JP7358627B2 - Actinic ray-sensitive or radiation-sensitive resin composition, actinic ray-sensitive or radiation-sensitive film, pattern forming method, photomask, electronic device manufacturing method, and compound - Google Patents

Description

The present invention relates to an actinic ray-sensitive or radiation-sensitive resin composition, an actinic ray-sensitive or radiation-sensitive film, a pattern forming method, a photomask, an electronic device manufacturing method, and a compound. More specifically, the present invention relates to an ultra-microlithography process applicable to the manufacturing process of ultra-LSI (Large Scale Integration) and high-capacity microchips, the manufacturing process of nanoimprint molds, the manufacturing process of high-density information recording media, etc. The present invention relates to actinic ray-sensitive or radiation-sensitive resin compositions, actinic ray-sensitive or radiation-sensitive films, pattern forming methods, photomasks, electronic device manufacturing methods, and compounds that are suitably used in other photofabrication processes.

Conventionally, in the manufacturing process of semiconductor devices such as ICs (Integrated Circuits) and LSIs, microfabrication is performed by lithography using a photoresist composition. In recent years, as integrated circuits have become more highly integrated, there has been a demand for ultra-fine pattern formation in the submicron region or quarter micron region. Along with this, there has been a trend towards shorter exposure wavelengths, from g-line to i-line and then to KrF excimer laser light, and now exposure machines that use ArF excimer laser light with a wavelength of 193 nm as a light source have been developed. ing. Furthermore, as a technique to further improve resolution, the so-called immersion method, in which a liquid with a high refractive index (hereinafter also referred to as "immersion liquid") is filled between the projection lens and the sample, has been developed.

In addition to excimer laser light, lithography using electron beams (EB), X-rays, extreme ultraviolet light (EUV), and the like is currently being developed. Along with this, chemically amplified resist compositions that are effectively sensitive to various types of radiation and have excellent sensitivity and resolution have been developed.

For example, Patent Document 1 describes a resin having a group that decomposes under the action of an acid and increases its solubility in an alkaline developer, and a resin with a specific general formula that generates sulfonic acid when irradiated with actinic rays or radiation. A positive-working photosensitive composition is described, which is characterized by containing the following compound.

Furthermore, Patent Document 2 describes a resin that decomposes under the action of an acid and increases its solubility in an alkaline developer, and a compound that generates an acid when irradiated with actinic rays or radiation, and which is expressed by a specific formula. An actinic ray-sensitive or radiation-sensitive resin composition containing a compound is described.

Japanese Patent Application Publication No. 9-258435 International Publication No. 2020/045534

However, in recent years, with the further miniaturization of formed patterns, it is possible to further improve LWR (line width roughness) and resolution in ultra-fine (especially line width or space width 30 nm or less) pattern formation methods, and development There is a need for actinic ray-sensitive or radiation-sensitive resin compositions that can further reduce defects.

The object of the present invention is to improve the roughness performance, improve resolution, and reduce development defects at a high level in the formation of ultra-fine patterns (in particular, line width or space width of 30 nm or less). Another object of the present invention is to provide a radiation-sensitive resin composition. Further, another object of the present invention is to provide an actinic ray-sensitive or radiation-sensitive film, a pattern forming method, a photomask, a method for manufacturing an electronic device, and a compound using the above-mentioned actinic ray-sensitive or radiation-sensitive resin composition. Our goal is to provide the following.

一般式（１）中、Ｒ _１ ～Ｒ _５ は、それぞれ独立に水素原子又は置換基を表す。Ｒ _１ ～Ｒ _５ のうち少なくとも一つは、下記一般式（Ｒ－１）で表される基を表す。（Ｍ ^＋ ） _ｎ は、カチオン部を表す。ｎは２以上の整数を表す。

一般式（Ｒ－１）中、Ａは単結合又は（ｍ＋１）価の連結基を表す。
Ｙは、それぞれ独立に下記式（Ａ１）～（Ａ６）のいずれかで表される基を表す。
ｍは１以上の整数を表す。
ｍが２以上の整数を表す場合、複数のＹは、それぞれ同一であってもよく、異なっていてもよい。
＊は、ベンゼン環への結合手を表す。

式（Ａ１）～（Ａ６）中、*はＡへの結合手を表す。
式（Ａ２）中、Ｒ _６ は、炭素原子を有する置換基を表す。式（Ａ２）のＳＯ _２ における硫黄原子は、Ｒ _６ 中の上記炭素原子と結合する。また、Ｒ _６ は、Ａ又はＬと互いに結合して環を形成してもよい。
Ｌは、単結合、カルボニル結合、アルキレン基、又は２価の芳香族基を表す。
式（Ａ３）中、Ｒ _７ は、炭素原子を有する置換基を表す。式（Ａ３）のＮ ^－ は、Ｒ _７ 中の上記炭素原子と結合する。また、Ｒ _７ は、Ａと互いに結合して環を形成してもよい。
式（Ａ４）中、Ｒ _８ は、炭素原子を有する置換基を表す。式（Ａ４）のカルボニル結合における炭素原子は、Ｒ _８ 中の上記炭素原子と結合する。また、Ｒ _８ は、Ａと互いに結合して環を形成してもよい。
式（Ａ５）中、Ｒ _９ 、及びＲ _９’ は、それぞれ独立に水素原子又は置換基を表す。Ｒ _９ 、及びＲ _９’ は互いに結合して環を形成してもよい。
＜２＞
上記化合物（Ｂ）が、下記一般式（２）で表される化合物である、＜１＞に記載の感活性光線性又は感放射線性樹脂組成物。

一般式（２）中、Ｒ _１ ～Ｒ _５ は、それぞれ独立に水素原子又は置換基を表す。Ｒ _１ ～Ｒ _５ のうち少なくとも一つは、上記一般式（Ｒ－１）で表される基を表す。
Ｒ _１０１ ～Ｒ _１０３ は、それぞれ独立に水素原子又は置換基を表す。Ｒ _１０１ ～Ｒ _１０３ の二つは、互いに結合して環を形成してもよい。
ｎは２以上の整数を表す。複数のＲ _１０１ 、複数のＲ _１０２ 、及び複数のＲ _１０３ は、それぞれ同一であってもよく、異なっていてもよい。
＜３＞
上記一般式（２）で表される化合物が、下記一般式（３）で表される化合物である、＜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（３）中、Ｑ _１ 、Ｑ _２ は、それぞれ独立に置換基を表す。
Ｒ _３ ～Ｒ _５ は、それぞれ独立に水素原子又は置換基を表す。Ｒ _３ ～Ｒ _５ のうち少なくとも一つは、上記一般式（Ｒ－１）で表される基を表す。
Ｒ _１０１ ～Ｒ _１０３ は、それぞれ独立に水素原子又は置換基を表す。Ｒ _１０１ ～Ｒ _１０３ の二つは、互いに結合して環を形成してもよい。
ｎは２以上の整数を表す。複数のＲ _１０１ 、複数のＲ _１０２ 、及び複数のＲ _１０３ は、それぞれ同一であってもよく、異なっていてもよい。
＜４＞
上記一般式（３）中、Ｑ _１ 、Ｑ _２ が、それぞれ独立に脂肪族炭化水素環基、アリール基、又はヘテロアリール基である、＜３＞に記載の感活性光線性又は感放射線性樹脂組成物。
＜５＞
上記一般式（３）中、Ｑ _１ 、Ｑ _２ が、それぞれアリール基である、＜３＞又は＜４＞に記載の感活性光線性又は感放射線性樹脂組成物。
＜６＞
上記一般式（３）中、Ｑ _１ 、Ｑ _２ が、それぞれ下記一般式（Ａｒ）で表される基である、＜３＞～＜５＞のいずれか１項に記載の感活性光線性又は感放射線性樹脂組成物。

