JP5775804B2 - Actinic ray-sensitive or radiation-sensitive resin composition, actinic ray-sensitive or radiation-sensitive film using the same, pattern formation method, electronic device manufacturing method, and electronic device - Google Patents

Description

  The present invention relates to an actinic ray-sensitive or radiation-sensitive resin composition, an actinic ray-sensitive or radiation-sensitive film using the same, a pattern formation method, an electronic device manufacturing method, and an electronic device. The present invention relates to an actinic ray-sensitive or radiation-sensitive resin composition suitably used in, for example, an ultramicrolithography process such as the manufacture of VLSI and high-capacity microchips, and other photofabrication processes, and a sensitivity using the same. The present invention relates to an actinic ray-sensitive or radiation-sensitive film, a pattern formation method, an electronic device manufacturing method, and an electronic device. More specifically, the present invention relates to an actinic ray-sensitive or radiation-sensitive resin composition particularly suitable for exposure using an ArF excimer laser as an irradiation source, an actinic ray-sensitive or radiation-sensitive film using the same, and pattern formation The present invention relates to a method, an electronic device manufacturing method, and an electronic device.

  Since the resist for KrF excimer laser (248 nm), an image forming method called chemical amplification has been used as an image forming method for a resist in order to compensate for sensitivity reduction due to light absorption. An example of a positive-type chemical amplification image forming method will be described. By exposure with an excimer laser, an electron beam, extreme ultraviolet light, or the like, an acid generator in an exposed area is decomposed to generate an acid, and a post-exposure baking (PEB) : Post Exposure Bake) using an acid generated as a reaction catalyst to change an alkali-insoluble group to an alkali-soluble group and removing an exposed portion with an alkali developer.

  In this method, when the solubility of the exposed portion in the developer is low, the pattern swells, and pattern collapse and line edge roughness become a problem. Since an acid anhydride is hydrolyzed with an alkali developer to produce two carboxylic acids, a composition containing a resin having an acid anhydride structure is preferable from the viewpoint of solubility in a developer (for example, Patent Documents 1 to 3). 3). However, further improvements in performance have been demanded for compositions containing resins having an acid anhydride structure having the above-mentioned advantages as pattern miniaturization has progressed in recent years.

JP 2007-31354 A Japanese Patent No. 4315756 Japanese Patent No. 4144957

  The object of the present invention is to reduce the number of development defects (bridge defects), to reduce the pattern line width (CD) variation per PEB temperature of 1 ° C. (PEBs: PEB temperature dependence), and to focus margin (Space) in the space portion. -DOF: actinic ray-sensitive or radiation-sensitive resin composition capable of satisfying all expansion of depth of focus in a high dimension, actinic ray-sensitive or radiation-sensitive film using the same, pattern formation method, electronic device A manufacturing method and an electronic device are provided.

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

一般式（１Ａ）中、
Ｌは、単結合又は２価の連結基を表し、
Ｒ_１１は、水素原子又はアルキル基を表し、
Ｚは、環状酸無水物基を表す。
一般式（１Ｂ）中、
Ｒ_２１は、水素原子又はアルキル基を表し、
Ｒ_２２は、メチル基、エチル基、ｎ−プロピル基、イソプロピル基、ｎ−ブチル基、イソブチル基又はｓｅｃ−ブチル基を表し、
Ｒ_２３は、炭素原子とともに単環の脂環炭化水素構造を形成するのに必要な原子団を表す。
前記脂環炭化水素構造は、環を構成する炭素原子の一部が、ヘテロ原子、又は、ヘテロ原子を有する基で置換されていてもよい。
〔２〕
上記一般式（１Ｂ）で表される繰り返し単位が、下記一般式（１Ｂ’）で表される繰り返し単位である、上記〔１〕に記載の感活性光線性又は感放射線性樹脂組成物。

一般式（１Ｂ’）中、Ｒ_２１及びＲ_２２は、上記一般式（１Ｂ）における各々と同義である。
〔３〕
前記一般式（１Ａ）におけるＺは、縮合環構造を含む上記〔１〕又は〔２〕に記載の感活性光線性又は感放射線性樹脂組成物。
〔４〕
前記一般式（１Ａ）におけるＺは、下記一般式（２）で表される上記〔１〕〜〔３〕のいずれか１項に記載の感活性光線性又は感放射線性樹脂組成物。

一般式（２）中、
Ｗは、存在しないか、又は、アルキレン基、酸素原子、若しくは硫黄原子を表し、Ｗが複数で存在する場合、複数のＷは同一であっても異なっていてもよい。
ｐは、１以上の整数を表す。
ｑは、０〜２の整数を表す。
ｍ_１及びｍ_２は、それぞれ独立に０〜２の整数を表す。
Ｒは、１価の置換基を表し、ｓは０以上の整数を表す。Ｒが複数で存在する場合、複数のＲは同一であっても異なっていてもよい。
＊は、前記一般式（１Ａ）のＬに接続する結合手である。
〔５〕
前記一般式（１Ａ）におけるＺは、下記一般式（３）で表される上記〔１〕〜〔３〕のいずれか１項に記載の感活性光線性又は感放射線性樹脂組成物。

一般式（３）中、
ｐ’は、１又は２を表す。
Ｒは、１価の置換基を表し、ｓは０以上の整数を表す。Ｒが複数で存在する場合、複数のＲは同一であっても異なっていてもよい。
＊は、前記一般式（１Ａ）のＬに接続する結合手である。
〔６〕
前記一般式（１Ａ）におけるＬが２価の連結基である、上記〔１〕〜〔５〕のいずれか１項に記載の感活性光線性又は感放射線性樹脂組成物。
〔７〕
前記Ｌとしての２価の連結基が、少なくとも１つの酸素原子を含む２価の連結基である、上記〔６〕に記載の感活性光線性又は感放射線性樹脂組成物。
〔８〕
前記一般式（１Ａ）で表される繰り返し単位の含有量が前記樹脂（Ａ）の全繰り返し単位に対して５〜５０ｍｏｌ％であり、前記一般式（１Ｂ）で表される繰り返し単位の含有量が前記樹脂（Ａ）の全繰り返し単位に対して３０〜７０ｍｏｌ％である、上記〔１〕〜〔７〕のいずれか１項に記載の感活性光線性又は感放射線性樹脂組成物。
〔９〕
上記〔１〕〜〔８〕のいずれか１項に記載の感活性光線性又は感放射線性樹脂組成物を用いて形成された感活性光線性又は感放射線性膜。
〔１０〕
上記〔９〕に記載の感活性光線性又は感放射線性膜を露光することと、露光した膜を現像することとを含むパターン形成方法。
〔１１〕
前記露光が液浸露光である、上記〔１０〕に記載のパターン形成方法。
〔１２〕
上記〔１１〕に記載のパターン形成方法を含む、電子デバイスの製造方法。
尚、本発明は、上記〔１〕〜〔１２〕に係る発明であるが、以下、その他についても参考のため記載した。
〔１３〕
上記〔１２〕に記載の電子デバイスの製造方法により製造された電子デバイス。 [1]
(A) a resin having a repeating unit represented by the following general formula (1A) and a repeating unit that decomposes by the action of an acid represented by the following general formula (1B) to generate a carboxyl group; and
(B) An actinic ray-sensitive or radiation-sensitive resin composition containing a compound that generates an acid upon irradiation with actinic rays or radiation.

In general formula (1A),
L represents a single bond or a divalent linking group;
R ₁₁ represents a hydrogen atom or an alkyl group,
Z represents a cyclic acid anhydride group.
In general formula (1B),
R ₂₁ represents a hydrogen atom or an alkyl group,
R ₂₂ represents a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group or a sec-butyl group,
R ₂₃ represents an atomic group necessary for forming a monocyclic alicyclic hydrocarbon structure together with a carbon atom.
In the alicyclic hydrocarbon structure, a part of carbon atoms constituting the ring may be substituted with a hetero atom or a group having a hetero atom.
[2]
The actinic ray-sensitive or radiation-sensitive resin composition according to the above [1], wherein the repeating unit represented by the general formula (1B) is a repeating unit represented by the following general formula (1B ′).

In General Formula (1B ′), R ₂₁ and R ₂₂ have the same meanings as those in General Formula (1B).
[3]
Z in the general formula (1A) is the actinic ray-sensitive or radiation-sensitive resin composition according to the above [1] or [2] containing a condensed ring structure.
[4]
Z in the general formula (1A) is the actinic ray-sensitive or radiation-sensitive resin composition according to any one of the above [1] to [3] represented by the following general formula (2).

In general formula (2),
W does not exist or represents an alkylene group, an oxygen atom, or a sulfur atom, and when a plurality of Ws are present, the plurality of Ws may be the same or different.
p represents an integer of 1 or more.
q represents the integer of 0-2.
m ₁ and m ₂ each independently represents an integer of 0 to 2.
R represents a monovalent substituent, and s represents an integer of 0 or more. When a plurality of R are present, the plurality of R may be the same or different.
* Is a bond connected to L in the general formula (1A).
[5]
Z in the general formula (1A) is the actinic ray-sensitive or radiation-sensitive resin composition according to any one of the above [1] to [3] represented by the following general formula (3).

In general formula (3),
p ′ represents 1 or 2.
R represents a monovalent substituent, and s represents an integer of 0 or more. When a plurality of R are present, the plurality of R may be the same or different.
* Is a bond connected to L in the general formula (1A).
[6]
The actinic ray-sensitive or radiation-sensitive resin composition according to any one of [1] to [5], wherein L in the general formula (1A) is a divalent linking group.
[7]
The actinic ray-sensitive or radiation-sensitive resin composition according to the above [6], wherein the divalent linking group as L is a divalent linking group containing at least one oxygen atom.
[8]
Content of the repeating unit represented by the said general formula (1A) is 5-50 mol% with respect to all the repeating units of the said resin (A), and content of the repeating unit represented by the said General formula (1B) The actinic ray-sensitive or radiation-sensitive resin composition according to any one of [1] to [7], wherein is 30 to 70 mol% with respect to all repeating units of the resin (A).
[9]
An actinic ray-sensitive or radiation-sensitive film formed using the actinic ray-sensitive or radiation-sensitive resin composition according to any one of [1] to [8].
[10]
The pattern formation method including exposing the actinic-ray-sensitive or radiation-sensitive film | membrane as described in said [9], and developing the exposed film | membrane.
[11]
The pattern forming method according to [10], wherein the exposure is immersion exposure.
[12]
The manufacturing method of an electronic device containing the pattern formation method as described in said [11].
In addition, although this invention is invention which concerns on said [1]-[12], the following was also described for reference below.
[13]
The electronic device manufactured by the manufacturing method of the electronic device as described in said [12].

  According to the present invention, the number of development defects (bridge defects) is reduced, the pattern line width (CD) fluctuation (PEBs: PEB temperature dependency) per 1 ° C. PEB temperature, and the focus margin (Space) of the space portion. -DOF: actinic ray-sensitive or radiation-sensitive resin composition capable of satisfying all expansion of depth of focus in a high dimension, actinic ray-sensitive or radiation-sensitive film using the same, pattern formation method, electronic device A manufacturing method and an electronic device can be provided.

Hereinafter, embodiments of the present invention will be described in detail.
In the description of groups and atomic groups in this specification, when substitution or non-substitution is not clearly indicated, both those having no substituent and those having a substituent are included. For example, an “alkyl group” that does not explicitly indicate substitution or unsubstituted includes not only an alkyl group having no substituent (unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group). I will do it.
In the present invention, “active light” or “radiation” means, for example, an emission line spectrum of a mercury lamp, far ultraviolet light represented by an excimer laser, extreme ultraviolet light (EUV light), X-ray, electron beam (EB), and the like. In the present invention, “light” means actinic rays or radiation.
In addition, the term “exposure” in the present specification is not limited to exposure with far ultraviolet rays such as mercury lamps and excimer lasers, X-rays, EUV light, etc., but also particle beams such as electron beams and ion beams unless otherwise specified. Drawing by is also included.

  The actinic ray-sensitive or radiation-sensitive resin composition according to the present invention has (A) a repeating unit represented by a general formula (1A) described later and a repeating unit represented by a general formula (1B) described later. Resin (hereinafter also referred to as resin (A)) and (B) a compound capable of generating an acid upon irradiation with actinic rays or radiation (hereinafter also referred to as compound (Z)). The reason for this is unknown, but the number of development defects (bridge defects) is reduced, the pattern line width (CD) fluctuation (PEBs: PEB temperature dependence) per 1 ° C PEB temperature, and the space portion All of the expansion of the focus margin (Space-DOF: Depth of Focus) can be satisfied in a high dimension.

  The actinic ray-sensitive or radiation-sensitive resin composition of the present invention is, for example, a positive composition, typically a positive resist composition. Hereinafter, each component of this composition is demonstrated.

[1] Resin (A)
(1) Repeating unit represented by general formula (1A) The resin (A) in the actinic ray-sensitive or radiation-sensitive resin composition according to the present invention has a repeating unit represented by the following general formula (1A). .

In general formula (1A),
L represents a single bond or a divalent linking group;
R ₁₁ represents a hydrogen atom or an alkyl group,
Z represents a cyclic acid anhydride group.

In the general formula (1A), the alkyl group represented by R ₁₁ is preferably a linear, branched, or cyclic alkyl group having 1 to 10 carbon atoms. The alkyl group of R ₁₁ may have a substituent, and preferred substituents include a hydroxyl group and a halogen atom. Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. R ₁₁ is preferably a hydrogen atom, a methyl group, a hydroxymethyl group, or a trifluoromethyl group, and particularly preferably a hydrogen atom or a methyl group.

Examples of the divalent linking group for L include, for example, an alkylene group, a cycloalkylene group, an arylene group, —O—, —S—, —C (═O) —, —SO ₂ —, —SO ₃ —, —N. And (Rd)-, or a divalent linking group in which a plurality of these are combined. In the formula, Rd represents a hydrogen atom or an alkyl group.
L is preferably a single bond, an alkylene group, a cycloalkylene group, —O—, —C (═O) —, —NH—, or a divalent linking group in which a plurality of these are combined. More preferably, a single bond, a divalent linking group in which an alkylene group and —O— are combined, or a divalent linking group in which an alkylene group, —C (═O) — and —O— are combined, or an alkylene group. And a divalent linking group in which —C (═O) — and —NH— are combined. More preferably, it is a single bond, a divalent linking group in which an alkylene group and —O— are combined, or a divalent linking group in which an alkylene group and —C (═O) —O— are combined.
When L contains an alkylene group, the alkylene group contained in L is preferably linked to an oxygen atom adjacent to L in the ester group of the general formula (1A).
The alkylene group, cycloalkylene group, and arylene group may have a substituent. Examples of the substituent include an alkyl group, a cycloalkyl group, an alkoxy group, an alkoxycarbonyl group, —OH, —NH ₂ , —SO ₂ NH ₂ , —N (Rd 2) SO ₂ (Rd 3). Rd2 and Rd3 are each independently a hydrogen atom or an alkyl group. The alkylene group may be linear or branched, preferably has 1 to 20 carbon atoms, more preferably has 1 to 10 carbon atoms, and still more preferably has 1 to 5 carbon atoms. The cycloalkylene group preferably has 3 to 20 carbon atoms, more preferably 4 to 10 carbon atoms, and still more preferably 5 to 7 carbon atoms, forming a cyclic structure.

  L preferably represents a divalent linking group, and more preferably a divalent linking group containing at least one oxygen atom.

  Z represents a cyclic acid anhydride group that is a cyclic structure containing —CO—O—CO—, and preferably has a condensed ring structure in which a plurality of rings are linked. When Z is a condensed ring structure, the storage stability when the actinic ray-sensitive or radiation-sensitive resin composition of the present invention is stored in a solvent is improved. This is because in the case of a multicyclic structure, the acid anhydride once hydrolyzed returns to its original state by a ring-closing reaction.

The carbon atom forming the cyclic acid anhydride group as Z may have a substituent, and the substituent is preferably a monovalent substituent. Examples of the monovalent substituent include an alkyl group, a cycloalkyl group, an alkoxy group, an alkoxycarbonyl _{group, -OH, -NH 2, -SO 2} NH 2, -N (Rd4) SO 2 (Rd5) and the like. Rd4 and Rd5 are each independently a hydrogen atom or an alkyl group. As the monovalent substituent, an alkyl group, an alkoxy group, and an alkoxycarbonyl group are preferable, and an alkyl group is more preferable. The alkyl group may be linear or branched, and the number of carbon atoms is preferably 1-20, more preferably 1-10, and even more preferably 1-5. 1-10 are preferable, as for the carbon atom number of an alkoxy group, 1-5 are more preferable, and 1-3 are more preferable. When there are a plurality of Z substituents, the substituents may be linked to each other to form a ring. The number of substituents is preferably 0 to 4, more preferably 0 to 2.

  Z is more preferably a structure represented by the following general formula (2).

In general formula (2),
W does not exist or represents an alkylene group, an oxygen atom, or a sulfur atom, and when a plurality of Ws are present, the plurality of Ws may be the same or different.
p represents an integer of 1 or more.
q represents the integer of 0-2.
m ₁ and m ₂ each independently represents an integer of 0 to 2.
R represents a monovalent substituent, and s represents an integer of 0 or more. When a plurality of R are present, the plurality of R may be the same or different.
* Is a bond connected to L in the general formula (1A).

