JPWO2016006364A1 - Actinic ray-sensitive or radiation-sensitive resin composition, pattern formation method, electronic device manufacturing method, and electronic device - Google Patents

Abstract

The actinic ray-sensitive or radiation-sensitive resin composition includes a repeating unit represented by the following general formula (I) and a repeating unit represented by the following general formula (II), and is represented by the general formula (II). The content of the repeating unit to be contained is 10 mol% or more with respect to all repeating units, and a compound that generates an acid upon irradiation with actinic rays or radiation.

Description

  The present invention relates to an actinic ray-sensitive or radiation-sensitive resin composition, a pattern formation method using the composition, an electronic device manufacturing method, and an electronic device. More specifically, the present invention is suitable for use in semiconductor manufacturing processes such as ICs, circuit boards such as liquid crystals and thermal heads, and other photofabrication processes, lithographic printing plates, and acid curable compositions. The present invention relates to an actinic ray-sensitive or radiation-sensitive resin composition, a pattern formation method using the composition, an electronic device manufacturing method, and an electronic device.

  Since the development of resists for KrF excimer laser (248 nm), an image forming method called chemical amplification has been used as an image forming method for resists in order to compensate for sensitivity reduction due to light absorption. In the positive chemical amplification image forming method, an acid generator is decomposed to generate an acid by exposure to an excimer laser, an electron beam, extreme ultraviolet light, or the like, and an acid is generated, and a post-exposure bake (PEB) is performed. In the image forming method, the generated acid is used as a reaction catalyst to change an alkali-insoluble group into an alkali-soluble group, and an exposed portion is removed with an alkali developer. At present, various alkali developers have been proposed as the alkali developer, but an aqueous alkali developer of 2.38% by mass TMAH (tetramethylammonium hydroxide aqueous solution) is widely used.

For the miniaturization of semiconductor elements, the wavelength of the exposure light source has been shortened and the projection lens has a high numerical aperture (high NA). An immersion lithography technique has been developed that fills the projection lens and the sample with a liquid having a high refractive index (hereinafter also referred to as “immersion liquid”), and immersion lithography is now the mainstream.
Various techniques have been proposed for the composition used in the above-described chemical amplification image forming method. For example, line width roughness (LWR) and mask error enhancement as described in Patent Document 1 are proposed. A radiation-sensitive resin composition having a small factor (MEEF), excellent in density bias, good storage stability, and a predetermined resin as described in Patent Document 2, and having excellent sensitivity and MEEF A functional resin composition is disclosed.

JP 2010-282189 A International Publication No. 2008/149701

In a resist image forming method such as immersion lithography, it is desirable that the cross-sectional shape of the resist be rectangular in order to faithfully transfer the pattern in the etching process when the pattern is transferred to the substrate.
In recent years, further miniaturization of patterns is desired, and accordingly, an improvement in exposure latitude (Exposure Latitude: EL) is also demanded.
Furthermore, when trying to reduce the size of the pattern, the management of the line width (CD) in the process is becoming more severe, and the PEB temperature dependency (PEBS (PEB sensitivity))
Has also become an important performance item. For example, in the past, when PEBS was 3 nm / ° C. with respect to a line width of 100 nm, the CD fluctuation at 1 degree was 3% of the line width. 7.5%, PEBS performance is becoming more important.
That is, an actinic ray-sensitive or radiation-sensitive resin composition that can form a highly rectangular cross-sectional film (resist) and exhibits good exposure margin and PEB temperature dependency is desired.
The present inventors evaluated the above characteristics using the compositions specifically disclosed in Examples of Patent Documents 1 and 2, and found that the above three characteristics (rectangularity, exposure margin). , PEB temperature dependency) could not be satisfied at the same time, and further improvement was necessary.

In view of the above circumstances, the present invention provides an actinic ray-sensitive or radiation-sensitive resin composition that can form a highly rectangular cross-sectional film (resist) and exhibits good exposure latitude and PEB temperature dependency. The task is to do.
Another object of the present invention is to provide a pattern forming method using the above composition, a method for manufacturing an electronic device, and an electronic device.

As a result of intensive studies on the problems of the prior art, the present inventors have found that the above problems can be solved by using a predetermined resin.
That is, it has been found that the above object can be achieved by the following configuration.

一般式（Ｉ）及び（ＩＩ）中、Ｔは、各々独立して、単結合又は２価の連結基を表す。
Ｒ_１及びＲ_３は、各々独立して、水素原子又はアルキル基を表す。
Ｒ_２は、炭素数３以上の炭化水素基を表す。
Ｒは、炭素原子とともに脂環構造を形成するのに必要な原子団を表す。
Ｒ_４、Ｒ_５、及び、Ｒ_６は、各々独立して、アルキル基を表す。
（２） Ｔが単結合である、（１）に記載の感活性光線性又は感放射線性樹脂組成物。
（３） 活性光線又は放射線の照射により酸を発生する化合物が、カチオン及びアニオンを含むイオン性化合物であり、アニオンが後述する一般式（２）で表されるスルホン酸アニオンである、（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。

一般式（２）中、Ｘｆは、各々独立に、フッ素原子、又は、少なくとも一つのフッ素原子で置換されたアルキル基を表す。Ｒ_７及びＲ_８は、各々独立に、水素原子、フッ素原子、アルキル基、又は、少なくとも一つのフッ素原子で置換されたアルキル基を表し、複数存在する場合のＲ_７及びＲ_８は、それぞれ同一でも異なっていてもよい。Ｌは、２価の連結基を表し、複数存在する場合のＬは同一でも異なっていてもよい。Ａは、環状構造を含む有機基を表す。ｘは、１〜２０の整数を表す。ｙは、０〜１０の整数を表す。ｚは、０〜１０の整数を表す。
（４） 活性光線又は放射線の照射により酸を発生する化合物が、カチオン及びアニオンを含むイオン性化合物であり、アニオンが後述する一般式（Ｂ−１）で表されるスルホン酸アニオンである、（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。

一般式（Ｂ−１）中、Ｒ_ｂ１は、各々独立に、水素原子、フッ素原子又はトリフルオロメチル基を表す。ｎは０〜４の整数を表す。Ｘ_ｂ１は、単結合、アルキレン基、エーテル結合、エステル結合、スルホン酸エステル結合、又はそれらの組み合わせを表す。Ｒ_ｂ２は炭素数６以上の有機基を表す。
（５） 活性光線又は放射線の照射により酸を発生する化合物が、カチオン及びアニオンを含むイオン性化合物であり、アニオン中に含まれるフッ素原子数が２〜３個である、（１）〜（４）のいずれかに記載の感活性光線性又は感放射線性樹脂組成物。
（６） 活性光線又は放射線の照射により酸を発生する化合物が、カチオン及びアニオンを含むイオン性化合物であり、カチオンが後述する一般式（ＺＩ−３Ａ）で表されるカチオン又は後述する一般式（ＺＩ−４）で表されるカチオンである、（１）〜（５）のいずれか記載の感活性光線性又は感放射線性樹脂組成物。

一般式（ＺＩ−３Ａ）中、Ｒ_１は、アルキル基、シクロアルキル基、アルコキシ基、シクロアルコキシ基、アリール基又はアルケニル基を表す。
Ｒ_２及びＲ_３は、各々独立に、水素原子、アルキル基、シクロアルキル基又はアリール基を表し、Ｒ_２とＲ_３が互いに連結して環を形成してもよく、Ｒ_１とＲ_２は、互いに連結して環を形成してもよい。ただし、Ｒ_２及びＲ_３のうち少なくとも１つは、アルキル基、シクロアルキル基、アリール基を表す。
Ｒ_Ｘ及びＲ_ｙは、各々独立に、アルキル基、シクロアルキル基、アルケニル基、アリール基、２−オキソアルキル基、２−オキソシクロアルキル基、アルコキシカルボニルアルキル基、又は、アルコキシカルボニルシクロアルキル基を表し、Ｒ_ＸとＲ_ｙが互いに連結して環を形成してもよく、この環構造は酸素原子、窒素原子、硫黄原子、ケトン基、エーテル結合、エステル結合又はアミド結合を含んでいてもよい。
一般式（ＺＩ−４Ａ）中、Ｒ_１３は、水素原子、フッ素原子、水酸基、アルキル基、シクロアルキル基、アルコキシ基、アルコキシカルボニル基、又は、シクロアルキル基を有する基を表す。
Ｒ_１４は、水酸基、アルキル基、シクロアルキル基、アルコキシ基、アルコキシカルボニル基、アルキルカルボニル基、アルキルスルホニル基、シクロアルキルスルホニル基、又は、シクロアルキル基を有する基を表す。Ｒ_１４が複数ある場合、Ｒ_１４は同一でも異なっていてもよい。
Ｒ_１５は、各々独立して、アルキル基、シクロアルキル基又はナフチル基を表す。２個のＲ_１５は互いに結合して環を形成してもよく、環を構成する原子として、酸素原子、硫黄原子又は窒素原子を含んでもよい。
ｌは０〜２の整数を表す。ｒは０〜８の整数を表す。
（７） 樹脂が、さらに、ラクトン構造またはスルトン構造を含む繰り返し単位を含む、（１）〜（６）のいずれかに記載の感活性光線性又は感放射線性樹脂組成物。
（８） さらに、疎水性樹脂を含有する、（１）〜（７）のいずれかに記載の感活性光線性又は感放射線性樹脂組成物。
（９） 疎水性樹脂が、アルカリ現像液の作用により分解してアルカリ現像液に対する溶解度が増大する基を有する、（８）に記載の感活性光線性又は感放射線性樹脂組成物。
（１０） さらに、活性光線又は放射線の照射により塩基性が低下する、塩基性化合物又はアンモニウム塩化合物を含有する、（１）〜（９）のいずれかに記載の感活性光線性又は感放射線性樹脂組成物。
（１１） さらに、窒素原子を有し、酸の作用により脱離する基を有する低分子化合物を含有する、（１）〜（９）のいずれかに記載の感活性光線性又は感放射線性樹脂組成物。
（１２） さらに、有機溶剤を含有し、
有機溶剤中にプロピレングリコールモノメチルエーテルアセテートが含まれ、プロピレングリコールモノメチルエーテルアセテートの有機溶剤全質量に対する含有量が９０質量％超である、（１）〜（１１）のいずれかに記載の感活性光線性又は感放射線性樹脂組成物。
（１３） さらに、γ−ブチロラクトンを含有する、（１）〜（１２）のいずれかに記載の感活性光線性又は感放射線性樹脂組成物。
（１４） （１）〜（１３）のいずれか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基板上に膜を形成する工程と、膜を露光する工程と、露光した膜を現像する工程を含むパターン形成方法。
（１５） （１４）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。
（１６） （１５）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。
（１７）樹脂が、シアノ基が置換されたラクトン構造又はスルトン構造を有する繰り返し単位を含有する、（１）〜（１３）のいずれかに記載の感活性光線性又は感放射線性樹脂組成物。
（１８）樹脂が、後述する一般式（ＩＩＩ）中のＲ_８がシアノ基を置換基として有するラクトン構造又はスルトン構造を有する１価の有機基である繰り返し単位を含有する、（１）〜（１３）のいずれかに記載の感活性光線性又は感放射線性樹脂組成物。(1) The content of the repeating unit represented by the general formula (II) includes the repeating unit represented by the general formula (I) described later and the repeating unit represented by the general formula (II) described later. A resin that is 10 mol% or more based on all repeating units;
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 formulas (I) and (II), each T independently represents a single bond or a divalent linking group.
R ₁ and R ₃ each independently represents a hydrogen atom or an alkyl group.
R ₂ represents a hydrocarbon group having 3 or more carbon atoms.
R represents an atomic group necessary for forming an alicyclic structure together with a carbon atom.
R ₄ , R ₅ and R ₆ each independently represents an alkyl group.
(2) The actinic ray-sensitive or radiation-sensitive resin composition according to (1), wherein T is a single bond.
(3) The compound that generates an acid upon irradiation with actinic rays or radiation is an ionic compound containing a cation and an anion, and the anion is a sulfonate anion represented by the general formula (2) described later, (1) Or the actinic-ray-sensitive or radiation-sensitive resin composition as described in (2).

In general formula (2), Xf each independently represents a fluorine atom or an alkyl group substituted with at least one fluorine atom. R ₇ and R ₈ each independently represent a hydrogen atom, a fluorine atom, an alkyl group, or an alkyl group substituted with at least one fluorine atom, and when there are a plurality of R ₇ and R ₈ , R ₇ and R ₈ are the same But it can be different. L represents a divalent linking group, and when there are a plurality of L, L may be the same or different. A represents an organic group containing a cyclic structure. x represents an integer of 1 to 20. y represents an integer of 0 to 10. z represents an integer of 0 to 10.
(4) The compound that generates an acid upon irradiation with actinic rays or radiation is an ionic compound containing a cation and an anion, and the anion is a sulfonate anion represented by the following general formula (B-1). The actinic ray-sensitive or radiation-sensitive resin composition according to 1) or (2).

In general formula (B-1), R _<b1> represents a hydrogen atom, a fluorine atom, or a trifluoromethyl group each independently. n represents an integer of 0 to 4. _Xb1 represents a single bond, an alkylene group, an ether bond, an ester bond, a sulfonate bond, or a combination thereof. R _b2 represents an organic group having 6 or more carbon atoms.
(5) The compound which generates an acid upon irradiation with actinic rays or radiation is an ionic compound containing a cation and an anion, and the number of fluorine atoms contained in the anion is 2 to 3, (1) to (4 The actinic ray-sensitive or radiation-sensitive resin composition according to any one of 1).
(6) The compound that generates an acid upon irradiation with actinic rays or radiation is an ionic compound containing a cation and an anion, and a cation represented by a general formula (ZI-3A) described later or a general formula (described later) The actinic ray-sensitive or radiation-sensitive resin composition according to any one of (1) to (5), which is a cation represented by ZI-4).

In General Formula (ZI-3A), R ₁ represents an alkyl group, a cycloalkyl group, an alkoxy group, a cycloalkoxy group, an aryl group, or an alkenyl group.
R ₂ and R ₃ each independently represents a hydrogen atom, an alkyl group, a cycloalkyl group or an aryl group, and R ₂ and R ₃ may be linked to each other to form a ring, and R ₁ and R ₂ may be , May be linked together to form a ring. However, at least one of R ₂ and R ₃ represents an alkyl group, a cycloalkyl group, or an aryl group.
R _X and R _y each independently represents an alkyl group, a cycloalkyl group, an alkenyl group, an aryl group, a 2-oxoalkyl group, a 2-oxocycloalkyl group, an alkoxycarbonylalkyl group, or an alkoxycarbonylcycloalkyl group. R _X and R _y may be linked to each other to form a ring, and this ring structure may contain an oxygen atom, a nitrogen atom, a sulfur atom, a ketone group, an ether bond, an ester bond or an amide bond. .
In General Formula (ZI-4A), R ₁₃ represents a hydrogen atom, a fluorine atom, a hydroxyl group, an alkyl group, a cycloalkyl group, an alkoxy group, an alkoxycarbonyl group, or a group having a cycloalkyl group.
R ₁₄ represents 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. If R ₁₄ there are a _{plurality, R 14} may be the same or different.
R ₁₅ each independently represents an alkyl group, a cycloalkyl group or a naphthyl group. Two R _{15 s} may be bonded to each other to form a ring, and the atoms constituting the ring may include an oxygen atom, a sulfur atom, or a nitrogen atom.
l represents an integer of 0-2. r represents an integer of 0 to 8.
(7) The actinic ray-sensitive or radiation-sensitive resin composition according to any one of (1) to (6), wherein the resin further contains a repeating unit containing a lactone structure or a sultone structure.
(8) The actinic ray-sensitive or radiation-sensitive resin composition according to any one of (1) to (7), further comprising a hydrophobic resin.
(9) The actinic ray-sensitive or radiation-sensitive resin composition according to (8), wherein the hydrophobic resin has a group that is decomposed by the action of an alkali developer to increase the solubility in the alkali developer.
(10) The actinic ray-sensitive or radiation-sensitive property according to any one of (1) to (9), further comprising a basic compound or an ammonium salt compound, the basicity of which decreases when irradiated with actinic rays or radiation. Resin composition.
(11) The actinic ray-sensitive or radiation-sensitive resin according to any one of (1) to (9), further comprising a low molecular compound having a nitrogen atom and a group capable of leaving by the action of an acid. Composition.
(12) Furthermore, an organic solvent is contained,
The actinic ray according to any one of (1) to (11), wherein propylene glycol monomethyl ether acetate is contained in the organic solvent, and the content of propylene glycol monomethyl ether acetate is more than 90% by mass relative to the total mass of the organic solvent. Or radiation sensitive resin composition.
(13) The actinic ray-sensitive or radiation-sensitive resin composition according to any one of (1) to (12), further comprising γ-butyrolactone.
(14) A step of forming a film on a substrate using the actinic ray-sensitive or radiation-sensitive resin composition according to any one of (1) to (13), a step of exposing the film, and an exposed film The pattern formation method including the process of developing this.
(15) A method for manufacturing an electronic device, comprising the pattern forming method according to (14).
(16) An electronic device manufactured by the method for manufacturing an electronic device according to (15).
(17) The actinic ray-sensitive or radiation-sensitive resin composition according to any one of (1) to (13), wherein the resin contains a repeating unit having a lactone structure or a sultone structure substituted with a cyano group.
(18) The resin contains a repeating unit in which R ₈ in the general formula (III) described later is a monovalent organic group having a lactone structure or a sultone structure having a cyano group as a substituent. 13) The actinic ray-sensitive or radiation-sensitive resin composition according to any one of the above.

ADVANTAGE OF THE INVENTION According to this invention, the actinic-ray sensitive or radiation sensitive resin composition which can form the film (resist) of highly rectangular cross-sectional shape, and shows a favorable exposure margin and PEB temperature dependence can be provided. .
Moreover, according to this invention, the pattern formation method using the said composition, the manufacturing method of an electronic device, and an electronic device can also be provided.

It is a typical sectional view showing angle α.

Hereinafter, embodiments of the present invention will be described in detail.
In the notation of a group (atomic group) in this specification, a notation that does not indicate substitution or non-substitution refers to a group (atomic group) having a substituent together with a group (atomic group) having no substituent. Is also included. For example, the “alkyl group” includes not only an alkyl group having no substituent (unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group).
In the present specification, “active light” or “radiation” means, for example, the emission line spectrum of a mercury lamp, far ultraviolet rays represented by excimer laser, extreme ultraviolet rays (EUV light), X-rays, electron beams (EB), etc. To do. In the present invention, light means actinic rays or radiation.
In addition, “exposure” in the present specification is not limited to exposure to far ultraviolet rays, extreme ultraviolet rays, X-rays, EUV light and the like represented by mercury lamps and excimer lasers, but also electron beams, ion beams, and the like, unless otherwise specified. The exposure with the particle beam is also included in the exposure.
In the present specification, “to” is used to mean that the numerical values described before and after it are included as a lower limit value and an upper limit value.
In the present specification, “(meth) acrylate” represents acrylate and methacrylate, “(meth) acryl” represents acryl and methacryl, and “(meth) acryloyl” represents acryloyl and methacryloyl.

A feature of the present invention is that a resin having a predetermined repeating unit described later is used.
More specifically, first, the present inventors have found that the hydrophobicity of the resin is important in order to obtain a highly rectangular cross-sectional shape. In particular, in the case of a so-called positive type, the hydrophobicity of the resin is more important. Based on this knowledge, the portion represented by R ₂ in the later-described general formula (I) can be made more hydrophobic by having 3 or more carbon atoms, and a desired effect is obtained.
In addition, for a good exposure margin, by using a predetermined amount or more of a repeating unit having a small protective group size such as the general formula (II) described later, a dissolution rate change due to the deprotection of one protective group occurs. It has been found to be advantageous for image formation that is small and faithful to the amount of acid generated. In addition, as described above, in the repeating unit represented by the general formula (I), when R ₂ has 3 or more carbon atoms, activation energy necessary for deprotection is suppressed, which is contrary to the high hydrophobicity. It has also been found that the resolution is high.
Furthermore, in order to obtain good PEB temperature dependence, it is necessary to suppress the dependence on temperature. By making R ₂ a carbon number of 3 or more in the repeating unit represented by the general formula (I), desorption is possible. It has been found that the activation energy required for protection is reduced and the above properties are good.

The actinic ray-sensitive or radiation-sensitive resin composition of the present invention (hereinafter also referred to as “composition”, “composition of the present invention”, or “resist composition of the present invention”) will be described below.
The composition of the present invention may be used for positive development (development where exposed areas (areas with high exposure) are removed and unexposed areas remain as patterns), or negative development (exposed areas (exposure) (exposure). May be used for development in which an unexposed portion is removed. That is, development may be performed using either an alkali developer or a developer containing an organic solvent.
The composition of the present invention is typically a chemically amplified resist composition.
The composition of the present invention comprises: [1] a resin having a repeating unit represented by the following general formula (I) and a repeating unit represented by the general formula (II), and [2] irradiation with actinic rays or radiation. Contains at least a compound capable of generating an acid.
Additional components that may be included in the composition according to the present invention include [3] hydrophobic resin, [4] acid diffusion controller, [5] solvent, and [6] surfactant. The composition of the present invention can be used for pattern formation, for example, according to a method described later as “pattern formation method”.
First, each component used for a composition is demonstrated in order, and the pattern formation method using a composition is explained in full detail after that.

[1] Resin The actinic ray-sensitive or radiation-sensitive resin composition of the present invention contains a resin having a repeating unit represented by the general formula (I) and a repeating unit represented by the general formula (II). This resin also corresponds to a resin that decomposes by the action of a so-called acid and increases the solubility in an alkaline developer (hereinafter also referred to as “acid-decomposable resin” or “resin”). In addition, the composition (mol%) of each repeating unit in resin is calculated | required by the measurement by < ¹³ > C-NMR, for example.
The resin is preferably insoluble or hardly soluble in an alkaline developer.

(Repeating unit represented by general formula (I) and general formula (II))
The resin includes a repeating unit represented by the general formula (I) and a repeating unit represented by the general formula (II).

In general formulas (I) and (II), each T independently represents a single bond or a divalent linking group.
Examples of the divalent linking group for T include an alkylene group, —COO—Rt— group, and —O—Rt— group. In the formula, Rt represents an alkylene group or a cycloalkylene group.
T is preferably a single bond or a —COO—Rt— group, and more preferably a single bond. 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.

In general formulas (I) and (II), R ₁ and R ₃ each independently represents a hydrogen atom or an alkyl group. The alkyl group may have a substituent.
Examples of the alkyl group which may have a substituent include a methyl group or a group represented by —CH ₂ —R ₁₁ . R ₁₁ represents a halogen atom (such as a fluorine atom), a hydroxyl group or a monovalent organic group, and examples thereof include an alkyl group having 5 or less carbon atoms and an acyl group having 5 or less carbon atoms, preferably 3 or less carbon atoms. And more preferably a methyl group. In one embodiment, R ₁ and R ₃ are preferably a hydrogen atom, a methyl group, a trifluoromethyl group, or a hydroxymethyl group.