一般式（Ａｒ）中、Ｒ _１０ ～Ｒ _１４ は、それぞれ独立に水素原子又は置換基を表す。Ｒ _１０ ～Ｒ _１４ のうち少なくとも一つは、極性基を含む基、酸の作用により分解し極性が増大する基を含む基、又はアルカリ現像液の作用により分解し、アルカリ現像液中での溶解度が増大する基を含む基である。
*は、一般式（３）におけるベンゼン環への結合手を表す。
＜７＞
上記一般式（３）中、Ｑ _１ 、Ｑ _２ が、それぞれ下記一般式（Ａｒ１）で表される基である、＜３＞～＜５＞のいずれか１項に記載の感活性光線性又は感放射線性樹脂組成物。

一般式（Ａｒ１）中、Ｒ _１５ ～Ｒ _１９ は、それぞれ独立に水素原子又は置換基を表す。Ｒ _１５ ～Ｒ _１９ のうち少なくとも一つは、下記置換基Ｘを表す。
*は、一般式（３）におけるベンゼン環への結合手を表す。
置換基Ｘ：ヒドロキシ基、カルボキシル基、カルボニル結合を有する基、アルコキシ基、アシルオキシ基、アルコキシカルボニルオキシ基、アリールオキシカルボニルオキシ基、アリールオキシカルボニル基、アルコキシカルボニル基、アリールオキシアルキルオキシ基、アルコキシアルキルオキシ基、カルバモイル基、又はイミド基
＜８＞
上記化合物（Ｂ）が、下記一般式（４）で表される化合物である、＜１＞～＜７＞のいずれか１項に記載の感活性光線性又は感放射線性樹脂組成物。

一般式（４）中、Ｒ _３ 、Ｒ _５ は、それぞれ独立に水素原子又は置換基を表す。
Ａは単結合又は（ｍ＋１）価の連結基を表す。
Ｙは、それぞれ独立に上記式（Ａ１）～（Ａ６）のいずれかで表される基を表す。
ｍは１以上の整数を表す。
ｍが２以上の整数を表す場合、複数のＹは、それぞれ同一であってもよく、異なっていてもよい。
Ｒ _２０ ～Ｒ _２４ は、それぞれ独立に水素原子又は置換基を表す。Ｒ _２０ ～Ｒ _２４ のうち少なくとも一つは下記置換基Ｘを表す。
Ｒ _２５ ～Ｒ _２９ は、それぞれ独立に水素原子又は置換基を表す。Ｒ _２５ ～Ｒ _２９ のうち少なくとも一つは、下記置換基Ｘを表す。
Ｒ _１０１ ～Ｒ _１０３ は、それぞれ独立に水素原子又は置換基を表す。Ｒ _１０１ ～Ｒ _１０３ の二つは、互いに結合して環を形成してもよい。
ｎは２以上の整数を表し、複数のＲ _１０１ 、複数のＲ _１０２ 、及び複数のＲ _１０３ は、それぞれ同一であってもよく、異なっていてもよい。
置換基Ｘ：ヒドロキシ基、カルボキシル基、カルボニル結合を有する基、アルコキシ基、アシルオキシ基、アルコキシカルボニルオキシ基、アリールオキシカルボニルオキシ基、アリールオキシカルボニル基、アルコキシカルボニル基、アリールオキシアルキルオキシ基、アルコキシアルキルオキシ基、カルバモイル基、又はイミド基
＜９＞
上記一般式（１）～（３）で表される化合物における上記一般式（Ｒ－１）中のＡ、及び上記一般式（４）中のＡが２価の芳香族基である、＜１＞～＜８＞のいずれか１項に記載の感活性光線性又は感放射線性樹脂組成物。
＜１０＞
上記一般式（４）で表される化合物が、下記一般式（５）で表される化合物である、＜８＞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（５）中、Ｒ _３ 、Ｒ _５ は、それぞれ独立に水素原子又は置換基を表す。
Ｒ _２０ ～Ｒ _２４ は、それぞれ独立に水素原子又は置換基を表す。Ｒ _２０ ～Ｒ _２４ のうち少なくとも一つは下記置換基Ｘを表す。
Ｒ _２５ ～Ｒ _２９ は、それぞれ独立に水素原子又は置換基を表す。Ｒ _２５ ～Ｒ _２９ のうち少なくとも一つは、下記置換基Ｘを表す。
Ｒ _３０ ～Ｒ _３４ は、それぞれ独立に水素原子又は置換基を表す。Ｒ _３０ ～Ｒ _３４ のうち少なくとも一つは、下記一般式（Ｒ－２）で表される基を表す。
Ｒ _１０１ ～Ｒ _１０３ は、それぞれ独立に水素原子又は置換基を表す。Ｒ _１０１ ～Ｒ _１０３ の二つは、互いに結合して環を形成してもよい。
ｎは２以上の整数を表し、複数のＲ _１０１ 、複数のＲ _１０２ 、及び複数のＲ _１０３ は、それぞれ同一であってもよく、異なっていてもよい。
置換基Ｘ：ヒドロキシ基、カルボキシル基、カルボニル結合を有する基、アルコキシ基、アシルオキシ基、アルコキシカルボニルオキシ基、アリールオキシカルボニルオキシ基、アリールオキシカルボニル基、アルコキシカルボニル基、アリールオキシアルキルオキシ基、アルコキシアルキルオキシ基、カルバモイル基、又はイミド基

一般式（Ｒ－２）中、Ａ’は単結合又は（ｍ１＋１）価の連結基を表す。
Ｙは、それぞれ独立に上記式（Ａ１）～（Ａ６）のいずれかで表される基を表す。
ｍ１は１以上の整数を表す。
ｍ１が２以上の整数を表す場合、複数のＹは、それぞれ同一であってもよく、異なっていてもよい。
＊は、一般式（５）におけるベンゼン環への結合手を表す。
＜１１＞
上記一般式（５）中、Ａ’が単結合又はメチレン基である、＜１０＞に記載の感活性光線性又は感放射線性樹脂組成物。
＜１２＞
上記一般式（１）～（５）中、ｎが２である、＜１＞～＜１１＞のいずれか１項に記載の感活性光線性又は感放射線性樹脂組成物。
＜１３＞
フォトマスク製造用である、＜１＞～＜１２＞のいずれか１項に記載の感活性光線性又は感放射線性樹脂組成物。
＜１４＞
＜１＞～＜１３＞のいずれか１項に記載の感活性光線性又は感放射線性樹脂組成物を用いて形成された感活性光線性又は感放射線性膜。
＜１５＞
＜１＞～＜１３＞のいずれか１項に記載の感活性光線性又は感放射線性樹脂組成物を用いてレジスト膜を形成するレジスト膜形成工程と、上記レジスト膜を露光する露光工程と、露光された上記レジスト膜を、現像液を用いて現像する現像工程と、を含むパターン形成方法。
＜１６＞
＜１５＞に記載のパターン形成方法を用いて作製されたフォトマスク。
＜１７＞
＜１５＞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。
本発明は、上記＜１＞～＜１７＞に係る発明であるが、以下、それ以外の事項（例えば、下記［１］～［１９］）についても記載している。 The present inventors have found that a compound having a specific anion structure in addition to the benzenesulfonic acid anion can be used as a compound that generates an acid upon irradiation with actinic rays or radiation in an actinic ray-sensitive or radiation-sensitive resin composition. The present invention has been completed based on the discovery that the above-mentioned problems can be solved.
That is, the present inventors discovered that the above-mentioned problem can be achieved by the following configuration.
<1>
An actinic ray-sensitive or radiation-sensitive resin composition containing the following (A) and (B).
(A) Resin whose polarity increases due to the action of acid
(B) A compound that generates an acid upon irradiation with actinic rays or radiation, and is represented by the following general formula (1)

In general formula (1), R ₁ to R ₅ each independently represent a hydrogen atom or a substituent. At least one of R ₁ to R ₅ represents a group represented by the following general formula (R-1). (M ⁺ ) _n represents a cation moiety. n represents an integer of 2 or more.