In the said General formula (2), the case where W does not exist means the case where the bridge part itself represented by "-W-" does not exist.
The alkylene group in W is preferably an alkylene group having 1 to 4 carbon atoms, and examples thereof include a methylene group, an ethylene group, and a dimethylmethylene group.
W is preferably a methylene group, an ethylene group or an oxygen atom, more preferably a methylene group or an oxygen atom, and even more preferably a methylene group.
p is preferably 1 or 2, and more preferably 1.
Both m ₁ and m ₂ are preferably 0.
q is preferably 0 or 1.
Examples of the monovalent substituent for R include the specific examples and preferred examples described above as the monovalent substituent for the substituent that the cyclic acid anhydride group as Z may have.
s is preferably an integer of 0 to 4, and more preferably an integer of 0 to 2.

  Of the structure represented by the general formula (2), the structure represented by the following general formula (3) is more preferable.

In general formula (3),
p ′ represents 1 or 2.
R represents a monovalent substituent, and s represents an integer of 0 or more. When a plurality of R are present, the plurality of R may be the same or different. Specific examples and preferred examples of R, and preferred ranges of s are the same as those described for R and s in the general formula (2).
* Is a bond connected to L in the general formula (1A).

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

  The content of the repeating unit represented by the general formula (1A) is preferably 1 to 60 mol%, more preferably 3 to 55 mol%, based on all repeating units in the resin (A). 5 to 50 mol% is more preferable.

(2) Repeating unit that decomposes by action of acid represented by general formula (1B) to generate carboxyl group Resin (A) in the actinic ray-sensitive or radiation-sensitive resin composition according to the present invention has the following general formula: It has a repeating unit represented by (1B). As a result, the resin (A) becomes a resin (hereinafter also referred to as “acid-decomposable resin”) that is decomposed by the action of an acid to increase the solubility in an alkaline developer. The resin (A) is preferably insoluble or hardly soluble in an alkali developer.

In general formula (1B),
R ₂₁ represents a hydrogen atom or an alkyl group,
R ₂₂ represents a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group or a sec-butyl group,
R ₂₃ represents an atomic group necessary for forming a monocyclic alicyclic hydrocarbon structure together with a carbon atom.
In the alicyclic hydrocarbon structure, a part of carbon atoms constituting the ring may be substituted with a hetero atom or a group having a hetero atom.

The alkyl group for R ₂₁ may have a substituent, and examples thereof include a fluorine atom and a hydroxyl group.
R ₂₁ preferably represents a hydrogen atom, a methyl group, a trifluoromethyl group or a hydroxymethyl group.
R ₂₂ is preferably a methyl group, an ethyl group, an n-propyl group, or an isopropyl group, and more preferably a methyl group or an ethyl group.
The monocyclic alicyclic hydrocarbon structure formed by R ₂₃ together with the carbon atom is preferably a 3- to 8-membered ring, and more preferably a 5- or 6-membered ring.
In the monocyclic alicyclic hydrocarbon structure formed by R ₂₃ together with the carbon atom, examples of the hetero atom that can substitute a part of the carbon atoms constituting the ring include an oxygen atom and a sulfur atom, and a group having a hetero atom Examples of the carbonyl group include a carbonyl group. However, the group having a hetero atom is preferably not an ester group (ester bond).
The monocyclic alicyclic hydrocarbon structure formed by R ₂₃ together with the carbon atom is preferably formed only from the carbon atom and the hydrogen atom.

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

In General Formula (1B ′), R ₂₁ and R ₂₂ have the same meanings as those in General Formula (1B).

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

  The content of the repeating unit having the structure represented by the general formula (1B) is preferably 20 to 80 mol% with respect to all repeating units in the resin (A), and preferably 25 to 75 mol%. Is more preferable, and it is further more preferable that it is 30-70 mol%.

  As mentioned above, although the repeating unit represented by General formula (1A) and the repeating unit represented by General formula (1B) which resin (A) has was demonstrated, inclusion of the repeating unit represented by General formula (1A) The amount is 5 to 50 mol% with respect to all the repeating units of the resin (A), and the content of the repeating unit represented by the general formula (1B) is 30 with respect to all the repeating units of the resin (A). It is preferable that it is -70 mol%.

(3) The repeating unit which is different from the repeating unit represented by the general formula (1B) and decomposes by the action of an acid to generate an alkali-soluble group. The resin (A) is further represented by the above general formula (1B). It may have a repeating unit (1C) that is decomposed by the action of an acid and generates an alkali-soluble group, which is different from the repeating unit. The repeating unit (1C) that generates an alkali-soluble group (hereinafter also referred to as an acid-decomposable group) by the action of an acid has a structure in which the alkali-soluble group is protected by a group that decomposes and leaves by the action of an acid. It is preferable to have.

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 groups), 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.
As the acid eliminable group, there can be, for _{example, -C (R 36) (R} 37) (R 38), - C (R 36) (R 37) (OR 39), - C (R 01) (R 02 ) (OR ₃₉ ) and the like.
In the formula, R _{36 to} R ₃₉ each independently represents an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, or an alkenyl group. R ₃₆ and R ₃₇ may be bonded to each other to form a ring.
R ₀₁ and R ₀₂ each independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group or an alkenyl group.

  The acid-decomposable group is preferably a cumyl ester group, an enol ester group, an acetal ester group, a tertiary alkyl ester group or the like. More preferably, it is a tertiary alkyl ester group.

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

In General Formula (AI), Xa ₁ represents a hydrogen atom, a methyl group which may have a substituent, or a group represented by —CH ₂ —R ₉ . R ₉ represents a hydroxy group or a monovalent organic group, and examples of the monovalent organic group include an alkyl group having 5 or less carbon atoms and an acyl group having 5 or less carbon atoms, preferably 3 or less carbon atoms. And more preferably a methyl group. Xa ₁ preferably represents a hydrogen atom, a methyl group, a trifluoromethyl group or a hydroxymethyl group.
T represents a single bond or a divalent linking group.
Rx _{1 to} Rx ₃ each independently represents an alkyl group (straight or branched) or a cycloalkyl group (monocyclic or polycyclic). Two of Rx _{1 to} Rx ₃ may combine to form a cycloalkyl group (monocyclic or polycyclic).
However, two are bonded in Rx ₁ to Rx _3, when forming a monocyclic cycloalkyl group, T is a divalent linking group.

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

  5-40 mol% is preferable with respect to all the repeating units in resin (A), and, as for content of a repeating unit (1C), it is more preferable that it is 10-35 mol%. More preferably, it is 15-30 mol%.

  Although the preferable specific example of a repeating unit (1C) is shown below, this invention is not limited to this.

In specific examples, Rx and Xa ₁ represent a hydrogen atom, CH ₃ , CF ₃ , or CH ₂ OH. Rxa and Rxb each represents an alkyl group having 1 to 4 carbon atoms. Z represents a substituent containing a polar group, and when there are a plurality of Z, the plurality of Z may be the same as or different from each other. p represents 0 or a positive integer. Z includes, for example, a hydroxyl group, a cyano group, an amino group, an alkylamide group or a sulfonamide group itself, or a linear or branched alkyl group or cycloalkyl group having at least one of these, and an alkyl having a hydroxyl group It is preferably a group, more preferably a branched alkyl group having a hydroxyl group. As the branched alkyl group, an isopropyl group is particularly preferable.

(4) Repeating unit containing lactone structure, sultone structure, and / or cyano group The resin (A) is at least selected from the group consisting of a lactone structure, a sultone structure (cyclic sulfonate structure) and a cyano group. You may have a repeating unit containing 1 type.
First, the repeating unit containing a lactone structure and the repeating unit containing a sultone structure will be described.
The lactone structure or sultone structure is preferably a 5- to 7-membered lactone structure or sultone structure, and other ring structures in the form of forming a bicyclo structure or a spiro structure in the 5- to 7-membered lactone structure or sultone structure. A condensed ring is preferred. It is more preferable to have a repeating unit having a lactone structure or a sultone structure represented by any of the following general formulas (LC1-1) to (LC1-17) and (SL1-1) to (SL1-3). A lactone structure or a sultone structure may be directly bonded to the main chain. Preferable lactone structure or sultone structure is (LC1-1), (LC1-4), (LC1-5), (LC1-8), and more preferably (LC1-4). By using a specific lactone structure or sultone structure, pattern collapse suppression, LER, and the like are improved.

The lactone structure portion or the sultone structure portion may or may not have a substituent (Rb ₂ ). Preferred substituents (Rb ₂ ) include an alkyl group having 1 to 8 carbon atoms, a cycloalkyl group having 4 to 7 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, an alkoxycarbonyl group having 2 to 8 carbon atoms, and a carboxyl group. , Halogen atom, hydroxyl group, cyano group, acid-decomposable group and the like. More preferably, they are a C1-C4 alkyl group, a cyano group, and an acid-decomposable group. n ₂ represents an integer of 0-4. When n ₂ is 2 or more, a plurality of substituents (Rb ₂ ) may be the same or different, and a plurality of substituents (Rb ₂ ) may be bonded to form a ring. .
In one embodiment, the resin (A) preferably contains a repeating unit represented by the following general formula (AII ′) as a repeating unit having a lactone structure or a sultone structure.

In general formula (AII ′),
Rb ₀ represents a hydrogen atom, a halogen atom or an alkyl group having 1 to 4 carbon atoms. Preferable substituents that the alkyl group of Rb ₀ may have include a hydroxyl group and a halogen atom. Examples of the halogen atom for Rb ₀ include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. Rb ₀ is preferably a hydrogen atom, a methyl group, a hydroxymethyl group or a trifluoromethyl group, and particularly preferably a hydrogen atom or a methyl group.
V represents a monovalent organic group containing a lactone structure or a sultone structure. Preferably, it represents a group having a structure represented by any of the general formulas (LC1-1) to (LC1-17) and (SL1-1) to (SL1-3) shown above.

  Specific examples of the repeating unit having a sultone structure represented by the general formula (AII ′) are shown below, but the present invention is not limited thereto.

  Specific examples of the repeating unit having a lactone group represented by formula (AII ′) are shown below, but the present invention is not limited thereto. In the following formulae, Me represents a methyl group.

  Particularly preferred repeating units having a lactone group represented by general formula (AII ′) include the following repeating units. By selecting an optimal lactone group, the performances of the number of development defects (bridge defects), PEB temperature dependency, and focus margin of the space portion are improved.

  In another embodiment, the resin (A) preferably contains a repeating unit represented by the following general formula (III) as a repeating unit having a lactone structure or a sultone structure.

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

Or urea bond

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

R ₈ represents a monovalent organic group having a lactone structure or a sultone structure.
n is the repeating number of the structure represented by —R ₀ —Z—, represents an integer of 1 to 5, and is preferably 1.
R ₇ represents a hydrogen atom, a halogen atom or an alkyl group.
The alkylene group and cycloalkylene group represented by R ₀ may have a substituent.
Z is preferably an ether bond or an ester bond, and particularly preferably an ester bond.
The alkyl group for R ₇ is preferably an alkyl group having 1 to 4 carbon atoms, more preferably a methyl group or an ethyl group, and particularly preferably a methyl group. The alkylene group of R ₀ , the cycloalkylene group, and the alkyl group in R ₇ may each be substituted. Examples of the substituent include a halogen atom such as a fluorine atom, a chlorine atom, and a bromine atom, a mercapto group, and a hydroxy group. Group, methoxy group, ethoxy group, isopropoxy group, t-butoxy group, alkoxy group such as benzyloxy group, acyl group such as acetyl group and propionyl group, and acetoxy group. R ₇ is preferably a hydrogen atom, a methyl group, a trifluoromethyl group, or a hydroxymethyl group.
A preferable chain alkylene group in R ₀ is preferably a chain alkylene having 1 to 10 carbon atoms, more preferably 1 to 5 carbon atoms, and examples thereof include a methylene group, an ethylene group, and a propylene group. . Preferred cycloalkylene is cycloalkylene 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 substituent having a lactone structure or a sultone structure represented by R ₈ is not limited as long as it has a lactone structure. Specific examples thereof include the general formulas (LC1-1) to (LC1-17) described above. The lactone structure or the sultone structure represented by (SL1-1) to (SL1-3) is exemplified, and the structure represented by (LC1-4) is particularly preferable. In addition, n ₂ in (LC1-1) to (LC1-17) and (SL1-1) to (SL1-3) is more preferably 2 or less.
R ₈ is preferably a monovalent organic group having an unsubstituted lactone structure or a sultone structure, or a monovalent organic group having a lactone structure or a sultone structure having a methyl group, a cyano group or an alkoxycarbonyl group as a substituent. A monovalent organic group having a lactone structure (cyanolactone) or a sultone structure (cyanosultone) having a cyano group as a substituent is more preferable.

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

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

  In order to enhance the effect of the present invention, two or more repeating units having a lactone group or a sultone group can be used in combination. In this case, it is preferable to use two or more types of lactone or sultone repeating units selected from general formula (III), and in particular, two types from lactone or sultone repeating units in which n is 1 in general formula (III). The above is preferably selected and used in combination.

Next, the repeating unit containing a cyano group will be described.
The repeating unit containing a cyano group contributes to suppressing pattern collapse and improving line edge roughness, like the repeating unit having a lactone structure or a sultone structure.
The repeating unit containing a cyano group is preferably a repeating unit having an alicyclic hydrocarbon structure substituted with a cyano group. As the alicyclic hydrocarbon structure, an adamantyl group, a diamantyl group, and a norbornane group are preferable. In the following formulae, Ra represents a hydrogen atom or an alkyl group (preferably an alkyl group having 1 to 4 carbon atoms). The alkyl group may have a substituent, and examples of such a substituent include a hydroxyl group and a halogen atom. Examples of the halogen atom for Ra include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. Ra is preferably a hydrogen atom, a methyl group, a hydroxymethyl group, or a trifluoromethyl group, and particularly preferably a hydrogen atom or a methyl group.

  In this invention, it is preferable that the repeating unit containing at least any one of the above-mentioned lactone structure, sultone structure, or cyano group is represented by any one of the following general formulas (II-1) to (II-4).

In the general formulas (II-1) to (II-4),
R ₂₁ , R ₂₂ , R ₂₃ and R ₂₄ each independently represent a monovalent substituent.
Rb ₁ , Rb ₂ , Rb ₃ and Rb ₄ each independently represent a hydrogen atom or an alkyl group.
W ₁ , W ₂ and W ₄ each independently represent an alkylene group or an oxygen atom.
Z ₂₁ , Z ₂₂ , Z ₂₃ and Z ₂₄ each independently represent a single bond or a divalent linking group.
l _II-1 represents an integer of 0 to 8,
l _II-2 represents an integer of 0 to 8,
l _II-3 represents an integer of 0 to 9,
l _II-4 represents an integer of 0-6.

Examples of the monovalent substituent for R ₂₁ , R ₂₂ , R ₂₃ and R ₂₄ include an alkyl group, a cycloalkyl group, an alkoxycarbonyl group, a cyano group, a hydroxyl group or an alkoxy group. Two or more of R ₂₁ , R ₂₂ , R ₂₃ or R ₂₄ may be bonded to form a ring.
The alkyl group for R ₂₁ , R ₂₂ , R ₂₃ and R ₂₄ 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 a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, and a cyclohexyl group. Examples of the alkoxycarbonyl group include a methoxycarbonyl group, an ethoxycarbonyl group, an n-butoxycarbonyl group, and a t-butoxycarbonyl group. Examples of the alkoxy group include a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, and a butoxy group. These groups may have a substituent, and examples of the substituent include an alkoxy group such as a hydroxy group, a methoxy group, and an ethoxy group, and a halogen atom such as a cyano group and a fluorine atom.

R ₂₁ , R ₂₂ , R ₂₃ and R ₂₄ are more preferably a methyl group, a cyano group or an alkoxycarbonyl group, and even more preferably a cyano group.
Rb ₁ , Rb ₂ , Rb ₃ and Rb ₄ are preferably a hydrogen atom, a methyl group or a trifluoromethyl group, and more preferably a hydrogen atom or a methyl group.
W ₁ , W ₂ and W ₄ are preferably an alkylene group having 1 to 3 carbon atoms (for example, a methylene group or an ethylene group) or an oxygen atom, and more preferably a methylene group or an oxygen atom.
Examples of the divalent linking group for Z ₂₁ , Z ₂₂ , Z ₂₃ and Z ₂₄ include an alkylene group, a divalent linking group having a monocyclic or polycyclic cycloalkyl structure, an ether bond, an ester bond, a carbonyl group, Or it is preferable that it is a bivalent coupling group which combined these.
Z ₂₁ , Z ₂₂ , Z ₂₃ and Z ₂₄ are more preferably a single bond or a divalent linking group represented by —Z _x —CO ₂ —.
Z _x is a linear or branched alkylene group, a monocyclic or polycyclic cycloalkylene group, preferably a methylene group, an ethylene group, a cyclohexylene group, an adamantylene group or a norbornylene group.

l _II-1 , l _II-2 and l _II-3 are preferably integers of 0 to 4, and more preferably 0 or 1.
l _II-4 is preferably an integer of 0 to 2, and more preferably 0.

  The content of repeating units containing any one of a lactone structure, a sultone structure, and a cyano group is preferably 5 to 50 mol%, more preferably 5 to the total repeating units in the resin when a plurality of types are contained. It is -45 mol%, More preferably, it is 5-40 mol%.

(5) Repeating unit having a hydroxyl group The resin (A) may further contain a repeating unit having a hydroxyl group. This improves the substrate adhesion and developer compatibility. The repeating unit having a hydroxyl group is preferably a repeating unit having an alicyclic hydrocarbon structure substituted with a hydroxyl group, and preferably has no acid-decomposable group. The alicyclic hydrocarbon structure in the alicyclic hydrocarbon structure substituted with a hydroxyl group is preferably an adamantyl group, a diamantyl group, or a norbornane group. As the alicyclic hydrocarbon structure substituted with a preferred hydroxyl group, partial structures represented by the following general formulas (VIIa) to (VIIc) are preferable.

