or different, and two R _{1 's} may be bonded to form a ring.
X represents an alkylene group, an oxygen atom or a sulfur atom.
m is the number of substituents and represents an integer of 0 to 5. The content of the repeating unit represented by the general formula (1) or (1-1) or (1-2) is 10 to 55 mol% with respect to all the repeating units in the resin (A), and The monomer according to any one of claims 1 to 6 , wherein the monomer represented by the general formula (2) is 0.7% by mass or less among the monomer components contained in the resin (A). An actinic ray-sensitive or radiation-sensitive resin composition.

In general formula (2),
L represents a lactone structure.
R ₀ represents an alkylene group, a cyclic alkylene group, or a combination thereof, and when there are a plurality of R _{0 s} , they may be the same or different.
Z represents an ether bond, an ester bond, an amide bond, a urethane bond or a urea bond, and when there are a plurality thereof, they may be the same or different.
n represents the number of repetitions and represents an integer of 1 to 5.
R represents a hydrogen atom or an alkyl group.
A represents a group of either —COO— or —CONH—. Furthermore, (C) hydrophobic resin is contained, The actinic-ray-sensitive or radiation-sensitive resin composition in any one of Claims 1-7 characterized by the above-mentioned . 9. The actinic ray-sensitive or radiation-sensitive resin composition according to claim 8, wherein the hydrophobic resin (C) has at least one group selected from the following groups (x) to (z). .
  (X) an alkali-soluble group,
  (Y) a group that decomposes by the action of an alkali developer and increases the solubility in the alkali developer;
  (Z) A group that decomposes by the action of an acid. A resist film formed from the actinic ray-sensitive or radiation-sensitive resin composition according to claim 1. The pattern formation method characterized by including the process of exposing and developing the resist film of Claim 10 .