In the general formula (R-1), A represents a single bond or a (m+1)-valent linking group.
Y each independently represents a group represented by any one of the following formulas (A1) to (A6).
m represents an integer of 1 or more.
When m represents an integer of 2 or more, the plurality of Y's may be the same or different.
* represents a bond to the benzene ring.

In formulas (A1) to (A6), * represents a bond to A.
In formula (A2), R ₆ represents a substituent having a carbon atom. The sulfur atom in SO ₂ of formula (A2) bonds with the carbon atom in R ₆ . Further, R ₆ may be combined with A or L to form a ring.
L represents a single bond, a carbonyl bond, an alkylene group, or a divalent aromatic group.
In formula (A3), R ₇ represents a substituent having a carbon atom. N ⁻ in formula (A3) is bonded to the above carbon atom in R ₇ . Furthermore, R ₇ may combine with A to form a ring.
In formula (A4), R ₈ represents a substituent having a carbon atom. The carbon atom in the carbonyl bond of formula (A4) is bonded to the carbon atom in R ₈ . Moreover, R ₈ may combine with A to form a ring.
In formula (A5), R ₉ and R _9' each independently represent a hydrogen atom or a substituent. R ₉ and R _9' may be combined with each other to form a ring.
<2>
The actinic ray-sensitive or radiation-sensitive resin composition according to <1>, wherein the compound (B) is a compound represented by the following general formula (2).

In general formula (2), R ₁ to R ₅ each independently represent a hydrogen atom or a substituent. At least one of R ₁ to R ₅ represents a group represented by the above general formula (R-1).
R ₁₀₁ to R ₁₀₃ each independently represent a hydrogen atom or a substituent. Two of R ₁₀₁ to R ₁₀₃ may be bonded to each other to form a ring.
n represents an integer of 2 or more. A plurality of R ₁₀₁ s , a plurality of R _{102 s} , and a plurality of R ₁₀₃ may be the same or different.
<3>
The actinic ray-sensitive or radiation-sensitive resin composition according to <2>, wherein the compound represented by the above general formula (2) is a compound represented by the following general formula (3).

In general formula (3), Q ₁ and Q ₂ each independently represent a substituent.
R ₃ to R ₅ each independently represent a hydrogen atom or a substituent. At least one of R ₃ to R ₅ represents a group represented by the above general formula (R-1).
R ₁₀₁ to R ₁₀₃ each independently represent a hydrogen atom or a substituent. Two of R ₁₀₁ to R ₁₀₃ may be bonded to each other to form a ring.
n represents an integer of 2 or more. A plurality of R ₁₀₁ s , a plurality of R _{102 s} , and a plurality of R ₁₀₃ may be the same or different.
<4>
The actinic ray-sensitive or radiation-sensitive resin according to <3>, wherein in the general formula (3), Q 1 and Q 2 are each independently an aliphatic hydrocarbon ring group, an aryl group, or a _heteroaryl group _. Composition.
<5>
The actinic ray-sensitive or radiation-sensitive resin composition according to <3> or <4>, wherein Q ₁ and Q ₂ in the general formula (3) are each an aryl group.
<6>
The _actinic ray- _sensitive or Radiation sensitive resin composition.

In the general formula (Ar), R ₁₀ to R ₁₄ each independently represent a hydrogen atom or a substituent. At least one of R ₁₀ to R ₁₄ is a group containing a polar group, a group containing a group whose polarity increases when decomposed by the action of an acid, or a group which decomposes by the action of an alkaline developer and has solubility in the alkaline developer. It is a group containing a group in which .
* represents a bond to the benzene ring in general formula (3).
<7>
The _actinic ray- _sensitive or Radiation sensitive resin composition.

In the general formula (Ar1), R ₁₅ to R ₁₉ each independently represent a hydrogen atom or a substituent. At least one of R ₁₅ to R ₁₉ represents the following substituent X.
* represents a bond to the benzene ring in general formula (3).
Substituent X: hydroxy group, carboxyl group, group having a carbonyl bond, alkoxy group, acyloxy group, alkoxycarbonyloxy group, aryloxycarbonyloxy group, aryloxycarbonyl group, alkoxycarbonyl group, aryloxyalkyloxy group, alkoxyalkyl Oxy group, carbamoyl group, or imide group
<8>
The actinic ray-sensitive or radiation-sensitive resin composition according to any one of <1> to <7>, wherein the compound (B) is a compound represented by the following general formula (4).

In general formula (4), R ₃ and R ₅ each independently represent a hydrogen atom or a substituent.
A represents a single bond or a (m+1)-valent linking group.
Y each independently represents a group represented by any one of the above formulas (A1) to (A6).
m represents an integer of 1 or more.
When m represents an integer of 2 or more, the plurality of Y's may be the same or different.
R ₂₀ to R ₂₄ each independently represent a hydrogen atom or a substituent. At least one of R ₂₀ to R ₂₄ represents the following substituent X.
R ₂₅ to R ₂₉ each independently represent a hydrogen atom or a substituent. At least one of R ₂₅ to R ₂₉ represents the following substituent X.
R ₁₀₁ to R ₁₀₃ each independently represent a hydrogen atom or a substituent. Two of R ₁₀₁ to R ₁₀₃ may be bonded to each other to form a ring.
n represents an integer of 2 or more, and R ₁₀₁ s , R ₁₀₂ s, and R _103s may be the same or different.
Substituent X: hydroxy group, carboxyl group, group having a carbonyl bond, alkoxy group, acyloxy group, alkoxycarbonyloxy group, aryloxycarbonyloxy group, aryloxycarbonyl group, alkoxycarbonyl group, aryloxyalkyloxy group, alkoxyalkyl Oxy group, carbamoyl group, or imide group
<9>
A in the above general formula (R-1) and A in the above general formula (4) in the compounds represented by the above general formulas (1) to (3) are divalent aromatic groups, <1 The actinic ray-sensitive or radiation-sensitive resin composition according to any one of items ＞ to <8>.
<10>
The actinic ray-sensitive or radiation-sensitive resin composition according to <8>, wherein the compound represented by the above general formula (4) is a compound represented by the following general formula (5).