In general formulas (VIIa) to (VIIc),
R ₂ c to R ₄ c each independently represents a hydrogen atom or a hydroxyl group. However, at least one of R ₂ c to R ₄ c represents a hydroxyl group. Preferably, one or two of R ₂ c to R ₄ c are a hydroxyl group and the rest are hydrogen atoms. In general formula (VIIa), more preferably, _two of R ₂ c to R ₄ c are a hydroxyl group and the rest are hydrogen atoms.

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

In the general formulas (AIIa) to (AIIc),
R ₁ c represents a hydrogen atom, a methyl group, a trifluoromethyl group, or a hydroxymethyl group.
R ₂ c to R ₄ c is a general formula (VIIa) ~ same meanings as in _R 2 c to R ₄ c to (VIIc).
The resin (A) may or may not contain a repeating unit having a hydroxyl group. However, when it is contained, the content of the repeating unit having a hydroxyl group is all repeating units in the resin (A). On the other hand, 5-30 mol% is preferable, More preferably, it is 5-20 mol%, More preferably, it is 10-15 mol%.

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

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

  The resin (A) may or may not contain a repeating unit having an alkali-soluble group, but when it is contained, the content of the repeating unit having an alkali-soluble group is in the resin (A). 1 to 15 mol% is preferable, more preferably 3 to 10 mol%, still more preferably 4 to 8 mol%, based on all repeating units.

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 .

(7) Repeating unit having alicyclic hydrocarbon structure having no polar group Resin (A) further has an alicyclic hydrocarbon structure having no polar group (for example, the alkali-soluble group, hydroxyl group, cyano group, etc.). And having a repeating unit that does not exhibit acid decomposability. Examples of such a repeating unit include a repeating unit represented by the general formula (IV).

In general formula (IV), R ₅ represents a hydrocarbon group having at least one cyclic structure and having no polar group.
Ra represents a hydrogen atom, an alkyl group, or a —CH ₂ —O—Ra ₂ group. In the formula, Ra ₂ represents a hydrogen atom, an alkyl group, or an acyl group. Ra is preferably a hydrogen atom, a methyl group, a hydroxymethyl group or a trifluoromethyl group, particularly preferably a hydrogen atom or a methyl group.
The cyclic structure possessed by R ₅ includes a monocyclic hydrocarbon group and a polycyclic hydrocarbon group. Examples of the monocyclic hydrocarbon group include cycloalkenyl having 3 to 12 carbon atoms such as cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclooctyl group and the like, and cycloalkyl groups having 3 to 12 carbon atoms and cyclohexenyl group. Groups. Preferable monocyclic hydrocarbon groups are monocyclic hydrocarbon groups having 3 to 7 carbon atoms, and more preferable examples include a cyclopentyl group and a cyclohexyl group.

  The polycyclic hydrocarbon group includes a ring assembly hydrocarbon group and a bridged cyclic hydrocarbon group, and examples of the ring assembly hydrocarbon group include a bicyclohexyl group and a perhydronaphthalenyl group. As the bridged cyclic hydrocarbon ring, for example, bicyclic such as pinane, bornane, norpinane, norbornane, bicyclooctane ring (bicyclo [2.2.2] octane ring, bicyclo [3.2.1] octane ring, etc.) Hydrocarbon rings and tricyclic hydrocarbon rings such as homobredan, adamantane, tricyclo [5.2.1.02,6] decane, tricyclo [4.3.1.12,5] undecane ring, tetracyclo [4. 4.0.12, 5.17, 10] dodecane, and tetracyclic hydrocarbon rings such as perhydro-1,4-methano-5,8-methanonaphthalene ring. The bridged cyclic hydrocarbon ring includes a condensed cyclic hydrocarbon ring such as perhydronaphthalene (decalin), perhydroanthracene, perhydrophenanthrene, perhydroacenaphthene, perhydrofluorene, perhydroindene, perhydroindene. A condensed ring in which a plurality of 5- to 8-membered cycloalkane rings such as a phenalene ring are condensed is also included.

Preferred examples of the bridged cyclic hydrocarbon ring include a norbornyl group, an adamantyl group, a bicyclooctanyl group, a tricyclo [5, 2, 1, 02, 6] decanyl group, and the like. More preferable examples of the bridged cyclic hydrocarbon ring include a norbornyl group and an adamantyl group.
These alicyclic hydrocarbon groups may have a substituent. Preferred examples of the substituent include a halogen atom, an alkyl group, a hydroxyl group substituted with a hydrogen atom, and an amino group substituted with a hydrogen atom. It is done. Preferred halogen atoms include bromine, chlorine and fluorine atoms, and preferred alkyl groups include methyl, ethyl, butyl and t-butyl groups. The alkyl group described above may further have a substituent, and examples of the substituent that may further include a halogen atom, an alkyl group, a hydroxyl group substituted with a hydrogen atom, and an amino group substituted with a hydrogen atom. The group can be mentioned.
Examples of the group in which the hydrogen atom is substituted include an alkyl group, a cycloalkyl group, an aralkyl group, a substituted methyl group, a substituted ethyl group, an alkoxycarbonyl group, and an aralkyloxycarbonyl group. Preferred alkyl groups include alkyl groups having 1 to 4 carbon atoms, preferred substituted methyl groups include methoxymethyl, methoxythiomethyl, benzyloxymethyl, t-butoxymethyl, 2-methoxyethoxymethyl groups, and preferred substituted ethyl groups. 1-ethoxyethyl, 1-methyl-1-methoxyethyl, preferred acyl groups include formyl, acetyl, propionyl, butyryl, isobutyryl, valeryl, pivaloyl groups, etc., aliphatic acyl groups having 1 to 6 carbon atoms, alkoxycarbonyl Examples of the group include an alkoxycarbonyl group having 1 to 4 carbon atoms.

The resin (A) has an alicyclic hydrocarbon structure having no polar group, and may or may not contain a repeating unit that does not exhibit acid decomposability. The content of is preferably from 1 to 20 mol%, more preferably from 2 to 15 mol%, based on all repeating units in the resin (A).
Specific examples of the repeating unit having an alicyclic hydrocarbon structure having no polar group and not exhibiting acid decomposability are shown below, but the present invention is not limited thereto.
In the formula, Ra represents H, CH ₃ , CH ₂ OH, or CF ₃ .

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

Examples of such repeating units include, but are not limited to, repeating units composed of the following monomers.
As a result, the performance required for the resin (A), in particular, (1) solubility in coating solvents, (2) film-forming properties (glass transition point), (3) alkali developability, (4) film slipping (familiarity) Fine adjustments such as (selection of aqueous and alkali-soluble groups), (5) adhesion of unexposed portions to the substrate, and (6) dry etching resistance are possible.

As such a monomer, for example, a compound having one addition polymerizable unsaturated bond selected from acrylic acid esters, methacrylic acid esters, acrylamides, methacrylamides, allyl compounds, vinyl ethers, vinyl esters, etc. Etc.
In addition, it may be a repeating unit obtained by copolymerizing an addition-polymerizable unsaturated compound that can be copolymerized with the monomers constituting the above various repeating units.
In the resin (A), the content molar ratio of each repeating unit is the resist dry etching resistance, standard developer suitability, substrate adhesion, resist profile, and resolution, heat resistance, and sensitivity, which are general required performance of the resist. It is set appropriately in order to adjust etc.

When the composition of the present invention is used in ArF exposure, the resin (A) preferably has substantially no aromatic group from the viewpoint of transparency to ArF light. More specifically, the repeating unit having an aromatic group is preferably 5% by mole or less, more preferably 3% by mole or less, and more ideally, during the entire repetition of the resin (A). More preferably, it is 0 mol%, that is, it does not have a repeating unit having an aromatic group.
The resin (A) preferably has a monocyclic or polycyclic alicyclic hydrocarbon structure.
In addition, it is preferable that resin (A) does not contain a fluorine atom and a silicon atom from a compatible viewpoint with the hydrophobic resin (HR) mentioned later.

  The resin (A) is preferably one in which all of the repeating units are composed of (meth) acrylate repeating units. In this case, all of the repeating units are methacrylate repeating units, all of the repeating units are acrylate repeating units, or all of the repeating units are methacrylate repeating units and acrylate repeating units. Although it can be used, the acrylate-based repeating unit is preferably 50 mol% or less of the total repeating units.

  Resin (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 heating is performed, and a solution of the monomer species and the initiator is dropped into the heating solvent over 1 to 10 hours. The dropping polymerization method is added, and the dropping polymerization method is preferable. Examples of the reaction solvent include ethers such as tetrahydrofuran, 1,4-dioxane, diisopropyl ether, ketones such as methyl ethyl ketone and methyl isobutyl ketone, ester solvents such as ethyl acetate, amide solvents such as dimethylformamide and dimethylacetamide, Furthermore, the solvent which melt | dissolves the composition of this invention like the below-mentioned propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, and cyclohexanone is mentioned. More preferably, the polymerization is performed using the same solvent as the solvent used in the actinic ray-sensitive or radiation-sensitive resin composition of the present invention. Thereby, the generation of particles during storage can be suppressed.

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

  The weight average molecular weight of the resin (A) is preferably 1,000 to 200,000, more preferably 2,000 to 20,000, and still more preferably 3,000, when converted into polystyrene values by the GPC method. -18,000, particularly preferably 3,000-16,000. By setting the weight average molecular weight to 1,000 to 200,000, deterioration of heat resistance and dry etching resistance can be prevented, and developability is deteriorated, and viscosity is increased and film forming property is lowered. Can be prevented.

  The dispersity (molecular weight distribution) is usually 1.0 to 3.0, preferably 1.0 to 2.6, more preferably 1.0 to 2.0, and particularly preferably 1.4 to 2.0. Those in the range are used. The smaller the molecular weight distribution, the better the resolution and the resist shape, and the smoother the side wall of the resist pattern, the better the roughness.

  In the actinic ray-sensitive or radiation-sensitive resin composition of the present invention, the blending amount of the resin (A) is preferably 30 to 99% by mass, more preferably 60 to 95% by mass in the total solid content of the composition. . Moreover, resin (A) may be used by 1 type and may be used together. In addition, you may use other resin other than resin (A) together in the range which does not impair the effect of this invention. Examples of the resin other than the resin (A) include an acid-decomposable resin that may contain a repeating unit that can be contained in the resin (A), and other known acid-decomposable resins. .

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

As the acid generator, photo-initiator of photocation polymerization, photo-initiator of photo-radical polymerization, photo-decoloring agent of dyes, photo-discoloring agent, irradiation of actinic ray or radiation used for micro resist, etc. The known compounds that generate an acid and mixtures thereof can be appropriately selected and used.
Examples include diazonium salts, phosphonium salts, sulfonium salts, iodonium salts, imide sulfonates, oxime sulfonates, diazodisulfones, disulfones, and o-nitrobenzyl sulfonates.

  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 to 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. Examples of the group formed by combining two of R _{201 to} R ₂₀₃ include an alkylene group (eg, butylene group, pentylene group).
Z ⁻ represents a non-nucleophilic anion.

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

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

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

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

  The aliphatic moiety in the aliphatic sulfonate anion and aliphatic carboxylate anion may be an alkyl group or a cycloalkyl group, preferably an alkyl group having 1 to 30 carbon atoms and a cyclohexane having 3 to 30 carbon atoms. It is an alkyl group. For example, 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, etc. Can do.

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

  The alkyl group, cycloalkyl group and aryl group 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 1 to 15 carbon atoms), a Alkyloxysulfonyl 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 Examples include a 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) and a cycloalkyl group (preferably C3-C15) can further be mentioned as a substituent.

  The aralkyl group in the aralkyl carboxylate anion is preferably an aralkyl group having 7 to 12 carbon atoms, such as a benzyl group, a phenethyl group, a naphthylmethyl group, a naphthylethyl group, and a naphthylbutyl group.

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 this substituent include the same halogen atom, alkyl group, cycloalkyl group, alkoxy group, alkylthio group and the like as those in the aromatic sulfonate anion.
Examples of the sulfonylimide anion include saccharin anion.

The alkyl group in the bis (alkylsulfonyl) imide anion and tris (alkylsulfonyl) methide anion is preferably an alkyl group having 1 to 5 carbon atoms, for example, methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, isobutyl. Group, sec-butyl group, pentyl group, neopentyl group and the like. 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 at least 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, an alkyl group Is preferably a bis (alkylsulfonyl) imide anion substituted with a fluorine atom, or a tris (alkylsulfonyl) methide anion wherein an alkyl group is substituted with a fluorine atom. 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.

  The acid generator is preferably a compound that generates a sulfonic acid represented by the following general formula (Iz). Since the sulfonic acid represented by the general formula (Iz) has a cyclic organic group, the resolution and roughness performance can be further improved for the same reason as described above.

  Therefore, when the acid generator is, for example, a compound represented by the general formula (ZI) or (ZII), the aromatic sulfonate anion is an anion that generates an acid represented by the following formula (Iz). Preferably there is.

In formula (Iz), Xf each independently represents a fluorine atom or an alkyl group substituted with at least one fluorine atom.
R ¹ and R ² each independently represent a hydrogen atom, a fluorine atom or an alkyl group, and when there are a plurality of R ¹ and R ² , they may be the same or different.
L represents a divalent linking group, and when there are a plurality of L, L may be the same or different.
A represents a cyclic organic group.
x represents an integer of 1 to 20, y represents an integer of 0 to 10, and z represents an integer of 0 to 10.

General formula (Iz) will be described in more detail.
The alkyl group in the alkyl group substituted with the fluorine atom of Xf preferably has 1 to 10 carbon atoms, more preferably 1 to 4 carbon atoms. The alkyl group substituted with a fluorine atom of Xf is preferably a perfluoroalkyl group.
Xf is preferably a fluorine atom or a perfluoroalkyl group having 1 to 4 carbon atoms. Specific examples of Xf include a fluorine atom, CF ₃ , C ₂ F ₅ , C ₃ F ₇ , C ₄ F ₉ , C ₅ F ₁₁ , C ₆ F ₁₃ , C ₇ F ₁₅ , C ₈ F ₁₇ , CH ₂ CF ₃ , CH ₂ CH ₂ CF ₃ , CH ₂ C ₂ F ₅ , CH ₂ CH ₂ C ₂ F ₅ , CH ₂ C ₃ F ₇ , CH ₂ CH ₂ C ₃ F ₇ , CH ₂ C ₄ F ₉ , CH ₂ CH ₂ C ₄ F ₉ can be mentioned, among which a fluorine atom and CF ₃ are preferable. In particular, it is preferable that both Xf are fluorine atoms.

The alkyl group of R ¹ and R ² may have a substituent (preferably a fluorine atom), and preferably has 1 to 4 carbon atoms. More preferably, it is a C1-C4 perfluoroalkyl group. Specific examples of the alkyl group having a substituent for R ¹ and R ² include CF ₃ , C ₂ F ₅ , C ₃ F ₇ , C ₄ F ₉ , C ₅ F ₁₁ , C ₆ F ₁₃ , and C ₇ F _{15. , C 8 F 17, CH 2} CF 3, CH 2 CH 2 CF 3, CH 2 C 2 F 5, CH 2 CH 2 C 2 F 5, CH 2 C 3 F 7, CH 2 CH 2 C 3 F 7, CH ₂ C ₄ F ₉ and CH ₂ CH ₂ C ₄ F ₉ can be mentioned, among which CF ₃ is preferable.
R ¹ and R ² are preferably a fluorine atom or CF ₃ .

  y is preferably 0 to 4, and more preferably 0. x is preferably 1 to 8, more preferably 1 to 4, and particularly preferably 1. z is preferably 0 to 8, particularly preferably 0 to 4.

The divalent linking group for L is not particularly limited, but is —COO—, —OCO—, —CONR—, —NRCO— (where R is a hydrogen atom, an alkyl group (preferably having 1 to 6 carbon atoms) or a cycloalkyl group. (Preferably 3 to 10 carbon atoms)), —CO—, —O—, —S—, —SO—, —SO ₂ —, an alkylene group (preferably having 1 to 6 carbon atoms), a cycloalkylene group (preferably C3-10), alkenylene groups (preferably C2-6), or a linking group in which a plurality of these are combined is exemplified, and a linking group having a total carbon number of 12 or less is preferred. Among these -COO -, - OCO -, - CONR -, - NRCO -, - CO -, - O -, - SO 2 -, - COO- alkylene group -, - OCO- alkylene group -, - -CONR- alkylene group -, - NRCO- alkylene group - is more preferable, -COO -, - OCO- or -SO ₂ - is more preferable.

  The cyclic organic group of A is not particularly limited as long as it has a cyclic structure, and includes an alicyclic group, an aryl group, and a heterocyclic group (not only those having an aromatic attribute but also those having no aromatic attribute). Including, for example, a tetrahydropyran ring and a lactone ring structure).

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

  The aryl group may be monocyclic or polycyclic and includes a benzene ring, a naphthalene ring, a phenanthrene ring, and an anthracene ring. Of these, naphthalene having low absorbance is preferred from the viewpoint of light absorbance at 193 nm.

  The heterocyclic group may be monocyclic or polycyclic and includes those derived from a furan ring, a thiophene ring, a benzofuran ring, a benzothiophene ring, a dibenzofuran ring, a dibenzothiophene ring, a pyridine ring, and a decahydroisoquinoline ring. Of these, those derived from a furan ring, a thiophene ring, a pyridine ring, and a decahydroisoquinoline ring are preferred.