In general formula (I), R ₂ represents a hydrocarbon group having 3 or more carbon atoms (the number of carbon atoms). Note that the hydrocarbon group may contain a hetero atom (for example, an oxygen atom (—O—) or the like).
The number of carbons contained in the hydrocarbon group is 3 or more, a more rectangular cross-sectional shape can be obtained, a better exposure margin, and / or better PEB temperature dependency. 3 to 10 are preferable, 3 to 5 are more preferable, and 3 is more preferable in view of the points shown (hereinafter, also simply referred to as “the point where the effect of the present invention is more excellent”).
One preferred embodiment of the hydrocarbon group is an alkyl group, a cycloalkyl group, or a combination thereof. More specifically, an alkyl group having 3 or more carbon atoms and a cycloalkyl group having 3 or more carbon atoms can be given. R ₂ may have a substituent (for example, a hydroxyl group).
The alkyl group may be linear or branched, but is preferably branched because the effects of the present invention are more excellent.
Examples of the alkyl group include an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, and a sec-butyl group.
Examples of the cycloalkyl group include monocyclic cycloalkyl groups such as cyclopentyl group and cyclohexyl group, and polycyclic cycloalkyl groups such as norbornyl group, tetracyclodecanyl group, tetracyclododecanyl group, and adamantyl group. .

R represents an atomic group necessary for forming an alicyclic structure together with a carbon atom. The alicyclic structure formed by R together with the carbon atom is preferably a monocyclic alicyclic structure, and the carbon number thereof is preferably 3 to 7, more preferably 5 or 6. In other words, the alicyclic structure is preferably a 3- to 7-membered ring, and more preferably a 5- to 6-membered ring.
In the alicyclic structure, a part of carbon atoms constituting the ring may be substituted with a heteroatom or a group having a heteroatom. Examples of the hetero atom that can form the ring include an oxygen atom and a sulfur atom. Examples of the group having a hetero atom include a carbonyl group. However, the group having a hetero atom is preferably not an ester group (ester bond).
Moreover, it is preferable that the said alicyclic structure is formed only from a carbon atom and a hydrogen atom.

R ₄ , R ₅ and R ₆ each independently represents an alkyl group. The alkyl group is linear or branched.
The alkyl group may have a substituent. As the alkyl group, those having 1 to 4 carbon atoms such as methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group and t-butyl group are preferable.
Two of R _{4 to} R ₆ are not bonded to each other to form a ring.

One preferred embodiment of the repeating unit represented by the general formula (I) is a repeating unit represented by the following general formula (IA). In addition, the definition of R < ₁ > and R < ₂ > in general formula (IA) is as the above-mentioned.

In the resin, the content of the repeating unit represented by the general formula (II) is 10 mol% or more with respect to all the repeating units in the resin. Especially, 12 mol% or more is preferable at the point which the effect of this invention is more excellent. Although an upper limit in particular is not restrict | limited, 60 mol% or less is preferable and 40 mol% or less is more preferable.
In the resin, the content of the repeating unit represented by the general formula (I) is not particularly limited, but is preferably 5 mol% or more with respect to all the repeating units in the resin in that the effect of the present invention is more excellent. 25 mol% or more is more preferable. The upper limit is not particularly limited, but is preferably 60 mol% or less, and more preferably 50 mol% or less.
Content ratio of repeating unit represented by general formula (I) and unit represented by general formula (II) (molar amount of repeating unit represented by general formula (I) / represented by general formula (II) The molar amount of the repeating unit is not particularly limited, but is preferably 0.2 to 10 and more preferably 0.3 to 1.0 from the viewpoint that the effect of the present invention is more excellent.

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

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

(Other repeat units)
The above resin may contain other repeating units other than the repeating units represented by the general formula (I) and the general formula (II).
In one aspect, the resin preferably contains a repeating unit having a cyclic carbonate structure. This cyclic carbonate structure is a structure having a ring including a bond represented by —O—C (═O) —O— as an atomic group constituting the ring. The ring containing a bond represented by —O—C (═O) —O— as the atomic group constituting the ring is preferably a 5- to 7-membered ring, and most preferably a 5-membered ring. Such a ring may be condensed with another ring to form a condensed ring.
The resin preferably contains a repeating unit having a lactone group or a sultone (cyclic sulfonic acid ester) group. In other words, the resin preferably contains a repeating unit having a lactone structure or a sultone structure. Among them, the resin preferably contains a repeating unit having a lactone structure substituted with a cyano group or a sultone (cyclic sulfonic acid ester) structure, in which the effect of the present invention is more excellent, and the cyano group is substituted. It is more preferable to contain two types of repeating units having a lactone structure or a sultone structure and a repeating unit having a lactone structure or a sultone structure in which the cyano group is not substituted (unsubstituted).
When the repeating unit having the lactone structure or sultone structure is contained in the resin, the content of the unit, the repeating unit represented by the general formula (I) and the repeating unit represented by the general formula (II) The molar ratio with the total content of is not particularly limited.
Any lactone group or sultone group can be used as long as it has a lactone structure or sultone structure, but a lactone structure or sultone structure having a 5- to 7-membered ring is preferable, and a lactone having a 5- to 7-membered ring is preferable. A group in which another ring structure is condensed to the structure or sultone structure to form a bicyclo structure or a spiro structure is preferable. 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), (SL1-1) and (SL1-2). A lactone structure or a sultone structure may be directly bonded to the main chain. Preferred lactone structures or sultone structures are (LC1-1), (LC1-4), (LC1-5), (LC1-8), and more preferably (LC1-4). By using a specific lactone structure or sultone structure, LWR and development defects 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. .

The acid-decomposable group preferably has a structure protected with a group capable of decomposing and leaving an alkali-soluble group by the action of an acid.
Alkali-soluble groups include phenolic hydroxyl groups, carboxyl groups, fluorinated alcohol groups, sulfonic acid groups, sulfonamido groups, sulfonylimide groups, (alkylsulfonyl) (alkylcarbonyl) methylene groups, (alkylsulfonyl) (alkylcarbonyl) imides. Group, bis (alkylcarbonyl) methylene group, bis (alkylcarbonyl) imide group, bis (alkylsulfonyl) methylene group, bis (alkylsulfonyl) imide group, tris (alkylcarbonyl) methylene group, tris (alkylsulfonyl) methylene group, etc. Is mentioned.
Preferred alkali-soluble groups include carboxyl groups, fluorinated alcohol groups (preferably hexafluoroisopropanol groups), and sulfonic acid groups.
A preferable group as the acid-decomposable group is a group in which the hydrogen atom of these alkali-soluble groups is substituted 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 resin preferably contains a repeating unit having a lactone structure or a sultone structure represented by the following general formula (III). In addition, the repeating unit represented by general formula (III) may use only 1 type, or may be used in combination of 2 or more type.
Among them, the resin is a monovalent resin in which R ₈ in the general formula (III) has a lactone structure (cyanolactone) or a sultone structure (cyanosultone) having a cyano group as a substituent in that the effect of the present invention is more excellent. It is preferable to contain a repeating unit that is an organic group, and R ₈ in the general formula (III) is a monovalent organic group having a lactone structure or a sultone structure having a cyano group as a substituent, and a general unit More preferably, R ₈ in the formula (III) contains two kinds of repeating units which are monovalent organic groups having a lactone structure or a sultone structure having no cyano group as a substituent.

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. If R ₀ is more, each R ₀ is may be the same or different.
Z is a single bond, ether bond, ester bond, amide bond, urethane bond

Or urea bond

Represents. Here, R represents a hydrogen atom, an alkyl group, a cycloalkyl group, or an aryl group each independently. When there are a plurality of Z, each Z may be the same or different.
R ₈ represents a monovalent organic group having a lactone structure or a sultone structure.
n _is the repetition number of the structure represented by -R 0 -Z-, represents an integer of 0 to 2.
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, a hydroxy group Group, alkoxy group such as methoxy group, ethoxy group, isopropoxy group, t-butoxy group and benzyloxy group, and acetoxy group such as acetyloxy group and propionyloxy 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 group 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. . A preferable cycloalkylene group is a cycloalkylene group having 3 to 20 carbon atoms, and examples thereof include a cyclohexylene group, a cyclopentylene group, a norbornylene group, and an adamantylene group. 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 monovalent organic group having a lactone structure or a sultone structure represented by R ₈ is not limited as long as it has a lactone structure or a sultone structure, and the general formula (LC1-1) described above as a specific example A lactone structure or a sultone structure represented by ~ (LC1-17), (SL1-1) and (SL1-2) is exemplified, and a structure represented by (LC1-4) is particularly preferable. Further, n ₂ in (LC1-1) to (LC1-17), (SL1-1) and (SL1-2) is more preferably 2 or less.
R ₈ is preferably a monovalent organic group having an unsubstituted lactone structure or sultone structure, or a monovalent organic group having a lactone structure or 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.
In general formula (III), it is preferable that n is 1 or 2.
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.
In the following formulae, Me represents a methyl group.

  As the repeating unit having a lactone structure or a sultone structure, a repeating unit represented by the following general formula (III-1) or (III-1 ′) is more preferable.

In general formulas (III-1) and (III-1 ′),
R ₇ , A, R ₀ , Z, and n are as defined in the general formula (III).
R ₇ ′, A ′, R ₀ ′, Z ′ and n ′ have the same meanings as R ₇ , A, R ₀ , Z and n in the general formula (III), respectively.
R ₉ is an alkyl group, a cycloalkyl group, an alkoxycarbonyl group, a cyano group, a hydroxyl group or an alkoxy group, attached the two R ₉ when R ₉ there is a plurality, may form a ring . When there are a plurality of R _{9 s} , each R ₉ may be the same or different.
R 9 _'represents an alkyl group, a cycloalkyl group, an alkoxycarbonyl group, a cyano group, a hydroxyl group or an alkoxy group, R _9' 2 both R _{9 'are} coupled if there is a plurality, to form a ring May be. When there are a plurality of R ₉ ′, each R ₉ ′ may be the same or different.
X and X ′ each independently represents an alkylene group, an oxygen atom or a sulfur atom.
m and m ′ are the number of substituents, and each independently represents an integer of 0 to 5. m and m ′ are preferably each independently 0 or 1.
The alkyl group for R ₉ and R ₉ ′ is preferably an alkyl group having 1 to 4 carbon atoms, more preferably a methyl group or an ethyl group, and most preferably a methyl group. Examples of the cycloalkyl group include 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 ₉ and R ₉ ′ are more preferably a methyl group, a cyano group or an alkoxycarbonyl group, and even more preferably a cyano group.
Examples of the alkylene group for X and X ′ include a methylene group and an ethylene group. X and X ′ are preferably an oxygen atom or a methylene group, more preferably a methylene group.
When m and m ′ are 1 or more, at least one of R ₉ and R ₉ ′ is preferably substituted at the α-position or β-position of the carbonyl group of lactone or the sulfoxide group of sultone, particularly substituted at the α-position. It is preferable.
Specific examples of the group having a lactone structure represented by the general formula (III-1) and the repeating unit having a sultone structure represented by the general formula (III-1 ′) are shown below, but the present invention is limited thereto. Is not to be done. In the following specific examples, R represents a hydrogen atom, an alkyl group which may have a substituent, or a halogen atom, preferably a hydrogen atom, a methyl group, a hydroxymethyl group or an acetoxymethyl group.

The content of the repeating unit represented by the general formula (III) is preferably 15 to 60 mol%, more preferably 20 to 60 mol%, based on the total repeating units in the resin when a plurality of types of repeating units are contained. More preferably, it is 30-50 mol%.
The resin may also contain a repeating unit having the above-mentioned lactone structure or sultone structure in addition to the unit represented by the general formula (III).
Specific examples of the repeating unit having a lactone group or a sultone group include the following in addition to the specific examples given above, but the present invention is not limited thereto.

  Among the specific examples, particularly preferred repeating units include the following repeating units. By selecting an optimal lactone group or sultone group, the pattern profile and the density dependency are improved.

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.
The content of the repeating unit having a lactone structure or a sultone structure other than the repeating unit represented by the general formula (III) is 5 to 50 mol% in total with respect to all the repeating units in the resin when a plurality of types are contained. Is preferable, and more preferably 10 to 30 mol%.

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

In general formulas (VIIa) to (VIIc),
R ₂ c to R ₄ c each independently represents a hydrogen atom, a hydroxyl group, or a cyano group. However, at least one of R ₂ c to R ₄ c represents a hydroxyl group or a cyano group. Preferably, one or two of R ₂ c to R ₄ c are a hydroxyl group and the 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 (VIId) include the repeating units represented by the following general formulas (AIIa) to (AIId).

In the general formulas (AIIa) to (AIId),
R ₁ c represents a hydrogen atom, a methyl group, a trifluoromethyl group, or a hydroxymethyl group.
R ₂ c to R ₄ c are in the general formula (VIIa) ~ _(VIIc), same meanings as R 2 c~R ₄ c.
The repeating unit having a hydroxyl group or a cyano group may or may not be contained in the resin, but when it is contained, its content is preferably 5 to 40 mol% with respect to all repeating units in the resin, More preferably, it is 5-30 mol%.
Specific examples of the repeating unit having a hydroxyl group or a cyano group are given below, but the present invention is not limited thereto.

The resin used in the actinic ray-sensitive or radiation-sensitive resin composition of the present invention may have a repeating unit having an alkali-soluble group. Examples of the alkali-soluble group include a carboxyl group, a sulfonamide group, a sulfonylimide group, a bissulfonylimide group, and an aliphatic alcohol (for example, a hexafluoroisopropanol group) in which the α-position is substituted with an electron withdrawing group. It is more preferable to have a repeating unit. By containing the repeating unit having an alkali-soluble group, the resolution in contact hole applications is increased. The repeating unit having an alkali-soluble group includes a repeating unit in which an alkali-soluble group is directly bonded to the main chain of the resin, such as a repeating unit of acrylic acid or methacrylic acid, or an alkali in the main chain of the resin through a linking group. Either a repeating unit to which a soluble group is bonded, or a polymerization initiator or chain transfer agent having an alkali-soluble group is used at the time of polymerization and introduced at the end of the polymer chain. Both are preferable, and the linking group is monocyclic or polycyclic. It may have a cyclic hydrocarbon structure. Particularly preferred are repeating units of acrylic acid or methacrylic acid.
The content of the repeating unit having an alkali-soluble group is preferably from 0 to 20 mol%, more preferably from 3 to 15 mol%, still more preferably from 5 to 10 mol%, based on all repeating units in the resin.
Specific examples of the repeating unit having an alkali-soluble group are shown below, but the present invention is not limited thereto.
In specific examples, Rx represents H, CH ₃ , CH ₂ OH, or CF ₃ .

  The resin of the present invention can further have a repeating unit that has an alicyclic hydrocarbon structure that does not have a polar group (for example, an alkali-soluble group, a hydroxyl group, a cyano group, etc.) and does not exhibit acid decomposability. Examples of such a repeating unit include a repeating unit represented by the general formula (IV).

In the 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 a cycloalkyl group having 3 to 12 carbon atoms such as a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, and a cyclooctyl group, and a cyclohexenyl group. Groups. The preferred monocyclic hydrocarbon group is a monocyclic hydrocarbon group having 3 to 7 carbon atoms, more preferably a cyclopentyl group or a cyclohexyl group.
The polycyclic hydrocarbon group includes a ring assembly hydrocarbon group and a bridged cyclic hydrocarbon group, and examples of the ring assembly hydrocarbon group include a bicyclohexyl group and a perhydronaphthalenyl group. As the bridged cyclic hydrocarbon ring, for example, bicyclic such as pinane, bornane, norpinane, norbornane, bicyclooctane ring (bicyclo [2.2.2] octane ring, bicyclo [3.2.1] octane ring, etc.) Hydrocarbon rings and tricyclic hydrocarbon rings such as homobredan, adamantane, tricyclo [5.2.1.0 ^2,6 ] decane, tricyclo [4.3.1.1 ^2,5 ] undecane ring, tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodecane, and tetracyclic hydrocarbon rings such as perhydro-1,4-methano-5,8-methanonaphthalene ring. The bridged cyclic hydrocarbon ring includes a condensed cyclic hydrocarbon ring such as perhydronaphthalene (decalin), perhydroanthracene, perhydrophenanthrene, perhydroacenaphthene, perhydrofluorene, perhydroindene, perhydroindene. A condensed ring in which a plurality of 5- to 8-membered cycloalkane rings such as a phenalene ring are condensed is also included.
Preferred examples of the bridged cyclic hydrocarbon ring include a norbornyl group, an adamantyl group, a bicyclooctanyl group, a tricyclo [5,2,1,0 ^2,6 ] decanyl group, and the like. More preferable examples of the bridged cyclic hydrocarbon ring include a norbornyl group and an adamantyl group.
These alicyclic hydrocarbon groups may have a substituent. 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 has an alicyclic hydrocarbon structure that does not have a polar group, and may or may not contain a repeating unit that does not exhibit acid decomposability. Is preferably from 1 to 40 mol%, more preferably from 2 to 20 mol%, based on all repeating units in the resin.
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 .

In addition to the above repeating structural units, the resin used in the composition of the present invention includes dry etching resistance, standard developer suitability, substrate adhesion, resist profile, and general required characteristics of resist, resolving power and heat resistance. In order to adjust sensitivity and the like, various repeating structural units can be included.
Examples of such repeating structural units include, but are not limited to, repeating structural units corresponding to the following monomers.
Thereby, performance required for the resin used in the composition of the present invention, in particular, (1) solubility in coating solvent, (2) film-forming property (glass transition point), (3) alkali developability, (4 Fine adjustments such as () film slippage (selection of hydrophilicity / hydrophobicity, alkali-soluble group), (5) adhesion of unexposed part to substrate, (6) dry etching resistance, etc. are possible.
As such a monomer, for example, it has one addition polymerizable unsaturated bond selected from acrylic esters, methacrylic esters, acrylamides, methacrylamides, allyl compounds, vinyl ethers, vinyl esters and the like. A compound etc. can be mentioned.
In addition, any addition-polymerizable unsaturated compound that can be copolymerized with monomers corresponding to the above various repeating structural units may be copolymerized.
In the resin used in the composition of the present invention, the molar ratio of each repeating structural unit is the resist dry etching resistance, standard developer suitability, substrate adhesion, resist profile, and resolution that is a general required performance of the resist. In order to adjust heat resistance, sensitivity, etc., it is set appropriately.

When the composition of the present invention is for ArF exposure, it is preferable that the resin used in the composition of the present invention 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, ideally 0% by mole during the entire repetition of the resin. That is, it is more preferable not to have a repeating unit having an aromatic group. The resin preferably has a monocyclic or polycyclic alicyclic hydrocarbon structure.
In addition, it is preferable that resin does not contain a fluorine atom and a silicon atom from a compatible viewpoint with hydrophobic resin (HR) mentioned later.
The resin used in the composition of the present invention 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. Moreover, the alicyclic hydrocarbon substituted by the (meth) acrylate type repeating unit 20-50 mol% which has an acid-decomposable group, the (meth) acrylate type repeating unit 20-50 mol% which has a lactone group, and a hydroxyl group or a cyano group. A copolymer containing 5 to 30 mol% of a (meth) acrylate-based repeating unit having a structure and further containing 0 to 20 mol% of another (meth) acrylate-based repeating unit is also preferred.
In the case where the composition of the present invention is irradiated with KrF excimer laser light, electron beam, X-ray, high energy light beam (EUV, etc.) having a wavelength of 50 nm or less, the resin preferably further has a hydroxystyrene-based repeating unit. . More preferably, it has a hydroxystyrene-based repeating unit, a hydroxystyrene-based repeating unit protected with an acid-decomposable group, and an acid-decomposable repeating unit such as a (meth) acrylic acid tertiary alkyl ester.
Examples of the repeating unit having a preferred acid-decomposable group based on hydroxystyrene include, for example, t-butoxycarbonyloxystyrene, 1-alkoxyethoxystyrene, a repeating unit of (meth) acrylic acid tertiary alkyl ester, and the like. More preferred are repeating units of 2-alkyl-2-adamantyl (meth) acrylate and dialkyl (1-adamantyl) methyl (meth) acrylate.
An example of a resin having a hydroxystyrene-based repeating unit is shown below.

The resin in the present invention can be synthesized according to a conventional method (for example, radical polymerization). For example, as a general synthesis method, a monomer polymerization method in which a monomer species and an initiator are dissolved in a solvent and heating is performed, and a solution of the monomer species and the initiator is dropped into the heating solvent over 1 to 10 hours. The dropping polymerization method is added, and the dropping polymerization method is preferable. Examples of the reaction solvent include ethers such as tetrahydrofuran, 1,4-dioxane and diisopropyl ether, ketones such as methyl ethyl ketone and methyl isobutyl ketone, ester solvents such as ethyl acetate, amide solvents such as dimethylformamide and dimethylacetamide, Furthermore, the solvent which melt | dissolves the composition of this invention like the below-mentioned propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, and cyclohexanone is mentioned. More preferably, the polymerization is performed using the same solvent as the solvent used in the actinic ray-sensitive or radiation-sensitive resin composition of the present invention. Thereby, generation | occurrence | production of the particle at the time of a preservation | save can be suppressed.
The polymerization reaction is preferably performed in an inert gas atmosphere such as nitrogen or argon. As a polymerization initiator, a commercially available radical initiator (azo initiator, peroxide, etc.) is used to initiate the polymerization. As the radical initiator, an azo initiator is preferable, and an azo initiator having an ester group, a cyano group, or a carboxyl group is preferable. Preferred examples of the initiator 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 solvent (precipitation or reprecipitation solvent) used when recovering the resin may be a poor solvent for the resin. Depending on the type of resin, hydrocarbon, halogenated hydrocarbon, nitro compound, ether, ketone, ester , Carbonate, alcohol, carboxylic acid, water, a mixed solvent containing these solvents, and the like. Among these, as a precipitation or reprecipitation solvent, a solvent containing at least an alcohol (particularly methanol or the like) or water is preferable.

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

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

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

In addition, after depositing and separating the resin once, it may be dissolved again in a solvent and brought into contact with a solvent in which the resin is hardly soluble or insoluble. That is, after completion of the radical polymerization reaction, a solvent in which the resin is hardly soluble or insoluble is brought into contact, the resin is precipitated (step a), the resin is separated from the solution (step b), and the resin solution A is dissolved again in the solvent. Preparation (step c), and then contacting the resin solution A with a solvent in which the resin is hardly soluble or insoluble in a volume amount less than 10 times that of the resin solution A (preferably not more than 5 times the volume amount). It may be a method including depositing a solid (step d) and separating the deposited resin (step e).
In order to prevent the resin from aggregating after the preparation of the composition, for example, as described in JP-A-2009-037108, the synthesized resin is dissolved in a solvent to form a solution. A step of heating at about 30 ° C. to 90 ° C. for about 30 minutes to 4 hours may be added.