In general formula (5), R ₃ and R ₅ each independently represent a hydrogen atom or a substituent.
R ₂₀ to R ₂₄ each independently represent a hydrogen atom or a substituent. At least one of R ₂₀ to R ₂₄ represents the following substituent X.
R ₂₅ to R ₂₉ each independently represent a hydrogen atom or a substituent. At least one of R ₂₅ to R ₂₉ represents the following substituent X.
R ₃₀ to R ₃₄ each independently represent a hydrogen atom or a substituent. At least one of R ₃₀ to R ₃₄ represents a group represented by the following general formula (R-2).
R ₁₀₁ to R ₁₀₃ each independently represent a hydrogen atom or a substituent. Two of R ₁₀₁ to R ₁₀₃ may be bonded to each other to form a ring.
n represents an integer of 2 or more, and R ₁₀₁ s , R ₁₀₂ s, and R _103s may be the same or different.
Substituent X: hydroxy group, carboxyl group, group having a carbonyl bond, alkoxy group, acyloxy group, alkoxycarbonyloxy group, aryloxycarbonyloxy group, aryloxycarbonyl group, alkoxycarbonyl group, aryloxyalkyloxy group, alkoxyalkyl Oxy group, carbamoyl group, or imide group

In the general formula (R-2), A' represents a single bond or a (m1+1)-valent linking group.
Y each independently represents a group represented by any one of the above formulas (A1) to (A6).
m1 represents an integer of 1 or more.
When m1 represents an integer of 2 or more, the plurality of Y's may be the same or different.
* represents a bond to the benzene ring in general formula (5).
<11>
The actinic ray-sensitive or radiation-sensitive resin composition according to <10>, wherein A' in the general formula (5) is a single bond or a methylene group.
<12>
The actinic ray-sensitive or radiation-sensitive resin composition according to any one of <1> to <11>, wherein in the general formulas (1) to (5), n is 2.
<13>
The actinic ray-sensitive or radiation-sensitive resin composition according to any one of <1> to <12>, which is used for producing a photomask.
<14>
An actinic ray-sensitive or radiation-sensitive film formed using the actinic ray-sensitive or radiation-sensitive resin composition according to any one of <1> to <13>.
<15>
a resist film forming step of forming a resist film using the actinic ray-sensitive or radiation-sensitive resin composition according to any one of <1> to <13>; an exposure step of exposing the resist film; A pattern forming method comprising a developing step of developing the exposed resist film using a developer.
<16>
A photomask produced using the pattern forming method described in <15>.
<17>
A method for manufacturing an electronic device, including the pattern forming method according to <15>.
The present invention relates to the above items <1> to <17>, but other matters (for example, the following items [1] to [19]) are also described below.

[1]
An actinic ray-sensitive or radiation-sensitive resin composition containing the following (A) and (B).
(A) A resin whose polarity increases due to the action of an acid. (B) A compound that generates an acid upon irradiation with actinic rays or radiation and is represented by the following general formula (1).

In general formula (1), R ₁ to R ₅ each independently represent a hydrogen atom or a substituent. At least one of R ₁ to R ₅ represents a group represented by the following general formula (R-1). M ⁿ⁺ represents a cation moiety. n represents an integer of 2 or more.

In the general formula (R-1), A represents a single bond or a (m+1)-valent linking group.
Y each independently represents a group represented by any one of the following formulas (A1) to (A6).
m represents an integer of 1 or more.
When m represents an integer of 2 or more, the plurality of Y's may be the same or different.
* represents a bond to the benzene ring.

In formulas (A1) to (A6), * represents a bond to A.
In formula (A2), R ₆ represents a substituent having a carbon atom. The sulfur atom in SO ₂ of formula (A2) bonds with the carbon atom in R ₆ . Further, R ₆ may be combined with A or L to form a ring.
L represents a single bond, a carbonyl bond, an alkylene group, or a divalent aromatic group.
In formula (A3), R ₇ represents a substituent having a carbon atom. N ⁻ in formula (A3) is bonded to the above carbon atom in R ₇ . Furthermore, R ₇ may combine with A to form a ring.
In formula (A4), R ₈ represents a substituent having a carbon atom. The carbon atom in the carbonyl bond of formula (A4) is bonded to the carbon atom in R ₈ . Moreover, R ₈ may combine with A to form a ring.
In formula (A5), R ₉ and R _9' each independently represent a hydrogen atom or a substituent. R ₉ and R _9' may be combined with each other to form a ring.

[2]
The actinic ray-sensitive or radiation-sensitive resin composition according to [1], wherein the compound (B) is a compound represented by the following general formula (2).

In general formula (2), R ₁ to R ₅ each independently represent a hydrogen atom or a substituent. At least one of R ₁ to R ₅ represents a group represented by the above general formula (R-1).
R ₁₀₁ to R ₁₀₃ each independently represent a hydrogen atom or a substituent. Two of R ₁₀₁ to R ₁₀₃ may be bonded to each other to form a ring.
n represents an integer of 2 or more. A plurality of R ₁₀₁ s, a plurality of R _{102 s} , and a plurality of R ₁₀₃ may be the same or different.

[3]
The actinic ray-sensitive or radiation-sensitive resin composition according to [2], wherein the compound represented by the above general formula (2) is a compound represented by the following general formula (3).

In general formula (3), Q ₁ and Q ₂ each independently represent a substituent.
R ₃ to R ₅ each independently represent a hydrogen atom or a substituent. At least one of R ₃ to R ₅ represents a group represented by the above general formula (R-1).
R ₁₀₁ to R ₁₀₃ each independently represent a hydrogen atom or a substituent. Two of R ₁₀₁ to R ₁₀₃ may be bonded to each other to form a ring.
n represents an integer of 2 or more. A plurality of R ₁₀₁ s, a plurality of R _{102 s} , and a plurality of R ₁₀₃ may be the same or different.

[4]
The actinic ray-sensitive or radiation-sensitive resin according to [3], wherein in the general formula (3), Q ₁ and Q ₂ are each independently an aliphatic hydrocarbon ring group, an aryl group, or a heteroaryl group. Composition.
[5]
The actinic ray-sensitive or radiation-sensitive resin composition according to [3] or [4], wherein Q ₁ and Q ₂ in the general formula (3) are each an aryl group.
[6]
The actinic ray- _{sensitive or} Radiation sensitive resin composition.

In the general formula (Ar), R ₁₀ to R ₁₄ each independently represent a hydrogen atom or a substituent. At least one of R ₁₀ to R ₁₄ is a group containing a polar group, a group containing a group whose polarity increases when decomposed by the action of an acid, or a group which decomposes by the action of an alkaline developer and has solubility in the alkaline developer. It is a group containing a group in which .
* represents a bond to the benzene ring in general formula (3).

[7]
The actinic ray- _{sensitive or} Radiation sensitive resin composition.

In the general formula (Ar1), R ₁₅ to R ₁₉ each independently represent a hydrogen atom or a substituent. At least one of R ₁₅ to R ₁₉ represents the following substituent X.
* represents a bond to the benzene ring in general formula (3).
Substituent X: hydroxy group, carboxyl group, group having a carbonyl bond, alkoxy group, acyloxy group, alkoxycarbonyloxy group, aryloxycarbonyloxy group, aryloxycarbonyl group, alkoxycarbonyl group, aryloxyalkyloxy group, alkoxyalkyl Oxy group, carbamoyl group, or imide group

[8]
The actinic ray-sensitive or radiation-sensitive resin composition according to any one of [1] to [7], wherein the compound (B) is a compound represented by the following general formula (4).

In general formula (4), R ₃ and R ₅ each independently represent a hydrogen atom or a substituent.
A represents a single bond or a (m+1)-valent linking group.
Y each independently represents a group represented by any one of the above formulas (A1) to (A6).
m represents an integer of 1 or more.
When m represents an integer of 2 or more, the plurality of Y's may be the same or different.
R ₂₀ to R ₂₄ each independently represent a hydrogen atom or a substituent. At least one of R ₂₀ to R ₂₄ represents the following substituent X.
R ₂₅ to R ₂₉ each independently represent a hydrogen atom or a substituent. At least one of R ₂₅ to R ₂₉ represents the following substituent X.
R ₁₀₁ to R ₁₀₃ each independently represent a hydrogen atom or a substituent. Two of R ₁₀₁ to R ₁₀₃ may be bonded to each other to form a ring.
n represents an integer of 2 or more, and R ₁₀₁ s, R ₁₀₂ s, and R _103s may be the same or different.
Substituent X: hydroxy group, carboxyl group, group having a carbonyl bond, alkoxy group, acyloxy group, alkoxycarbonyloxy group, aryloxycarbonyloxy group, aryloxycarbonyl group, alkoxycarbonyl group, aryloxyalkyloxy group, alkoxyalkyl Oxy group, carbamoyl group, or imide group

[9]
In the compounds represented by the above general formulas (1) to (3), A in the above general formula (R-1) and A in the above general formula (4) are divalent aromatic groups, [1 The actinic ray-sensitive or radiation-sensitive resin composition according to any one of [8] to [8].