Moreover, a lactone structure can also be mentioned as a cyclic | annular organic group.
The cyclic organic group may have a substituent, and examples of the substituent include an alkyl group (which may be linear or branched and preferably have 1 to 12 carbon atoms), a cycloalkyl group. (A monocyclic ring, a polycyclic ring or a spiro ring may be used, preferably having 3 to 20 carbon atoms), aryl group (preferably having 6 to 14 carbon atoms), hydroxyl group, alkoxy group, ester group, amide group, urethane Group, ureido group, thioether group, sulfonamide group, sulfonic acid ester group and the like. The carbon constituting the cyclic organic group (carbon contributing to ring formation) may be a carbonyl carbon.

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

In addition, the compound which has two or more structures represented by general formula (ZI) may be sufficient. For example, at least one of R _{201 to} R ₂₀₃ of the compound represented by the general formula (ZI) is a single bond or at least one of R _{201 to} R ₂₀₃ of another compound represented by the general formula (ZI) It may be a compound having a structure bonded through a linking group.

  Further preferred examples of the (ZI) component include compounds (ZI-1), (ZI-2), (ZI-3) and (ZI-4) described below.

The compound (ZI-1) is an arylsulfonium compound in which at least one of R _{201 to} R _{203 in} the general formula (ZI) is an aryl group, that is, a compound having arylsulfonium as a cation.

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

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

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

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

The organic group not containing an 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.

As the alkyl group and cycloalkyl group of R _{201 to} R ₂₀₃ , a linear or branched alkyl group having 1 to 10 carbon atoms (for example, methyl group, ethyl group, propyl group, butyl group, pentyl group), carbon Examples thereof include cycloalkyl groups of several 3 to 10 (cyclopentyl group, cyclohexyl group, norbornyl group). More preferred examples of the alkyl group include a 2-oxoalkyl group and an alkoxycarbonylmethyl group. More preferred examples of the cycloalkyl group include a 2-oxocycloalkyl group.

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

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

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

Next, the compound (ZI-3) will be described.
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 are each independently a hydrogen atom, alkyl group, cycloalkyl group, aryl group, alkoxy group, aryloxy group, alkoxycarbonyl group, alkylcarbonyloxy group, cycloalkylcarbonyloxy group, halogen atom, hydroxyl group Represents a nitro group, an alkylthio group or an arylthio group.
R _6c and R _7c each independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, a cyano group or an aryl group.
R _x and R _y each independently represents an alkyl group, a cycloalkyl group, a 2-oxoalkyl group, a 2-oxocycloalkyl group, an alkoxycarbonylalkyl group, an allyl group, or a vinyl group.

Any two or more of R _{1c to} R _5c , R _5c and R _6c , R _6c and R _7c , R _5c and R _x , and R _x and R _y may be bonded to form a ring structure. The ring structure may include an oxygen atom, a sulfur atom, a ketone group, an ester bond, and an amide bond.
Examples of the ring structure include an aromatic or non-aromatic hydrocarbon ring, an aromatic or non-aromatic heterocycle, or a polycyclic fused ring formed by combining two or more of these rings. Examples of the ring structure include 3- to 10-membered rings, preferably 4- to 8-membered rings, and more preferably 5- or 6-membered rings.
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.
The group formed by combining R _5c and R _6c and R _5c and R _x is preferably a single bond or an alkylene group, and examples of the alkylene group include a methylene group and an ethylene group. .

Zc ^- represents a non-nucleophilic anion, in the general formula (ZI) Z ^- and include the same non-nucleophilic anion.

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 10 carbon atoms. An alkyl group (for example, a cyclopentyl group, a cyclohexyl group) can be mentioned.

The aryl group as R _{1c to} R _5c preferably has 5 to 15 carbon atoms, and examples thereof include a phenyl group and a naphthyl group.

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-C10 cyclic alkoxy group (for example, cyclopentyloxy group, cyclohexyloxy group) ).

Specific examples of the alkoxy group in the alkoxycarbonyl group as R _1c to R _5c are the same as specific examples of the alkoxy group of _R 1c _{to R 5c.}

Specific examples of the alkyl group in the alkylcarbonyloxy group and alkylthio group as R _1c to R _5c are the same as specific examples of the alkyl group of _R 1c _{to R 5c.}

Specific examples of the cycloalkyl group in the cycloalkyl carbonyl group as R _1c to R _5c are the same as specific examples of the cycloalkyl group of _R 1c _{to R 5c.}

Specific examples of the aryl group in the aryloxy group and arylthio group as R _1c to R _5c are the same as specific examples of the aryl group of _R 1c _{to R 5c.} Preferably, any one 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 carbon numbers of R _{1c to} R _5c. Is 2-15. Thereby, solvent solubility improves more and generation | occurrence | production of a particle is suppressed at the time of a preservation | save.

The ring structure that any two or more of R _{1c to} R _5c may be bonded to each other is preferably a 5-membered or 6-membered ring, particularly preferably a 6-membered ring (eg, a phenyl ring). It is done.

The ring structure which may be formed by R _5c and R _6c are bonded to each other, bonded R _5c and R _6c are each other a single bond or an alkylene group (methylene group, ethylene group, etc.) by configuring the generally Examples thereof include a carbonyl carbon atom in formula (ZI-3) and a 4-membered ring (particularly preferably a 5-6 membered ring) formed together with the carbon atom.
The aryl group as R _6c and R _7c preferably has 5 to 15 carbon atoms, and examples thereof include a phenyl group and a naphthyl group. As an aspect of R _6c and R _7c , it is preferable that both of them are alkyl groups. In particular, R _6c and R _7c are each preferably a linear or branched alkyl group having 1 to 4 carbon atoms, and particularly preferably both are methyl groups.

In addition, when R _6c and R _7c are combined to form a ring, the group formed by combining R _6c and R _7c is preferably an alkylene group having 2 to 10 carbon atoms, such as ethylene group, propylene Group, butylene group, pentylene group, hexylene group and the like. The ring formed by combining R _6c and R _7c may have a hetero atom such as an oxygen atom in the ring.

_Examples of the alkyl group and cycloalkyl group as R _x and R _y include the same alkyl group and cycloalkyl group as in R _{1c to} R _7c .

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

With respect to the alkoxy group in the alkoxycarbonylalkyl group as R _x and R _y , the same alkoxy group as in R _{1c to} R _5c can be exemplified. For the alkyl group, for example, an alkyl group having 1 to 12 carbon atoms, Preferably, a C1-C5 linear alkyl group (for example, a methyl group, an ethyl group) can be mentioned.

The allyl group as R _x and R _y is not particularly limited, but is substituted with an unsubstituted allyl group or a monocyclic or polycyclic cycloalkyl group (preferably a cycloalkyl group having 3 to 10 carbon atoms). It is preferable that it is an allyl group.

The vinyl group as R _x and R _y is not particularly limited, but is substituted with an unsubstituted vinyl group or a monocyclic or polycyclic cycloalkyl group (preferably a cycloalkyl group having 3 to 10 carbon atoms). It is preferably a vinyl group.

The ring structure which may be formed by R _5c and R _x are bonded to each other, R _5c and R _x is bonded to a single bond or an alkylene group to each other (a methylene group, an ethylene group, etc.) by configuring the generally Examples thereof include a 5-membered ring or more (particularly preferably a 5-membered ring) formed together with the sulfur atom and the carbonyl carbon atom in the formula (ZI-3).

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

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

R _{1c to} R _7c , R _x and R _y may further have a substituent. Examples of such a substituent include a halogen atom (for example, a fluorine atom), a hydroxyl group, a carboxyl group, a cyano group, and a nitro group. Group, alkyl group, cycloalkyl group, aryl group, alkoxy group, aryloxy group, acyl group, arylcarbonyl group, alkoxyalkyl group, aryloxyalkyl group, alkoxycarbonyl group, aryloxycarbonyl group, alkoxycarbonyloxy group, aryl An oxycarbonyloxy group etc. can be mentioned.

In the general formula (ZI-3), R _1c , R _2c , R _4c and R _5c each independently represent a hydrogen atom, and R _3c is a group other than a hydrogen atom, that is, an alkyl group, a cycloalkyl group, More preferably, it represents an aryl group, alkoxy group, aryloxy group, alkoxycarbonyl group, alkylcarbonyloxy group, cycloalkylcarbonyloxy group, halogen atom, hydroxyl group, nitro group, alkylthio group or arylthio group.

  Examples of the cation of the compound represented by the general formula (ZI-2) or (ZI-3) include the following specific examples.

Next, the compound (ZI-4) will be described.
The compound (ZI-4) is represented by the following general formula (ZI-4).

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

In the general formula (ZI-4), the alkyl group of R ₁₃ , R ₁₄ and R ₁₅ is linear or branched and preferably has 1 to 10 carbon atoms, and is preferably a methyl group, an ethyl group, n -A butyl group, a t-butyl group, etc. are preferable.

Examples of the cycloalkyl group represented by R ₁₃ , R ₁₄ and R ₁₅ include monocyclic or polycyclic cycloalkyl groups (preferably cycloalkyl groups having 3 to 20 carbon atoms), and in particular, cyclopropyl, cyclopentyl, cyclohexyl, Cycloheptyl 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, and is preferably a methoxy group, an ethoxy group, an n-propoxy group, an n-butoxy group, or the like.

The alkoxycarbonyl group for R ₁₃ and R ₁₄ is linear or branched and preferably has 2 to 11 carbon atoms, and is preferably a methoxycarbonyl group, an ethoxycarbonyl group, an n-butoxycarbonyl group, or the like.
Examples of the group having a cycloalkyl group of R ₁₃ and R ₁₄ include a group having a monocyclic or polycyclic cycloalkyl group (preferably a cycloalkyl group having 3 to 20 carbon atoms). Examples thereof include a polycyclic cycloalkyloxy group and an alkoxy group having a monocyclic or polycyclic cycloalkyl group. These groups may further have a substituent.

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

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

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

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

The alkylsulfonyl group and cycloalkylsulfonyl group of R ₁₄ are linear, branched, or cyclic, and preferably those having 1 to 10 carbon atoms, such as methanesulfonyl group, ethanesulfonyl group, n-propanesulfonyl. Group, n-butanesulfonyl group, cyclopentanesulfonyl group, cyclohexanesulfonyl group and the like are preferable.

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

Examples of the alkoxy group include methoxy group, ethoxy group, n-propoxy group, i-propoxy group, n-butoxy group, 2-methylpropoxy group, 1-methylpropoxy group, t-butoxy group, cyclopentyloxy group, Examples thereof include a linear, branched or cyclic alkoxy group having 1 to 20 carbon atoms such as a cyclohexyloxy group.
Examples of the alkoxyalkyl group include straight chain having 2 to 21 carbon atoms such as methoxymethyl group, ethoxymethyl group, 1-methoxyethyl group, 2-methoxyethyl group, 1-ethoxyethyl group, and 2-ethoxyethyl group. Examples thereof include a chain, branched or cyclic alkoxyalkyl group.

Examples of the alkoxycarbonyl group include methoxycarbonyl group, ethoxycarbonyl group, n-propoxycarbonyl group, i-propoxycarbonyl group, n-butoxycarbonyl group, 2-methylpropoxycarbonyl group, 1-methylpropoxycarbonyl group, t Examples thereof include linear, branched or cyclic alkoxycarbonyl groups having 2 to 21 carbon atoms such as butoxycarbonyl group, cyclopentyloxycarbonyl group, cyclohexyloxycarbonyl and the like.
Examples of the alkoxycarbonyloxy group include methoxycarbonyloxy group, ethoxycarbonyloxy group, n-propoxycarbonyloxy group, i-propoxycarbonyloxy group, n-butoxycarbonyloxy group, t-butoxycarbonyloxy group, and cyclopentyloxy. Examples thereof include linear, branched or cyclic alkoxycarbonyloxy groups having 2 to 21 carbon atoms such as carbonyloxy group and cyclohexyloxycarbonyloxy.

As a ring structure that two R ₁₅ may be bonded to each other, a 5-membered or 6-membered ring formed by two R ₁₅ together with a sulfur atom in the general formula (ZI-4) is particularly preferable. Includes a 5-membered ring (that is, a tetrahydrothiophene ring), and may be condensed with an aryl group or a cycloalkyl group. The ring structure may have a substituent. Examples of the substituent include a hydroxyl group, a carboxyl group, a cyano group, a nitro group, an alkyl group, a cycloalkyl group, an alkoxy group, an alkoxyalkyl group, and an alkoxycarbonyl group. And an alkoxycarbonyloxy group. There may be a plurality of substituents for the ring structure, and they may be bonded to each other to form a ring (aromatic or non-aromatic hydrocarbon ring, aromatic or non-aromatic heterocyclic ring, or these A polycyclic fused ring formed by combining two or more rings may be formed.
R ₁₅ in the general formula (ZI-4) is preferably a methyl group, an ethyl group, a naphthyl group, a divalent group in which two R _15s are bonded to each other to form a tetrahydrothiophene ring structure together with a sulfur atom.
The substituent that R ₁₃ and R ₁₄ may have is preferably a hydroxyl group, an alkoxy group, an alkoxycarbonyl group, or a halogen atom (particularly a fluorine atom).

l is preferably 0 or 1, and more preferably 1.
As r, 0-2 are preferable.

  Specific examples of the cation of the compound represented by formula (ZI-4) in the present invention include the following.

Next, general formulas (ZII) and (ZIII) will be described.
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.
The aryl group for R _{204 to} R ₂₀₇ is preferably a phenyl group or a naphthyl group, and more preferably a phenyl group. The aryl group of R _{204 to} R ₂₀₇ 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 skeleton of the aryl group having a heterocyclic structure include pyrrole, furan, thiophene, indole, benzofuran, and benzothiophene.
The alkyl group and cycloalkyl group in R _{204 to} R ₂₀₇ are preferably a linear or branched alkyl group having 1 to 10 carbon atoms (for example, 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).
The aryl group, alkyl group, and cycloalkyl group of R _{204 to} R ₂₀₇ 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.
Specific examples of the aryl group of Ar ₃ , Ar ₄ , R ₂₀₈ , R ₂₀₉ and R ₂₁₀ are the same as the specific examples of the aryl group as R ₂₀₁ , R ₂₀₂ and R ₂₀₃ in the general formula (ZI-1). Things can be mentioned.
Specific examples of the alkyl group and cycloalkyl group represented by R ₂₀₈ , R _209, and R ₂₁₀ include specific examples of the alkyl group and cycloalkyl group represented by R ₂₀₁ , R _202, and R ₂₀₃ in the general formula (ZI-2), respectively. The same thing as an example can be mentioned.
The alkylene group of A is alkylene having 1 to 12 carbon atoms (for example, methylene group, ethylene group, propylene group, isopropylene group, butylene group, isobutylene group, etc.), and the alkenylene group of A is 2 to 2 carbon atoms. 12 alkenylene groups (for example, ethenylene group, propenylene group, butenylene group, etc.), and as the arylene group for A, arylene groups having 6 to 10 carbon atoms (for example, phenylene group, tolylene group, naphthylene group, etc.) Can be mentioned.

  The acid generator is more preferably a compound represented by the general formulas (ZI) to (ZIII). 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 a monovalent fluorine atom or an imide acid substituted with a monovalent fluorine atom or a group containing a fluorine atom. Even more preferably, it is a sulfonium salt of a fluorinated substituted alkanesulfonic acid, a fluorine substituted benzenesulfonic acid, a fluorine substituted imide acid or a fluorine substituted methide acid. The acid generator is particularly preferably a fluorinated substituted alkane sulfonic acid, a fluorinated substituted benzene sulfonic acid, or a fluorinated substituted imido acid having a generated pKa of −1 or less, and the sensitivity is improved.

  It is mentioned as one preferable embodiment of the present invention that the acid generator is represented by the following general formula (I '). By using the compound represented by the following general formula (I ′), the light transmittance of the film for exposure can be improved, which can contribute to the improvement of line edge roughness and depth of focus (DOF).

In the general formula (I ′),
X ′ represents an oxygen atom, a sulfur atom or —N (Rx ′) —.
R ₁ ′ and R ₂ ′ may be connected to each other to form a ring. Any two or more of R ₆ ′ to R ₉ ′, R ₃ ′ and R ₉ ′, R ₄ ′ and R ₅ ′, R ₅ ′ and R _x ′, R ₆ ′ and R _x ′
May be connected to each other to form a ring.
R ₁ ′ and R ₂ ′ each independently represents an alkyl group, a cycloalkyl group, or an aryl group.
R ₃ ′ to R ₉ ′ are each independently a hydrogen atom, alkyl group, cycloalkyl group, alkoxy group, alkoxycarbonyl group, acyl group, alkylcarbonyloxy group, aryl group, aryloxy group, aryloxycarbonyl group or aryl. Represents a carbonyloxy group.
R _x ′ represents a hydrogen atom, an alkyl group, a cycloalkyl group, an acyl group, an alkenyl group, an alkoxycarbonyl group, an aryl group, an arylcarbonyl group or an aryloxycarbonyl group.
Z ^- represents a non-nucleophilic anion, in the general formula (ZI) Z ^- and include the same non-nucleophilic anion.

  Among acid generators, particularly preferred examples are given below.

  The acid generator can be synthesized by a known method, for example, according to the method described in JP-A No. 2007-161707. An acid generator can be used individually by 1 type or in combination of 2 or more types. The content of the acid generator in the composition is preferably 0.1 to 35% by mass, more preferably 5 to 30% by mass, and still more preferably 10 to 25% by mass, based on the total solid content of the composition. is there.

[3] Hydrophobic resin (HR)
The actinic ray-sensitive or radiation-sensitive resin composition of the present invention is a resin containing a repeating unit having at least either a fluorine atom or a silicon atom, and is a resin (B) (hereinafter referred to as resin (A)). , Also referred to as “hydrophobic resin”).