The weight average molecular weight of the resin is preferably 1,000 to 200,000, more preferably 2,000 to 20,000, still more preferably 3,000 to 15,000, as a polystyrene equivalent value by GPC method. Particularly preferred is 5,000 to 11,000. By setting the weight average molecular weight to 1,000 to 200,000, deterioration of heat resistance and dry etching resistance can be prevented, developability is deteriorated, and viscosity is increased, resulting in deterioration of film forming property. Can be prevented.
The dispersity (molecular weight distribution) is usually 1.0 to 3.0, preferably 1.0 to 2.6, and more preferably 1.0 to 2.0. The smaller the molecular weight distribution, the better the resolution and the resist shape, and the smoother the sidewall of the resist pattern, the better the roughness.
In addition, the measurement of a weight average molecular weight and dispersion degree is performed using GPC (gel permeation chromatography) on the following conditions. Specifically, 0.2 g of a 10 wt% propylene glycol-1-monomethyl ether-2-acetate (PGMEA) solution sample was weighed, and then 2 ml of tetrahydrofuran (THF) was added and dissolved uniformly through a filter. Then, a measurement solution is prepared. This solution is subjected to GPC measurement under the following conditions.
<GPC measurement conditions>
Column: TSK gel HXL series Guard column: TSK guard column MP (XL)
This column: TSK gel Multipore Hxl-M Eluent: THF injection amount / flow rate: 100 μl / 1.0 ml / min constant temperature bath: 40 ° C. detection: RI calibration curve: polystyrene

In the present invention, the content of the resin in the entire composition is preferably 30 to 99% by mass, more preferably 55 to 95% by mass in the total solid content.
In addition, the resin of the present invention may be used alone or in combination in the composition. Furthermore, you may use combining resin of this invention, and resin which does not correspond to resin of this invention. In that case, it is preferable that 50 mass% or more of resin of this invention is used on the basis of all the resins contained in a composition.

[2] Compound that generates acid upon irradiation with actinic ray or radiation The composition of the present invention contains a compound that generates acid upon irradiation with actinic ray or radiation (hereinafter also referred to as “acid generator”).
Although it will not specifically limit if it is a well-known thing as an acid generator, As a preferable example, the compound represented by the following general formula (ZI), (ZII), or (ZIII) can be mentioned.

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).

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.

Z ⁻ represents a non-nucleophilic anion (an anion having an extremely low ability to cause a nucleophilic reaction).
Examples of Z ⁻ include a sulfonate anion (an aliphatic sulfonate anion, an aromatic sulfonate anion, a camphor sulfonate anion, etc.), a carboxylate anion (an aliphatic carboxylate anion, an aromatic carboxylate anion, an aralkyl carboxylate anion). Etc.), sulfonylimide anion, bis (alkylsulfonyl) imide anion, tris (alkylsulfonyl) methide anion and the like.

The aliphatic moiety in the aliphatic sulfonate anion and the aliphatic carboxylate anion may be an alkyl group or a cycloalkyl group, preferably a linear or branched alkyl group having 1 to 30 carbon atoms and a carbon number. 3-30 cycloalkyl groups are mentioned.
The aromatic group in the aromatic sulfonate anion and aromatic carboxylate anion is preferably an aryl group having 6 to 14 carbon atoms such as a phenyl group, a tolyl group, and a naphthyl group.

  The alkyl group, cycloalkyl group and aryl group mentioned above may have a substituent. Specific examples thereof include nitro groups, halogen atoms such as fluorine atoms, carboxyl groups, hydroxyl groups, amino groups, cyano groups, alkoxy groups (preferably having 1 to 15 carbon atoms), cycloalkyl groups (preferably having 3 to 15 carbon atoms). ), An aryl group (preferably 6 to 14 carbon atoms), an alkoxycarbonyl group (preferably 2 to 7 carbon atoms), an acyl group (preferably 2 to 12 carbon atoms), an alkoxycarbonyloxy group (preferably 2 to 2 carbon atoms). 7), an alkylthio group (preferably 1 to 15 carbon atoms), an alkylsulfonyl group (preferably 1 to 15 carbon atoms), an alkyliminosulfonyl group (preferably 2 to 15 carbon atoms), an aryloxysulfonyl group (preferably carbon) Number 6-20), alkylaryloxysulfonyl group (preferably C7-20), cycloalkylary Examples thereof include an oxysulfonyl group (preferably having 10 to 20 carbon atoms), an alkyloxyalkyloxy group (preferably having 5 to 20 carbon atoms), a cycloalkylalkyloxyalkyloxy group (preferably having 8 to 20 carbon atoms), and the like. . About the aryl group and ring structure which each group has, you may have an alkyl group (preferably C1-C15) further 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.
Examples of the sulfonylimide anion include saccharin anion.
The alkyl group in the bis (alkylsulfonyl) imide anion and tris (alkylsulfonyl) methide anion is preferably an alkyl group having 1 to 5 carbon atoms. Examples of substituents for these alkyl groups include halogen atoms, alkyl groups substituted with halogen atoms, alkoxy groups, alkylthio groups, alkyloxysulfonyl groups, aryloxysulfonyl groups, cycloalkylaryloxysulfonyl groups, and the like. A fluorine atom or an alkyl group substituted with a fluorine atom is preferred.

Examples of other Z ⁻ include fluorinated phosphorus (for example, PF ₆ ⁻ ), fluorinated boron (for example, BF ₄ ⁻ ), fluorinated antimony (for example, SbF ₆ ⁻ ), and the like.
Z ^- The at least α-position by an aliphatic sulfonate anion substituted with a fluorine atom, a fluorine atom or a fluorine atom is substituted with a group having a aromatic sulfonate anion of a sulfonic acid, an alkyl group substituted with a fluorine atom Bis (alkylsulfonyl) imide anions and tris (alkylsulfonyl) methide anions in which the alkyl group is substituted with a fluorine atom are preferred. More preferably, the non-nucleophilic anion is a perfluoroaliphatic sulfonate anion (more preferably 4 to 8 carbon atoms), a benzenesulfonate anion having a fluorine atom, still more preferably a nonafluorobutanesulfonate anion, perfluoro An octane sulfonate anion, a pentafluorobenzene sulfonate anion, and a 3,5-bis (trifluoromethyl) benzene sulfonate anion.

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

_Examples of the organic group for R ₂₀₁ , R ₂₀₂ and R ₂₀₃ include an aryl group (preferably having 6 to 15 carbon atoms), a linear or branched alkyl group (preferably having 1 to 10 carbon atoms), and a cycloalkyl group (having 3 carbon atoms). ~ 15 are preferred).
Of R ₂₀₁ , R ₂₀₂ and R ₂₀₃ , at least one is preferably an aryl group, more preferably all three are aryl groups. As the aryl group, in addition to a phenyl group, a naphthyl group, and the like, a heteroaryl group such as an indole residue and a pyrrole residue can be used.

These aryl groups, alkyl groups and cycloalkyl groups as R ₂₀₁ , R ₂₀₂ and R ₂₀₃ may further have a substituent. Examples of the substituent include halogen atoms such as nitro groups and fluorine atoms, carboxyl groups, hydroxyl groups, amino groups, cyano groups, alkoxy groups (preferably having 1 to 15 carbon atoms), cycloalkyl groups (preferably having 3 to 15 carbon atoms). ), An aryl group (preferably 6 to 14 carbon atoms), an alkoxycarbonyl group (preferably 2 to 7 carbon atoms), an acyl group (preferably 2 to 12 carbon atoms), an alkoxycarbonyloxy group (preferably 2 to 2 carbon atoms). 7) and the like, but are not limited thereto.

Two selected from R ₂₀₁ , R ₂₀₂ and R ₂₀₃ may be bonded via a single bond or a linking group. Examples of the linking group include an alkylene group (preferably having 1 to 3 carbon atoms), —O—, —S—, —CO—, —SO ₂ — and the like, but are not limited thereto.
Preferred structures when at least one of R ₂₀₁ , R ₂₀₂ and R ₂₀₃ is not an aryl group include paragraphs 0046 and 0047 of JP-A-2004-233661, paragraphs 0040 to 0046 of JP-A-2003-35948, US Compounds exemplified as formulas (I-1) to (I-70) in Patent Publication No. 2003 / 0224288A1, and Formulas (IA-1) to (I) in U.S. Patent Publication No. 2003 / 0077540A1 IA-54) and cation structures such as compounds exemplified as formulas (IB-1) to (IB-24).

  More preferable examples of the compound represented by the general formula (ZI) include a compound represented by the general formula (ZI-3) or the general formula (ZI-4) described below. First, the compound represented by general formula (ZI-3) is demonstrated.

In the general formula (ZI-3),
R ₁ represents an alkyl group, a cycloalkyl group, an alkoxy group, a cycloalkoxy group, an aryl group or an alkenyl group,
R ₂ and R ₃ each independently represents a hydrogen atom, an alkyl group, a cycloalkyl group or an aryl group, and R ₂ and R ₃ may be linked to each other to form a ring,
R ₁ and R ₂ may combine with each other to form a ring,
R _X and R _y each independently represents an alkyl group, a cycloalkyl group, an alkenyl group, an aryl group, a 2-oxoalkyl group, a 2-oxocycloalkyl group, an alkoxycarbonylalkyl group, or an alkoxycarbonylcycloalkyl group, R _X and R _y may be connected to each other to form a ring, and this ring structure may contain an oxygen atom, a nitrogen atom, a sulfur atom, a ketone group, an ether bond, an ester bond, or an amide bond.
Z ⁻ represents a non-nucleophilic anion.

The alkyl group as R ₁ is preferably a linear or branched alkyl group having 1 to 20 carbon atoms, and may have an oxygen atom, a sulfur atom, or a nitrogen atom in the alkyl chain. Specifically, methyl group, ethyl group, n-propyl group, n-butyl group, n-pentyl group, n-hexyl group, n-octyl group, n-dodecyl group, n-tetradecyl group, n-octadecyl group And a branched alkyl group such as a linear alkyl group such as isopropyl group, isobutyl group, t-butyl group, neopentyl group, and 2-ethylhexyl group. The alkyl group of R ₁ may have a substituent, and examples of the alkyl group having a substituent include a cyanomethyl group, a 2,2,2-trifluoroethyl group, a methoxycarbonylmethyl group, and an ethoxycarbonylmethyl group. Can be mentioned.

The cycloalkyl group as R ₁ is preferably a cycloalkyl group having 3 to 20 carbon atoms, and may have an oxygen atom or a sulfur atom in the ring. Specific examples include a cyclopropyl group, a cyclopentyl group, a cyclohexyl group, a norbornyl group, an adamantyl group, and the like. The cycloalkyl group represented by R ₁ may have a substituent, and examples of the substituent include an alkyl group and an alkoxy group.

The alkoxy group as R ₁ is preferably an alkoxy group having 1 to 20 carbon atoms. Specific examples include a methoxy group, an ethoxy group, an isopropyloxy group, a t-butyloxy group, a t-amyloxy group, and an n-butyloxy group. The alkoxy group of R ₁ may have a substituent, and examples of the substituent include an alkyl group and a cycloalkyl group.

The cycloalkoxy group as R ₁ is preferably a C3-C20 cycloalkoxy group, and examples thereof include a cyclohexyloxy group, a norbornyloxy group, and an adamantyloxy group. The cycloalkoxy group for R ₁ may have a substituent, and examples of the substituent include an alkyl group and a cycloalkyl group.

The aryl group as R ₁ is preferably an aryl group having 6 to 14 carbon atoms, and examples thereof include a phenyl group, a naphthyl group, and a biphenyl group. The aryl group of R ₁ may have a substituent, and preferred substituents include an alkyl group, a cycloalkyl group, an alkoxy group, a cycloalkoxy group, an aryloxy group, an alkylthio group, and an arylthio group. When the substituent is an alkyl group, a cycloalkyl group, an alkoxy group or a cycloalkoxy group, the same groups as the alkyl group, cycloalkyl group, alkoxy group and cycloalkoxy group as R ₁ described above can be used.

Examples of the alkenyl group as R ₁ include a vinyl group and an allyl group.

R ₂ and R ₃ represent a hydrogen atom, an alkyl group, a cycloalkyl group, or an aryl group, and R ₂ and R ₃ may be connected to each other to form a ring. However, at least one of R ₂ and R ₃ represents an alkyl group, a cycloalkyl group, or an aryl group. Specific examples and preferred examples of the alkyl group, cycloalkyl group and aryl group for R ₂ and R ₃ include those similar to the specific examples and preferred examples described above for R ₁ . When R ₂ and R ₃ are connected to each other to form a ring, the total number of carbon atoms contributing to the formation of the ring contained in R ₂ and R ₃ is preferably 4 to 7, and 4 or 5 It is particularly preferred that

R ₁ and R ₂ may be connected to each other to form a ring. When R ₁ and R ₂ are connected to each other to form a ring, R ₁ is an aryl group (preferably a phenyl group or a naphthyl group which may have a substituent), and R ₂ has 1 to 4 carbon atoms. An alkylene group (preferably a methylene group or an ethylene group) is preferable, and examples of the preferable substituent include the same substituents that the aryl group as R ₁ may have. As another form in the case where R ₁ and R ₂ are connected to each other to form a ring, it is also preferable that R ₁ is a vinyl group and R ₂ is an alkylene group having 1 to 4 carbon atoms.

The alkyl group represented by R _X and R _y is preferably an alkyl group having 1 to 15 carbon atoms, for example, methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group. , Pentyl, neopentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, eicosyl Groups and the like.

The cycloalkyl group represented by R _X and R _y is preferably a cycloalkyl group having 3 to 20 carbon atoms, such as a cyclopropyl group, a cyclopentyl group, a cyclohexyl group, a norbornyl group, an adamantyl group and the like.

The alkenyl group represented by R _X and R _y is preferably 2 to 30 alkenyl groups such as vinyl group, allyl group, and styryl group.

As the aryl group represented by R _X and R _y , for example, an aryl group having 6 to 20 carbon atoms is preferable. Specifically, a phenyl group, a naphthyl group, an azulenyl group, an acenaphthylenyl group, a phenanthrenyl group, a penalenyl group, a phenyl group, Examples thereof include a nantracenyl group, a fluorenyl group, an anthracenyl group, a pyrenyl group, and a benzopyrenyl group. Preferred are a phenyl group and a naphthyl group, and more preferred is a phenyl group.

The alkyl group moiety of the 2-oxoalkyl group and alkoxycarbonylalkyl group represented by R _X and R _y, for example, those previously listed as R _X and R _y.

Examples of the cycloalkyl group part of the 2-oxocycloalkyl group and alkoxycarbonylcycloalkyl group represented by R _X and R _y include those enumerated above as R _X and Ry.

Z ^- is, for example, Z in the above general formula (ZI) ^- include those listed as.

  The compound represented by the general formula (ZI-3) is preferably a compound represented by the following general formulas (ZI-3a) and (ZI-3b).

In the general formulas (ZI-3a) and (ZI-3b), R ₁ , R ₂ and R ₃ are as defined in the general formula (ZI-3).

Y represents an oxygen atom, a sulfur atom or a nitrogen atom, and is preferably an oxygen atom or a nitrogen atom. m, n, p, and q represent integers, preferably 0 to 3, more preferably 1 to 2, and particularly preferably 1. The alkylene group connecting S ⁺ and Y may have a substituent, and preferred examples of the substituent include an alkyl group.

R ₅ represents a monovalent organic group when Y is a nitrogen atom, and is absent when Y is an oxygen atom or a sulfur atom. R ₅ is preferably a group containing an electron withdrawing group, and particularly preferably a group represented by the following general formulas (ZI-3a-1) to (ZI-3a-4).

In the above (ZI-3a-1) to (ZI-3a-3), R represents a hydrogen atom, an alkyl group, a cycloalkyl group, or an aryl group, preferably an alkyl group. Specific examples and preferred examples of the alkyl group, cycloalkyl group and aryl group for R include the same specific examples and preferred examples as those described above for R ₁ in the general formula (ZI-3).
In the above (ZI-3a-1) to (ZI-3a-4), * represents a bond connected to a nitrogen atom as Y in the compound represented by the general formula (ZI-3a).

When Y is a nitrogen atom, R ₅ is particularly preferably a group represented by —SO ₂ —R ₄ . R ₄ represents an alkyl group, a cycloalkyl group or an aryl group, preferably an alkyl group. Specific examples and preferred examples of the alkyl group, cycloalkyl group and aryl group for R ₄ include those similar to the specific examples and preferred examples described above for R ₁ .

Z ^- is, for example, Z in the above general formula (ZI) ^- include those listed as.

  The compound represented by the general formula (ZI-3) is particularly preferably a compound represented by the following general formulas (ZI-3a ′) and (ZI-3b ′).

In the general formulas (ZI-3a ′) and (ZI-3b ′), R ₁ , R ₂ , R ₃ , Y and R ₅ are as defined in the general formulas (ZI-3a) and (ZI-3b). It is.

Z ^- is, for example, Z in the above general formula (ZI) ^- include those listed as.

  Specific examples of the cation moiety of the compound represented by the general formula (ZI-3) are shown below.

  Next, the compound represented by general formula (ZI-4) is demonstrated.

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 represents 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. These groups may have a substituent. When there are a plurality of R ₁₄ , each R ₁₄ may be the same or different.
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, and the atoms constituting the ring may include heteroatoms such as an oxygen atom, a sulfur atom and a nitrogen atom. 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 General Formula (ZI-4), the alkyl groups represented by R ₁₃ , R _14, and R ₁₅ are linear or branched and preferably have 1 to 10 carbon atoms.
Examples of the cycloalkyl group represented by R ₁₃ , R ₁₄ and R ₁₅ include a monocyclic or polycyclic cycloalkyl group.
The alkoxy group for R ₁₃ and R ₁₄ is linear or branched and preferably has 1 to 10 carbon atoms.
The alkoxycarbonyl group for R ₁₃ and R ₁₄ is linear or branched and preferably has 2 to 11 carbon atoms.
Examples of the group having a cycloalkyl group of R ₁₃ and R ₁₄ include a group having a monocyclic or polycyclic cycloalkyl group. These groups may further have a substituent.
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 for R ₁₄ are linear, branched, or cyclic, and preferably those having 1 to 10 carbon atoms.

  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 an alkoxycarbonyloxy group. Etc.

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 or a 2,5-dihydrothiophene ring), and may be condensed with an aryl group or a cycloalkyl group. This divalent R ₁₅ may have a substituent. Examples of the substituent include a hydroxyl group, a carboxyl group, a cyano group, a nitro group, an alkyl group, a cycloalkyl group, an alkoxy group, an alkoxyalkyl group, an alkoxycarbonyl group. Group, alkoxycarbonyloxy group and the like. There may be a plurality of substituents for the ring structure, or they may be bonded to each other to form a ring.

R ₁₅ in the general formula (ZI-4) is preferably a methyl group, an ethyl group, a naphthyl group, or a divalent group in which two R ₁₅ are bonded to each other to form a tetrahydrothiophene ring structure together with a sulfur atom. A divalent group in which two R ₁₅ are bonded to each other to form a tetrahydrothiophene ring structure together with a sulfur atom is particularly preferable.

The substituent that R ₁₃ and R ₁₄ may have is preferably a hydroxyl group, an alkoxy group, an alkoxycarbonyl group, or a halogen atom (particularly a fluorine atom).
l is preferably 0 or 1, and more preferably 1.
As r, 0-2 are preferable.

  Specific examples of the cation moiety of the compound represented by the general formula (ZI-4) are given below.

  Specific examples of the cation structure possessed by the compound represented by the general formula (ZI-3) or the general formula (ZI-4) described above include the above-mentioned JP-A Nos. 2004-233661 and 2003-35948. In addition to cation structures such as compounds exemplified in Japanese Patent Publication No. 2003 / 0224288A1 and US Patent Application Publication No. 2003 / 0077540A1, for example, paragraph 0046 of JP2011-53360A , 0047, 0072 to 0077, cation structures in chemical structures and the like exemplified in 0107 to 0110, cations in chemical structures and the like exemplified in paragraphs 0135 to 0137, 0151 and 0196 to 0199 in JP2011-53430A Examples include the structure.

In general formula (ZII) and general formula (ZIII),
R ₂₀₄ to R ₂₀₇ each independently represents an aryl group, an alkyl group or a cycloalkyl group.
The aryl group, alkyl group, and cycloalkyl group of R _{204 to} R ₂₀₇ are the same as the aryl group, alkyl group, and cycloalkyl group of R _{201 to} R ₂₀₃ in the aforementioned compound (ZI).
The aryl group, alkyl group, and cycloalkyl group of R _{204 to} R ₂₀₇ may have a substituent. Even the substituent, an aryl group of R ₂₀₁ to R ₂₀₃ in the above compound (ZI), alkyl groups include those which may have a cycloalkyl group.
Z ^- is, for example, Z in the above general formula (ZI) ^- include those listed as.

  In addition to the compound represented by the general formula (ZI-3) or (ZI-4), a compound represented by the following general formula (I ′) is also preferable as the acid generator. By using a compound represented by the following general formula (I ′), the exposure light transmittance is improved, and LWR and DOF (Depth of Focus) are improved.

In the general formula (I ′),
X ′ represents an oxygen atom, a sulfur atom or —N (Rx) —.
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 arylcarbonyl Represents an oxy group.
Rx 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.
R ₁ ′ and R ₂ ′ may be connected to each other to form a ring. Also, any two or more of R ₆ ′ to R ₉ ′, R ₃ ′ and R ₉ ′, R ₄ ′ and R ₅ ′, R ₅ ′ and Rx, and R ₆ ′ and Rx are connected to each other. To form a ring.
X ′ is preferably a sulfur atom or —N (Rx) — from the viewpoint of keeping light absorbency (for example, absorbance at a wavelength of 193 nm) low.
Z ^- is, for example, Z in the above general formula (ZI) ^- include those listed as.

The alkyl groups as R ₁ ′ to R ₉ ′ and Rx may have a substituent, preferably a linear or branched alkyl group having 1 to 20 carbon atoms, and an oxygen atom, sulfur in the alkyl chain You may have an atom and a nitrogen atom. Specifically, methyl group, ethyl group, n-propyl group, n-butyl group, n-pentyl group, n-hexyl group, n-octyl group, n-dodecyl group, n-tetradecyl group, n-octadecyl group, etc. And a branched alkyl group such as isopropyl group, isopropyl group, isobutyl group, t-butyl group, neopentyl group, 2-ethylhexyl group.