[10]
The actinic ray-sensitive or radiation-sensitive resin composition according to [8], wherein the compound represented by the above general formula (4) is a compound represented by the following general formula (5).

In general formula (5), R ₃ and R ₅ each independently represent a hydrogen atom or a substituent.
R ₂₀ to R ₂₄ each independently represent a hydrogen atom or a substituent. At least one of R ₂₀ to R ₂₄ represents the following substituent X.
R ₂₅ to R ₂₉ each independently represent a hydrogen atom or a substituent. At least one of R ₂₅ to R ₂₉ represents the following substituent X.
R ₃₀ to R ₃₄ each independently represent a hydrogen atom or a substituent. At least one of R ₃₀ to R ₃₄ represents a group represented by the following general formula (R-2).
R ₁₀₁ to R ₁₀₃ each independently represent a hydrogen atom or a substituent. Two of R ₁₀₁ to R ₁₀₃ may be bonded to each other to form a ring.
n represents an integer of 2 or more, and R ₁₀₁ s, R ₁₀₂ s, and R _103s may be the same or different.
Substituent X: hydroxy group, carboxyl group, group having a carbonyl bond, alkoxy group, acyloxy group, alkoxycarbonyloxy group, aryloxycarbonyloxy group, aryloxycarbonyl group, alkoxycarbonyl group, aryloxyalkyloxy group, alkoxyalkyl Oxy group, carbamoyl group, or imide group

In the general formula (R-2), A' represents a single bond or a (m1+1)-valent linking group.
Y each independently represents a group represented by any one of the above formulas (A1) to (A6).
m1 represents an integer of 1 or more. When m1 represents an integer of 2 or more, the plurality of Y's may be the same or different.
* represents a bond to the benzene ring in general formula (5).

[11]
The actinic ray-sensitive or radiation-sensitive resin composition according to [10], wherein in the general formula (5), A' is a single bond or a methylene group.
[12]
The actinic ray-sensitive or radiation-sensitive resin composition according to any one of [1] to [11], wherein in the general formulas (1) to (5), n is 2.
[13]
The actinic ray-sensitive or radiation-sensitive resin composition according to any one of [1] to [12], which is used for producing a photomask.
[14]
An actinic ray-sensitive or radiation-sensitive film formed using the actinic ray-sensitive or radiation-sensitive resin composition according to any one of [1] to [13].

[15]
A resist film forming step of forming a resist film using the actinic ray-sensitive or radiation-sensitive resin composition according to any one of [1] to [13], and an exposure step of exposing the resist film to light; A pattern forming method comprising a developing step of developing the exposed resist film using a developer.
[16]
A photomask produced using the pattern forming method described in [15].
[17]
A method for manufacturing an electronic device, comprising the pattern forming method according to [15].

[18]
A compound represented by the following general formula (3).

In general formula (3), Q ₁ and Q ₂ each independently represent a substituent.
R ₃ to R ₅ each independently represent a hydrogen atom or a substituent. At least one of R ₃ to R ₅ represents a group represented by the following general formula (R-1).
R ₁₀₁ to R ₁₀₃ each independently represent a hydrogen atom or a substituent. Two of R ₁₀₁ to R ₁₀₃ may be bonded to each other to form a ring.
n represents an integer of 2 or more. A plurality of R ₁₀₁ s, a plurality of R _{102 s} , and a plurality of R ₁₀₃ may be the same or different.

In the general formula (R-1), A represents a single bond or a (m+1)-valent linking group.
Y each independently represents a group represented by any one of the following formulas (A1) to (A6).
m represents an integer of 1 or more.
When m represents an integer of 2 or more, the plurality of Y's may be the same or different.
* represents a bond to the benzene ring.

In formulas (A1) to (A6), * represents a bond to A.
In formula (A2), R ₆ represents a substituent having a carbon atom. The sulfur atom in SO ₂ of formula (A2) bonds with the carbon atom in R ₆ . Further, R ₆ may be combined with A or L to form a ring.
L represents a single bond, a carbonyl bond, an alkylene group, or a divalent aromatic group.
In formula (A3), R ₇ represents a substituent having a carbon atom. N ⁻ in formula (A3) is bonded to the above carbon atom in R ₇ . Furthermore, R ₇ may combine with A to form a ring.
In formula (A4), R ₈ represents a substituent having a carbon atom. The carbon atom in the carbonyl bond of formula (A4) is bonded to the carbon atom in R ₈ . Moreover, R ₈ may combine with A to form a ring.
In formula (A5), R ₉ and R _9' each independently represent a hydrogen atom or a substituent. R ₉ and R _9' may be combined with each other to form a ring.

[19]
The compound according to [18], wherein in the general formula (3), Q ₁ and Q ₂ are each independently an aliphatic hydrocarbon ring group, an aryl group, or a heteroaryl group.

According to the present invention, in the formation of ultra-fine patterns (in particular, line width or space width of 30 nm or less), actinic ray sensitivity or sensitivity can be achieved at a high level to improve roughness performance, improve resolution, and reduce development defects. A radioactive resin composition can be provided. According to the present invention, it is possible to provide an actinic ray-sensitive or radiation-sensitive film, a pattern forming method, a photomask, an electronic device manufacturing method, and a compound using the above-mentioned actinic ray-sensitive or radiation-sensitive resin composition. .

The present invention will be explained in detail below.
Although the description of the constituent elements described below may be made based on typical embodiments of the present invention, the present invention is not limited to such embodiments.
In this specification, "active rays" or "radiation" include, for example, the bright line spectrum of a mercury lamp, far ultraviolet rays typified by excimer lasers, extreme ultraviolet (EUV), X-rays, soft X-rays, and electron It means a line (EB: Electron Beam) or the like. "Light" in this specification means actinic rays or radiation. In this specification, "exposure" refers not only to exposure to the bright line spectrum of a mercury lamp, far ultraviolet rays typified by excimer lasers, extreme ultraviolet rays, X-rays, and EUV, but also to electron beams and ion beams, unless otherwise specified. It also includes drawing using particle beams such as beams.
In the present specification, "~" is used to include the numerical values described before and after it as a lower limit value and an upper limit value.

In this specification, (meth)acrylate represents at least one of acrylate and methacrylate. Further, (meth)acrylic acid represents at least one of acrylic acid and methacrylic acid.
In this specification, the weight average molecular weight (Mw), number average molecular weight (Mn), and degree of dispersion (also referred to as molecular weight distribution) (Mw/Mn) of the resin are determined using a GPC (Gel Permeation Chromatography) device (HLC manufactured by Tosoh Corporation). -8120GPC) GPC measurement (solvent: tetrahydrofuran, flow rate (sample injection amount): 10 μL, column: Tosoh Corporation TSK gel Multipore HXL-M, column temperature: 40°C, flow rate: 1.0 mL/min, detector: It is defined as a polystyrene equivalent value determined by a differential refractive index detector (Refractive Index Detector).