At least one of the fluorine atom and the silicon atom in the resin (B) may be contained in the main chain of the resin or in the side chain.
When the resin (B) contains a fluorine atom, the partial structure having a fluorine atom is preferably an alkyl group having a fluorine atom, a cycloalkyl group having a fluorine atom, or an aryl group having a fluorine atom.
The alkyl group having a fluorine atom is a linear or branched alkyl group in which at least one hydrogen atom is substituted with a fluorine atom, preferably 1 to 10 carbon atoms, more preferably 1 to 4 carbon atoms, You may have the substituent of.

The cycloalkyl group having a fluorine atom is a monocyclic or polycyclic cycloalkyl group in which at least one hydrogen atom is substituted with a fluorine atom, and may further have another substituent.
Examples of the aryl group having a fluorine atom include those in which at least one hydrogen atom of an aryl group such as a phenyl group or a naphthyl group is substituted with a fluorine atom, and may further have another substituent.
As the alkyl group having a fluorine atom, the cycloalkyl group having a fluorine atom, or the aryl group having a fluorine atom, a group represented by any one of the following general formulas (F2) to (F4) is preferable. However, the present invention is not limited to this.

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

R _{57 to} R ₆₁ and R _{65 to} R ₆₇ are preferably all fluorine atoms. R ₆₂ , R ₆₃ and R ₆₈ are preferably a fluoroalkyl group (preferably having 1 to 4 carbon atoms), more preferably a perfluoroalkyl group having 1 to 4 carbon atoms. When R ₆₂ and _{R 63} is a perfluoroalkyl _group, it is preferred that _{R 64} is a hydrogen atom. 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 , 3,3-tetrafluorocyclobutyl group, perfluorocyclohexyl group and the like. Hexafluoroisopropyl group, heptafluoroisopropyl group, hexafluoro (2-methyl) isopropyl group, octafluoroisobutyl group, nonafluoro-t-butyl group and perfluoroisopentyl group are preferable, and hexafluoroisopropyl group and heptafluoroisopropyl group are preferable. Further preferred.

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

  The partial structure containing a fluorine atom may be directly bonded to the main chain, and further from the group consisting of an alkylene group, a phenylene group, an ether bond, a thioether bond, a carbonyl group, an ester bond, an amide bond, a urethane bond and a ureylene bond. You may couple | bond with the principal chain through the group selected or the group which combined these 2 or more.

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

In formulas (C-Ia) to (C-Id), R ₁₀ and R ₁₁ each independently represents a hydrogen atom, a fluorine atom or an alkyl group. The alkyl group is preferably a linear or branched alkyl group having 1 to 4 carbon atoms, which may have a substituent, and examples of the alkyl group having a substituent include a fluorinated alkyl group. it can.

W _{3 to} W ₆ each independently represents an organic group containing at least one fluorine atom. Specific examples include the atomic groups (F2) to (F4).
In addition to these, the resin (B) may have a unit as shown below as a repeating unit having a fluorine atom.

In formulas (C-II) and (C-III), R _{4 to} R ₇ each independently represents a hydrogen atom, a fluorine atom, or an alkyl group. The alkyl group is preferably a linear or branched alkyl group having 1 to 4 carbon atoms, which may have a substituent, and examples of the alkyl group having a substituent include a fluorinated alkyl group. it can.

However, at least one of R _{4 to} R ₇ represents a fluorine atom. R ₄ and R ₅ or R ₆ and R ₇ may form a ring.

W ₂ represents an organic group containing at least one fluorine atom. Specific examples include the atomic groups (F2) to (F4).
L ₂ represents a single bond or a divalent linking group. Examples of the divalent linking group include a substituted or unsubstituted arylene group, a substituted or unsubstituted alkylene group, a substituted or unsubstituted cycloalkylene group, —O—, —SO ₂ —, —CO—, —N (R )-(Wherein R represents a hydrogen atom or alkyl), —NHSO ₂ — or a divalent linking group in which a plurality of these are combined.

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

Resin (B) may contain a silicon atom.
The partial structure having a silicon atom preferably has an alkylsilyl structure (preferably a trialkylsilyl group) or a cyclic siloxane structure.
Specific examples of the alkylsilyl structure or the cyclic siloxane structure include groups represented by the following general formulas (CS-1) to (CS-3).

In general formulas (CS-1) to (CS-3),
R _{12 to} R ₂₆ each independently represent a linear or branched alkyl group (preferably having 1 to 20 carbon atoms) or a cycloalkyl group (preferably having 3 to 20 carbon atoms).
L < ₃ > -L < ₅ > represents a single bond or a bivalent coupling group. The divalent linking group includes an alkylene group, a phenylene group, an ether bond, a thioether bond, a carbonyl group, an ester bond, an amide bond, a urethane bond, or a group of two or more groups selected from the group consisting of a ureylene bond. Combinations are listed.
n represents an integer of 1 to 5. n is preferably an integer of 2 to 4.

  The repeating unit having at least either a fluorine atom or a silicon atom is preferably a (meth) acrylate-based repeating unit.

Hereinafter, although the specific example of the repeating unit which has at least any one of a fluorine atom and a silicon atom is given, this invention is not limited to this. In specific examples, X ₁ represents a hydrogen atom, —CH ₃ , —F or —CF ₃ , and X ₂ represents —F or —CF ₃ .

The resin (B) preferably has a repeating unit (b) having at least one group selected from the group consisting of the following (x) to (z).
(X) Alkali-soluble group (y) A group that decomposes by the action of an alkali developer and increases the solubility in an alkali developer (hereinafter also referred to as a polar conversion group).
(Z) A group that is decomposed by the action of an acid to increase the solubility in an alkali developer.

Examples of the repeating unit (b) include the following types.
A repeating unit (b ′) having at least one of a fluorine atom and a silicon atom and at least one group selected from the group consisting of the above (x) to (z) on one side chain
A repeating unit (b *) having at least one group selected from the group consisting of (x) to (z) and having no fluorine atom and no silicon atom
A fluorine atom and silicon on one side chain having at least one group selected from the group consisting of (x) to (z) above and on a side chain different from the side chain in the same repeating unit Repeating unit (b ″) having at least one of atoms

  The resin (B) more preferably has a repeating unit (b ′) as the repeating unit (b). That is, it is more preferable that the repeating unit (b) having at least one group selected from the group consisting of the above (x) to (z) has at least one of a fluorine atom and a silicon atom.

  When the resin (B) has a repeating unit (b *), a repeating unit having at least one of a fluorine atom and a silicon atom (a repeating unit different from the repeating units (b ′) and (b ″)). And a side chain having at least one group selected from the group consisting of (x) to (z) in the repeating unit (b ″) and at least one of a fluorine atom and a silicon atom. These side chains are preferably bonded to the same carbon atom in the main chain, that is, in a positional relationship as shown in the following formula (K1).

  In the formula, B1 represents a partial structure having at least one group selected from the group consisting of the above (x) to (z), and B2 represents a partial structure having at least one of a fluorine atom and a silicon atom.

  The group selected from the group consisting of the above (x) to (z) is preferably (x) an alkali-soluble group or (y) a polar conversion group, and more preferably (y) a polar conversion group.

Examples of the alkali-soluble group (x) include phenolic hydroxyl group, carboxylic acid group, fluorinated alcohol group, sulfonic acid group, sulfonamide group, sulfonylimide group, (alkylsulfonyl) (alkylcarbonyl) methylene group, (alkylsulfonyl) ( Alkylcarbonyl) imide group, bis (alkylcarbonyl) 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.

  As the repeating unit (bx) having an alkali-soluble group (x), 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 linking group is used. Examples include a repeating unit in which an alkali-soluble group is bonded to the main chain of the resin. 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. Either case is preferred.

  In the case where the repeating unit (bx) is a repeating unit having at least one of a fluorine atom and a silicon atom (that is, corresponding to the repeating unit (b ′) or (b ″)), the repeating unit (bx) Examples of the partial structure having a fluorine atom include the same ones as mentioned in the repeating unit having at least one of the fluorine atom and the silicon atom, and preferably represented by the general formulas (F2) to (F4). In this case, the partial structure having a silicon atom in the repeating unit (bx) is the same as that described in the repeating unit having at least one of the fluorine atom and the silicon atom. Preferably, groups represented by the general formulas (CS-1) to (CS-3) can be exemplified.

  The content of the repeating unit (bx) having an alkali-soluble group (x) is preferably 1 to 50 mol%, more preferably 3 to 35 mol%, still more preferably 5 to 5 mol% with respect to all repeating units in the resin (B). 20 mol%.

Specific examples of the repeating unit (bx) having an alkali-soluble group (x) are shown below, but the present invention is not limited thereto. In specific examples, X ₁ represents a hydrogen atom, —CH ₃ , —F or —CF ₃ .

Examples of the polar conversion group (y) include a lactone group, a carboxylic acid ester group (—COO—), an acid anhydride group (—C (O) OC (O) —), an acid imide group (—NHCONH—), A carboxylic acid thioester group (—COS—), a carbonic acid ester group (—OC (O) O—), a sulfate ester group (—OSO ₂ O—), a sulfonic acid ester group (—SO ₂ O—), and the like. A lactone group is preferred.
The polarity converting group (y) is, for example, introduced into the side chain of the resin by being included in a repeating unit of acrylic acid ester or methacrylic acid ester, or a polymerization initiator or chain having the polarity converting group (y). Any form in which a transfer agent is introduced at the end of the polymer chain using the polymerization is preferred.

Specific examples of the repeating unit (by) having a polar conversion group (y) include a repeating unit having a lactone structure represented by formulas (KA-1-1) to (KA-1-17) described later. Can do.
Further, the repeating unit (by) having the polarity converting group (y) is a repeating unit having at least one of a fluorine atom and a silicon atom (that is, the repeating unit (b ′), (b ″) corresponds to the repeating unit (b ′)). The resin having the repeating unit (by) is hydrophobic, but is particularly preferable from the viewpoint of reducing development defects.

  As the repeating unit (by), for example, a repeating unit represented by the formula (K0) can be given.

In the formula, R _k1 represents a hydrogen atom, a halogen atom, a hydroxyl group, an alkyl group, a cycloalkyl group, an aryl group, or a group containing a polarity converting group.
R _k2 represents an alkyl group, a cycloalkyl group, an aryl group, or a group containing a polarity converting group.
However, at least one of R _k1 and R _k2 represents a group containing a polarity converting group.
The polar converting group represents a group that decomposes by the action of the alkali developing image solution and increases the solubility in the alkali developing solution as described above. The polar conversion group is preferably a group represented by X in the partial structure represented by the following general formula (KA-1) or (KB-1).

X in the general formula (KA-1) or (KB-1) is a carboxylic acid ester group: —COO—, an acid anhydride group: —C (O) OC (O) —, an acid imide group: —NHCONH—, Carboxylic acid thioester group: —COS—, carbonate ester group: —OC (O) O—, sulfate ester group: —OSO ₂ O—, sulfonate ester group: —SO ₂ O—.
Y ¹ and Y ² may be the same or different and each represents an electron-withdrawing group.
The repeating unit (by) has a group that increases the solubility in a preferable alkali developer by having a group having a partial structure represented by the general formula (KA-1) or (KB-1). Is a partial structure represented by the general formula (KA-1), and a partial structure represented by (KB-1) when Y1 and Y2 are monovalent, the partial structure has a bond. When not having, the group having the partial structure is a group having a monovalent or higher valent group excluding at least one arbitrary hydrogen atom in the partial structure.
The partial structure represented by the general formula (KA-1) or (KB-1) is linked to the main chain of the resin (B) via a substituent at an arbitrary position.

The partial structure represented by the general formula (KA-1) is a structure that forms a ring structure with the group as X.
X in the general formula (KA-1) is preferably a carboxylic acid ester group (that is, when a lactone ring structure is formed as KA-1), an acid anhydride group, and a carbonic acid ester group. More preferably, it is a carboxylic acid ester group.
The ring structure represented by the general formula (KA-1) may have a substituent, for example, may have nka substituents Z _ka1 .
Z _ka1 independently represents a halogen atom, an alkyl group, a cycloalkyl group, an ether group, a hydroxyl group, an amide group, an aryl group, a lactone ring group, or an electron-withdrawing group, when there are a plurality of Z _ka1 .
Z _ka1 may be linked to form a ring. Examples of the ring formed by connecting Z _{ka1 to} each other include a cycloalkyl ring and a hetero ring (a cyclic ether ring, a lactone ring, etc.).
nka represents an integer of 0 to 10. Preferably it is an integer of 0 to 8, more preferably an integer of 0 to 5, more preferably an integer of 1 to 4, and most preferably an integer of 1 to 3.

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

Z _ka1 is preferably an alkyl group, a cycloalkyl group, an ether group, a hydroxyl group, or an electron-withdrawing group, more preferably an alkyl group, a cycloalkyl group, or an electron-withdrawing group. In addition, as an ether group, the thing substituted by the alkyl group or the cycloalkyl group, ie, the alkyl ether group, etc. are preferable. The electron withdrawing group has the same meaning as described above.
Examples of the halogen atom as Z _ka1 include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom, and a fluorine atom is preferable.
The alkyl group as Z _ka1 may have a substituent and may be linear or branched. As a linear alkyl group, Preferably it is C1-C30, More preferably, it is 1-20, For example, a methyl group, an ethyl group, n-propyl group, n-butyl group, sec-butyl group, t-butyl Group, n-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, n-nonyl group, n-decanyl group and the like. As a branched alkyl group, Preferably it is C3-C30, More preferably, it is 3-20, for example, i-propyl group, i-butyl group, t-butyl group, i-pentyl group, t-pentyl group, Examples include i-hexyl group, t-hexyl group, i-heptyl group, t-heptyl group, i-octyl group, t-octyl group, i-nonyl group, t-decanoyl group and the like. C1-C4 things, such as a methyl group, an ethyl group, n-propyl group, i-propyl group, n-butyl group, i-butyl group, t-butyl group, are preferable.
The cycloalkyl group as Z _ka1 may have a substituent, and may be monocyclic or polycyclic. In the case of a polycyclic type, the cycloalkyl group may be a bridged type. That is, in this case, the cycloalkyl group may have a bridged structure. The monocyclic type is preferably a cycloalkyl group having 3 to 8 carbon atoms, and examples thereof include a cyclopropyl group, a cyclopentyl group, a cyclohexyl group, a cyclobutyl group, and a cyclooctyl group. Examples of the polycyclic type include groups having a bicyclo, tricyclo, tetracyclo structure or the like having 5 or more carbon atoms, and a cycloalkyl group having 6 to 20 carbon atoms is preferable. For example, an adamantyl group, norbornyl group, isobornyl group, Examples thereof include a camphanyl group, a dicyclopentyl group, an α-pinel group, a tricyclodecanyl group, a tetocyclododecyl group, and an androstanyl group. As the cycloalkyl group, the following structure is also preferable. A part of carbon atoms in the cycloalkyl group may be substituted with a hetero atom such as an oxygen atom.

Preferred examples of the alicyclic moiety include adamantyl group, noradamantyl group, decalin group, tricyclodecanyl group, tetracyclododecanyl group, norbornyl group, cedrol group, cyclohexyl group, cycloheptyl group, cyclooctyl group, cyclodecanyl group. And cyclododecanyl group. More preferred are an adamantyl group, a decalin group, a norbornyl group, a cedrol group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, a cyclodecanyl group, a cyclododecanyl group, and a tricyclodecanyl group.
Examples of the substituent of these alicyclic structures include an alkyl group, a halogen atom, a hydroxyl group, an alkoxy group, a carboxyl group, and an alkoxycarbonyl group. The alkyl group is preferably a lower alkyl group such as a methyl group, an ethyl group, a propyl group, an isopropyl group or a butyl group, more preferably a methyl group, an ethyl group, a propyl group or an isopropyl group. Preferred examples of the alkoxy group include those having 1 to 4 carbon atoms such as a methoxy group, an ethoxy group, a propoxy group, and a butoxy group. Examples of the substituent that the alkyl group and the alkoxy group may have include a hydroxyl group, a halogen atom, and an alkoxy group (preferably having 1 to 4 carbon atoms).

  Further, the above group may further have a substituent, and examples of the further substituent include a hydroxyl group, a halogen atom (fluorine, chlorine, bromine, iodine), a nitro group, a cyano group, the above alkyl group, and a methoxy group. , Ethoxy group, hydroxyethoxy group, propoxy group, hydroxypropoxy group, n-butoxy group, isobutoxy group, sec-butoxy group, alkoxy group such as t-butoxy group, alkoxycarbonyl group such as methoxycarbonyl group, ethoxycarbonyl group, Aralkyl groups such as benzyl group, phenethyl group, cumyl group, aralkyloxy group, formyl group, acetyl group, butyryl group, benzoyl group, cyanyl group, acyl group such as valeryl group, acyloxy group such as butyryloxy group, the above alkenyl group , Vinyloxy group, propenyloxy group, allyloxy group, buteni May be mentioned an alkenyloxy group such as oxy group, said aryl group, an aryloxy group such as phenoxy group, aryloxycarbonyl group such as benzoyloxy group.