Examples of the alkyl group having a substituent for Rx include a cyanomethyl group, a 2,2,2-trifluoroethyl group, a methoxycarbonylmethyl group, and an ethoxycarbonylmethyl group.
Examples of the alkyl group having a substituent for R ₁ ′ and R ₂ ′ include a methoxyethyl group.
In addition, a group in which a cycloalkyl group is substituted on a linear or branched alkyl group (for example, an adamantylmethyl group, an adamantylethyl group, a cyclohexylethyl group, a camphor residue, etc.) and the like are also included.

The cycloalkyl group as R ₁ ′ to R ₉ ′ and Rx may have a substituent, preferably a cycloalkyl group having 3 to 20 carbon atoms, and has an oxygen atom in the ring. Also good. Specific examples include a cyclopropyl group, a cyclopentyl group, a cyclohexyl group, a norbornyl group, an adamantyl group, and the like.
The acyl group as R < ₃ >'-R< ₉ >', Rx may have a substituent, Preferably it is a C1-C10 acyl group. Specific examples include an acetyl group, a propionyl group, and an isobutyryl group.
The alkenyl group as Rx is preferably an alkenyl group having 2 to 8 carbon atoms, and examples thereof include a vinyl group, an allyl group, and a butenyl group.
The alkoxy group as R ₃ ′ to R ₉ ′ may have a substituent, and is preferably an alkoxy group having 1 to 20 carbon atoms. Specific examples include a methoxy group, an ethoxy group, an isopropyloxy group, a cyclohexyloxy group, and the like.

The alkoxycarbonyl group as R < ₃ >'-R< ₉ >> may have a substituent, Preferably it is a C2-C20 alkoxycarbonyl group. Specific examples include a methoxycarbonyl group, an ethoxycarbonyl group, an isopropyloxycarbonyl group, and a cyclohexyloxycarbonyl group.

The alkylcarbonyloxy group as R ₃ ′ to R ₉ ′ may have a substituent, and is preferably an alkylcarbonyloxy group having 2 to 20 carbon atoms. Specific examples include a methylcarbonyloxy group, an ethylcarbonyloxy group, an isopropylcarbonyloxy group, and a cyclohexylcarbonyloxy group.

The aryl groups as R ₁ ′ to R ₉ ′ and Rx may have a substituent, preferably an aryl group having 6 to 14 carbon atoms, and examples thereof include a phenyl group and a naphthyl group.

The aryloxy group as R ₃ ′ to R ₉ ′ may have a substituent, and preferably an aryloxy group having 6 to 14 carbon atoms, such as a phenyloxy group and a naphthyloxy group. .

The aryloxycarbonyl group as R ₃ ′ to R ₉ ′ and Rx may have a substituent, preferably an aryloxycarbonyl group having 7 to 15 carbon atoms, such as a phenyloxycarbonyl group or naphthyloxy group. A carbonyl group etc. are mentioned.
The arylcarbonyloxy group as R ₃ ′ to R ₉ ′ may have a substituent, preferably an arylcarbonyloxy group having 7 to 15 carbon atoms, such as a phenylcarbonyloxy group or a naphthylcarbonyloxy group. Etc.
The arylcarbonyl group as Rx may have a substituent and is preferably an arylcarbonyl group having 7 to 15 carbon atoms, such as a phenylcarbonyl group and a naphthylcarbonyl group.

R ₃ ′ to R ₉ ′ as an alkyl group, R ₁ ′ to R ₉ ′, a cycloalkyl group as Rx, R ₃ ′ to R ₉ ′, an acyl group as Rx, and R ₃ ′ to R ₉ ′ alkoxy group, _{R 3} '~R _9' alkoxycarbonyl group as an alkyl carbonyloxy group as _{R 3 '~R 9', R} 1 '~R 9', the aryl group as Rx, _{R 3} '~R ₉ An aryloxy group as', R ₃ 'to R ₉ ', an aryloxycarbonyl group as Rx, an arylcarbonyloxy group as R ₃ 'to R ₉ ', and an arylcarbonyl group as Rx Preferred substituents include alkyl groups (which may be linear, branched or cyclic, preferably having 1 to 12 carbon atoms), aryl groups (preferably having 6 to 14 carbon atoms), nitro groups, fluorine atoms. Halogen source such as 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), acyl group (preferably having 2 to 12 carbon atoms) and the like. Can be mentioned.
Examples of the ring structure that R ₁ ′ and R ₂ ′ may be bonded to each other include divalent R ₁ ′ and R ₂ ′ (for example, ethylene group, propylene group, 1,2-cyclohexylene group, etc.) 5 or 6-membered ring formed together with the sulfur atom in the general formula (I ′), particularly preferably a 5-membered ring (that is, a tetrahydrothiophene ring). However, from the viewpoint of decomposition efficiency of acid anion generation, it is preferable that R ₁ ′ and R ₂ ′ are not bonded 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 Rx, and R ₆ ′ and Rx are bonded together. Preferred ring structures include preferably 5 or 6 membered rings, particularly preferably 6 membered rings.
R ₁ ′ and R ₂ ′ are particularly preferably an alkyl group or an aryl group.
Particularly preferred examples of R ₃ ′ to R ₉ ′ include an alkyl group which may have a substituent, or a hydrogen atom. When used in an ArF resist application, hydrogen is used in terms of absorption intensity at 193 nm. Atoms are particularly preferred.
Rx is particularly preferably an alkyl group or an acyl group.

Next, general formula (2), general formula (2 ′) and general formula (2 ″), which are preferred structures of the non-nucleophilic anion Z ⁻ , will be described.
First, the sulfonate anion represented by the general formula (2) will be described.

In general formula (2),
Xf each independently represents a fluorine atom or an alkyl group substituted with at least one fluorine atom.
R ₇ and R ₈ each independently represent a hydrogen atom, a fluorine atom, an alkyl group, or an alkyl group substituted with at least one fluorine atom, and when there are a plurality of R ₇ and R ₈ , R ₇ and R ₈ are the same But it can be different.
L represents a divalent linking group, and when there are a plurality of L, L may be the same or different.
A represents an organic group containing a cyclic structure.
x represents an integer of 1 to 20. y represents an integer of 0 to 10. z represents an integer of 0 to 10.

The anion of the general formula (2) will be described in more detail.
Xf is a fluorine atom or an alkyl group substituted with at least one fluorine atom as described above, and the alkyl group in the alkyl group substituted with a fluorine atom is preferably an alkyl group having 1 to 10 carbon atoms, An alkyl group having 1 to 4 carbon atoms is more preferable. The alkyl group substituted with a fluorine atom of Xf is preferably a perfluoroalkyl group.

Xf is preferably a fluorine atom or a perfluoroalkyl group having 1 to 4 carbon atoms. Specifically, fluorine atom, CF ₃ , C ₂ F ₅ , C ₃ F ₇ , C ₄ F ₉ , C ₅ F ₁₁ , C ₆ F ₁₃ , C ₇ F 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 is mentioned, among which fluorine atom and CF ₃ are preferable. In particular, it is preferable that both Xf are fluorine atoms.

R ₇ and R ₈ represent a hydrogen atom, a fluorine atom, an alkyl group, or an alkyl group substituted with at least one fluorine atom as described above, and the alkyl group preferably has 1 to 4 carbon atoms. More preferably, it is a C1-C4 perfluoroalkyl group. Specific examples of the alkyl group substituted with at least one fluorine atom of R ₇ and R ₈ include CF ₃ , C ₂ F ₅ , C ₃ F ₇ , C ₄ F ₉ , C ₅ F ₁₁ , and 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 Examples thereof include C ₃ F ₇ , CH ₂ C ₄ F ₉ , and CH ₂ CH ₂ C ₄ F ₉ , among which CF ₃ is preferable.

L represents a divalent linking group, and represents —COO—, —OCO—, —CO—, —O—, —S—, —SO—, —SO ₂ —, —N (Ri) — (wherein Ri represents a hydrogen atom or alkyl), an alkylene group (preferably 1 to 6 carbon atoms), a cycloalkylene group (preferably 3 to 10 carbon atoms), an alkenylene group (preferably 2 to 6 carbon atoms), or a plurality of these such divalent linking group formed by combining can be _{mentioned, -COO -, - OCO -,} - CO -, - SO 2 -, - CON (Ri) -, - SO 2 N (Ri) -, - CON (Ri ) - alkylene radical -, - N (Ri) CO- alkylene group -, - is preferably, -COO - - COO- alkylene group - or -OCO- alkylene group, - OCO -, - _SO 2 -, - CON (Ri) - or _-SO 2 N (Ri) - is that Is more preferable. When there are a plurality of L, they may be the same or different.

  The alkyl group as Ri is preferably a linear or branched alkyl group having 1 to 20 carbon atoms, and may have an oxygen atom, a sulfur atom, or a nitrogen atom in the alkyl chain. Specifically, methyl group, ethyl group, n-propyl group, n-butyl group, n-pentyl group, n-hexyl group, n-octyl group, n-dodecyl group, n-tetradecyl group, n-octadecyl group, etc. And a branched alkyl group such as isopropyl group, isopropyl group, isobutyl group, t-butyl group, neopentyl group, 2-ethylhexyl group. Examples of the alkyl group having a substituent include a cyanomethyl group, a 2,2,2-trifluoroethyl group, a methoxycarbonylmethyl group, and an ethoxycarbonylmethyl group.

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

  The alicyclic group may be monocyclic or polycyclic, and may be a monocyclic cycloalkyl group such as a cyclopentyl group, a cyclohexyl group, or a cyclooctyl group, a norbornyl group, a norbornene-yl group, or a tricyclodecanyl group (for example, tricyclo [ 5.2.1.0 (2,6)] decanyl group), tetracyclodecanyl group, tetracyclododecanyl group, adamantyl group and the like are preferable. Also preferred are nitrogen atom-containing alicyclic groups such as piperidine group, decahydroquinoline group, decahydroisoquinoline group. Among them, an alicyclic group having a bulky structure of 7 or more carbon atoms such as a norbornyl group, a tricyclodecanyl group, a tetracyclodecanyl group, a tetracyclododecanyl group, an adamantyl group, a decahydroquinoline group, and a decahydroisoquinoline group. And diffusibility in the film in the PEB (post-exposure heating) step can be suppressed, which is preferable from the viewpoint of improving exposure latitude.

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

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

  The organic group containing the cyclic structure may have a substituent, and the substituent may be an alkyl group (which may be linear, branched or cyclic, preferably having 1 to 12 carbon atoms), An aryl group (preferably having 6 to 14 carbon atoms), a hydroxy group, an alkoxy group, an ester group, an amide group, a urethane group, a ureido group, a thioether group, a sulfonamide group, a sulfonic acid ester group, a cyano group and the like can be mentioned.

  The carbon constituting the organic group containing a cyclic structure (carbon contributing to ring formation) may be a carbonyl carbon.

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

  In one embodiment of the present invention, the number of fluorine atoms contained in the anion represented by the general formula (2) is preferably 2 or 3. Thereby, the effect by combined use with resin (A) can further be heightened.

  Next, the disulfonyl imido acid anion represented by the general formula (2 ′) and the trisulfonylmethide acid anion represented by the general formula (2 ″) will be described.

In general formula (2 ′) and general formula (2 ″),
Xf is as defined in the general formula (2), and preferred examples are also the same. In the general formula (2 ′), two Xf's may be linked to each other to form a ring structure.

Z ^- The disulfonylimide anion of, preferably a bis (alkylsulfonyl) imide anion.
The alkyl group in the bis (alkylsulfonyl) imide anion is preferably an alkyl group having 1 to 5 carbon atoms.
Two alkyl groups in the bis (alkylsulfonyl) imide anion may be linked to each other to form an alkylene group (preferably having 2 to 4 carbon atoms), and may form a ring together with the imide group and the two sulfonyl groups. The ring structure that may be formed by the bis (alkylsulfonyl) imide anion is preferably a 5- to 7-membered ring, and more preferably a 6-membered ring.

  These alkyl groups and alkylene groups formed by connecting two alkyl groups to each other can have a halogen atom, an alkyl group substituted with a halogen atom, an alkoxy group, an alkylthio group, an alkyloxysulfonyl group, an aryl Examples thereof include an oxysulfonyl group and a cycloalkylaryloxysulfonyl group, and a fluorine atom or an alkyl group substituted with a fluorine atom is preferred.

Z ⁻ is also preferably a sulfonate anion represented by the following general formula (B-1).

In the general formula (B-1),
R _b1 each independently represents a hydrogen atom, a fluorine atom or a trifluoromethyl group (CF ₃ ).
n represents an integer of 0 to 4.
n is preferably an integer of 0 to 3, and more preferably 0 or 1.
X _b1 represents a single bond, an alkylene group, an ether bond, an ester bond (-OCO- or -COO-), a sulfonate ester bond (-OSO ₂ - or _-SO 3 -), or an combination thereof.
X _b1 is preferably an ester bond (—OCO— or —COO—) or a sulfonate ester bond (—OSO ₂ — or —SO ₃ —), and preferably an ester bond (—OCO— or —COO—). Is more preferable.
R _b2 represents an organic group having 6 or more carbon atoms.

The organic group having 6 or more carbon atoms for R _b2 is preferably a bulky group, and examples thereof include alkyl groups, alicyclic groups, aryl groups, and heterocyclic groups having 6 or more carbon atoms.

The alkyl group having 6 or more carbon atoms for R _b2 may be linear or branched, and is preferably a linear or branched alkyl group having 6 to 20 carbon atoms. Examples thereof include a linear or branched hexyl group, a linear or branched heptyl group, and a linear or branched octyl group. From the viewpoint of bulkiness, a branched alkyl group is preferable.

The alicyclic group having 6 or more carbon atoms for R _b2 may be monocyclic or polycyclic. Examples of the monocyclic alicyclic group include monocyclic cycloalkyl groups such as a cyclohexyl group and a cyclooctyl group. Examples of the polycyclic alicyclic group include polycyclic cycloalkyl groups such as a norbornyl group, a tricyclodecanyl group, a tetracyclodecanyl group, a tetracyclododecanyl group, and an adamantyl group. Among them, an alicyclic group having a bulky structure having 7 or more carbon atoms such as a norbornyl group, a tricyclodecanyl group, a tetracyclodecanyl group, a tetracyclododecanyl group, and an adamantyl group is used in a PEB (post-exposure heating) step. From the viewpoints of suppressing diffusibility in the film and improving MEEF (Mask Error Enhancement Factor).

The aryl group having 6 or more carbon atoms for R _b2 may be monocyclic or polycyclic. Examples of the aryl group include a phenyl group, a naphthyl group, a phenanthryl group, and an anthryl group. Among these, a naphthyl group having a relatively low light absorbance at 193 nm is preferable.

The heterocyclic group having 6 or more carbon atoms for R _b2 may be monocyclic or polycyclic, but polycyclic can suppress acid diffusion more. Moreover, the heterocyclic group may have aromaticity or may not have aromaticity. Examples of the heterocyclic ring having aromaticity include a benzofuran ring, a benzothiophene ring, a dibenzofuran ring, and a dibenzothiophene ring. Examples of the heterocyclic ring not having aromaticity include a tetrahydropyran ring, a lactone ring, a sultone ring, and a decahydroisoquinoline ring.

The organic group having 6 or more carbon atoms for R _b2 may further have a substituent. Examples of the further substituent include an alkyl group (which may be linear or branched, preferably 1 to 12 carbon atoms), and a cycloalkyl group (monocyclic, polycyclic, or spiro ring). And preferably having 3 to 20 carbon atoms), an aryl group (preferably having 6 to 14 carbon atoms), a hydroxy group, an alkoxy group, an ester group, an amide group, a urethane group, a ureido group, a thioether group, a sulfonamide group, And sulfonic acid ester groups. In addition, carbonyl carbon may be sufficient as the carbon (carbon which contributes to ring formation) which comprises the above-mentioned alicyclic group, an aryl group, or a heterocyclic group.
Specific examples of the sulfonate anion structure represented by the general formula (B-1) are shown below, but the present invention is not limited thereto.

Z ⁻ is also preferably a sulfonate anion represented by the following general formula (AI).

In general formula (AI),
R ₁ is an alkyl group, a monovalent alicyclic hydrocarbon group, an aryl group, or a heteroaryl group.
R ₂ is a divalent linking group.
Rf is a fluorine atom or an alkyl group substituted with at least one fluorine atom.
n ₁ and n ₂ are each independently 0 or 1.

The alkyl group represented by R ₁ is preferably an alkyl group having 1 to 20 carbon atoms, more preferably an alkyl group having 1 to 10 carbon atoms, and an alkyl group having 1 to 5 carbon atoms. It is further more preferable, and it is especially preferable that it is a C1-C4 alkyl group. Specific examples of the alkyl group include, for example, a methyl group, an ethyl group, a 1-propyl group, a 2-propyl group, a 1-butyl group, a 2-butyl group, a 2- (2-methylpropyl) group, and a 1-pentyl group. 2-pentyl group, 3-pentyl group, 1- (2-methylbutyl) group, 1- (3-methylbutyl) group, 2- (2-methylbutyl) group, 2- (3-methylbutyl) group, neopentyl group, 1-hexyl group, 2-hexyl group, 3-hexyl group, 1- (2-methylpentyl) group, 1- (3-methylpentyl) group, 1- (4-methylpentyl) group, 2- (2- A methylpentyl) group, a 2- (3-methylpentyl) group, a 2- (4-methylpentyl) group, a 3- (2-methylpentyl) group, a 3- (3-methylpentyl) group, and the like.

  The alkyl group may have a substituent (preferably a fluorine atom), and the alkyl group having a substituent is an alkyl group having 1 to 5 carbon atoms substituted with at least one fluorine atom. It is preferable that it is a C1-C5 perfluoroalkyl group.

The alkyl group represented by R ₁ is preferably a methyl group, an ethyl group, or a trifluoromethyl group, and more preferably a methyl group or an ethyl group.

The monovalent alicyclic hydrocarbon group represented by R ₁ preferably has 5 or more carbon atoms. In addition, the monovalent alicyclic hydrocarbon group preferably has 20 or less carbon atoms, and more preferably 15 or less. The monovalent alicyclic hydrocarbon group may be a monocyclic alicyclic hydrocarbon group or a polycyclic alicyclic hydrocarbon group. A part of —CH ₂ — of the alicyclic hydrocarbon group may be substituted with —O— or —C (═O) —.

  As the monocyclic alicyclic hydrocarbon group, those having 5 to 12 carbon atoms are preferable, and cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclooctyl group, cyclododecanyl group, cyclopentenyl group, cyclohexenyl group, Examples thereof include a cyclooctadienyl group and a piperidine ring group, and a cyclopentyl group, a cyclohexyl group, and a cyclooctyl group are particularly preferable.

As the polycyclic alicyclic hydrocarbon group, those having 10 to 20 carbon atoms are preferable, and bicyclo [4.3.0] nonanyl group, decahydronaphthalenyl group, 1,2,3,4-tetrahydronaphtha. Renyl group, tricyclo [5.2.1.0 (2,6)] decanyl group, tetracyclodecanyl group, tetracyclododecanyl group, bornyl group, isobornyl group, norbornyl group, adamantyl group, noradamantyl group, 1,7,7-trimethyltricyclo [2.2.1.0 ^2,6 ] heptanyl group, 3,7,7-trimethylbicyclo [4.1.0] heptanyl group, decahydroisoquinoline ring group and the like. A norbornyl group, an adamantyl group and a noradamantyl group are preferred.

The aryl group represented by R ₁ preferably has 6 or more carbon atoms. The aryl group preferably has 20 or less carbon atoms, more preferably 15 or less.
The heteroaryl group represented by R ₁ preferably has 2 or more carbon atoms. The heteroaryl group preferably has 20 or less carbon atoms, and more preferably 15 or less.
The aryl group and heteroaryl group may be a monocyclic aryl group or a monocyclic heteroaryl group, or may be a polycyclic aryl group or a polycyclic heteroaryl group.

Examples of the monocyclic aryl group include a phenyl group.
Examples of the polycyclic aryl group include a naphthyl group and an anthracenyl group.
Examples of the monocyclic heteroaryl group include a pyridyl group, a thienyl group, and a furanyl group.
Examples of the polycyclic heteroaryl group include a quinolyl group and an isoquinolyl group.

The monovalent alicyclic hydrocarbon group, aryl group, and heteroaryl group as R ₁ may further have a substituent. Examples of such a further substituent include a hydroxyl group, a halogen atom, Atom (fluorine atom, chlorine atom, bromine atom, iodine atom, etc.), nitro group, cyano group, amide group, sulfonamido group, methyl group, ethyl group, propyl group, n-butyl group, sec-butyl group, hexyl group Alkyl groups such as 2-ethylhexyl group and octyl group, alkoxy groups such as methoxy group, ethoxy group, hydroxyethoxy group, propoxy group, hydroxypropoxy group and butoxy group, alkoxycarbonyl groups such as methoxycarbonyl group and ethoxycarbonyl group, Acyloxy such as formyl, acetyl, benzoyl and other acyl groups, acetoxy and butyryloxy Group and carboxy group.

R ₁ is particularly preferably a cyclohexyl group or an adamantyl group.

The divalent linking group represented by R ₂ is not particularly limited, but is —COO—, —OCO—, —CO—, —O—, —S—, —SO—, —SO ₂ —, alkylene. A group (preferably an alkylene group having 1 to 30 carbon atoms), a cycloalkylene group (preferably a cycloalkylene group having 3 to 30 carbon atoms), an alkenylene group (preferably an alkenylene group having 2 to 30 carbon atoms), an arylene group (preferably May be a C6-C30 arylene group), a heteroarylene group (preferably a C2-C30 heteroarylene group), or a group in which two or more of these are combined. The above alkylene group, cycloalkylene group, alkenylene group, arylene group and heteroarylene group may further have a substituent, and specific examples of such a substituent include a monovalent alicyclic ring as R _1. The substituents that the hydrocarbon group, aryl group, and heteroaryl group may further have are the same as those described above.

The divalent linking group represented by R ₂ is preferably an alkylene group, a cycloalkylene group, an alkenylene group, an arylene group, or a heteroarylene group, more preferably an alkylene group, and further an alkylene group having 1 to 10 carbon atoms. An alkylene group having 1 to 5 carbon atoms is preferable.