Regarding the notation of a group (atomic group) in this specification, the notation that does not indicate substituted or unsubstituted includes a group having a substituent as well as a group having no substituent. For example, the term "alkyl group" includes not only an alkyl group without a substituent (unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group). Furthermore, the term "organic group" as used herein refers to a group containing at least one carbon atom.

Moreover, in this specification, when "it may have a substituent", the type of substituent, the position of the substituent, and the number of substituents are not particularly limited. The number of substituents may be, for example, one, two, three, or more. Examples of the substituent include monovalent nonmetallic atomic groups excluding hydrogen atoms, and can be selected from the following substituents T, for example.

(Substituent T)
As the substituent T, halogen atoms such as fluorine atom, chlorine atom, bromine atom and iodine atom; alkoxy groups such as methoxy group, ethoxy group and tert-butoxy group; aryloxy groups such as phenoxy group and p-tolyloxy group; Alkoxycarbonyl groups such as methoxycarbonyl group, butoxycarbonyl group and phenoxycarbonyl group; Acyloxy groups such as acetoxy group, propionyloxy group and benzoyloxy group; Acetyl group, benzoyl group, isobutyryl group, acryloyl group, methacryloyl group and methoxalyl group, etc. Acyl group; Alkylsulfanyl group such as methylsulfanyl group and tert-butylsulfanyl group; Arylsulfanyl group such as phenylsulfanyl group and p-tolylsulfanyl group; Alkyl group (for example, having 1 to 10 carbon atoms); cycloalkyl group ( For example, 3 to 20 carbon atoms); aryl group (for example, 6 to 20 carbon atoms); heteroaryl group; hydroxyl group; carboxy group; formyl group; sulfo group; cyano group; alkylaminocarbonyl group; arylaminocarbonyl group; sulfone Examples include amide group; silyl group; amino group; monoalkylamino group; dialkylamino group; arylamino group, nitro group; formyl group; and combinations thereof.

The actinic ray-sensitive or radiation-sensitive resin composition according to the present invention (hereinafter also referred to as "composition of the present invention") is an actinic ray-sensitive or radiation-sensitive resin composition containing the following (A) and (B). It is a composition.
(A) A resin whose polarity increases due to the action of an acid. (B) A compound that generates an acid upon irradiation with actinic rays or radiation, and is represented by the following general formula (1).

In general formula (1), R ₁ to R ₅ each independently represent a hydrogen atom or a substituent. At least one of R ₁ to R ₅ represents a group represented by the following general formula (R-1). M ⁿ⁺ represents a cation moiety. n represents an integer of 2 or more.

In the general formula (R-1), A represents a single bond or a (m+1)-valent linking group.
Y each independently represents a group represented by any one of the following formulas (A1) to (A6).
m represents an integer of 1 or more.
When m represents an integer of 2 or more, the plurality of Y's may be the same or different.
* represents a bond to the benzene ring.

In formulas (A1) to (A6), * represents a bond to A.
In formula (A2), R ₆ represents a substituent having a carbon atom. The sulfur atom in SO ₂ of formula (A2) bonds with the carbon atom in R ₆ . Further, R ₆ may be combined with A or L to form a ring.
L represents a single bond, a carbonyl bond, an alkylene group, or a divalent aromatic group.
In formula (A3), R ₇ represents a substituent having a carbon atom. N ⁻ in formula (A3) is bonded to the above carbon atom in R ₇ . Furthermore, R ₇ may combine with A to form a ring.
In formula (A4), R ₈ represents a substituent having a carbon atom. The carbon atom in the carbonyl bond of formula (A4) is bonded to the carbon atom in R ₈ . Moreover, R ₈ may combine with A to form a ring.
In formula (A5), R ₉ and R _9' each independently represent a hydrogen atom or a substituent. R ₉ and R _9' may be combined with each other to form a ring.

The composition of the present invention is preferably a resist composition, and may be a positive resist composition or a negative resist composition. Moreover, it may be a resist composition for alkaline development or a resist composition for organic solvent development. Among these, a positive resist composition and a resist composition for alkaline development are preferred.
Further, the composition of the present invention is preferably a chemically amplified resist composition, more preferably a chemically amplified positive resist composition.

The reason why the composition of the present invention can achieve a high level of improvement in roughness performance, improvement in resolution, and reduction in development defects in ultrafine pattern formation (especially with a line width or space width of 30 nm or less) is as follows. Although it is not completely clear, the present inventors estimate as follows.
First, resist compositions containing a photoacid generator and an acid diffusion control agent as individual compounds have been widely known. In a resist film formed from such a resist composition, the acid diffusion control agent in the unexposed area captures the acid generated from the photoacid generator in the exposed area, and prevents excessive acid from flowing into the unexposed area. It is believed that the spread can be suppressed. Salts of acids (so-called weak acid salts) whose acid strength is weaker than that of the acid generated by the photoacid generator are known as acid diffusion control agents.
In this way, it is thought that a pattern with excellent resolution can be formed by including a photoacid generator and an acid diffusion control agent such as the above-mentioned weak acid salt in the resist composition. In response to the demand for fine pattern formation, conventional resist compositions have difficulty achieving the required performance, such as not only excellent resolution but also excellent roughness performance and the reduction of development defects. It's getting difficult.
As a result of intensive studies, the present inventors found that in the resist film formed by the conventional resist composition described above, the photoacid generator and the acid diffusion control agent, which are each contained as individual compounds, are strictly speaking Agents and acid diffusion control agents tend to aggregate with each other, in other words, in the formed resist film, there are areas where the concentration of the photoacid generator is high (or low) and the concentration of the acid diffusion control agent is high. It is thought that there are likely to be (or low) areas, and as a result, the concentration distribution of the photoacid generator and the acid diffusion control agent becomes non-uniform. Such non-uniformity is considered to be a cause that leads to a decrease in roughness performance, an increase in development defects, etc. when a resist film is exposed, especially when forming an ultra-fine pattern.

On the other hand, the actinic ray-sensitive or radiation-sensitive composition of the present invention contains (B) a compound that generates an acid upon irradiation with actinic rays or radiation, and is represented by the above general formula (1). do.
The compound represented by the above general formula (I) has a structural site (sulfonic acid anion that binds to benzene) having a function corresponding to a photoacid generator, and a structural site (Y (a structural moiety that captures the sulfonic acid generated from the sulfonic acid anion)) in one molecule, it functions both as a photoacid generator and as an acid diffusion control agent in the resist film. Compounds can be present more uniformly.
Therefore, excellent resolution can be obtained, and the width of the pattern obtained after development is likely to be stable. In other words, it is considered that the roughness performance of the formed pattern is further improved. Further, by suppressing aggregation of compound (B) in the composition, development defects can be reduced.
The above structural moiety (Y group) in the compound (B) of the composition of the present invention can interact with the resin as a so-called polar group, so that the aggregation of the compound (B) is further suppressed, and the acid generated by exposure It is believed that this can suppress the diffusion of the particles into unexposed areas, and further improve the roughness performance of the formed pattern.
Furthermore, if the strength of the acid generated from the photoacid generator is too strong, the acid generated in the exposed area does not remain in the exposed area but tends to excessively diffuse into the unexposed area. However, in the above compound (B), the strength of the acid generated from the structural site (sulfonic acid anion that binds to benzene) that has a function equivalent to a photoacid generator is an acid with moderate strength, It is presumed that excessive diffusion into the unexposed areas can be suppressed, and the roughness performance of the formed pattern is further improved, especially in the formation of ultra-fine patterns.

[(A) Resin whose polarity increases due to the action of acid]
(A) A resin whose polarity increases due to the action of an acid (hereinafter also referred to as "acid-decomposable resin" or "resin (A)") will be explained.
Note that, as described later, the resin (A) may have a repeating unit having a photoacid generating group.