X in the general formula (KA-1) is a carboxylic acid ester group, and the partial structure represented by the general formula (KA-1) is preferably a lactone ring, and more preferably a 5- to 7-membered lactone ring.
In addition, as in the following (KA-1-1) to (KA-1-17), a 5- to 7-membered lactone ring as a partial structure represented by the general formula (KA-1) has a bicyclo structure, a spiro It is preferred that other ring structures are condensed in a form that forms the structure.
As for the peripheral ring structure to which the ring structure represented by the general formula (KA-1) may be bonded, for example, those in the following (KA-1-1) to (KA-1-17), or The thing according to can be mentioned.
As a structure containing a lactone ring structure represented by the general formula (KA-1), a structure represented by any one of the following (KA-1-1) to (KA-1-17) is more preferable. The lactone structure may be directly bonded to the main chain. Preferred structures include (KA-1-1), (KA-1-4), (KA-1-5), (KA-1-6), (KA-1-13), (KA-1- 14) and (KA-1-17).

The structure containing the lactone ring structure may or may not have a substituent. Preferable substituents include those similar to the substituent Z _ka1 that the ring structure represented by the general formula (KA-1) may have.

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

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

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

In formula (EW),
n _ew is the repeating number of the linking group represented by —C (R _ew1 ) (R _ew2 ) — and represents an integer of 0 or 1. When n _ew is 0, it represents a single bond, indicating that Y _ew1 is directly bonded.
Y _ew1 is a halogen atom, a cyano group, a nitrile group, a nitro group, a halo (cyclo) alkyl group or a haloaryl group represented by —C (R _f1 ) (R _f2 ) —R _f3 , an oxy group, a carbonyl group, a sulfonyl group The group may be a group, a sulfinyl group, and a combination thereof, and the electron-withdrawing group may have the following structure, for example. The “halo (cyclo) alkyl group” represents an alkyl group and a cycloalkyl group that are at least partially halogenated, and the “haloaryl group” represents an aryl group that is at least partially halogenated. In the following structural formula, R _ew3 and R _ew4 each independently represent an arbitrary structure. R _{EW3, R ew4} is in any structure, the partial structure represented by formula (EW) may have electron-withdrawing. R _ew3 and R _ew4 may be linked to the main chain of the resin, for example, but are preferably an alkyl group, a cycloalkyl group, or a fluorinated alkyl group.

When Y _ew1 is a divalent or higher group, the remaining bond forms a bond with an arbitrary atom or substituent. At least one group of Y _ew1 , R _ew1 , and R _ew2 may be connected to the main chain of the resin (B) through a further substituent.
Y _ew1 is preferably a halogen atom, or a halo (cyclo) alkyl group or haloaryl group represented by —C (R _f1 ) (R _f2 ) —R _f3 .
R _ew1 and R _ew2 each independently represent an arbitrary substituent, for example, a hydrogen atom, an alkyl group, a cycloalkyl group, or an aryl group.
At least two of R _ew1 , R _ew2 and Y _ew1 may be connected to each other to form a ring.

Here, R _f1 represents a halogen atom, a perhaloalkyl group, a perhalocycloalkyl group, or a perhaloaryl group, more preferably a fluorine atom, a perfluoroalkyl group or a perfluorocycloalkyl group, still more preferably a fluorine atom or Represents a trifluoromethyl group.
R _f2 and R _f3 each independently represent a hydrogen atom, a halogen atom or an organic group, and R _f2 and R _f3 may be linked to form a ring. Examples of the organic group include an alkyl group, a cycloalkyl group, and an alkoxy group. More preferably, R _f2 represents the same group as R _f1 or is linked to R _f3 to form a ring.
R _{f1 to} R _f3 may be linked to form a ring, and examples of the ring formed include a (halo) cycloalkyl ring and a (halo) aryl ring.
Examples of the (halo) alkyl group in R _{f1 to} R _f3 include the alkyl group in Z _ka1 described above and a structure in which this is halogenated.
Examples of the (per) halocycloalkyl group and the (per) haloaryl group in R _{f1 to} R _f3 or in the ring formed by linking R _f2 and R _f3 include, for example, the aforementioned cycloalkyl group in Z _ka1 is a halogen atom. And a perfluoroaryl group represented by -C _(n) F _(n-1) and more preferably a fluorocycloalkyl group represented by -C _(n) F _(2n-2) H Can be mentioned. Although carbon number n is not specifically limited here, the thing of 5-13 is preferable and 6 is more preferable.

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

In the repeating unit (by), a plurality of partial structures represented by the general formula (KA-1), a plurality of partial structures represented by the general formula (KB-1), or a general formula (KA) It may have both a partial structure represented by -1) and a partial structure represented by the general formula (KB-1).
Note that part or all of the partial structure of the general formula (KA-1) may also serve as an electron withdrawing group as Y ¹ or Y ² in the general formula (KB-1). For example, when X in the general formula (KA-1) is a carboxylic acid ester group, the carboxylic acid ester group functions as an electron withdrawing group as Y ¹ or Y ² in the general formula (KB-1). There is also a possibility.
In addition, when the repeating unit (by) corresponds to the repeating unit (b *) or the repeating unit (b ″) and has a partial structure represented by the general formula (KA-1), the general formula (KA) As for the partial structure represented by -1), it is more preferable that the polarity conversion group is a partial structure represented by -COO- in the structure represented by the general formula (KA-1).

  The repeating unit (by) may be a repeating unit having a partial structure represented by the following general formula (KY-0).

In the general formula (KY-0),
R ₂ represents a chain or cyclic alkylene group, and when there are a plurality of R ₂ groups, they may be the same or different.
R ₃ represents a linear, branched or cyclic hydrocarbon group in which part or all of the hydrogen atoms on the constituent carbons are substituted with fluorine atoms.
R ₄ is a halogen atom, cyano group, hydroxy group, amide group, alkyl group, cycloalkyl group, alkoxy group, phenyl group, acyl group, alkoxycarbonyl group, or R—C (═O) — or R—C ( = O) A group represented by O- (R represents an alkyl group or a cycloalkyl group). If R ₄ is a plurality may be the same or different, and two or more R ₄ are attached, may form a ring.
X represents an alkylene group, an oxygen atom, or a sulfur atom.
Z and Za represent a single bond, an ether bond, an ester bond, an amide bond, a urethane bond or a urea bond, and when there are a plurality of them, they may be the same or different.
* Represents a bond to the main chain or side chain of the resin.
o is the number of substituents and represents an integer of 1 to 7.
m is the number of substituents and represents an integer of 0 to 7.
n represents the number of repetitions and represents an integer of 0 to 5.
The structure represented by —R ₂ —Z— is preferably a structure represented by — (CH ₂ ) _p —COO— (p represents an integer of 1 to 5).

The preferred carbon number range and specific examples of the chain or cyclic alkylene group as R ₂ are the same as those described for the chain alkylene group and cyclic alkylene group in Z ₂ of the general formula (bb).
The linear, branched or cyclic hydrocarbon group as R ₃ has preferably 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, and preferably 3 carbon atoms when branched. -30, more preferably 3-20, and in the case of a ring, it is 6-20. Specific examples of R ₃ include specific examples of the alkyl group and cycloalkyl group as Z _ka1 described above.
Preferred carbon numbers and specific examples of the alkyl group and cycloalkyl group as R ₄ and R are the same as those described in the alkyl group and cycloalkyl group as Z _ka1 described above.
The acyl group as R ₄ is preferably one having 1 to 6 carbon atoms, and examples thereof include a formyl group, acetyl group, propionyl group, butyryl group, isobutyryl group, valeryl group, and pivaloyl group.
Examples of the alkyl moiety in the alkoxy group and alkoxycarbonyl group as R ₄ include a linear, branched or cyclic alkyl moiety, and the preferred carbon number of the alkyl moiety and specific examples thereof are those described above for Z _ka1. The same as those described in the alkyl group and cycloalkyl group.
Examples of the alkylene group as X include a chain or cyclic alkylene group, and preferred carbon numbers and specific examples thereof are the same as those described for the chain alkylene group and cyclic alkylene group as R ₂ .

  When the polarity conversion group is decomposed by the action of an alkali developer and converted in polarity, the receding contact angle with water of the resin composition film after alkali development can be lowered. It is preferable from the viewpoint of suppressing development defects that the receding contact angle with water of the film after alkali development is lowered.

The receding contact angle with water of the resin composition film after alkali development is preferably 50 ° or less, more preferably 40 ° or less, and still more preferably 35 ° at a temperature of 23 ± 3 ° C. and a humidity of 45 ± 5%. Hereinafter, it is most preferably 30 ° or less.
The receding contact angle is a contact angle measured when the contact line at the droplet-substrate interface recedes, and is useful for simulating the ease of movement of the droplet in a dynamic state. It is generally known. In simple terms, it can be defined as the contact angle when the droplet interface recedes when the droplet discharged from the needle tip is deposited on the substrate and then sucked into the needle again. It can be measured by using a contact angle measuring method generally called an expansion / contraction method.
The hydrolysis rate of the resin (B) with respect to the alkaline developer is preferably 0.001 nm / second or more, more preferably 0.01 nm / second or more, and further preferably 0.1 nm / second or more. Most preferably, it is 1 nm / second or more.
Here, the hydrolysis rate of the resin (B) with respect to the alkaline developer was 23.degree. C. TMAH (tetramethylammonium hydroxide aqueous solution) (2.38 mass%), and the resin film was formed only with the resin (B). This is the rate at which the film thickness decreases.

The repeating unit (by) is more preferably a repeating unit having at least two or more polar conversion groups.
When the repeating unit (by) has at least two polar conversion groups, the repeating unit (by) preferably has a group having a partial structure having two polar conversion groups represented by the following general formula (KY-1). Note that the structure represented by the general formula (KY-1) is a group having a monovalent or higher valent group in which at least one arbitrary hydrogen atom in the structure is removed when it does not have a bond.

In general formula (KY-1),
R _ky1 and R _ky4 are each independently a hydrogen atom, halogen atom, alkyl group, cycloalkyl group, carbonyl group, carbonyloxy group, oxycarbonyl group, ether group, hydroxyl group, cyano group, amide group, or aryl group Represents. Alternatively, R _ky1 and R _ky4 may be bonded to the same atom to form a double bond. For example, R _ky1 and R _ky4 are bonded to the same oxygen atom to form a part of a carbonyl group (═O). May be formed.
R _ky2 and R _ky3 are each independently an electron withdrawing group, or R _ky1 and R _ky2 are linked to form a lactone ring and R _ky3 is an electron withdrawing group. As the lactone ring to be formed, the structures (KA-1-1) to (KA-1-17) are preferable. Examples of the electron withdrawing group include the same groups as those described above for Y ¹ and Y ² in the formula (KB-1), and preferably a halogen atom or the aforementioned —C (R _f1 ) (R _f2 ) —R _f3. A halo (cyclo) alkyl group or a haloaryl group represented by the formula: Preferably _{R ky3} halogen atom, or the _{-C (R f1)} (R f2) is represented by the halo (cyclo) alkyl groups or haloaryl groups _{-R f3,} lactone _{R ky2} is linked to _{R ky1} An electron withdrawing group that forms a ring or has no halogen atom.
R _ky1 , R _ky2 , and R _ky4 may be connected to each other to form a monocyclic or polycyclic structure.

Specific examples of R _ky1 and R _ky4 include the same groups as Z _ka1 in formula (KA-1).
As the lactone ring formed by linking R _ky1 and R _ky2 , the structures (KA-1-1) to (KA-1-17) are preferable. Examples of the electron withdrawing group include those similar to Y ¹ and Y ² in the formula (KB-1).
The structure represented by the general formula (KY-1) is more preferably a structure represented by the following general formula (KY-2). Note that the structure represented by the general formula (KY-2) is a group having a monovalent or higher group obtained by removing at least one arbitrary hydrogen atom in the structure.

In formula (KY-2),
R _{ky6 to} R _ky10 are each independently a hydrogen atom, halogen atom, alkyl group, cycloalkyl group, carbonyl group, carbonyloxy group, oxycarbonyl group, ether group, hydroxyl group, cyano group, amide group, or aryl. Represents a group.
Two or more of R _{ky6 to} R _ky10 may be connected to each other to form a monocyclic or polycyclic structure.
R _ky5 represents an electron withdrawing group. Examples of the electron withdrawing group include the same groups as those described above for Y ¹ and Y ² , and preferably a halogen atom or a halo (cyclo (cyclo) represented by —C (R _f1 ) (R _f2 ) —R _f3. ) An alkyl group or a haloaryl group.
Specific examples of R _{ky6 to} R _ky10 include the same groups as Z _ka1 in formula (KA-1).
The structure represented by the formula (KY-2) is more preferably a partial structure represented by the following general formula (KY-3).

Wherein _{(KY-3), Z ka1} , nka have the same meanings as _Z ka1, nka in each said general formula (KA-1). R _ky5 is synonymous with Z _ka1 and nka in the formula (KY-2).
L _ky represents an alkylene group, an oxygen atom or a sulfur atom. _Examples of the alkylene group for L _ky include a methylene group and an ethylene group. L _ky is preferably an oxygen atom or a methylene group, and more preferably a methylene group.

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

  When the repeating unit (by) is a repeating unit having at least one of a fluorine atom and a silicon atom (that is, when the repeating unit (by) corresponds to the repeating unit (b ′) or (b ″)), the repeating unit (by) Examples of the partial structure having a fluorine atom include the same ones as mentioned in the repeating unit having at least one of the fluorine atom and the silicon atom, and preferably represented by the general formulas (F2) to (F4). In this case, the partial structure having a silicon atom in the repeating unit (by) has the same structure as that described in the repeating unit having at least one of the fluorine atom and the silicon atom. Preferably, groups represented by the general formulas (CS-1) to (CS-3) can be exemplified.

The content of the repeating unit (by) in the resin (B) is preferably 10 to 100 mol%, more preferably 20 to 99 mol%, and still more preferably 30 to the total repeating units in the resin (B). 97 mol%, most preferably 40-95 mol%.
Specific examples of the repeating unit (by) having a group capable of increasing the solubility in an alkali developer are shown below, but are not limited thereto. In specific examples, Ra represents a hydrogen atom, a fluorine atom, a methyl group or a trifluoromethyl group.

  Examples of the repeating unit (bz) having a group (z) that decomposes by the action of an acid in the resin (B) include the same repeating units as those having an acid-decomposable group in the resin (A).

  In the case where the repeating unit (bz) is a repeating unit having at least one of a fluorine atom and a silicon atom (that is, corresponding to the repeating unit (b ′) or (b ″)), the repeating unit (bz) Examples of the partial structure having a fluorine atom include the same ones as mentioned in the repeating unit having at least one of the fluorine atom and the silicon atom, and preferably represented by the general formulas (F2) to (F4). In this case, the partial structure having a silicon atom in the repeating unit (by) has the same structure as that described in the repeating unit having at least one of the fluorine atom and the silicon atom. Preferably, groups represented by the general formulas (CS-1) to (CS-3) can be exemplified.

  In the resin (B), the content of the repeating unit (bz) having a group (z) that decomposes by the action of an acid is preferably 1 to 80 mol% with respect to all the repeating units in the resin (B). Preferably it is 10-80 mol%, More preferably, it is 20-60 mol%.

Hereinabove, the repeating unit (b) having at least one group selected from the group consisting of the above (x) to (z) has been described, but the content of the repeating unit (b) in the resin (B) is as follows: 1-98 mol% is preferable with respect to all the repeating units in resin (B), More preferably, it is 3-98 mol%, More preferably, it is 5-97 mol%, Most preferably, it is 10-95 mol%.
The content of the repeating unit (b ′) is preferably 1 to 100 mol%, more preferably 3 to 99 mol%, still more preferably 5 to 97 mol%, and most preferably 10 to the total repeating units in the resin (B). -95 mol%.
The content of the repeating unit (b *) is preferably 1 to 90 mol%, more preferably 3 to 80 mol%, still more preferably 5 to 70 mol%, most preferably 10 with respect to all repeating units in the resin (B). ~ 60 mol%. The content of the repeating unit having at least one of a fluorine atom and a silicon atom used together with the repeating unit (b *) is preferably 10 to 99 mol%, more preferably based on all repeating units in the resin (B). It is 20-97 mol%, More preferably, it is 30-95 mol%, Most preferably, it is 40-90 mol%.
The content of the repeating unit (b ″) is preferably 1 to 100 mol%, more preferably 3 to 99 mol%, still more preferably 5 to 97 mol%, and most preferably 10 to the total repeating units in the resin (B). -95 mol%.

  The resin (B) may further have a repeating unit represented by the following general formula (V).

In general formula (V),
R _c31 represents a hydrogen atom, an alkyl group (which may be substituted with a fluorine atom or the like), a cyano group, or a —CH ₂ —O—Rac ₂ group. In the formula, Rac ₂ represents a hydrogen atom, an alkyl group or an acyl group. R _c31 is preferably a hydrogen atom, a methyl group, a hydroxymethyl group or a trifluoromethyl group, particularly preferably a hydrogen atom or a methyl group.
R _c32 represents a group having an alkyl group, a cycloalkyl group, an alkenyl group, a cycloalkenyl group or an aryl group. These groups may be substituted with a fluorine atom, a group containing a silicon atom, or the like.
L _c3 represents a single bond or a divalent linking group.

In general formula (V), the alkyl group represented by R _c32 is preferably a linear or branched alkyl group having 3 to 20 carbon atoms.
The cycloalkyl group is preferably a cycloalkyl group having 3 to 20 carbon atoms.
The alkenyl group is preferably an alkenyl group having 3 to 20 carbon atoms.
The cycloalkenyl group is preferably a cycloalkenyl group having 3 to 20 carbon atoms.
The aryl group is preferably a phenyl group or naphthyl group having 6 to 20 carbon atoms, and these may have a substituent.
R _c32 is preferably an unsubstituted alkyl group or an alkyl group substituted with a fluorine atom.
The divalent linking group of L _c3 is preferably an alkylene group (preferably having 1 to 5 carbon atoms), an oxy group, a phenylene group, or an ester bond (a group represented by —COO—).