Rf is a fluorine atom or an alkyl group substituted with at least one fluorine atom. The alkyl group preferably has 1 to 30 carbon atoms, preferably 1 to 10 carbon atoms, and more preferably 1 to 4 carbon atoms. The alkyl group substituted with at least one fluorine atom is preferably a perfluoroalkyl group.
Rf is preferably a fluorine atom or a perfluoroalkyl group having 1 to 4 carbon atoms. More specifically, Rf is a fluorine atom, CF ₃ , C ₂ F ₅ , C ₃ F ₇ , C ₄ F ₉ , C ₅ F ₁₁ , C ₆ F ₁₃ , C ₇ F ₁₅ , C ₈ F ₁₇ , _{CH 2 CF 3, CH 2 CH} 2 CF 3, CH 2 C 2 F 5, CH 2 CH 2 C 2 F 5, CH 2 C 3 F 7, CH 2 CH 2 C 3 F 7, CH 2 C 4 F 9 Or CH ₂ CH ₂ C ₄ F ₉ , and more preferably a fluorine atom or CF ₃ .

n ₁ is preferably 1.
n ₂ is preferably 1.
Although the preferable specific example of the sulfonate anion represented by the said general formula (AI) is given to the following, this invention is not limited to these.

[Sulfonic acid anion represented by general formula (AI)]

  Examples of the acid generator further include compounds represented by the following general formula (ZV).

In general formula (ZV),
R ₂₀₈ 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 R ₂₀₈ include the same examples as the specific examples of the aryl group as R _{201 to} R ₂₀₃ in the general formula (ZI).
Specific examples of the alkyl group and cycloalkyl group represented by R ₂₀₈ include the same examples as the specific examples of the alkyl group and cycloalkyl group represented by R _{201 to} R ₂₀₃ in the general formula (ZI).

  The alkylene group of A is an alkylene group 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 carbon atoms. ˜12 alkenylene groups (for example, vinylene 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.) Each can be mentioned.

  The acid generator has a fluorine content represented by (total mass of all fluorine atoms contained in the acid generator) / (total mass of all atoms contained in the acid generator) of 0.30. Or less, more preferably 0.25 or less, still more preferably 0.20 or less, particularly preferably 0.15 or less, and most preferably 0.10 or less. .

(Preferred embodiment)
As a suitable aspect of an acid generator, the ionic compound containing a cation and an anion is mentioned by the point which the effect of this invention is more excellent, and it is more preferable that it is a salt.
Hereinafter, a preferred embodiment when the acid generator is an ionic compound will be described in detail.

A preferred embodiment of the acid generator is an ionic compound containing a cation and an anion in that the effect of the present invention is more excellent, and an embodiment in which the anion is a sulfonate anion represented by the above general formula (2). It is done. The description of the sulfonate anion represented by the general formula (2) is as described above.
In addition, the kind in particular of a cation is not restrict | limited, A well-known cation can be used, For example, the cation (cation structure part) in the general formula (ZI) or (ZII) mentioned above is mentioned.

A preferred embodiment of the acid generator is an ionic compound containing a cation and an anion in that the effect of the present invention is more excellent, and the anion is a sulfonate anion represented by the above general formula (B-1). Is mentioned. The description of the sulfonate anion represented by formula (B-1) is as described above.
In addition, the kind in particular of a cation is not restrict | limited, A well-known cation can be used, For example, the cation (cation structure part) in the general formula (ZI) or (ZII) mentioned above is mentioned.

As a suitable aspect of an acid generator, the point which is the ionic compound containing a cation and an anion at the point which the effect of this invention is more excellent, and the aspect whose number of fluorine atoms contained in an anion is 2-3 are mentioned.
The kind of anion is not particularly limited, and a known anion can be used. For example, a sulfonate anion represented by the above general formula (2) (or general formula (B-1)) or a general formula ( 2 ′) or a trisulfonylmethide acid anion represented by the general formula (2 ″).
In addition, the kind in particular of a cation is not restrict | limited, A well-known cation can be used, For example, the cation (cation structure part) in the general formula (ZI) or (ZII) mentioned above is mentioned.

  A preferred embodiment of the acid generator is an ionic compound containing a cation and an anion, and the cation is a cation represented by the general formula (ZI-3A) or a cation represented by the general formula (ZI-4) Is mentioned.

The cations represented by the general formula (ZI-3A) and the general formula (ZI-4A) are cations in the acid generator represented by the general formula (ZI-3) and the general formula (ZI-4), respectively. And the definition of each group in the general formula (ZI-3A) and the general formula (ZI-4A) is as described above.
The kind of anion is not particularly limited, and a known anion can be used. For example, the sulfonate anion represented by the above general formula (2) (or general formula (B-1)), 2 ') and the disulfonyl imido acid anion represented by the general formula (2'').

  Among acid generators, particularly preferred examples are given below.

An acid generator can be used individually by 1 type or in combination of 2 or more types.
The content of the acid generator in the composition is preferably 0.1 to 30% by mass, more preferably 3 to 25% by mass, and still more preferably 7 to 20% by mass, based on the total solid content of the composition. is there.

[3] Hydrophobic resin The actinic ray-sensitive or radiation-sensitive resin composition of the present invention contains a composition resin (hereinafter also referred to as “hydrophobic resin (HR)”), particularly when applied to immersion exposure. May be. As a result, the hydrophobic resin (HR) is unevenly distributed on the surface layer of the film, and when the immersion medium is water, the static / dynamic contact angle of the resist film surface with water is improved, and the immersion liquid followability is improved. be able to. Moreover, when applying the composition of this invention to the patterning by extreme ultraviolet light (EUV light), it can anticipate suppressing what is called outgas by applying hydrophobic resin (HR).
Hydrophobic resin (HR) is unevenly distributed at the interface as described above, but unlike a surfactant, it does not necessarily have a hydrophilic group in the molecule, and polar / nonpolar substances should be mixed uniformly. It does not have to contribute to

The hydrophobic resin preferably has at least one of a fluorine atom and a silicon atom. The fluorine atom and / or silicon atom in the hydrophobic resin (HR) may be contained in the main chain of the resin or may be contained in the side chain.
When the hydrophobic resin contains a fluorine atom, it may be a resin having an alkyl group having a fluorine atom, a cycloalkyl group having a fluorine atom, or an aryl group having a fluorine atom as a partial structure having a fluorine atom. preferable.
The alkyl group having a fluorine atom is a linear or branched alkyl group in which at least one hydrogen atom is substituted with a fluorine atom, preferably 1 to 10 carbon atoms, more preferably 1 to 4 carbon atoms, You may have the substituent of.
The cycloalkyl group having a fluorine atom is a monocyclic or polycyclic cycloalkyl group in which at least one hydrogen atom is substituted with a fluorine atom, and may further have another substituent.
Examples of the aryl group having a fluorine atom include those in which at least one hydrogen atom of an aryl group such as a phenyl group or a naphthyl group is substituted with a fluorine atom, and the aryl group may further have another substituent.
As the alkyl group having a fluorine atom, the cycloalkyl group having a fluorine atom, or the aryl group having a fluorine atom, a group represented by any one of the following general formulas (F2) to (F4) is preferable. However, the present invention is not limited to this.

In general formulas (F2) to (F4),
R _{57 to} R ₆₈ each independently represent a hydrogen atom, a fluorine atom, or an alkyl group (straight or branched). Provided that at least one of R _{57 to} R ₆₁ , at least one of R _{62 to} R ₆₄ and at least one of R _{65 to} R ₆₈ are a fluorine atom or an alkyl group in which at least one hydrogen atom is substituted with a fluorine atom. (Preferably having 1 to 4 carbon atoms).
R _{57 to} R ₆₁ and R _{65 to} R ₆₇ are preferably all fluorine atoms. R ₆₂ , R ₆₃ and R ₆₈ are preferably a fluoroalkyl group (preferably having 1 to 4 carbon atoms), and more preferably a perfluoroalkyl group having 1 to 4 carbon atoms. 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 a 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. .
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 hydrophobic resin 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. .
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. Note that at least one carbon atom in the cycloalkyl group may be substituted with a heteroatom such as an oxygen atom. Particularly preferred examples of Q include a norbornyl group, a tricyclodecanyl group, a tetocyclododecyl group, and the like.
The hydrophobic resin 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. A combination is mentioned.
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 repeating unit.
Specific examples of the repeating unit having at least one of a fluorine atom and a silicon atom include the repeating unit disclosed in paragraph 0576 of US Publication No. 2012/0135348, but the present invention is not limited thereto. Is not to be done.

The hydrophobic resin 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 “polar conversion group”).
(Z) A group that decomposes 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) and different from the side chain in the same repeating unit Repeating unit (b ″) having at least one of atoms
It is more preferable that the hydrophobic resin 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 hydrophobic resin 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 above repeating units (b ′) and (b ″)) In addition, in the repeating unit (b ″), a side chain having at least one group selected from the group consisting of the above (x) to (z), and at least one of a fluorine atom and a silicon atom 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 repeating units in which an alkali-soluble group is bonded to the main chain of the resin, and a polymerization initiator or chain transfer agent having an alkali-soluble group can also be introduced at the end of the polymer chain during polymerization. In any case, it is preferable.
When the repeating unit (bx) is a repeating unit having at least one of a fluorine atom and a silicon atom (that is, when the repeating unit (bx) corresponds 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 above 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 from 1 to 50 mol%, more preferably from 3 to 35 mol%, still more preferably from 5 to 20 mol, based on all repeating units in the hydrophobic resin. %.
Specific examples of the repeating unit (bx) having an alkali-soluble group (x) include the repeating unit disclosed in paragraph 0595 of US Published Patent Application 2012/0135348, but the present invention is not limited thereto. Is not to be done.

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 above 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 polarity converting group represents a group that decomposes by the action of an alkali developer and increases the solubility in the alkali developer as described above. The polar conversion group is preferably a group represented by X in the partial structure represented by the general formula (KA-1) or (KB-1).

X in the general formula (KA-1) or (KB-1) is a carboxylic acid ester group: —COO—, an acid anhydride group: —C (O) OC (O) —, an acid imide group: —NHCONH—, Carboxylic acid thioester group: —COS—, carbonate ester group: —OC (O) O—, sulfate ester group: —OSO ₂ O—, sulfonate ester group: —SO ₂ O—.
Y ¹ and Y ² may be the same or different and each represents an electron-withdrawing group.
The repeating unit (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 bond having a bond as in the case of the partial structure represented by the general formula (KA-1) and the partial structure represented by (KB-1) when Y ¹ and Y ² are monovalent. When it does not have, the group having a 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 hydrophobic resin through a substituent at an arbitrary position.
The partial structure represented by the general formula (KA-1) is a structure that forms a ring structure (for example, an alicyclic structure) together with a group as X.

X in the general formula (KA-1) is preferably a carboxylic acid ester group (that is, when a lactone ring structure is formed as KA-1), an acid anhydride group, or a 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 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. If Z _ka1 there are a plurality, each _{Z ka1} may or may not be the same.
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, and more preferably an alkyl group, a cycloalkyl group, or an electron withdrawing group. In addition, as an ether group, the thing substituted by the alkyl group or the cycloalkyl group, ie, the alkyl ether group, etc. are preferable. The electron withdrawing group is as defined 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. The linear alkyl group preferably has 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms. The branched alkyl group preferably has 3 to 30 carbon atoms, and more preferably 3 to 20 carbon atoms. 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, structural formulas (1) to (50) disclosed in paragraph 0619 of US Patent Publication No. 2012/0135348 are also preferable. Note that at least one carbon atom in the cycloalkyl group may be substituted with a heteroatom such as an oxygen atom.
Preferred examples of the alicyclic moiety include an adamantyl group, a noradamantyl group, a decalin group, a tricyclodecanyl group, a tetracyclododecanyl group, a norbornyl group, a cedrol group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, and a cyclodecanyl group. And cyclododecanyl group. More preferred are an adamantyl group, a decalin group, a norbornyl group, a cedrol group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, a cyclodecanyl group, a cyclododecanyl group, and a tricyclodecanyl group.
Examples of the substituent of these alicyclic structures include an alkyl group, a halogen atom, a hydroxyl group, an alkoxy group, a carboxyl group, and an alkoxycarbonyl group.

Moreover, the said group may have a substituent further.
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),
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.
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 Examples thereof include a group, a sulfinyl group, and a combination thereof. The electron-withdrawing group may have the following structure, for example. The “halo (cyclo) alkyl group” represents an alkyl group 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 and R _ew4 may have any structure, and the partial structure represented by the formula (EW) may have an electron withdrawing property, and may be linked to, for example, the main chain of the resin. An alkyl group and a fluorinated alkyl group;

When Y _ew1 is a divalent or higher group, the remaining bond forms a bond with an arbitrary atom or substituent. At least one group of Y _ew1 , R _ew1 , and R _ew2 may be connected to the main chain of the hydrophobic resin 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 .
At least two of R _ew1 , R _ew2 and Y _ew1 may be connected to each other to form a ring.
Here, R _f1 represents a halogen atom, a perhaloalkyl group, a perhalocycloalkyl group, or a perhaloaryl group, more preferably a fluorine atom, a perfluoroalkyl group, or a perfluorocycloalkyl group, still more preferably a fluorine atom or a trialkyl group. Represents a fluoromethyl group.
R _f2 and R _f3 each independently represent a hydrogen atom, a halogen atom or an organic group, and R _f2 and R _f3 may be linked to form a ring. Examples of the organic group include an alkyl group, a cycloalkyl group, and an alkoxy group. More preferably, R _f2 represents the same group as R _f1 or is linked to R _f3 to form a ring.
R _{f1 to} R _f3 may be linked to form a ring, and examples of the ring formed include a (halo) cycloalkyl ring and a (halo) aryl ring.
Examples of the (halo) alkyl group in R _{f1 to} R _f3 include the alkyl group in Z _ka1 described above and a structure in which this is halogenated.
Examples of the (per) halocycloalkyl group and the (per) haloaryl group in R _{f1 to} R _f3 or 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) can be a repeating unit having a partial structure represented by the 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). When there are a plurality of R _{4 s} , they may be the same or different, and two or more R ₄ may be bonded to form a ring.
X represents an alkylene group, an oxygen atom, or a sulfur atom.
Z 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 ) ₁ —COO— (l 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 preferred chain alkylene group and preferred cycloalkylene group in R ₀ of formula (III).
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 .
Moreover, the repeating unit which has a partial structure shown below as a specific structure of a repeating unit (by) is mentioned.

In general formulas (rf-1) and (rf-2),
X ′ represents an electron-withdrawing substituent, preferably a carbonyloxy group, an oxycarbonyl group, an alkylene group substituted with a fluorine atom, or a cycloalkylene group substituted with a fluorine atom.
A represents a single bond or a divalent linking group represented by -C (Rx) (Ry)-. Here, Rx and Ry are each independently a hydrogen atom, a fluorine atom, an alkyl group (preferably having 1 to 6 carbon atoms and optionally substituted with a fluorine atom or the like), or a cycloalkyl group (preferably a carbon atom). And may be substituted with a fluorine atom or the like. Rx and Ry are preferably a hydrogen atom, an alkyl group, or an alkyl group substituted with a fluorine atom.

X represents an electron withdrawing group, and specific examples thereof include the above-mentioned electron withdrawing groups as Y ¹ and Y ² , preferably a fluorinated alkyl group or a fluorinated cycloalkyl group. An aryl group substituted with a fluorine or fluorinated alkyl group, an aralkyl group substituted with a fluorine or fluorinated alkyl group, a cyano group, or a nitro group.
* Represents a bond to the main chain or side chain of the resin. That is, it represents a bond that bonds to the main chain of the resin through a single bond or a linking group.
When X ′ is a carbonyloxy group or an oxycarbonyl group, A is not a single bond.
When the polarity conversion group is decomposed by the action of the alkali developer and the polarity is changed, the receding contact angle with water of the resist 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 resist film after alkali development is preferably 50 ° or less at a temperature of 23 ± 3 ° C. and a humidity of 45 ± 5%, more preferably 40 ° or less, still more preferably 35 ° or less. Most preferably, it is 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 hydrophobic resin with respect to the alkaline developer is preferably 0.001 nm / second or more, more preferably 0.01 nm / second or more, still more preferably 0.1 nm / second or more, Most preferably, it is 1 nm / second or more.
Here, the hydrolysis rate of the hydrophobic resin with respect to the alkaline developer was 23 ° C. when TMAH (tetramethylammonium hydroxide aqueous solution) (2.38 mass%) was used to form the resin film with only the hydrophobic resin. 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). In addition, when the structure represented by general formula (KY-1) does not have a bond, it is a group having a monovalent or higher valent group in which at least one arbitrary hydrogen atom in this structure is removed.

In general formula (KY-1),
R _ky1 and R _ky4 are each independently a hydrogen atom, halogen atom, alkyl group, cycloalkyl group, carbonyl group, carbonyloxy group, oxycarbonyl group, ether group, hydroxyl group, cyano group, amide group, or aryl group Represents. Alternatively, R _ky1 and R _ky4 may be bonded to the same atom to form a double bond. For example, R _ky1 and R _ky4 are bonded to the same oxygen atom to form a part of a carbonyl group (═O). May be formed.
R _ky2 and R _ky3 are each independently an electron withdrawing group, or R _ky1 and R _ky2 are linked to form a lactone ring and R _ky3 is an electron withdrawing group. As the lactone ring to be formed, the structures (KA-1-1) to (KA-1-17) are preferable. Examples of the electron withdrawing group include those similar to Y ₁ and Y ₂ in the above formula (KB-1), and preferably a halogen atom or the above —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) halo (cyclo) alkyl groups or haloaryl groups represented by _{-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 above 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 linked 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 , preferably a halogen atom or a halo (cyclo (cyclo) represented by —C (R _f1 ) (R _f2 ) —R _f3 above. ) An alkyl group or a haloaryl group.
Specific examples of R _{ky5 to} R _ky10 include the same groups as Z _ka1 in formula (KA-1).
The structure represented by the formula (KY-2) is more preferably a partial structure represented by the following general formula (KY-3).

In the formula (KY-3), Z _ka1 and nka are each synonymous with the general formula (KA-1). R _ky5 has the same meaning as _{R ky5} of 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, repeating units of maleic acid derivatives (maleic anhydride and derivatives thereof, maleimides, etc.), acrylate repeating units, styrene repeating units, vinyl ether repeating units, norbornene 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 above 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 above general formulas (CS-1) to (CS-3) can be exemplified.
The content of the repeating unit (by) in the hydrophobic resin is preferably from 10 to 100 mol%, more preferably from 20 to 99 mol%, still more preferably from 30 to 97 mol%, based on all repeating units in the hydrophobic resin. Most preferably, it is 40-95 mol%.
Specific examples of the repeating unit (by) having a group that increases the solubility in an alkali developer include the repeating unit disclosed in paragraph 0725 of US Patent Publication No. 2012/0135348. It is not limited.

Examples of the method for synthesizing the monomer corresponding to the repeating unit (by) having the polar conversion group (y) as described above include the method described in International Publication No. 2010/069705, International Publication No. 2010/069705, or the like. Can be synthesized with reference to
In the hydrophobic resin, examples of the repeating unit (bz) having a group (z) capable of decomposing by the action of an acid are the same as the repeating unit having an acid-decomposable group exemplified in the resin.
When the repeating unit (bz) is a repeating unit having at least one of a fluorine atom and a silicon atom (that is, when the repeating unit corresponds to the above 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 above general formulas (CS-1) to (CS-3) can be exemplified.

In the hydrophobic resin, the content of the repeating unit (bz) having a group (z) that is decomposed by the action of an acid is preferably 1 to 80 mol%, more preferably based on all repeating units in the hydrophobic resin. 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 hydrophobic resin is hydrophobic. It is preferably 1 to 98 mol%, more preferably 3 to 98 mol%, still more preferably 5 to 97 mol%, and most preferably 10 to 95 mol% with respect to all repeating units in the conductive resin.
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 10 mol% with respect to all repeating units in the hydrophobic resin. 95 mol%.
The content of the repeating unit (b *) is preferably from 1 to 90 mol%, more preferably from 3 to 80 mol%, still more preferably from 5 to 70 mol%, most preferably from 10 to 10%, based on all repeating units in the hydrophobic resin. 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 20 with respect to all repeating units in the hydrophobic resin. It is -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 10 mol% based on all repeating units in the hydrophobic resin. 95 mol%.

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

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

Specific examples of the repeating unit represented by the general formula (CIII) are listed below, but the present invention is not limited thereto. 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 described above, the hydrophobic resin is naturally low in impurities such as metals, and the residual monomer or oligomer component is preferably 0 to 10% by mass, more preferably 0 to 5% by mass. %, 0 to 1% by mass is even 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, in terms of resolution, resist shape, resist pattern side walls, roughness, and the like. It is in the range of 1 to 1.8, most preferably 1 to 1.5.
As the hydrophobic resin, various commercially available products can be used, and 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 above for the resin (more specifically, the repeating unit represented by the general formula (I) and the general unit described above). This is the same as the content described for the resin having a repeating unit represented by formula (II).
Specific examples of the hydrophobic resin (HR) are shown below. Table 1 below shows the molar ratio of 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 composition ratio numbers in Table 1), weight average Indicates molecular weight and degree of dispersion.

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.
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.
Hydrophobic resins are hydrophobic, so that development residues (scum) and BLOB defects are likely to deteriorate after alkali development, but they have three or more polymer chains via at least one branch, compared to linear resins. Further, since the alkali dissolution rate is improved, development residue (scum) and BLO defect performance are improved.
When the hydrophobic resin has a fluorine atom, the fluorine atom content is preferably 5 to 80% by mass and more preferably 10 to 80% by mass with respect to the molecular weight of the hydrophobic resin. Moreover, it is preferable that the repeating unit containing a fluorine atom is 10-100 mol% with respect to all the repeating units in hydrophobic resin, and it is more preferable that it is 30-100 mol%.
When the hydrophobic resin 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 hydrophobic resin. Moreover, it is preferable that it is 10-90 mol% with respect to all the repeating units of hydrophobic resin, 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 hydrophobic resin is preferably 1,000 to 100,000, more preferably 2,000 to 50,000, and still more preferably 3,000 to 35,000. 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 hydrophobic resin 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-sensitive or radiation-sensitive resin film falls within the above range. The content is preferably 0.01 to 20% by mass, more preferably 0.1 to 15% by mass, still more preferably 0.1 to 10%, based on the total solid content of the actinic ray-sensitive or radiation-sensitive resin composition. It is mass%, Most preferably, it is 0.2-8 mass%.
Hydrophobic resins can be used alone or in combination of two or more.

[4] Acid diffusion control agent (quencher)
The actinic ray-sensitive or radiation-sensitive resin composition of the present invention preferably contains an acid diffusion controller (quencher). The acid diffusion controller acts as a quencher that traps the acid generated from the acid generator or the like. Examples of the acid diffusion controller include a basic compound, a low molecular compound having a nitrogen atom and a group capable of leaving by the action of an acid, a basic compound whose basicity is reduced or disappeared by irradiation with actinic rays or radiation, and onium Salts (onium salts that are weak acids relative to acid generators) and betaine compounds can be used, and are exemplified below.

(1) Basic compound (N)
Preferred examples of the basic compound include compounds (N) having a structure represented by the following formulas (A) to (E).