In pattern formation using a resist composition containing resin (A), typically, when an alkaline developer is used as the developer, a positive pattern is suitably formed, and an organic developer is typically used as the developer. When this is adopted, a negative pattern is suitably formed.
The resin (A) usually contains a group whose polarity increases when decomposed by the action of an acid (hereinafter also referred to as an "acid-decomposable group"), and preferably contains a repeating unit having an acid-decomposable group.
The repeating units that the resin (A) may contain will be explained below.

(Repeating unit with acid-decomposable group)
An acid-decomposable group refers to a group that is decomposed by the action of an acid to produce a polar group. The acid-decomposable group preferably has a structure in which a polar group is protected with a leaving group that is eliminated by the action of an acid. That is, the resin (A) has a repeating unit having a group that is decomposed by the action of an acid to produce a polar group. A resin having this repeating unit has increased polarity due to the action of an acid, increasing its solubility in an alkaline developer and decreasing its solubility in an organic solvent.
The polar group is preferably an alkali-soluble group, such as a carboxy group, phenolic hydroxyl group, fluorinated alcohol group, sulfonic acid group, phosphoric 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) Examples include acidic groups such as methylene group and tris(alkylsulfonyl)methylene group, and alcoholic hydroxyl group.
Among these, as the polar group, a carboxy group, a phenolic hydroxyl group, a fluorinated alcohol group (preferably a hexafluoroisopropanol group), or a sulfonic acid group is preferable. In particular, as the polar group, a carboxy group or a phenolic hydroxyl group is more preferable. That is, the acid-decomposable group is preferably a group that is decomposed by the action of an acid to produce a carboxy group, or a group that is decomposed by the action of an acid to produce a phenolic hydroxyl group.

Examples of the leaving group that leaves by the action of an acid include groups represented by formulas (Y1) to (Y4).
Formula (Y1): -C(Rx ₁ )(Rx ₂ )(Rx ₃ )
Formula (Y2): -C(=O)OC(Rx ₁ )(Rx ₂ )(Rx ₃ )
Formula (Y3): -C(R ₃₆ )(R ₃₇ )(OR ₃₈ )
Formula (Y4): -C(Rn)(H)(Ar)

In formulas (Y1) and (Y2), Rx ₁ to Rx ₃ each independently represent an alkyl group (linear or branched chain), a cycloalkyl group (monocyclic or polycyclic), an aryl group (monocyclic or polycyclic), an aralkyl group (linear or branched), or an alkenyl group (linear or branched). Note that when all of Rx ₁ to Rx ₃ are alkyl groups (linear or branched), it is preferable that at least two of Rx ₁ to Rx ₃ are methyl groups.
Among these, it is preferable that Rx ₁ to Rx ₃ each independently represent a linear or branched alkyl group, and Rx ₁ to Rx ₃ each independently represent a linear alkyl group. is more preferable.
Two of Rx ₁ to Rx ₃ may be bonded to each other to form a ring (which may be monocyclic or polycyclic).
As the alkyl group for Rx ₁ to Rx ₃ , an alkyl group having 1 to 5 carbon atoms such as a methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, and t-butyl group is preferable. .
Examples of the cycloalkyl group for Rx ₁ to Rx ₃ include monocyclic cycloalkyl groups such as cyclopentyl group and cyclohexyl group, and polycyclic groups such as norbornyl group, tetracyclodecanyl group, tetracyclododecanyl group, and adamantyl group. A cycloalkyl group is preferred.
The aryl group for Rx ₁ to Rx ₃ is preferably an aryl group having 6 to 10 carbon atoms, such as a phenyl group, a naphthyl group, an anthryl group, and the like.
The aralkyl group of Rx ₁ to Rx ₃ is preferably a group in which one hydrogen atom in the alkyl group of Rx ₁ to Rx ₃ described above is substituted with an aryl group having 6 to 10 carbon atoms (preferably a phenyl group), For example, a benzyl group and the like can be mentioned.
As the alkenyl group for Rx ₁ to Rx ₃ , a vinyl group is preferred.
The ring formed by bonding two of Rx ₁ to Rx ₃ is preferably a cycloalkyl group. The cycloalkyl group formed by combining two of Rx ₁ to Rx ₃ is a cyclopentyl group or a monocyclic cycloalkyl group such as a cyclohexyl group, or a norbornyl group, a tetracyclodecanyl group, or a tetracyclododecanyl group. or a polycyclic cycloalkyl group such as an adamantyl group, and a monocyclic cycloalkyl group having 5 to 6 carbon atoms is more preferable.
The cycloalkyl group formed by bonding two of Rx ₁ to Rx ₃ is, for example, a group in which one of the methylene groups constituting the ring has a hetero atom such as an oxygen atom, a hetero atom such as a carbonyl group, or a group in which one of the methylene groups constituting the ring has a hetero atom such as a carbonyl group, or It may be replaced with a group. Further, in these cycloalkyl groups, one or more of the ethylene groups constituting the cycloalkane ring may be replaced with a vinylene group.
The group represented by formula (Y1) or formula (Y2) is, for example, an embodiment in which Rx ₁ is a methyl group or an ethyl group, and Rx ₂ and Rx ₃ are bonded to form the above-mentioned cycloalkyl group. is preferred.

In formula (Y3), R ₃₆ to R ₃₈ each independently represent a hydrogen atom or a monovalent organic group. R ₃₇ and R ₃₈ may be combined with each other to form a ring. Examples of monovalent organic groups include alkyl groups, cycloalkyl groups, aryl groups, aralkyl groups, and alkenyl groups. It is also preferable that R ₃₆ is a hydrogen atom.
Note that the alkyl group, cycloalkyl group, aryl group, and aralkyl group may include a group having a hetero atom such as an oxygen atom and/or a hetero atom such as a carbonyl group. For example, in the above alkyl group, cycloalkyl group, aryl group, and aralkyl group, one or more methylene groups are replaced with a group having a hetero atom such as an oxygen atom and/or a hetero atom such as a carbonyl group. Good too.
Further, R ₃₈ may be bonded to another substituent in the main chain of the repeating unit to form a ring. The group formed by bonding R ₃₈ and another substituent of the main chain of the repeating unit to each other is preferably an alkylene group such as a methylene group.

As formula (Y3), a group represented by the following formula (Y3-1) is preferable.

Here, L ₁ and L ₂ each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, or a group combining these (for example, a group combining an alkyl group and an aryl group).
M represents a single bond or a divalent linking group.
Q is an alkyl group that may contain a hetero atom, a cycloalkyl group that may contain a hetero atom, an aryl group that may contain a hetero atom, an amino group, an ammonium group, a mercapto group, a cyano group, an aldehyde represents a group or a group combining these (for example, a group combining an alkyl group and a cycloalkyl group).
In the alkyl group and cycloalkyl group, for example, one of the methylene groups may be replaced with a hetero atom such as an oxygen atom, or a group having a hetero atom such as a carbonyl group.
Note that one of L ₁ and L ₂ is preferably a hydrogen atom, and the other is an alkyl group, a cycloalkyl group, an aryl group, or a combination of an alkylene group and an aryl group.
At least two of Q, M, and L ₁ may be combined to form a ring (preferably a 5-membered or 6-membered ring).
In terms of pattern refinement, _L2 is preferably a secondary or tertiary alkyl group, more preferably a tertiary alkyl group. Examples of the secondary alkyl group include isopropyl group, cyclohexyl group, or norbornyl group, and examples of the tertiary alkyl group include tert-butyl group or adamantane group. In these embodiments, Tg (glass transition temperature) and activation energy are increased, so that in addition to ensuring film strength, fogging can be suppressed.