  The resin (B) preferably further has a repeating unit represented by the following general formula (BII-AB).

In the formula (BII-AB),
R _c11 ′ and R _c12 ′ each independently represents a hydrogen atom, a cyano group, a halogen atom or an alkyl group.
Z _c ′ includes two bonded carbon atoms (C—C) and represents an atomic group for forming an alicyclic structure.

When each group in the repeating unit represented by the general formula (V) or (BII-AB) is substituted with a fluorine atom or a group containing a silicon atom, the repeating unit includes at least the fluorine atom and the silicon atom. It corresponds also to the repeating unit which has either.
Although the specific example of the repeating unit represented by general formula (V) and (BII-AB) below is given, this invention is not limited to these. In the formula, Ra represents H, CH ₃ , CH ₂ OH, CF ₃ or CN. Note that the repeating unit in the case where Ra is CF ₃ also corresponds to the repeating unit having at least one of the fluorine atom and the silicon atom.

  As with the resin (A), the resin (B) is, as a matter of course, free of impurities such as metals, and preferably has a residual monomer or oligomer component of 0 to 10% by mass, more preferably 0 to 0%. 5 mass% and 0-1 mass% are still more preferable. Thereby, a resist composition having no change over time such as foreign matter in liquid or sensitivity can be obtained. The molecular weight distribution (Mw / Mn, also referred to as dispersity) is preferably in the range of 1 to 3, more preferably 1 to 2, and still more preferably from the viewpoints of resolution, resist shape, resist pattern sidewall, roughness, and the like. It is in the range of 1 to 1.8, most preferably 1 to 1.5.

As the resin (B), various commercially available products can be used, or they can be synthesized according to a conventional method (for example, radical polymerization). For example, as a general synthesis method, a monomer polymerization method in which a monomer species and an initiator are dissolved in a solvent and heating is performed, and a solution of the monomer species and the initiator is dropped into the heating solvent over 1 to 10 hours. The dropping polymerization method is added, and the dropping polymerization method is preferable.
The reaction solvent, the polymerization initiator, the reaction conditions (temperature, concentration, etc.) and the purification method after the reaction are the same as those described for the resin (A).

  Specific examples of the resin (B) are shown below. Table 1 below shows the composition ratio of the repeating units in each resin (the positional relationship of each repeating unit in each resin shown in the specific example corresponds to the positional relationship of the numerical values of the composition ratio in Table 1), weight Average molecular weight and degree of dispersion are shown.

  The actinic ray-sensitive or radiation-sensitive resin composition of the present invention contains an actinic ray-sensitive or radiation-sensitive resin by containing a hydrophobic resin (B) containing at least one of a fluorine atom and a silicon atom. When the resin (B) is unevenly distributed on the surface layer of the film formed from the composition and the immersion medium is water, the receding contact angle of the film surface with respect to water can be improved, and the immersion water followability can be improved.

  After baking the coating film comprising the actinic ray-sensitive or radiation-sensitive resin composition of the present invention and before exposure, the receding contact angle of the film is the temperature at the time of exposure, usually room temperature 23 ± 3 ° C., humidity 45 ± 5%. 60 ° to 90 °, more preferably 65 ° or more, still more preferably 70 ° or more, and particularly preferably 75 ° or more.

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

  In the immersion exposure process, the immersion head needs to move on the wafer following the movement of the exposure head to scan the wafer at high speed to form the exposure pattern. In this case, the contact angle of the immersion liquid with respect to the resist film is important, and the resist is required to follow the high-speed scanning of the exposure head without remaining droplets.

  Since the resin (B) is hydrophobic, development residue (scum) and BLOB defects are likely to deteriorate after alkali development. However, the resin (B) has three or more polymer chains via at least one branch portion, thereby forming a linear resin. In comparison, the alkali dissolution rate is improved, so that development residue (scum) and BLO defect performance are improved.

When resin (B) has a fluorine atom, it is preferable that the content rate of a fluorine atom is 5-80 mass% with respect to the molecular weight of resin (B), and it is more preferable that it is 10-80 mass%. Moreover, it is preferable that the repeating unit containing a fluorine atom is 10-100 mol% with respect to all the repeating units in resin (B), and it is more preferable that it is 30-100 mol%.
When the resin (B) has a silicon atom, the content of the silicon atom is preferably 2 to 50% by mass, and more preferably 2 to 30% by mass with respect to the molecular weight of the resin (B). Moreover, it is preferable that it is 10-90 mol% with respect to all the repeating units of resin (B), and, as for the repeating unit containing a silicon atom, it is more preferable that it is 20-80 mol%.

  The weight average molecular weight of the resin (B) is preferably 1,000 to 100,000, more preferably 2,000 to 50,000, and still more preferably 3,000 to 30,000. Here, the weight average molecular weight of the resin indicates a molecular weight in terms of polystyrene measured by GPC (carrier: tetrahydrofuran (THF)).

The content of the resin (B) in the actinic ray-sensitive or radiation-sensitive resin composition can be appropriately adjusted and used so that the receding contact angle of the actinic ray- or radiation-sensitive resin film falls within the above range. It is preferably 0.01 to 20% by mass, more preferably 0.1 to 15% by mass, and still more preferably 0.1 to 10% by mass based on the total solid content of the light-sensitive or radiation-sensitive resin composition. %, Particularly preferably 0.5 to 8% by mass.
Resin (B) can be used individually by 1 type or in combination of 2 or more types.

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

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

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

In the compound represented by the general formula (BS-1), it is preferable that only one of three Rs is a hydrogen atom, or all Rs are not hydrogen atoms.
Specific examples of the compound of the general formula (BS-1) include tri-n-butylamine, tri-n-pentylamine, tri-n-octylamine, tri-n-decylamine, triisodecylamine, dicyclohexylmethylamine, Tetradecylamine, pentadecylamine, hexadecylamine, octadecylamine, didecylamine, methyloctadecylamine, dimethylundecylamine, N, N-dimethyldodecylamine, methyldioctadecylamine, N, N-dibutylaniline, N, N- Examples include dihexylaniline, 2,6-diisopropylaniline, 2,4,6-tri (t-butyl) aniline.
In addition, in the general formula (BS-1), a compound in which at least one R is an alkyl group substituted with a hydroxyl group is mentioned as one of preferable embodiments. Specific examples of the compound include triethanolamine and N, N-dihydroxyethylaniline.
The alkyl group as R may have an oxygen atom in the alkyl chain, and an oxyalkylene chain may be formed. As the oxyalkylene chain, —CH ₂ CH ₂ O— is preferable. Specific examples include tris (methoxyethoxyethyl) amine and compounds exemplified in column 3, line 60 and thereafter of US Pat. No. 6,040,112.

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

(3) Amine compound having a phenoxy group An amine compound having a phenoxy group has a phenoxy group at the terminal opposite to the nitrogen atom of the alkyl group of the amine compound. The phenoxy group is, for example, a substituent such as an alkyl group, an alkoxy group, a halogen atom, a cyano group, a nitro group, a carboxyl group, a carboxylic acid ester group, a sulfonic acid ester group, an aryl group, an aralkyl group, an acyloxy group, and an aryloxy group. You may have.
More preferably, it is a compound having at least one oxyalkylene chain between the phenoxy group and the nitrogen atom. The number of oxyalkylene chains in one molecule is preferably 3-9, more preferably 4-6. Among the oxyalkylene chains, —CH ₂ CH ₂ O— is preferable.
Specific examples include 2- [2- {2- (2,2-dimethoxy-phenoxyethoxy) ethyl} -bis- (2-methoxyethyl)]-amine and US Patent Application Publication No. 2007 / 0224539A1. The compounds (C1-1) to (C3-3) exemplified in paragraph [0066] of the above.

(4) Ammonium salt Ammonium salts are also used as appropriate. Preferred is hydroxide or carboxylate. More specifically, tetraalkylammonium hydroxide represented by tetrabutylammonium hydroxide is preferable.
In addition, examples of compounds that can be used in the composition of the present application include compounds synthesized in Examples of JP-A-2002-363146, compounds described in paragraph 0108 of JP-A-2007-298869, and the like.
A basic compound is used individually or in combination of 2 or more types.
The amount of the basic compound used is usually 0.001 to 10% by mass, preferably 0.01 to 5% by mass, based on the solid content of the actinic ray-sensitive or radiation-sensitive resin composition of the present invention. .
The molar ratio of acid generator / basic compound is preferably 2.5 to 300. That is, the molar ratio is preferably 2.5 or more from the viewpoints of sensitivity and resolution, and is preferably 300 or less from the viewpoint of suppressing the reduction in resolution due to pattern thickening over time until post-exposure heat treatment. This molar ratio is more preferably 5.0 to 200, and still more preferably 7.0 to 150.

[5] Surfactant The composition of the present invention may further contain a surfactant. When contained, the surfactant is preferably a fluorine-based and / or silicon-based surfactant.
Surfactants corresponding to these include Megafac F176, Megafac R08 manufactured by DIC Corporation, PF656, PF6320 manufactured by OMNOVA, Troisol S-366 manufactured by Troy Chemical Co., Ltd., and Sumitomo 3M Co., Ltd. Fluorado FC430, polysiloxane polymer KP-341 manufactured by Shin-Etsu Chemical Co., Ltd., and the like.
Further, other surfactants other than fluorine-based and / or silicon-based surfactants can also be used. More specific examples include polyoxyethylene alkyl ethers and polyoxyethylene alkyl aryl ethers.
In addition, known surfactants can be used as appropriate. Examples of the surfactant that can be used include surfactants described in [0273] et seq. Of US Patent Application Publication No. 2008 / 0248425A1.
Surfactants may be used alone or in combination of two or more.

The actinic ray-sensitive or radiation-sensitive resin composition of the present invention may or may not contain a surfactant, but when it is contained, the amount of surfactant used is actinic ray-sensitive or Preferably it is 0-2 mass% with respect to the total solid content (total quantity except a solvent) of a radiation sensitive resin composition, More preferably, it is 0.0001-2 mass%, Most preferably, it is 0.0005-1 mass%. is there.
On the other hand, it is also preferable that the addition amount of the surfactant is 10 ppm or less or not contained. Thereby, the surface uneven distribution property of the hydrophobic resin is increased, whereby the surface of the resist film can be made more hydrophobic, and the water followability at the liquid immersion exposure can be improved.

[6] Solvent The actinic ray-sensitive or radiation-sensitive resin composition according to the present invention usually further contains a solvent.
Examples of the solvent include alkylene glycol monoalkyl ether carboxylate, alkylene glycol monoalkyl ether, alkyl lactate ester, alkyl alkoxypropionate, cyclic lactone (preferably having 4 to 10 carbon atoms), and monoketone which may contain a ring. Examples include organic solvents such as compounds (preferably having 4 to 10 carbon atoms), alkylene carbonate, alkyl alkoxyacetate, and alkyl pyruvate.

Examples of the alkylene glycol monoalkyl ether carboxylate include propylene glycol monomethyl ether acetate (PGMEA, also known as 1-methoxy-2-acetoxypropane), propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, propylene glycol monobutyl ether acetate. And 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, also known as 1-methoxy-2-propanol), propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, ethylene glycol monomethyl ether, ethylene Preferred is glycol monoethyl ether.

Preferred examples of the alkyl lactate include methyl lactate, ethyl lactate, propyl lactate and butyl lactate.
Preferable examples of the alkyl alkoxypropionate include ethyl 3-ethoxypropionate, methyl 3-methoxypropionate, methyl 3-ethoxypropionate, and ethyl 3-methoxypropionate.

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

Preferred examples of the alkylene carbonate include propylene carbonate, vinylene carbonate, ethylene carbonate, and butylene carbonate.
Examples of the alkyl alkoxyacetate include 2-methoxyethyl acetate, 2-ethoxyethyl acetate, 2- (2-ethoxyethoxy) ethyl acetate, 3-methoxy-3-methylbutyl acetate, and 1-methoxy-acetate. 2-propyl is preferred.
Preferred examples of the alkyl pyruvate include methyl pyruvate, ethyl pyruvate, and propyl pyruvate.
As a solvent which can be preferably used, a solvent having a boiling point of 130 ° C. or higher under normal temperature and normal pressure can be mentioned. Specifically, cyclopentanone, γ-butyrolactone, cyclohexanone, ethyl lactate, ethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, ethyl 3-ethoxypropionate, ethyl pyruvate, 2-ethoxyethyl acetate, acetic acid -2- (2-ethoxyethoxy) ethyl and propylene carbonate are mentioned.
In the present invention, the above solvents may be used alone or in combination of two or more.

In this invention, you may use the mixed solvent which mixed the solvent which contains a hydroxyl group in a structure, and the solvent which does not contain a hydroxyl group as an organic solvent.
As the solvent containing a hydroxyl group and the solvent not containing a hydroxyl group, the above-mentioned exemplary compounds can be selected as appropriate, but as the solvent containing a hydroxyl group, alkylene glycol monoalkyl ether, alkyl lactate, etc. are preferable, propylene glycol monomethyl ether, More preferred is ethyl lactate. Further, as the solvent not containing a hydroxyl group, alkylene glycol monoalkyl ether acetate, alkyl alkoxypropionate, monoketone compound which may contain a ring, cyclic lactone, alkyl acetate and the like are preferable, and among these, propylene glycol monomethyl ether Acetate, ethyl ethoxypropionate, 2-heptanone, γ-butyrolactone, cyclohexanone and butyl acetate are particularly preferred, and propylene glycol monomethyl ether acetate, ethyl ethoxypropionate and 2-heptanone are most preferred.
The mixing ratio (mass) of the solvent containing a hydroxyl group and the solvent not containing a hydroxyl group is 1/99 to 99/1, preferably 10/90 to 90/10, more preferably 20/80 to 60/40. . A mixed solvent containing 50% by mass or more of a solvent not containing a hydroxyl group is particularly preferred from the viewpoint of coating uniformity.
The solvent is preferably a mixed solvent of two or more containing propylene glycol monomethyl ether acetate.

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

[8] Pattern Forming Method The pattern forming method of the present invention includes exposing an actinic ray-sensitive or radiation-sensitive film (resist film) and developing the exposed film.
The resist film is formed from the actinic ray-sensitive or radiation-sensitive resin composition of the present invention described above, and more specifically, is preferably formed on a substrate. In the pattern forming method of the present invention, the step of forming a film of a resist composition on the substrate, the step of exposing the film, and the developing step can be performed by generally known methods.

The actinic ray-sensitive or radiation-sensitive resin 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. preferable. By setting the solid content concentration in the actinic ray-sensitive or radiation-sensitive resin composition to an appropriate range to have an appropriate viscosity, and improving the coating property and film forming property, such a film thickness is obtained. Can do.
The total solid concentration in the actinic ray-sensitive or radiation-sensitive resin composition of the present invention is generally 1 to 10% by mass, more preferably 1 to 8.0% by mass, and still more preferably 1.0 to 6.0% by mass.
The actinic ray-sensitive or radiation-sensitive resin composition of the present invention is used by dissolving the above components in a solvent, filtering the solution, and applying the solution to a support. The filter is preferably made of polytetrafluoroethylene, polyethylene or nylon having a pore size of 0.1 microns or less, more preferably 0.05 microns or less, and still more preferably 0.03 microns or less. Note that a plurality of types of filters may be connected in series or in parallel. The composition may be filtered multiple times. Furthermore, you may perform a deaeration process etc. with respect to a composition before and after filter filtration.

The composition of the present invention can be applied on a substrate (eg, silicon / silicon dioxide coating) used in the manufacture of integrated circuit elements by a suitable application method such as a spinner. Thereafter, it can be dried to form a photosensitive resist film.
The resist film is irradiated with actinic rays or radiation through a predetermined mask, preferably baked (heated), developed and rinsed. Thereby, a good pattern can be obtained. Note that in electron beam irradiation, drawing (direct drawing) without using a mask is common.
It is also preferable to include a preheating step (PB; Prebake) after the film formation and before the exposure step.
It is also preferable to include a post-exposure heating step (PEB; Post Exposure Bake) after the exposure step and before the development step.
The heating temperature is preferably 70 to 140 ° C for both PB and PEB, and more preferably 80 to 135 ° C.
The heating time is preferably 30 to 300 seconds, more preferably 30 to 180 seconds, and still more preferably 30 to 90 seconds.
Heating can be performed by means provided in a normal exposure / developing machine, and may be performed using a hot plate or the like.
The reaction of the exposed part is promoted by baking, and the sensitivity and pattern profile are improved.

Although it does not specifically limit as actinic light or a radiation, For example, they are a KrF excimer laser (248 nm), an ArF excimer laser (193 nm), EUV light (13 nm), an electron beam etc., ArF excimer laser, EUV light, and an electron beam are preferable.
As the alkaline developer in the development step, a quaternary ammonium salt typified by tetramethylammonium hydroxide (TMAH) is usually used. In addition, inorganic alkali, primary to tertiary amine, alcohol amine, cyclic amine are also used. An alkaline aqueous solution such as can also be used. Furthermore, an appropriate amount of alcohol or surfactant may be added to the alkaline developer.
The alkali concentration of the alkali developer is usually from 0.1 to 20% by mass.
The pH of the alkali developer is usually from 10.0 to 15.0.
As the rinsing liquid, pure water is preferable, and an appropriate amount of a surfactant can be added and used.
As a developing method, for example, a method in which a substrate is immersed in a tank filled with a developer for a certain period of time (dip method), a method in which the developer is raised on the surface of the substrate by surface tension and is left stationary for a certain time (paddle) Method), a method of spraying the developer on the substrate surface (spray method), a method of continuously discharging the developer while scanning the developer discharge nozzle on the substrate rotating at a constant speed (dynamic dispensing method) Etc. can be applied.