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

About the said alkyl group, as an alkyl group which has a substituent, a C1-C20 aminoalkyl group, a C1-C20 hydroxyalkyl group, or a C1-C20 cyanoalkyl group is preferable.
The alkyl groups in the general formulas (A) and (E) are more preferably unsubstituted.
Preferable compound (N) includes guanidine, aminopyrrolidine, pyrazole, pyrazoline, piperazine, aminomorpholine, aminoalkylmorpholine, piperidine, and more preferable compound (N) includes imidazole structure, diazabicyclo structure, onium hydroxy group. Compound (N) having an alkyl group structure, an onium carboxylate structure, a trialkylamine structure, an aniline structure or a pyridine structure, an alkylamine derivative having a hydroxyl group and / or an ether bond, an aniline derivative having a hydroxyl group and / or an ether bond, etc. be able to.

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

  Preferred examples of the basic compound (N) further include an amine compound having a phenoxy group, an ammonium salt compound having a phenoxy group, an amine compound having a sulfonic acid ester group, and an ammonium salt compound having a sulfonic acid ester group. Examples of these compounds include compounds (C1-1) to (C3-3) exemplified in paragraph <0066> of US Patent Application Publication No. 2007 / 02245539A1.

  The following compounds are also preferable as the basic compound (N).

As the basic compound (N), in addition to the above-mentioned compounds, paragraphs <0180> to <0225> of JP2011-22560A, paragraph [0] of JP2012-137735A.
218] to <0219>, and the compounds described in paragraphs <0416> to <0438> of International Publication No. 2011/158687 can also be used.
These basic compounds (N) may be used alone or in combination of two or more.

The actinic ray-sensitive or radiation-sensitive resin composition may or may not contain the basic compound (N), but when it is contained, the content of the basic compound (N) is actinic ray-sensitive or The amount is usually 0.001 to 10% by mass, preferably 0.01 to 5% by mass, based on the solid content of the radiation-sensitive resin composition.
The use ratio of the acid generator and the basic compound (N) in the composition is preferably acid generator / basic compound (N) (molar ratio) = 2.5 to 300. That is, the molar ratio is preferably 2.5 or more from the viewpoint of sensitivity and resolution, and is preferably 300 or less from the viewpoint of suppressing resolution from being reduced due to the thickening of the resist pattern over time until post-exposure heat treatment. The acid generator / basic compound (N) (molar ratio) is more preferably 5.0 to 200, still more preferably 7.0 to 150.

(2) Basic compound or ammonium salt compound (E) whose basicity is reduced by irradiation with actinic rays or radiation
The actinic ray-sensitive or radiation-sensitive resin composition contains a basic compound or an ammonium salt compound (hereinafter also referred to as “compound (E)”) whose basicity is lowered by irradiation with actinic rays or radiation. Is preferred.
The compound (E) is preferably a compound (E-1) having a basic functional group or an ammonium group and a group that generates an acidic functional group upon irradiation with actinic rays or radiation. That is, the compound (E) is a basic compound having a basic functional group and a group capable of generating an acidic functional group upon irradiation with active light or radiation, or an acidic functional group upon irradiation with an ammonium group and active light or radiation. An ammonium salt compound having a group to be generated is preferable.
The compound (E) or (E-1) is decomposed by irradiation with actinic rays or radiation, and the compound with reduced basicity is represented by the following general formula (PA-I), (PA-II) or (PA -III) can be mentioned. Among these, from the viewpoint that the excellent effects regarding LWR, local pattern dimension uniformity, and DOF can be achieved at a high level, the compound represented by formula (PA-II) or (PA-III) is particularly preferred. preferable.

First, the compound represented by general formula (PA-I) is demonstrated.
_{Q-A 1 - (X)} n -B-R (PA-I)
In general formula (PA-I),
A ₁ represents a single bond or a divalent linking group. The divalent linking group is preferably a divalent linking group having 2 to 12 carbon atoms, and examples thereof include an alkylene group and a phenylene group. The alkylene chain may have a linking group such as an oxygen atom or a sulfur atom. More preferably, it is an alkylene group having at least one fluorine atom, and a preferable carbon number is 2 to 6, more preferably 2 to 4. The alkylene chain may have a linking group such as an oxygen atom or a sulfur atom. The alkylene group is particularly preferably an alkylene group in which 30 to 100% of the number of hydrogen atoms are substituted with fluorine atoms, and more preferably, the carbon atom bonded to the Q site has a fluorine atom. Further, a perfluoroalkylene group is preferable, and a perfluoroethylene group, a perfluoropropylene group, and a perfluorobutylene group are more preferable.
Q represents -SO ₃ H, or -CO ₂ H. Q corresponds to an acidic functional group generated by irradiation with actinic rays or radiation.
X represents —SO ₂ — or —CO—.
n represents 0 or 1.
B represents a single bond, an oxygen atom or -N (Rx)-.
Rx represents a hydrogen atom or a monovalent organic group. The monovalent organic group in Rx preferably has 4 to 30 carbon atoms, and examples thereof include an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, and an alkenyl group.
When B is -N (Rx)-, R and Rx are preferably bonded to form a ring. By forming the ring structure, the stability is improved, and the storage stability of the composition using the ring structure is improved. The number of carbon atoms forming the ring is preferably 4 to 20, and may be monocyclic or polycyclic, and may contain an oxygen atom, a sulfur atom, or a nitrogen atom in the ring.
Examples of the monocyclic structure include a 4- to 8-membered ring containing a nitrogen atom. Examples of the polycyclic structure include a structure composed of a combination of two or three or more monocyclic structures. The monocyclic structure and polycyclic structure may have a substituent.

R represents a monovalent organic group having a basic functional group or a monovalent organic group having an ammonium group.
Preferable partial structures of basic functional groups include, for example, the structures of crown ethers, primary to tertiary amines, and nitrogen-containing heterocyclic rings (pyridine, imidazole, pyrazine, etc.). Preferable partial structures of the ammonium group include, for example, primary to tertiary ammonium, pyridinium, imidazolinium, pyrazinium structures and the like.
In addition, as a basic functional group, the functional group which has a nitrogen atom is preferable, and the structure which has a 1-3 primary amino group, or a nitrogen-containing heterocyclic structure is more preferable. In these structures, it is preferable from the viewpoint of improving basicity that all atoms adjacent to the nitrogen atom contained in the structure are carbon atoms or hydrogen atoms. From the viewpoint of improving basicity, it is preferable that an electron-withdrawing functional group (such as a carbonyl group, a sulfonyl group, a cyano group, or a halogen atom) is not directly connected to the nitrogen atom.
As the monovalent organic group in the monovalent organic group (group R) having such a structure, a preferable carbon number is 4 to 30, and an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, an alkenyl group, etc. Each group may have a substituent.

Next, the compound represented by general formula (PA-II) is demonstrated.
_{Q 1 -X 1 -NH-X 2} -Q 2 (PA-II)
In general formula (PA-II),
Q ₁ and Q ₂ each independently represents a monovalent organic group. However, either Q ₁ or Q ₂ has a basic functional group. Q ₁ and Q ₂ may combine to form a ring, and the formed ring may have a basic functional group. The monovalent organic group as Q ₁ and Q ₂ preferably has 1 to 40 carbon atoms, and examples thereof include an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, and an alkenyl group. The definition of the basic functional group is as described above.
X ₁ and X ₂ each independently represent —CO— or —SO ₂ —.
Note that —NH— corresponds to an acidic functional group generated by irradiation with actinic rays or radiation.

Next, the compound represented by general formula (PA-III) is demonstrated.
_{Q 1 -X 1 -NH-X 2} -A 2 - (X 3) m -B-Q 3 (PA-III)
In general formula (PA-III),
Q ₁ and Q ₃ each independently represents a monovalent organic group. However, either Q ₁ or Q ₃ has a basic functional group. Q ₁ and Q ₃ may combine to form a ring, and the formed ring may have a basic functional group. Q ₁ has the same meaning as Q _{1 in} formula (PA-II). Examples of the organic group of Q ₃ include the same organic groups as Q ₁ and Q ₂ in formula (PA-II). The definition of the basic functional group is as described above.
X ₁ , X ₂ and X ₃ each independently represent —CO— or —SO ₂ —.
A ₂ represents a divalent linking group. The divalent linking group for A ₂ is preferably a divalent linking group having a fluorine atom having 1 to 8 carbon atoms. Examples thereof include an alkylene group having 1 to 8 carbon atoms and a phenylene group having fluorine atoms. An alkylene group having a fluorine atom is more preferable, and a preferable carbon number is 2 to 6, more preferably 2 to 4. The alkylene chain may have a linking group such as an oxygen atom or a sulfur atom. The alkylene group is preferably an alkylene group in which 30 to 100% of the number of hydrogen atoms are substituted with fluorine atoms, more preferably a perfluoroalkylene group, and particularly preferably a C 2-4 perfluoroalkylene group.
B represents a single bond, an oxygen atom, or —N (Qx) —.
Qx represents a hydrogen atom or a monovalent organic group. The monovalent organic group in Qx is preferably an organic group having 4 to 30 carbon atoms, and examples thereof include an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, and an alkenyl group.
When B is —N (Qx) —, Q ₃ and Qx may combine to form a ring.
m represents 0 or 1.
Note that —NH— corresponds to an acidic functional group generated by irradiation with actinic rays or radiation.

  As the compound (E), a sulfonium salt compound of the compound represented by the general formula (PA-I), (PA-II) or (PA-III), the general formula (PA-I), (PA-II) or The iodonium salt compound of the compound represented by (PA-III) is preferable, and the compound represented by the following general formula (PA1) or (PA2) is more preferable.

In general formula (PA1):
R ′ ₂₀₁ , R ′ ₂₀₂ and R ′ ₂₀₃ each independently represent an organic group, and specifically, are the same as R ₂₀₁ , R ₂₀₂ and R ₂₀₃ of the formula ZI in the acid generator.
X ⁻ represents a sulfonate anion or carboxylate anion from which a hydrogen atom of the —SO ₃ H site or —COOH site of the compound represented by the general formula (PA-I) is eliminated, or a general formula (PA-II) or ( PA-III) represents an anion in which a hydrogen atom is eliminated from the -NH- site of the compound represented by PA-III).

In general formula (PA2),
R ′ ₂₀₄ and R ′ ₂₀₅ each independently represents an aryl group, an alkyl group, or a cycloalkyl group, and specifically, are the same as R ₂₀₄ and R ₂₀₅ of Formula ZII in the acid generator.
X ⁻ represents a sulfonate anion or carboxylate anion from which a hydrogen atom of the —SO ₃ H site or —COOH site of the compound represented by the general formula (PA-I) is eliminated, or a general formula (PA-II) or ( PA-III) represents an anion in which a hydrogen atom is eliminated from the -NH- site of the compound represented by PA-III).

  In the present invention, the decrease in basicity upon irradiation with actinic rays or radiation means that the acceptor property to the proton (acid generated by irradiation with actinic rays or radiation) of compound (E) upon irradiation with actinic rays or radiation. Means lower. The acceptor property decreases when an equilibrium reaction occurs in which a non-covalent complex that is a proton adduct is formed from a compound having a basic functional group and a proton, or the counter cation of a compound having an ammonium group is exchanged for a proton. This means that when an equilibrium reaction occurs, the equilibrium constant at that chemical equilibrium decreases.

  Preferable specific examples of the compound (E) include compounds (A-1) to (A-44) of US Patent Application Publication No. 2010/0233629, and those of US Patent Application Publication No. 2012/0156617. (A-1)-(A-23) etc. are mentioned.

  Although the specific example of the compound (E) which generate | occur | produces the compound represented with general formula (PA-I) by irradiation of actinic light or a radiation is given, this invention is not limited to this.

  Hereinafter, although the specific example of the compound (E) which generate | occur | produces the compound represented by general formula (PA-II) or (PA-III) by irradiation of actinic light or a radiation is given, this invention is limited to this. is not.

It is preferable that the molecular weight of a compound (E) is 500-1000.
The actinic ray-sensitive or radiation-sensitive resin composition may or may not contain the compound (E), but when it is contained, the content of the compound (E) is the actinic ray-sensitive or radiation-sensitive resin. 0.1-20 mass% is preferable on the basis of solid content of the composition, more preferably 0.1-10 mass%.
Further, as one aspect of the compound (E), a compound (E-2) that generates an acid (weak acid) having a strength that does not decompose the acid-decomposable group of the resin (A) by acid irradiation or radiation irradiation. Can also be mentioned.
Examples of the compound include an onium salt of a carboxylic acid having no fluorine atom (preferably a sulfonium salt) and an onium salt of a sulfonic acid having no fluorine atom (preferably a sulfonium salt). More specifically, for example, among onium salts represented by the following general formula (6A), those in which the carboxylic acid anion does not have a fluorine atom, among onium salts represented by the following general formula (6B) Examples include those in which the sulfonate anion does not have a fluorine atom. As a cation structure of a sulfonium salt, the sulfonium cation structure mentioned by the acid generator (B) can be mentioned preferably.
More specifically, as compound (E-2), compounds listed in paragraph <0170> of International Publication No. 2012/053527, paragraphs <0268> to <0269> of JP 2012-173419 A Compound etc. are mentioned.
A compound (E) may be used individually by 1 type, and may be used in combination of 2 or more type.

(3) Low molecular weight compound (F) having a nitrogen atom and a group capable of leaving by the action of an acid
The actinic ray-sensitive or radiation-sensitive resin composition may contain a compound having a nitrogen atom and a group capable of leaving by the action of an acid (hereinafter also referred to as “compound (F)”).
The group capable of leaving by the action of an acid is not particularly limited, but is preferably an acetal group, a carbonate group, a carbamate group, a tertiary ester group, a tertiary hydroxyl group, or a hemiaminal ether group, and a carbamate group or a hemiaminal ether group. It is particularly preferred.
The molecular weight of the compound (F) having a group capable of leaving by the action of an acid is preferably 100 to 1000, more preferably 100 to 700, and particularly preferably 100 to 500.
As the compound (F), an amine derivative having a group capable of leaving by the action of an acid on the nitrogen atom is preferable.

  Compound (F) may have a carbamate group having a protecting group on the nitrogen atom. The protecting group constituting the carbamate group can be represented by the following general formula (d-1).

In general formula (d-1),
R _b is independently a hydrogen atom, an alkyl group (preferably 1 to 10 carbon atoms), a cycloalkyl group (preferably 3 to 30 carbon atoms), an aryl group (preferably 3 to 30 carbon atoms), an aralkyl group. (Preferably having 1 to 10 carbon atoms) or an alkoxyalkyl group (preferably having 1 to 10 carbon atoms). R _b may be connected to each other to form a ring.

The alkyl group, cycloalkyl group, aryl group, and aralkyl group represented by R _b are substituted with a functional group such as a hydroxyl group, a cyano group, an amino group, a pyrrolidino group, a piperidino group, a morpholino group, and an oxo group, an alkoxy group, and a halogen atom. May be. The same applies to the alkoxyalkyl group represented by R _b .
R _b is preferably a linear or branched alkyl group, cycloalkyl group, or aryl group. More preferably, it is a linear or branched alkyl group or cycloalkyl group.

Examples of the ring formed by connecting two R _b to each other include an alicyclic hydrocarbon group, an aromatic hydrocarbon group, a heterocyclic hydrocarbon group, or a derivative thereof.
Specific examples of the group represented by the general formula (d-1) include a structure disclosed in paragraph <0466> of US Patent Application Publication No. 2012/0135348, and examples thereof include It is not limited.

  The compound (F) particularly preferably has a structure represented by the following general formula (6).

In the general formula (6), R _a represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, or an aralkyl group. When l is 2, two R _a may be the same or different, and two R _a may be connected to each other to form a heterocyclic ring together with the nitrogen atom in the formula. The heterocycle may contain a heteroatom other than the nitrogen atom in the formula.
R _b has the same meaning as R _b in formula (d-1), and preferred examples are also the same.
l represents an integer of 0 to 2, m represents an integer of 1 to 3, and satisfies l + m = 3.

In the general formula (6), an alkyl group, a cycloalkyl group, an aryl group, and an aralkyl group as R _a are groups in which the alkyl group, cycloalkyl group, aryl group, and aralkyl group as R _b may be substituted. It may be substituted with a group similar to the group described above.
Preferred examples of the alkyl group, cycloalkyl group, aryl group, and aralkyl group represented by R _a (these alkyl group, cycloalkyl group, aryl group, and aralkyl group may be substituted with the above groups) The same group as the preferable example mentioned above about _Rb is mentioned.
Further, the heterocyclic ring formed by connecting R _a to each other preferably has 20 or less carbon atoms. For example, pyrrolidine, piperidine, morpholine, 1,4,5,6-tetrahydropyrimidine, 1,2,3 , 4-tetrahydroquinoline, 1,2,3,6-tetrahydropyridine, homopiperazine, 4-azabenzimidazole, benzotriazole, 5-azabenzotriazole, 1H-1,2,3-triazole, 1,4,7 -Triazacyclononane, tetrazole, 7-azaindole, indazole, benzimidazole, imidazo [1,2-a] pyridine, (1S, 4S)-(+)-2,5-diazabicyclo [2.2.1] Heptane, 1,5,7-triazabicyclo [4.4.0] dec-5-ene, indole, indoline, 1,2,3 -Groups derived from heterocyclic compounds such as tetrahydroquinoxaline, perhydroquinoline, 1,5,9-triazacyclododecane, and groups derived from these heterocyclic compounds derived from linear and branched alkanes Groups derived from cycloalkanes, groups derived from aromatic compounds, groups derived from heterocyclic compounds, hydroxyl groups, cyano groups, amino groups, pyrrolidino groups, piperidino groups, morpholino groups, oxo groups, etc. Or a group substituted with one or more of the above.

Specific examples of the preferred compound (F) include, but are not limited to, compounds disclosed in paragraph <0475> of US Patent Application Publication No. 2012/0135348.
Specific examples of the compound (F) are shown below.

The compound represented by the general formula (6) can be synthesized based on JP2007-298869A, JP2009-199021A, and the like.
In the present invention, the low molecular compound (F) can be used singly or in combination of two or more.
The content of the compound (F) in the actinic ray-sensitive or radiation-sensitive resin composition is preferably 0.001 to 20% by mass, more preferably 0.001 based on the total solid content of the composition. -10 mass%, More preferably, it is 0.01-5 mass%.

(4) Onium salt Moreover, as a basic compound, you may include the onium salt represented by the following general formula (6A) or (6B). This onium salt is expected to control the diffusion of the generated acid in the resist system in relation to the acid strength of the photoacid generator usually used in the resist composition.

In general formula (6A),
Ra represents an organic group. However, those in which a fluorine atom is substituted for a carbon atom directly bonded to a carboxylic acid group in the formula are excluded. X ⁺ represents an onium cation.
In General Formula (6B), Rb represents an organic group. However, those in which a fluorine atom is substituted for a carbon atom directly bonded to the sulfonic acid group in the formula are excluded. X ⁺ represents an onium cation.

In the organic group represented by Ra and Rb, the atom directly bonded to the carboxylic acid group or sulfonic acid group in the formula is preferably a carbon atom. However, in this case, in order to make the acid relatively weaker than the acid generated from the above-mentioned photoacid generator, the fluorine atom does not substitute for the carbon atom directly bonded to the sulfonic acid group or carboxylic acid group.
Examples of the organic group represented by Ra and Rb include an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, and an aralkyl group having 7 to 30 carbon atoms. Or a C3-C30 heterocyclic group etc. are mentioned. In these groups, some or all of the hydrogen atoms may be substituted.
Examples of the substituent that the alkyl group, cycloalkyl group, aryl group, aralkyl group and heterocyclic group may have include a hydroxyl group, a halogen atom, an alkoxy group, a lactone group, and an alkylcarbonyl group.

Examples of the onium cation represented by X ⁺ in the general formulas (6A) and (6B) include a sulfonium cation, an ammonium cation, an iodonium cation, a phosphonium cation, and a diazonium cation. Of these, a sulfonium cation is more preferable.
As the sulfonium cation, for example, an arylsulfonium cation having at least one aryl group is preferable, and a triarylsulfonium cation is more preferable. The aryl group may have a substituent, and the aryl group is preferably a phenyl group.
Preferred examples of the sulfonium cation and the iodonium cation include the aforementioned sulfonium cation structure of the general formula (ZI) and the iodonium structure of the general formula (ZII) in the compound (B).

A specific structure of the onium salt represented by the general formula (6A) or (6B) is shown below.
In addition, onium salt may be used individually by 1 type, and may be used in combination of 2 or more types.

(5) Betaine compound Furthermore, the composition includes a compound contained in formula (I) of JP2012-189777A, a compound represented by formula (I) of JP2013-6827A, and JP2013- Both an onium salt structure and an acid anion structure in one molecule, such as a compound represented by the formula (I) of No. 8020 and a compound represented by the formula (I) of JP 2012-252124 A A compound having the same (hereinafter also referred to as betaine compound) can be preferably used. Examples of the onium salt structure include a sulfonium, iodonium, and ammonium structure, and a sulfonium or iodonium salt structure is preferable. Moreover, as an acid anion structure, a sulfonate anion or a carboxylate anion is preferable. Examples of this compound include the following.
In addition, a betaine compound may be used individually by 1 type, and may be used in combination of 2 or more type.

[5] Solvent The actinic ray-sensitive or radiation-sensitive resin composition used in the present invention may contain a solvent. Examples of the solvent include water and organic solvents.
Examples of the organic solvent that can be used in preparing the actinic ray-sensitive or radiation-sensitive resin composition include, for example, alkylene glycol monoalkyl ether carboxylate, alkylene glycol monoalkyl ether, alkyl lactate ester, and alkyl alkoxypropionate. And organic solvents such as cyclic lactone (preferably having 4 to 10 carbon atoms), monoketone compound (preferably having 4 to 10 carbon atoms) which may have a ring, alkylene carbonate, alkyl alkoxyacetate and alkyl pyruvate. it can.
Specific examples of these solvents can include those described in paragraphs <0441> to <0455> of US Patent Application Publication No. 2008/0187860.

In the present invention, a mixed solvent may be used as the solvent.
For example, alkylene glycol monoalkyl ether, alkyl lactate and the like are preferable, and propylene glycol monomethyl ether (PGME, also known as 1-methoxy-2-propanol), ethyl lactate, alkylene glycol monoalkyl ether acetate, alkyl alkoxypropionate, containing a ring Two or more kinds of mixed solvents selected from monoketone compounds, cyclic lactones, alkyl acetates, etc., which may be used, are preferred, and among these, propylene glycol monomethyl ether acetate (PGMEA, also known as 1-methoxy-2-acetoxypropane) (hereinafter, Solvent A), and selected from propylene glycol monomethyl ether, ethyl ethoxypropionate, 2-heptanone, γ-butyrolactone, cyclohexanone, and butyl acetate. Species or two solvents (hereinafter also referred to as a solvent B) mixed solvent of is preferred. As the solvent B, γ-butyrolactone is most preferable.
The mixing ratio (solvent A / solvent B) (mass ratio) of the mixed solvent is from 1/99 to 99/1, preferably from 10/90 to 90/10, more preferably from 20/80 to 60/40.
The solvent preferably contains propylene glycol monomethyl ether acetate, and is preferably a propylene glycol monomethyl ether acetate single solvent or a mixed solvent of two or more containing propylene glycol monomethyl ether acetate.