  In the rinsing step, the developed wafer is cleaned using a rinsing liquid. The cleaning method is not particularly limited. For example, a method of continuing to discharge the rinse liquid onto the substrate rotating at a constant speed (rotary coating method), or immersing the substrate in a tank filled with the rinse liquid for a certain period of time. A method (dip method), a method of spraying a rinsing liquid on the substrate surface (spray method), and the like can be applied. Among them, a cleaning treatment is performed by a spin coating method, and after cleaning, the substrate is rotated at a speed of 2000 rpm to 4000 rpm. It is preferable to rotate and remove the rinse liquid from the substrate. It is also preferable to include a heating step (Post Bake) after the rinsing step. The developing solution and the rinsing solution remaining between the patterns and inside the patterns are removed by baking. The heating step after the rinsing step is usually 40 to 160 ° C., preferably 70 to 95 ° C., and usually 10 seconds to 3 minutes, preferably 30 seconds to 90 seconds.

  Moreover, the process which removes the developing solution or rinse liquid adhering on a pattern with a supercritical fluid can be performed after a image development process or a rinse process.

  In addition, before forming an actinic ray-sensitive or radiation-sensitive film (resist film), an antireflection film may be coated on the substrate in advance. As the antireflection film, any of an inorganic film type such as titanium, titanium dioxide, titanium nitride, chromium oxide, carbon, and amorphous silicon, and an organic film type made of a light absorber and a polymer material can be used. In addition, as the organic antireflection film, commercially available organic antireflection films such as DUV30 series, DUV-40 series manufactured by Brewer Science, AR-2, AR-3, AR-5 manufactured by Shipley, etc. may be used. it can.

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

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

When water is used as the immersion liquid, the surface tension of the water is decreased and the surface activity is increased, so that the resist film on the wafer is not dissolved and the influence on the optical coating on the lower surface of the lens element can be ignored. An additive (liquid) may be added in a small proportion. The additive is preferably an aliphatic alcohol having a refractive index substantially equal to that of water, and specifically includes methyl alcohol, ethyl alcohol, isopropyl alcohol and the like. By adding an alcohol having a refractive index substantially equal to that of water, even if the alcohol component in water evaporates and the content concentration changes, an advantage that the change in the refractive index of the entire liquid can be made extremely small can be obtained. On the other hand, when an opaque material or impurities whose refractive index is significantly different from that of water are mixed with 193 nm light, the optical image projected on the resist film is distorted. . Further, pure water filtered through an ion exchange filter or the like may be used.
The electrical resistance of water is desirably 18.3 MQcm or more, the TOC (organic substance concentration) is desirably 20 ppb or less, and deaeration treatment is desirably performed. Moreover, it is possible to improve lithography performance by increasing the refractive index of the immersion liquid. From such a viewpoint, an additive that increases the refractive index may be added to water, or heavy water (D ₂ O) may be used instead of water.
As described above, when the film made of the composition of the present invention is exposed through an immersion medium, a hydrophobic resin (HR) can be further added as necessary.

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

From the viewpoint of 193 nm transparency, the top coat is preferably a polymer that does not contain abundant aromatics. Specifically, the polymer contains a hydrocarbon polymer, an acrylate polymer, polymethacrylic acid, polyacrylic acid, polyvinyl ether, and silicon. Examples thereof include a polymer and a fluorine-containing polymer. The aforementioned hydrophobic resin (HR) is also suitable as a top coat. From the viewpoint of contaminating the optical lens when impurities are eluted from the top coat into the immersion liquid, it is preferable that the residual monomer component of the polymer contained in the top coat is small.
When peeling the top coat, a developer may be used, or a separate release agent may be used. As the release agent, a solvent having low penetration into the film is preferable. In terms of being able to perform the peeling process simultaneously with the film development process, it is preferable that the peeling process can be performed with an alkaline developer. The top coat is preferably acidic from the viewpoint of peeling with an alkali developer, but may be neutral or alkaline from the viewpoint of non-intermixability with the film.
The resolution is improved when there is no difference in refractive index between the top coat and the immersion liquid. In the case of using water as the immersion liquid in an ArF excimer laser (wavelength: 193 nm), the top coat for ArF immersion exposure is preferably close to the refractive index of the immersion liquid. From the viewpoint of making the refractive index close to the immersion liquid, it is preferable to have fluorine atoms in the topcoat. A thin film is more preferable from the viewpoint of transparency and refractive index.
The topcoat is preferably not mixed with the membrane and further not mixed with the immersion liquid. From this point of view, when the immersion liquid is water, the solvent used for the top coat is preferably a water-insoluble medium that is hardly soluble in the solvent used for the composition of the present invention. Further, when the immersion liquid is an organic solvent, the topcoat may be water-soluble or water-insoluble.

  The present invention also relates to an electronic device manufacturing method including the above-described pattern forming method of the present invention, and an electronic device manufactured by this manufacturing method. The electronic device of the present invention is suitably mounted on electrical and electronic equipment (home appliances, OA / media related equipment, optical equipment, communication equipment, etc.).

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

(Acid-decomposable resin)
The following resins (P-1) to (P-32) and (PA-1) to (PA-4) were synthesized as shown below.

  Hereinafter, polymer structures, weight average molecular weight (Mw), and dispersity (Mw / Mn) of resins (P-1) to (P-32) and (PA-1) to (PA-4) are shown. Moreover, the composition ratio of each repeating unit of the following polymer structure was shown by molar ratio.

(Synthesis example of monomer 1)
Anhydrous 5-norbornene-2,3-dicarboxylic acid (65.66 g, 0.4 mol) and chloroacetic acid (75.60 g, 0.8 mol) were put into a three-necked flask and heated and melted at 80 ° C. to obtain a uniform solution. . Trifluorosulfonic acid (3.5 ml, 40 mmol) was added dropwise thereto, and the mixture was stirred at 100 ° C. for 3 hours. After completion of the reaction, the reaction solution was cooled to 50 ° C., 500 ml of toluene was added, and the mixture was cooled to 25 ° C. This solution was added to a solution of 40 g of sodium hydrogen carbonate, 320 ml of distilled water, and 160 ml of saturated brine with stirring to carry out liquid separation purification. Thereafter, the organic layer was washed with 480 ml of saturated saline, and then the solvent was distilled off under reduced pressure to obtain 80 g of an oily compound.
The obtained oil was put into a three-necked flask, 550 ml of dimethylacetamide was added, methacrylic acid (34.61 g, 0.402 mol), sodium hydrogen carbonate (33.77 g, 0.402 mol), potassium iodide (12.82 g). 0.077 mol) was added and the mixture was stirred at 60 ° C. for 4 hours. After adding 1.5 L of toluene and cooling to 25 ° C., 1N hydrochloric acid was added until pH = 3, and a liquid separation operation was performed. The organic layer was washed with an aqueous sodium hydrogen carbonate solution and saturated brine, and then the solvent was distilled off under reduced pressure to obtain 50 g of an oily compound.
The obtained oil was subjected to column purification (hexane / ethyl acetate = 2/1), and the obtained oil was crystallized from ethyl acetate / heptane to obtain 26.4 g of the following monomer 1 (white crystals).
¹ H-NMR (400 MHz in (CD ₃ ) ₂ CO): δ (ppm) = 1.17-2.31 (m, 7H), 2.70-3.44 (m, 4H), 4.58- 5.18 (m, 3H), 6.22 (s, 1H), 7.27 (s, 1H).

(Synthesis example of acid-decomposable resin (P-1))
Under a nitrogen stream, 4.2 g of cyclohexanone was placed in a three-necked flask and heated to 85 ° C. In this way, solvent 1 was obtained. Next, the following monomer 1 (1.85 g), the following monomer 2 (2.64 g), and the following monomer 3 (1.00 g) were dissolved in cyclohexanone (17.0 g) to prepare a monomer solution. Furthermore, 6.5 mol% of polymerization initiator V-601 (manufactured by Wako Pure Chemical Industries, Ltd.) was added to the total amount of monomers, and the dissolved solution was added dropwise to the solvent 1 over 6 hours. After completion of dropping, the reaction was further continued at 85 ° C. for 2 hours. The reaction solution was allowed to cool and then added dropwise to a mixed solvent of 173 g of heptane / 74 g of ethyl acetate, and the precipitated powder was collected by filtration and dried to obtain 5.0 g of a resin (P-1). The obtained resin (P-1) has a weight average molecular weight (Mw) of 10,000, a dispersity (Mw / Mn) of 1.7, and a composition ratio measured by ¹³ C-NMR of 40/50/10. Met.

  In the same manner as the resin (P-1), the above resins (P-2) to (P-32) and (PA-1) to (PA-4) were synthesized.

(Acid generator)
As the acid generator, the acid generators z1 to z112 listed above were appropriately selected and used.

(Hydrophobic resin)
As the hydrophobic resin, the hydrophobic resins (B-1) to (B-55) listed above were appropriately selected and used.

(Basic compound)
DIA: 2,6-diisopropylaniline TMEA: Tris (methoxyethoxyethyl) amine PEA: N-phenyldiethanolamine TOA: Trioctylamine PBI: 2-phenylbenzimidazole DHA: N, N-dihexylaniline

(Surfactant)
W-1: Megafuck F176 (manufactured by DIC Corporation; fluorine-based)
W-2: Megafuck R08 (manufactured by DIC Corporation; fluorine and silicon-based)
W-3: Troisol S-366 (manufactured by Troy Chemical Co .; fluorine type)
W-4: PF656 (manufactured by OMNOVA; fluorine-based)
W-5: PF6320 (manufactured by OMNOVA; fluorine-based)

(solvent)
S1-1: Propylene glycol monomethyl ether acetate (PGMEA; 1-methoxy-2-acetoxypropane)
S1-2: Cyclohexanone S2-1: Propylene glycol monomethyl ether (PGME; 1-methoxy-2-propanol)
S2-2: Propylene carbonate S2-3: γ-Butyrolactone

Examples 1-42 and Comparative Examples 1-4
[Exposure conditions: ArF immersion exposure]
<Preparation of actinic ray-sensitive or radiation-sensitive resin composition>
The components shown in Table 2 below are dissolved in a solvent, and a solution having a solid content concentration of 4% by mass is prepared for each, and this is filtered through a polyethylene filter having a pore size of 0.1 μm, and an actinic ray-sensitive or radiation-sensitive resin. A composition (positive resist composition) was prepared. The prepared positive resist composition was evaluated by the following method, and the results are shown in Table 2.

<Image performance test>
An organic antireflection film ARC29SR (manufactured by Nissan Chemical Industries, Ltd.) was applied on a silicon wafer (12 inch diameter), and baked at 205 ° C. for 60 seconds to form an antireflection film having a thickness of 98 nm. The positive resist composition prepared thereon was applied and baked at 100 ° C. for 60 seconds to form an actinic ray-sensitive or radiation-sensitive film (resist film) having a thickness of 100 nm. The obtained wafer was used with an ArF excimer laser immersion scanner (manufactured by ASML, XT1700i, NA 1.20, C-Quad, outer sigma 0.981, inner sigma 0.895, XY deflection), 1: 1 with a line width of 45 nm. Exposure was through a 6% halftone mask with a line and space pattern. Ultra pure water was used as the immersion liquid. After heating at 100 ° C. for 60 seconds (PEB), developing with tetramethylammonium hydroxide aqueous solution (2.38% by mass) for 30 seconds, rinsing with pure water, spin drying, and 1 line width of 45 nm. 1: A line and space resist pattern was obtained.

<Development defects (bridge defects)>
The exposure amount for reproducing a 1: 1 line-and-space resist pattern having a line width of 45 nm is set as an optimum exposure amount, and exposure is performed through the mask at the optimum exposure amount as described above, and then development is performed. A 1: 1 line and space resist pattern having a width of 45 nm was obtained. Thereafter, the defect distribution on the silicon wafer was detected with UVvision 3+ (manufactured by AMAT), and the shape of the defect was observed using SEMVision G4 (manufactured by AMAT). Of the observed defects, the number corresponding to bridge defects was calculated. The bridging defects were evaluated by the number of bridging defects per 12-inch diameter silicon wafer.

<Pattern line width (CD) variation per PEB temperature of 1 ° C. (PEB temperature dependency; PEBs)>
Except for exposure through a 6% halftone mask with a 1: 1 line and space pattern with a line width of 45 nm, followed by heating (PEB) for 60 seconds under three temperature conditions of 97 ° C., 100 ° C., and 103 ° C. A line pattern was formed by the same method as in the above <image performance test>. The exposure amount at which a line pattern is finished at 45 nm is obtained by observing with a line width measurement scanning electron microscope SEM (Hitachi, Ltd. S-9380) for the one subjected to PEB at 100 ° C., and the exposure amount. Line pattern dimensions were determined for those subjected to PEB at 97 ° C and 103 ° C. By subtracting the size of the sample subjected to PEB at 103 ° C. from the size of the sample subjected to PEB at 97 ° C. and dividing the difference by the PEB temperature difference of 6 ° C., the dimensional change rate per 1 ° C. was expressed as PEB temperature dependency. .

<Space-DOF: Depth of Focus>
The exposure amount is the optimum exposure amount for forming a pattern with a line width of 45 nm under the exposure and development conditions in <Image Performance Test> above, and a 3: 1 line-and-space resist pattern with a line width of 150 nm and a space width of 50 nm is obtained. In addition, a resist pattern having the above-mentioned shape was formed by the same method as in the above <Image performance test> except that exposure was performed with the focus adjusted. At that time, exposure and development are performed by changing the exposure focus conditions in increments of 0.02 μm in the focus direction, and the space line width (CD) of each pattern obtained is measured by a line width measurement scanning electron microscope SEM ) Hitachi S-9380) was used, and the focus corresponding to the minimum or maximum of the curve obtained by plotting each of the above CDs was taken as the best focus. When the focus was changed around the best focus, a focus fluctuation range allowing a space width of 50 nm ± 10%, that is, a focus margin (μm) was calculated.

  Compared with Comparative Examples 1 to 3 that do not use a resin having a repeating unit represented by the general formula (1A) and a repeating unit that is decomposed by the action of an acid represented by the general formula (1B) to generate a carboxyl group. The examples were found to give excellent results for all of the bridge defects, PEBs and Space-DOF.

Claims (12)

(A) a resin having a repeating unit represented by the following general formula (1A) and a repeating unit that decomposes by the action of an acid represented by the following general formula (1B) to generate a carboxyl group; and
(B) An actinic ray-sensitive or radiation-sensitive resin composition containing a compound that generates an acid upon irradiation with actinic rays or radiation.

In general formula (1A),
L represents a single bond or a divalent linking group;
R ₁₁ represents a hydrogen atom or an alkyl group,
Z represents a cyclic acid anhydride group.
In general formula (1B),
R ₂₁ represents a hydrogen atom or an alkyl group,
R ₂₂ represents a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group or a sec-butyl group,
R ₂₃ represents an atomic group necessary for forming a monocyclic alicyclic hydrocarbon structure together with a carbon atom.
In the alicyclic hydrocarbon structure, a part of carbon atoms constituting the ring may be substituted with a hetero atom or a group having a hetero atom. The actinic ray-sensitive or radiation-sensitive resin composition according to claim 1, wherein the repeating unit represented by the general formula (1B) is a repeating unit represented by the following general formula (1B ′).

In General Formula (1B ′), R ₂₁ and R ₂₂ have the same meanings as those in General Formula (1B).   The actinic ray-sensitive or radiation-sensitive resin composition according to claim 1 or 2, wherein Z in the general formula (1A) includes a condensed ring structure. Z in the said General formula (1A) is an actinic-ray-sensitive or radiation-sensitive resin composition of any one of Claims 1-3 represented by following General formula (2).

In general formula (2),
W does not exist or represents an alkylene group, an oxygen atom, or a sulfur atom, and when a plurality of Ws are present, the plurality of Ws may be the same or different.
p represents an integer of 1 or more.
q represents the integer of 0-2.
m ₁ and m ₂ each independently represents an integer of 0 to 2.
R represents a monovalent substituent, and s represents an integer of 0 or more. When a plurality of R are present, the plurality of R may be the same or different.
* Is a bond connected to L in the general formula (1A). Z in the said General formula (1A) is an actinic-ray sensitive or radiation sensitive resin composition of any one of Claims 1-3 represented by following General formula (3).

In general formula (3),
p ′ represents 1 or 2.
R represents a monovalent substituent, and s represents an integer of 0 or more. When a plurality of R are present, the plurality of R may be the same or different.
* Is a bond connected to L in the general formula (1A).   The actinic ray-sensitive or radiation-sensitive resin composition according to any one of claims 1 to 5, wherein L in the general formula (1A) is a divalent linking group.   The actinic ray-sensitive or radiation-sensitive resin composition according to claim 6, wherein the divalent linking group as L is a divalent linking group containing at least one oxygen atom.   Content of the repeating unit represented by the said general formula (1A) is 5-50 mol% with respect to all the repeating units of the said resin (A), and content of the repeating unit represented by the said General formula (1B) The actinic-ray sensitive or radiation sensitive resin composition of any one of Claims 1-7 whose is 30-70 mol% with respect to all the repeating units of the said resin (A).   An actinic ray-sensitive or radiation-sensitive film formed using the actinic ray-sensitive or radiation-sensitive resin composition according to any one of claims 1 to 8.   A pattern forming method comprising exposing the actinic ray-sensitive or radiation-sensitive film according to claim 9 and developing the exposed film.   The pattern formation method according to claim 10, wherein the exposure is immersion exposure.   The manufacturing method of an electronic device containing the pattern formation method of Claim 11.