  Among these, the organic solvent is contained in the composition, the propylene glycol monomethyl ether acetate is contained in the organic solvent, and the content of the propylene glycol monomethyl ether acetate with respect to the total mass of the organic solvent is more excellent in the effect of the present invention. The aspect which is more than 90 mass% is mentioned. As a suitable aspect of content with respect to the organic solvent total mass of propylene glycol monomethyl ether acetate, 92 mass% or more is preferable.

[6] Surfactant The actinic ray-sensitive or radiation-sensitive resin composition used in the present invention may further contain a surfactant. In the case of containing a surfactant, either fluorine and / or silicon surfactant (fluorine surfactant, silicon surfactant, surfactant having both fluorine atom and silicon atom), or two kinds It is more preferable to contain the above.

When the actinic ray-sensitive or radiation-sensitive resin composition contains a surfactant, a resist pattern with good sensitivity and resolution and less adhesion and development defects when using an exposure light source of 250 nm or less, particularly 220 nm or less. Can be given.
Examples of the fluorine-based and / or silicon-based surfactant include surfactants described in paragraph <0276> of U.S. Patent Application Publication No. 2008/0248425. For example, Ftop EF301, EF303, (Shin-Akita Kasei Co., Ltd.) ), FLORARD FC430, 431, 4430 (manufactured by Sumitomo 3M Co., Ltd.), Megafac F171, F173, F176, F189, F113, F110, F177, F120, R08 (manufactured by DIC Corporation), Surflon S- 382, SC101, 102, 103, 104, 105, 106, KH-20 (manufactured by Asahi Glass Co., Ltd.), Troisol S-366 (manufactured by Troy Chemical Co., Ltd.), GF-300, GF-150 (Toa Gosei Chemical ( Co., Ltd.), Surflon S-393 (Seimi Chemical Co., Ltd.), F Top EF121, F122A, EF122B, RF122C, EF125M, EF135M, EF351, EF352, EF801, EF802, EF601 (manufactured by Gemco), PF636, PF656, PF6320, PF6520 (manufactured by OMNOVA), FTX-204G, 230G, 230G, 230G 204D, 208D, 212D, 218D, 222D (manufactured by Neos Co., Ltd.) and the like. Polysiloxane polymer KP-341 (manufactured by Shin-Etsu Chemical Co., Ltd.) can also be used as a silicon-based surfactant. Furthermore, PolyFox PF-6320 (manufactured by OMNOVA Solutions Inc .; fluorine type) can also be used.

In addition to the known surfactants described above, surfactants are derived from fluoroaliphatic compounds produced by the telomerization method (also referred to as the telomer method) or the oligomerization method (also referred to as the oligomer method). A surfactant using a polymer having a fluoroaliphatic group can be used. The fluoroaliphatic compound can be synthesized by the method described in JP-A-2002-90991.
As the surfactant corresponding to the above, Megafac F178, F-470, F-473, F-475, F-476, F-472 (manufactured by DIC Corporation), acrylate having C ₆ F ₁₃ group (or methacrylate) and (poly (oxyalkylene)) acrylate (copolymer of or methacrylate), and acrylate having a C ₃ F ₇ group (or methacrylate) (poly (oxyethylene) and) acrylate (or methacrylate) (poly ( And a copolymer with oxypropylene)) acrylate (or methacrylate).

  In the present invention, surfactants other than the fluorine-based and / or silicon-based surfactants described in paragraph <0280> of US Patent Application Publication No. 2008/0248425 can also be used.

  These surfactants may be used alone or in several combinations.

When the actinic ray-sensitive or radiation-sensitive resin composition contains a surfactant, the amount of the surfactant used is based on the total amount of the actinic ray-sensitive or radiation-sensitive resin composition (excluding the solvent). Preferably it is 0.0001-2 mass%, More preferably, it is 0.0005-1 mass%.
On the other hand, when the amount of the surfactant added is 10 ppm or less with respect to the total amount of the actinic ray-sensitive or radiation-sensitive resin composition (excluding the solvent), the surface unevenness of the hydrophobic resin is increased. As a result, the surface of the resist film can be made more hydrophobic, and the water followability during immersion exposure can be improved.

[7] Other additives The composition in the present invention preferably contains a compound having a partial structure represented by the general formula (1).

In the general formula (1), R ₁₁ represents an alkylene group which may have a substituent. The number of carbon atoms of the alkylene group is not particularly limited, but is preferably 1 to 15 and more preferably 2. The substituent is not particularly limited, but is preferably an alkyl group (preferably having 1 to 10 carbon atoms).
In the general formula (1), n represents an integer of 1 or more. Especially, it is preferable that it is an integer of 1-20. When n is 2 or more, a plurality of R ₁₁ may be the same or different. The average value of n is preferably 1-10.
In the general formula (1), * represents a bond.

  The compound having the partial structure represented by the general formula (1) is a compound represented by the following general formula (1-1) or the following general formula (1-2) in that the effect of the present invention is more excellent. Preferably there is.

Definition of R ₁₁ in the general formula (1-1), specific examples and preferred embodiment is the same as R ₁₁ in general formula (1).
In the general formula (1-1), R ₁₂ and R ₁₃ each independently represent a hydrogen atom or an alkyl group. The number of carbon atoms of the alkyl group is not particularly limited, but is preferably 1-15.
In the general formula (1-1), m represents an integer of 1 or more. Especially, it is preferable that it is an integer of 1-20, and it is more preferable that it is 10 or less among them. The average value of m is preferably 20 or less, more preferably 1 to 10, more preferably 8 or less, particularly 4 to 6. Is particularly preferred. When m is 2 or more, a plurality of R ₁₁ may be the same or different.

Definition of R ₁₁ in the general formula (1-2), specific examples and preferred embodiment is the same as R ₁₁ in general formula (1). The definition and preferred embodiment of m in the general formula (1-2) are the same as m in the general formula (1-1) described above. Examples of the compound represented by the general formula (1-2) include crown ether.

The average molecular weight of the compound is not particularly limited, but is preferably 80 to 1000, more preferably 80 to 500, and still more preferably 100 to 300.
When the compound is a compound represented by the general formula (1-1), the average molecular weight of the compound is preferably 400 or less.
It is preferable that a compound does not contain a basic site | part (for example, an amino group, the proton acceptor functional group mentioned later).
In the composition of the present invention, the content of the compound is not particularly limited, but is preferably 1 to 30 parts by mass, more preferably 3 to 25 parts by mass with respect to 100 parts by mass of the resin described above. The amount is more preferably 4 to 15 parts by mass, and particularly preferably 5 to 10 parts by mass.

The composition in the present invention may or may not contain a carboxylic acid onium salt. Examples of such carboxylic acid onium salts include those described in US Patent Application Publication No. 2008/0187860 <0605> to <0606>.
These carboxylic acid onium salts can be synthesized by reacting sulfonium hydroxide, iodonium hydroxide, ammonium hydroxide and carboxylic acid with silver oxide in a suitable solvent.

When the composition contains a carboxylic acid onium salt, the content is generally 0.1 to 20% by mass, preferably 0.5 to 10% by mass, more preferably based on the total solid content of the composition. Is 1-7 mass%.
If necessary, the composition of the present invention may further include an acid proliferator, a dye, a plasticizer, a photosensitizer, a light absorber, an alkali-soluble resin, a dissolution inhibitor, and a compound that promotes solubility in a developer ( For example, a phenol compound having a molecular weight of 1000 or less, an alicyclic compound having a carboxyl group, or an aliphatic compound) can be contained.

Such a phenol compound having a molecular weight of 1000 or less can be obtained by referring to, for example, the methods described in JP-A-4-1222938, JP-A-2-28531, US Pat. No. 4,916,210, European Patent 219294, etc. It can be easily synthesized by those skilled in the art.
Specific examples of alicyclic or aliphatic compounds having a carboxyl group include carboxylic acid derivatives having a steroid structure such as cholic acid, deoxycholic acid, lithocholic acid, adamantane carboxylic acid derivatives, adamantane dicarboxylic acid, cyclohexane carboxylic acid, cyclohexane Examples thereof include, but are not limited to, dicarboxylic acids.

The composition in the present invention is preferably a resist film having a thickness of 80 nm or less from the viewpoint of improving the resolution. Such a film thickness can be obtained by setting the solid content concentration in the composition to an appropriate range to give an appropriate viscosity and improving the coating property and film forming property.
The solid content concentration of the composition in the present invention is usually 1.0 to 10% by mass, preferably 2.0 to 5.7% by mass, and more preferably 2.0 to 5.3% by mass. By setting the solid content concentration within the above range, the resist solution can be uniformly applied on the substrate, and further, a resist pattern having excellent line width roughness can be formed. The reason for this is not clear, but perhaps the solid content concentration is 10% by mass or less, preferably 5.7% by mass or less, which suppresses aggregation of the material in the resist solution, particularly the photoacid generator. As a result, it is considered that a uniform resist film was formed.
The solid content concentration is a mass percentage of the mass of other resist components excluding the solvent with respect to the total weight of the composition.

The composition in the present invention and various materials used in the pattern forming method of the present invention (for example, a developer, a rinsing liquid, a composition for forming an antireflection film, a composition for forming a top coat, etc.) Prior to use, it is preferable to reduce various impurities as much as possible by filter filtration or the like. The pore size of the filter used for filter filtration is preferably 0.1 μm or less, more preferably 0.05 μm or less, and still more preferably 0.03 μm or less made of polytetrafluoroethylene, polyethylene, or nylon. In filter filtration, for example, as in JP-A-2002-62667, circulation filtration may be performed, or filtration may be performed by connecting a plurality of types of filters 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 behind filter filtration.
Furthermore, it is needless to say that the content of the metal impurity element in the composition is preferably low for the use of the composition / various materials. For this reason, it is preferable that the metal impurity content of various raw materials be managed low. In addition, it is preferable to use a container for storing and transporting the composition in consideration of reduction of impurity elution.

  The composition of the present invention relates to an actinic ray-sensitive or radiation-sensitive resin composition whose properties change upon irradiation with actinic rays or radiation. More specifically, the present invention relates to semiconductor manufacturing processes such as ICs, circuit boards such as liquid crystals and thermal heads, production of imprint mold structures, and other photofabrication processes, lithographic printing plates, acid-curing properties. The present invention relates to an actinic ray-sensitive or radiation-sensitive resin composition used in the composition.

<Pattern formation method>
Next, the pattern forming method according to the present invention will be described.
The pattern forming method of the present invention preferably includes at least the following steps.
(1) forming a film (composition film, resist film) containing the composition of the present invention on a substrate;
(2) a step of exposing the film (exposure step), and (3) a step of developing the exposed film (development step),
As will be described later, a heating step (PB; Prebake) is provided between step (1) and step (2), and a heating step (PEB; Post) is provided between step (2) and step (3). (Exposure Bake) may be performed after the step (3), respectively. In the following, these steps are also described in detail.

[Step (1)]
Step (1) is a step of forming a film on the substrate using the actinic ray-sensitive or radiation-sensitive resin composition.
The method for forming a film on the substrate using the actinic ray-sensitive or radiation-sensitive resin composition is not particularly limited, and a known method can be adopted. Especially, the method of apply | coating an actinic-light sensitive or radiation sensitive resin composition on a board | substrate from the point which adjustment of the thickness of a film | membrane is easier is mentioned.
The application method is not particularly limited, and a known method can be adopted. Among these, spin coating is preferably used in the semiconductor manufacturing field.
Moreover, you may implement the drying process for removing a solvent as needed after apply | coating actinic-ray-sensitive or radiation-sensitive resin composition. The method for the drying treatment is not particularly limited, and examples thereof include heat treatment and air drying treatment.

The substrate on which the film is formed is not particularly limited, and an inorganic substrate such as silicon, SiN, SiO ₂ or SiN, a coated inorganic substrate such as SOG (Spin-On-Glass), a semiconductor manufacturing process such as an IC, A substrate generally used in a manufacturing process of a circuit board such as a liquid crystal or a thermal head, and also in other photofabrication lithography processes can be used. Further, if necessary, an organic antireflection film may be formed between the film and the substrate.

The receding contact angle of the film (resist film) formed using the actinic ray-sensitive or radiation-sensitive resin composition is preferably 70 ° or more at a temperature of 23 ± 3 ° C. and a humidity of 45 ± 5%. It is suitable when it exposes via, It is more preferable that it is 75 degrees or more, and it is still more preferable that it is 75-85 degrees. When the receding contact angle of the resist film is in the above range, it is suitable for exposure through an immersion medium.
If the receding contact angle is too small, it cannot be suitably used for exposure through an immersion medium, and the effect of reducing water residue (watermark) defects cannot be sufficiently exhibited. In order to realize a preferable receding contact angle, it is preferable to include the hydrophobic resin in the actinic ray-sensitive or radiation-sensitive composition. Alternatively, the receding contact angle may be improved by forming a coating layer (so-called “topcoat”) of a hydrophobic resin composition on the resist film. As the top coat, those known in the art can be appropriately used.
Further, the top coat includes not only a resin but also a basic compound (quencher) as described in JP 2013-61647 A, particularly OC-5 to OC-11 in Example 3 of the example. It is also preferable to apply a top coat. The top coat described in this publication is considered to be particularly useful when pattern formation is performed in the organic solvent development step described later.
The thickness of the resist film is not particularly limited, but is preferably 1 to 500 nm and more preferably 1 to 100 nm because a fine pattern with higher accuracy can be formed.

(Heating process (PB; Prebake))
It is also preferable to include a preheating step (PB; Prebake) after the film formation and before the step (2) described later.
The heating temperature is preferably 70 to 130 ° C, more preferably 80 to 120 ° 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.

[Step (2)]
Step (2) is a step of exposing the film formed in step (1). More specifically, it is a step of selectively exposing the film so that a desired pattern is formed. As a result, the film is exposed in a pattern, and the solubility of the resist film changes only in the exposed part.
“Exposing” intends to irradiate actinic rays or radiation.

Although there is no restriction | limiting in the light source wavelength used for exposure, Infrared light, visible light, ultraviolet light, far ultraviolet light, extreme ultraviolet light, X-rays, an electron beam, etc. can be mentioned, Preferably it is 250 nm or less, More preferably Far ultraviolet light with a wavelength of 220 nm or less, particularly preferably 1 to 200 nm, specifically, KrF excimer laser (248 nm), ArF excimer laser (193 nm), F ₂ excimer laser (157 nm), X-ray, EUV (13 nm) , An electron beam, etc., preferably a KrF excimer laser, an ArF excimer laser, EUV or an electron beam, more preferably an ArF excimer laser.

The method for selectively exposing the film is not particularly limited, and a known method can be used. For example, a binary mask (Binary-Mask) in which the light transmittance of the light shielding portion is 0% or a halftone phase shift mask (HT-Mask) in which the light transmittance of the light shielding portion is 6% can be used.
In general, a binary mask is used in which a chromium film, a chromium oxide film, or the like is formed on a quartz glass substrate as a light shielding portion.
As the halftone phase shift mask, generally, a quartz glass substrate on which a MoSi (molybdenum silicide) film, a chromium film, a chromium oxide film, a silicon oxynitride film, or the like is formed as a light shielding portion is used.
In the present invention, the exposure is not limited to exposure through a photomask, and selective exposure (pattern exposure) may be performed by exposure without using a photomask, for example, drawing with an electron beam or the like.
This step may include multiple exposures.

(Preferred embodiment: immersion exposure)
As a suitable aspect of exposure, for example, liquid immersion exposure can be mentioned. By using immersion exposure, a finer pattern can be formed. Note that immersion exposure can be combined with super-resolution techniques such as a phase shift method and a modified illumination method.

The immersion liquid used for immersion exposure is transparent to the exposure wavelength and has a refractive index temperature coefficient as much as possible so as to minimize distortion of the optical image projected onto the resist film. Small liquids are preferred. In particular, when the exposure light source is an ArF excimer laser (wavelength: 193 nm), it is preferable to use water from the viewpoints of availability and ease of handling in addition to the above-described viewpoints.
When water is used as the immersion liquid, an additive (liquid) that decreases the surface tension of water and increases the surface activity may be added in a small proportion. This additive is preferably one that does not dissolve the resist film and can ignore the influence on the optical coating on the lower surface of the lens element.
As such an additive, for example, an aliphatic alcohol having a refractive index substantially equal to that of water is preferable, and specific examples include 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 water are mixed with respect to 193 nm light, the optical image projected on the resist is distorted. For this reason, distilled water is preferable as the water to be used. Further, pure water filtered through an ion exchange filter or the like may be used.
The water used as the immersion liquid preferably has an electric resistance of 18.3 MΩcm or more, a TOC (organic substance concentration) of 20 ppb or less, and is preferably deaerated.
Moreover, it is possible to improve lithography performance by increasing the refractive index of the immersion liquid. From such a viewpoint, an additive for increasing the refractive index may be added to water, or heavy water (D ₂ O) may be used instead of water.

  In immersion exposure, the surface of the resist film may be washed with an aqueous chemical before exposure and / or after exposure (before heat treatment).

(Heating process (PEB; Post Exposure Bake))
It is preferable to include a post-exposure heating step (PEB; Post Exposure Bake) after the step (2) and before the step (3).
The heating temperature is preferably 70 to 130 ° C, more preferably 80 to 120 ° 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.

[Step (3)]
Step (3) is a step of developing the exposed film. By carrying out this step, a desired pattern is formed.

(Alkali development process)
Although the method in this step is not particularly limited, one preferred embodiment includes a step of developing the exposed film using an alkali developer (alkali developing step). By this method, a portion having a high exposure intensity is removed.

  Examples of the alkaline developer include inorganic alkalis such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, and aqueous ammonia, primary amines such as ethylamine and n-propylamine, diethylamine, Secondary amines such as di-n-butylamine, tertiary amines such as triethylamine and methyldiethylamine, alcohol amines such as dimethylethanolamine and triethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium Hydroxide, tetrabutylammonium hydroxide, tetrapentylammonium hydroxide, tetrahexylammonium hydroxide, tetraoctylammonium hydroxide, ethyl Tetraalkylammonium hydroxide such as methylammonium hydroxide, butyltrimethylammonium hydroxide, methyltriamylammonium hydroxide, dibutyldipentylammonium hydroxide, trimethylphenylammonium hydroxide, trimethylbenzylammonium hydroxide, triethylbenzylammonium hydroxide, etc. Alkaline aqueous solutions such as quaternary ammonium salts, cyclic amines such as pyrrole and piperidine can be used. Furthermore, an appropriate amount of alcohol or surfactant may be added to the alkaline aqueous solution. 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. The alkali concentration and pH of the alkali developer can be appropriately adjusted and used. The alkali developer may be used after adding a surfactant or an organic solvent.

  The surfactant used in the alkaline developer is not particularly limited. For example, ionic or nonionic fluorine-based and / or silicon-based surfactants can be used. Examples of these fluorine and / or silicon surfactants include, for example, JP-A No. 62-36663, JP-A No. 61-226746, JP-A No. 61-226745, JP-A No. 62-170950, JP 63-34540 A, JP 7-230165 A, JP 8-62834 A, JP 9-54432 A, JP 9-5988 A, US Pat. No. 5,405,720, etc. The surfactants described in US Pat. Nos. 5,360,692, 5,298,881, 5,296,330, 5,346,098, 5,576,143, 5,294,511, and 5,824,451 can be mentioned. Preferably, it is a nonionic surfactant. Although it does not specifically limit as a nonionic surfactant, It is still more preferable to use a fluorochemical surfactant or a silicon-type surfactant.

  The amount of the surfactant used is usually 0.001 to 5% by mass, preferably 0.005 to 2% by mass, and more preferably 0.01 to 0.5% by mass with respect to the total amount of the developer.

  As a development 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.

When the various development methods described above include a step of discharging the developer from the developing nozzle of the developing device toward the resist film, the discharge pressure of the discharged developer (the flow rate per unit area of the discharged developer) is Preferably it is 2 mL / sec / mm ² or less, More preferably, it is 1.5 mL / sec / mm ² or less, More preferably, it is 1 mL / sec / mm ² or less. There is no particular lower limit on the flow rate, but 0.2 mL / sec / mm ² or more is preferable in consideration of throughput.
By setting the discharge pressure of the discharged developer to be in the above range, pattern defects derived from the resist residue after development can be remarkably reduced.
The details of this mechanism are not clear, but perhaps by setting the discharge pressure within the above range, the pressure applied by the developer to the resist film will decrease, and the resist film / resist pattern may be inadvertently cut or collapsed. This is considered to be suppressed.
The developer discharge pressure (mL / sec / mm ² ) is a value at the developing nozzle outlet in the developing device.

  Examples of the method for adjusting the discharge pressure of the developer include a method of adjusting the discharge pressure with a pump or the like, and a method of changing the pressure by adjusting the pressure by supply from a pressurized tank.

(Organic solvent development process)
Although the alkali development step has been described above, in this step, a developer containing a solvated solvent is used without performing alkali development or before or after the alkali development step (hereinafter also referred to as “organic developer” as appropriate). You may implement the process (organic solvent image development process) which develops the film | membrane exposed using.
This step is the same as the alkali development step described above except for the type of developer to be used, the description of the procedure is omitted, and the organic developer to be used will be described below.

As the organic developer, polar solvents such as ketone solvents, ester solvents, alcohol solvents, amide solvents, ether solvents, and hydrocarbon solvents can be used.
Examples of the ketone solvent include 1-octanone, 2-octanone, 1-nonanone, 2-nonanone, acetone, 2-heptanone (methyl amyl ketone), 4-heptanone, 1-hexanone, 2-hexanone, diisobutyl ketone, Examples include cyclohexanone, methylcyclohexanone, phenylacetone, methylethylketone, methylisobutylketone, acetylacetone, acetonylacetone, ionone, diacetylalcohol, acetylcarbinol, acetophenone, methylnaphthylketone, isophorone, and propylene carbonate.
Examples of ester solvents include methyl acetate, butyl acetate, ethyl acetate, isopropyl acetate, pentyl acetate, isopentyl acetate, amyl acetate, propylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, diethylene glycol monoethyl. Ether acetate, ethyl-3-ethoxypropionate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, methyl formate, ethyl formate, butyl formate, propyl formate, ethyl lactate, butyl lactate, propyl lactate, etc. Can be mentioned.
Examples of the alcohol solvent include methyl alcohol, ethyl alcohol, n-propyl alcohol, isopropyl alcohol, n-butyl alcohol, sec-butyl alcohol, tert-butyl alcohol, isobutyl alcohol, n-hexyl alcohol, n-heptyl alcohol, alcohols such as n-octyl alcohol and n-decanol, glycol solvents such as ethylene glycol, diethylene glycol and triethylene glycol, ethylene glycol monomethyl ether, propylene glycol monomethyl ether, ethylene glycol monoethyl ether, propylene glycol monoethyl ether, Diethylene glycol monomethyl ether, triethylene glycol monoethyl ether, methoxymethyl butano It can be mentioned glycol ether solvents such as Le.

Examples of the ether solvent include dioxane, tetrahydrofuran and the like in addition to the glycol ether solvent.
Examples of the amide solvent include N-methyl-2-pyrrolidone, N, N-dimethylacetamide, N, N-dimethylformamide, hexamethylphosphoric triamide, 1,3-dimethyl-2-imidazolidinone and the like. Can be mentioned.
Examples of the hydrocarbon solvent include aromatic hydrocarbon solvents such as toluene and xylene, and aliphatic hydrocarbon solvents such as pentane, hexane, octane and decane.
A plurality of the above solvents may be mixed, or may be used by mixing with a solvent other than those described above or water. However, in order to fully exhibit the effects of the present invention, the water content of the developer as a whole is preferably less than 10% by mass and more preferably substantially free of moisture.
That is, the amount of the organic solvent used in the organic developer is preferably 90% by mass or more and 100% by mass or less, and more preferably 95% by mass or more and 100% by mass or less, with respect to the total amount of the developer.

  In particular, the organic developer is preferably a developer containing at least one organic solvent selected from the group consisting of ketone solvents, ester solvents, alcohol solvents, amide solvents and ether solvents. .

  The vapor pressure of the organic developer is preferably 5 kPa or less, more preferably 3 kPa or less, and particularly preferably 2 kPa or less at 20 ° C. By setting the vapor pressure of the organic developer to 5 kPa or less, the evaporation of the developer on the substrate or in the developing cup is suppressed, and the temperature uniformity in the wafer surface is improved. As a result, the dimensions in the wafer surface are uniform. Sexuality improves.

An appropriate amount of a surfactant can be added to the organic developer as required.
Examples of the surfactant include surfactant love that may be contained in the alkali developer described above.
The amount of the surfactant used is usually 0.001 to 5% by mass, preferably 0.005 to 2% by mass, and more preferably 0.01 to 0.5% by mass with respect to the total amount of the developer.

  The organic developer may contain a basic compound. Examples of the basic compound include nitrogen-containing basic compounds, for example, nitrogen-containing compounds described in JP-A-2013-11833, particularly <0021> to <0063>. When the organic developer contains a basic compound, an improvement in contrast during development, suppression of film loss, and the like can be expected.

  In the above, although the alkali development process and the organic solvent development process were explained in full detail, you may carry out combining both. For example, the organic solvent development step may be performed after the alkali development step. In the case of this embodiment, a portion with high exposure intensity is removed by performing an alkali development step, and further, a portion with low exposure strength is removed by performing an organic solvent development step to form a finer pattern. it can. In this way, by the multiple development process in which development is performed a plurality of times, a pattern can be formed without dissolving only the intermediate exposure intensity region, so that a finer pattern than usual can be formed (Japanese Patent Laid-Open No. 2008-292975 <0077). The same mechanism as>.

(Rinsing process)
After the development step, it is preferable to use a rinse solution as necessary.
The rinsing liquid is not particularly limited as long as the resist film is not dissolved, and a solution containing a general organic solvent can be used.

  The rinsing liquid is a rinsing liquid containing at least one organic solvent selected from the group consisting of hydrocarbon solvents, ketone solvents, ester solvents, alcohol solvents, amide solvents, and ether solvents. More preferably, it is a rinsing liquid containing at least one organic solvent selected from the group consisting of ketone solvents, ester solvents, alcohol solvents, amide solvents, alcohol solvents or ester solvents. More preferably, it is a rinsing liquid containing a monohydric alcohol, and most preferably a rinsing liquid containing a monohydric alcohol with 5 or more carbon atoms.

Specific examples of the hydrocarbon solvent, ketone solvent, ester solvent, alcohol solvent, amide solvent and ether solvent are the same as those of the organic developer described above.
Examples of the monohydric alcohol include linear, branched, and cyclic monohydric alcohols. More specifically, 1-hexanol, 2-hexanol, 4-methyl-2-pentanol, 1 -Pentanol, 3-methyl-1-butanol and the like.
The rinse liquid may contain a plurality of solvents. Moreover, the rinse liquid may contain an organic solvent other than the above.

  The water content of the rinse liquid is preferably 10% by mass or less, more preferably 5% by mass or less, and particularly preferably 3% by mass or less. By setting the water content to 10% by mass or less, better development characteristics can be obtained.

  The vapor pressure of the rinse liquid is preferably 0.05 kPa or more and 5 kPa or less at 20 ° C., more preferably 0.1 kPa or more and 5 kPa or less, and most preferably 0.12 kPa or more and 3 kPa or less. By setting the vapor pressure of the rinse liquid to 0.05 kPa or more and 5 kPa or less, the temperature uniformity in the wafer surface is improved, and further, the swelling due to the penetration of the rinse solution is suppressed, and the dimensional uniformity in the wafer surface. Improves.

  An appropriate amount of a surfactant can be added to the rinse solution. Specific examples and usage amounts of the surfactant are the same as those of the organic developer described above.

In the rinsing process, the wafer subjected to the organic solvent development is cleaned using the rinsing liquid. The method of the cleaning process 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), and immersing the substrate in a bath filled with the rinse liquid for a certain period of time. A method (dip method), a method of spraying a rinsing liquid onto the substrate surface (spray method), and the like can be applied. Among these, a method of performing a cleaning process by a spin coating method, rotating the substrate at a rotational speed of 2000 rpm to 4000 rpm after cleaning, and removing the rinse liquid from the substrate is preferable.
Moreover, it is preferable to perform a heat treatment (Post Bake) after the rinsing treatment. The developer and the rinsing liquid remaining between the patterns and inside the patterns are removed by heat treatment. The heat treatment after the rinsing treatment is usually performed at 40 to 160 ° C., preferably 70 to 95 ° C., and usually 10 seconds to 3 minutes, preferably 30 seconds to 90 seconds.

  In general, the pattern obtained by the pattern forming method of the present invention is suitably used as an etching mask for a semiconductor device, but can also be used for other purposes. As other applications, for example, guide pattern formation in DSA (Directed Self-Assembly) (see, for example, ACS Nano Vol. 4 No. 8 Pages 4815-4823), use as a core material (core) of a so-called spacer process (for example, JP-A-3-270227, JP-A-2013-164509, etc.).

The present invention also relates to an electronic device manufacturing method including the pattern forming method of the present invention described above, 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 are shown below, but the present invention is not limited thereto.

<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 3.5% by mass is prepared for each, and this is filtered through a polyethylene filter having a pore size of 0.03 μm, and actinic ray sensitive or radiation sensitive. A photosensitive resin composition (positive photosensitive resin composition) was prepared. The prepared positive photosensitive resin composition was evaluated by the following method, and the results are shown in Table 2.

  The various components used in Table 2 are summarized below.

[resin]
In Table 2, the “type of repeating unit” column indicates the type of repeating unit contained in the resin, and the “composition of repeating unit (mol%)” column indicates the content of each repeating unit with respect to all the repeating units in the resin. (Mol%). "General formula (III) (n = 0)" intends a repeating unit in which n in general formula (III) is 0, and "general formula (III) (n = 1)" is the general formula described above. A repeating unit in which n in (III) is 1 is intended.
Structural formulas corresponding to symbols described in the “type of repeating unit” column in Table 2 are shown below. In the following formula, “I-8” does not correspond to the repeating unit represented by the general formula (I).
In the following formulae, “A” corresponds to the repeating unit represented by the general formula (I).

In addition, the structures and properties (molecular weight, dispersity) of the resins (P-1) to (P-33) are summarized in Table 3 below.
In Table 3 below, the “structure” column is the structure of the repeating unit of each resin, the “composition (mol%)” column is the composition (mol%) of each repeating unit relative to all repeating units in the resin, and “molecular weight (Mw)”. The column shows the weight average molecular weight Mw of each resin, and the “dispersion degree (Mw / Mn)” column shows the dispersion degree (Mw / Mn) of each resin. In Table 3, in the “Composition (mol%)” column, the composition (mol%) of the repeating unit shown in the “Structure” column is shown in order from the left. For example, in the “Structure” column of the resin P-1 The mol% of the leftmost repeating unit corresponds to 35 mol%.

[Acid generator]
The acid generators in Table 2 correspond to the above-mentioned compounds, but the structures are shown below again.
In Table 2 above, “ratio (mass ratio)” in the “acid generator” column represents mass% of the usage ratio (type 1 / type 2) of the acid generator described in type 1 and type 2. .

[Acid diffusion control agent (quencher)]
As the acid diffusion control agent, the following were used.
In the following formulae, “Q-1”, “Q-2”, and “Q-3” correspond to a low molecular compound (F) having a nitrogen atom and a group capable of leaving by the action of an acid. “PA-67” corresponds to a basic compound or an ammonium salt compound (E) whose basicity is reduced by irradiation with actinic rays or radiation.

[Surfactant]
As the surfactant, the following were used.
W-1: Megafuck F176 (manufactured by DIC Corporation; fluorine-based)
W-2: Megafuck R08 (manufactured by DIC Corporation; fluorine and silicon)
W-3: Polysiloxane polymer KP-341 (manufactured by Shin-Etsu Chemical Co., Ltd .; silicon-based)
W-4: Troisol S-366 (manufactured by Troy Chemical Co., Ltd.)
W-5: KH-20 (Asahi Glass Co., Ltd.)
W-6: PolyFox PF-6320 (manufactured by OMNOVA Solutions Inc .; fluorine-based)

[Hydrophobic resin]
The hydrophobic resin in the table corresponds to the above-mentioned compound, but the structure is shown below again.
In the following hydrophobic resins, “B-23”, “B-29”, “B-33”, and “B-52” have groups that are decomposed by the action of an alkali developer to increase the solubility in the alkali developer. .

[Additive]
The following additive M was used as an additive.

[solvent]
The following were used as the solvent.
In Table 2, the “ratio (mass ratio)” in the “solvent” column represents mass% of the amount of each solvent used, and the composition (mass%) of the solvent shown in the “kind” column is shown in order from the left.
SL-1: Propylene glycol monomethyl ether acetate (PGMEA)
SL-2: Propylene glycol monomethyl ether propionate SL-3: 2-heptanone SL-4: Ethyl lactate SL-5: Propylene glycol monomethyl ether (PGME)
SL-6: Cyclohexanone SL-7: γ-Butyrolactone SL-8: Propylene carbonate

<Examples and Comparative Examples>
An organic antireflection coating composition ARC29SR (Nissan Chemical Co., Ltd.) is applied onto a 300 mm aperture (12 inch aperture) silicon wafer and baked at 205 ° C. for 60 seconds to form an organic antireflection coating with a thickness of 98 nm. did. The positive photosensitive resin composition prepared thereon was applied and baked at 100 ° C. for 60 seconds to form a photosensitive film (resist film) having a thickness of 90 nm. The obtained wafer was used with an ArF excimer laser immersion scanner (XTML1700i, NA1.20, C-Quad, outer sigma 0.981, inner sigma 0.895, XY deflection, manufactured by ASML), 1: 1 with a line width of 50 nm. Exposure was through a 6% halftone mask with a line and space pattern. Ultra pure water was used as the immersion liquid. Then, after heating at 95 ° C. for 60 seconds (PEB treatment), developing with an aqueous tetramethylammonium hydroxide solution (2.38 mass%) for 30 seconds, rinsing with pure water, and spin drying to obtain a resist pattern .

<Various evaluations>
Each evaluation shown below was implemented. In addition, the obtained result is put together in Table 4 mentioned later, and is shown.

[Exposure latitude evaluation: EL (%)]
The obtained line pattern was observed with a length-measuring scanning electron microscope (S9380II manufactured by Hitachi, Ltd.). The exposure amount for reproducing a line-and-space mask pattern having a line width of 50 nm was determined as the optimum exposure amount, and the exposure amount width allowing a pattern size of 50 nm ± 10% when the exposure amount was changed was determined. EL is a value expressed as a percentage by dividing the exposure width by the optimum exposure. The larger the value, the smaller the change in performance due to the change in exposure amount, and the better the exposure latitude.
In practice, 20.0% or more is preferable.

[LWR evaluation: LWR (nm)]
The line pattern of the line width of 50 nm with the optimum exposure amount obtained by the exposure latitude evaluation was measured for 50 points of the line width in the range of 2 μm in the longitudinal direction of the line pattern, the standard deviation was obtained, and 3σ was calculated. A smaller value indicates better performance. In addition, 4.0 or less is preferable.

[PEB temperature dependence: PEBS (nm / ° C)]
Using three silicon wafers in which an antireflection film with a film thickness of 98 nm and a photosensitive film (resist film) with a film thickness of 90 nm are arranged in this order according to the above procedure, exposure is performed with the optimum exposure amount obtained by exposure latitude evaluation. went. Next, PEB treatment was performed at three temperatures of + 2 ° C., ± 0 ° C., and −2 ° C. (93 ° C., 95 ° C., 97 ° C.) with respect to 95 ° C. (PEB treatment), and developed to obtain a pattern. Each obtained line and space was measured to determine their line widths L1, L0, and L2. The PEB temperature dependency was defined as the fluctuation of the line width per 1 ° C. PEB temperature change, and was calculated by the following formula.
PEB temperature dependency (nm / ° C.) = | L1-L2 | / 4
The smaller the value, the smaller the performance change with respect to the temperature change.
In practice, 3.0 nm / ° C. or less is preferable.

[Evaluation of cross-sectional shape of pattern]
The cross-sectional shape of the line-and-space (1: 1) pattern with a line width of 50 nm obtained in the image performance test was observed with SEM (Hitachi Ltd. S-4800), and the pattern shape was vertical. The angle α was measured and evaluated according to the following criteria. Note that the angle α is intended to be an angle α formed by the substrate 12 (silicon wafer) that supports the pattern and the pattern 12, as shown in FIG.
In practice, A to C are preferable.
“A”: 88 ° ≦ α ≦ 92 °
“B”: 86 ° ≦ α <88 ° or 92 ° <α ≦ 94 °
“C”: 84 ° ≦ α <86 ° or 94 ° <α ≦ 96 °
“D”: 82 ° ≦ α <84 ° or 96 ° <α ≦ 98 °
“E”: 82 ° <α or α> 98 °

As shown in Table 8 above, it was confirmed that the desired effect was obtained when the composition of the present invention was used.
From the comparison between Example 2 and Example 31, the compound that generates an acid upon irradiation with actinic rays or radiation is an ionic compound containing a cation and an anion, and the anion is represented by the general formula (2). It was confirmed that a more excellent effect was obtained when the sulfonate anion (or the sulfonate anion represented by formula (B-1)) was obtained. From the comparison between Example 2 and Example 31, the compound that generates an acid upon irradiation with actinic rays or radiation is an ionic compound containing a cation and an anion, and the number of fluorine atoms contained in the anion is 2 to 2. If it is three, it can be said that a more excellent effect is obtained.
From the comparison between Example 2 and Example 32, the compound that generates an acid upon irradiation with actinic rays or radiation is an ionic compound containing a cation and an anion, and the cation is represented by the above general formula (ZI-4). In the case of the cation represented, it was confirmed that a more excellent effect was obtained.
Further, from the comparison between Example 2 and Example 33, when the composition contains a basic compound or an ammonium salt compound whose basicity is lowered by irradiation with actinic rays or radiation, a more excellent effect can be obtained. Was confirmed.
Further, from the comparison between Example 2 and Example 34, when the composition contains a low molecular compound having a nitrogen atom and having a group capable of leaving by the action of an acid, a more excellent effect can be obtained. confirmed.
Further, from the comparison between Example 1 and Example 35, when the hydrophobic resin has a group that is decomposed by the action of the alkali developer and increases the solubility in the alkali developer, a more excellent effect can be obtained. confirmed.
On the other hand, in Comparative Examples 1 to 3 in which the predetermined resin was not used, the desired effect was not obtained.

In the above examples, except that EUV exposure was performed instead of ArF immersion exposure, a resist pattern was formed by the same procedure as described above, and the same evaluation was performed to confirm that the pattern could be formed. .
Moreover, in the said Example, it developed by the butyl acetate solvent instead of the development by tetramethylammonium hydroxide aqueous solution, and it confirmed that pattern formation could be performed. Furthermore, in this development with a butyl acetate solvent, a specific topcoat composition (topcoat composition) as described in OC-5 to OC-11 in Example Table 3 of JP2013-61647A is used. It was confirmed that the pattern could be formed even when the resist film was further coated and evaluated.

10 base materials 12 patterns

Claims (16)

The repeating unit represented by the following general formula (I) and the repeating unit represented by the following general formula (II), and the content of the repeating unit represented by the above general formula (II) in all repeating units Resin with respect to 10 mol% or more,
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 formulas (I) and (II), each T independently represents a single bond or a divalent linking group.
R ₁ and R ₃ each independently represents a hydrogen atom or an alkyl group.
R ₂ represents a hydrocarbon group having 3 or more carbon atoms.
R represents an atomic group necessary for forming an alicyclic structure together with a carbon atom.
R ₄ , R ₅ and R ₆ each independently represents an alkyl group.   The actinic ray-sensitive or radiation-sensitive resin composition according to claim 1, wherein T is a single bond. The compound that generates an acid upon irradiation with actinic rays or radiation is an ionic compound containing a cation and an anion, and the anion is a sulfonate anion represented by the general formula (2). The actinic ray-sensitive or radiation-sensitive resin composition described.

In general formula (2), Xf each independently represents a fluorine atom or an alkyl group substituted with at least one fluorine atom. R ₇ and R ₈ each independently represent a hydrogen atom, a fluorine atom, an alkyl group, or an alkyl group substituted with at least one fluorine atom, and when there are a plurality of R ₇ and R ₈ , R ₇ and R ₈ are the same But it can be different. L represents a divalent linking group, and when there are a plurality of L, L may be the same or different. A represents an organic group containing a cyclic structure. x represents an integer of 1 to 20. y represents an integer of 0 to 10. z represents an integer of 0 to 10. The compound that generates an acid upon irradiation with active light or radiation is an ionic compound containing a cation and an anion, and the anion is a sulfonate anion represented by the general formula (B-1). 2. The actinic ray-sensitive or radiation-sensitive resin composition according to 2.

In general formula (B-1), R _<b1> represents a hydrogen atom, a fluorine atom, or a trifluoromethyl group each independently. n represents an integer of 0 to 4. _Xb1 represents a single bond, an alkylene group, an ether bond, an ester bond, a sulfonate bond, or a combination thereof. R _b2 represents an organic group having 6 or more carbon atoms.   5. The compound according to claim 1, wherein the compound that generates an acid upon irradiation with actinic rays or radiation is an ionic compound containing a cation and an anion, and the number of fluorine atoms contained in the anion is 2 to 3. 2. The actinic ray-sensitive or radiation-sensitive resin composition according to item 1. The compound that generates an acid upon irradiation with active light or radiation is an ionic compound containing a cation and an anion, and the cation is represented by the general formula (ZI-3A) or the general formula (ZI-4) The actinic ray-sensitive or radiation-sensitive resin composition according to any one of claims 1 to 5, which is a cation represented.

In General Formula (ZI-3A), R ₁ represents an alkyl group, a cycloalkyl group, an alkoxy group, a cycloalkoxy group, an aryl group, or an alkenyl group.
R ₂ and R ₃ each independently represents a hydrogen atom, an alkyl group, a cycloalkyl group or an aryl group, and R ₂ and R ₃ may be linked to each other to form a ring, and R ₁ and R ₂ may be , May be linked together to form a ring. However, at least one of R ₂ and R ₃ represents an alkyl group, a cycloalkyl group, or an aryl group.
R _X and R _y each independently represents an alkyl group, a cycloalkyl group, an alkenyl group, an aryl group, a 2-oxoalkyl group, a 2-oxocycloalkyl group, an alkoxycarbonylalkyl group, or an alkoxycarbonylcycloalkyl group. R _X and R _y may be linked to each other to form a ring, and this ring structure may contain an oxygen atom, a nitrogen atom, a sulfur atom, a ketone group, an ether bond, an ester bond or an amide bond. .
In General Formula (ZI-4A), R ₁₃ represents a hydrogen atom, a fluorine atom, a hydroxyl group, an alkyl group, a cycloalkyl group, an alkoxy group, an alkoxycarbonyl group, or a group having a cycloalkyl group.
R ₁₄ represents 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. If R ₁₄ there are a _{plurality, R 14} may be the same or different.
R ₁₅ each independently represents an alkyl group, a cycloalkyl group or a naphthyl group. Two R _{15 s} may be bonded to each other to form a ring, and the atoms constituting the ring may include an oxygen atom, a sulfur atom, or a nitrogen atom.
l represents an integer of 0-2. r represents an integer of 0 to 8.   The actinic-ray sensitive or radiation sensitive resin composition of any one of Claims 1-6 in which the said resin contains the repeating unit containing a lactone structure or a sultone structure further.   Furthermore, the actinic-ray sensitive or radiation sensitive resin composition of any one of Claims 1-7 containing hydrophobic resin.   The actinic ray-sensitive or radiation-sensitive resin composition according to claim 8, wherein the hydrophobic resin has a group that is decomposed by the action of an alkali developer to increase the solubility in the alkali developer.   Furthermore, the actinic ray sensitive or radiation sensitive resin composition of any one of Claims 1-9 containing the basic compound or ammonium salt compound which basicity falls by irradiation of actinic light or a radiation. .   Furthermore, the actinic-ray-sensitive or radiation-sensitive resin composition of any one of Claims 1-9 containing the low molecular compound which has a nitrogen atom and has a group which remove | eliminates by the effect | action of an acid. In addition, it contains an organic solvent,
The propylene glycol monomethyl ether acetate is contained in the organic solvent, and the content of the propylene glycol monomethyl ether acetate with respect to the total mass of the organic solvent is more than 90% by mass. An actinic ray-sensitive or radiation-sensitive resin composition.   The actinic ray-sensitive or radiation-sensitive resin composition according to claim 1, further comprising γ-butyrolactone.   The process of forming a film | membrane on a board | substrate using the actinic-ray-sensitive or radiation-sensitive resin composition of any one of Claims 1-13, the process of exposing the said film | membrane, and developing the exposed film | membrane The pattern formation method including the process to do.   The manufacturing method of an electronic device containing the pattern formation method of Claim 14.   An electronic device manufactured by the electronic device manufacturing method according to claim 15.

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