In formula (Y4), Ar represents an aromatic ring group. Rn represents an alkyl group, a cycloalkyl group, or an aryl group. Rn and Ar may be bonded to each other to form a non-aromatic ring. Ar is more preferably an aryl group.

In view of the excellent acid decomposition properties of the repeating unit, when a non-aromatic ring is directly bonded to the polar group (or its residue) in the leaving group that protects the polar group, in the non-aromatic ring, It is also preferable that the ring member atom adjacent to the ring member atom directly bonded to the polar group (or its residue) does not have a halogen atom such as a fluorine atom as a substituent.

Leaving groups that are eliminated by the action of acids include 2-cyclopentenyl groups having substituents (alkyl groups, etc.) such as 3-methyl-2-cyclopentenyl groups, and 1,1,4-cyclopentenyl groups. , 4-tetramethylcyclohexyl group having a substituent (alkyl group, etc.).

As the repeating unit having an acid-decomposable group, repeating units represented by the following general formulas (2U) to (6U) are preferable in that the effects of the present invention are more excellent, and the following general formula (2U) or the following general formula A repeating unit represented by (3U) is more preferred.

In general formula (2U), R _U21 , R _U22 , and R _U23 each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, a cyano group, or an alkoxycarbonyl group. L _U21 represents a single bond or a divalent linking group. R _U24 to R _U26 each independently represent an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, or an alkenyl group. Note that two of R _U24 to R _U26 may be bonded to each other to form a ring.

The alkyl groups represented by R _U21 , R _U22 , and R _U23 may be either linear or branched. The number of carbon atoms in the alkyl group is not particularly limited, but is preferably 1 to 5, more preferably 1 to 3.
The cycloalkyl groups represented by R _U21 , R _U22 , and R _U23 include monocyclic cycloalkyl groups such as cyclopentyl group and cyclohexyl group, as well as norbornyl group, tetracyclodecanyl group, tetracyclododecanyl group, and polycyclic cycloalkyl groups such as adamantyl groups are preferred.
Examples of the halogen atom represented by R _U21 , R _U22 , and R _U23 include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, with a fluorine atom or an iodine atom being preferred.
The alkyl group contained in the alkoxycarbonyl group represented by R _U21 , R _U22 , and R _U23 may be either linear or branched. The number of carbon atoms in the alkyl group contained in the alkoxycarbonyl group is not particularly limited, but is preferably 1 to 5, more preferably 1 to 3.

The divalent linking group represented by L _U21 includes -CO-, -O-, -S-, -SO-, -SO ₂ -, a hydrocarbon group (for example, an alkylene group, a cycloalkylene group, an alkenylene group) , arylene group, etc.), and a linking group in which a plurality of these are linked.

The alkyl group represented by R _U24 to R _U26 may be either linear or branched. The number of carbon atoms in the alkyl group is not particularly limited, but is preferably 1 to 5, more preferably 1 to 3. In the alkyl groups represented by R _U24 to R _U26 , the methylene group may be substituted with -CO- and/or -O-.
Examples of the cycloalkyl group represented by R _U24 to R _U26 include monocyclic cycloalkyl groups such as a cyclopentyl group and a cyclohexyl group, a norbornyl group, a tetracyclodecanyl group, a tetracyclododecanyl group, and an adamantyl group. A polycyclic cycloalkyl group is preferred.
The aryl group represented by R _U24 to R _U26 is preferably a phenyl group.
As the aralkyl group represented by R _U24 to R _U26 , one hydrogen atom in the alkyl group represented by R _U24 to R _U26 mentioned above is replaced with an aryl group having 6 to 10 carbon atoms (preferably a phenyl group). Substituted groups are preferred, such as benzyl groups.
The alkenyl group represented by R _U24 to R _U26 is preferably a vinyl group.
The ring formed by bonding two of R _U24 to R _U26 is preferably a cycloalkyl group. The cycloalkyl group formed by bonding two of R _U24 to R _U26 includes a cyclopentyl group, a monocyclic cycloalkyl group such as a cyclohexyl group, a norbornyl group, a tetracyclodecanyl group, and a tetracyclododecanyl group. or a polycyclic cycloalkyl group such as an adamantyl group, and a monocyclic cycloalkyl group having 5 to 6 carbon atoms is more preferable.
The cycloalkyl group formed by combining two of R _U24 to R _U26 is, for example, a group in which one of the methylene groups constituting the ring has a hetero atom such as an oxygen atom, a hetero atom such as a carbonyl group, or a group in which one of the methylene groups constituting the ring has a hetero atom such as a carbonyl group, or a group in which one of the methylene groups constituting the ring has a hetero atom such as a carbonyl group, It may be replaced with a group. Further, in these cycloalkyl groups, one or more of the ethylene groups constituting the cycloalkane ring may be replaced with a vinylene group.

Each of the above groups in general formula (2U) may have a substituent, and examples of the substituent include the above substituent T.

In general formula (3U), R _U31 to R _U34 each independently represent a hydrogen atom or an organic group. However, at least one of R _U31 and R _U32 represents an organic group. X _U31 represents -CO-, -SO-, or -SO ₂ -. Y _U31 represents -O-, -S-, -SO-, -SO ₂ -, or -NR _U38 -. R _U38 represents a hydrogen atom or an organic group. L _U31 represents a single bond or a divalent linking group. R _U35 to R _U37 each independently represent an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, or an alkenyl group. Note that two of R _U35 to R _U37 may be bonded to each other to form a ring.

The organic group represented by R _U31 to R _U34 represents an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, or an alkenyl group.
Examples of the alkyl group, cycloalkyl group, aryl group, aralkyl group, and alkenyl group represented by R _U31 to R _U34 include the alkyl group represented by R _U24 to R _U26 in the general formula (2U), cyclo Examples include groups similar to alkyl groups, aryl groups, aralkyl groups, and alkenyl groups.

Among these, -CO- is preferable as X _U31 .
The organic group represented by R _U38 has the same meaning as the organic group represented by R _U31 to R _U34 described above, and the preferred embodiments are also the same.
Y _U31 is preferably -O-.
The divalent linking group represented by L _U31 has the same meaning as the divalent linking group represented by L _U21 in the above-mentioned general formula (2U), and the preferred embodiments are also the same.
Examples of the alkyl group, cycloalkyl group, aryl group, aralkyl group, and alkenyl group represented by R _U35 to R _U37 include the alkyl group represented by R _U24 to R _U26 in the general formula (2U), cyclo Examples include groups similar to alkyl groups, aryl groups, aralkyl groups, and alkenyl groups.

The ring formed by bonding two of R _U35 to R _U37 is preferably a cycloalkyl group. The cycloalkyl group formed by combining two of R _U35 to R _U37 includes a cyclopentyl group, a monocyclic cycloalkyl group such as a cyclohexyl group, a norbornyl group, a tetracyclodecanyl group, and a tetracyclododecanyl group. or a polycyclic cycloalkyl group such as an adamantyl group, and a monocyclic cycloalkyl group having 5 to 6 carbon atoms is more preferable.
The cycloalkyl group formed by combining two of R _U35 to R _U37 is, for example, a group in which one of the methylene groups constituting the ring has a hetero atom such as an oxygen atom, a hetero atom such as a carbonyl group, or a group in which one of the methylene groups constituting the ring has a hetero atom such as a carbonyl group, or a group in which one of the methylene groups constituting the ring has a hetero atom such as a carbonyl group, It may be replaced with a group. Further, in these cycloalkyl groups, one or more of the ethylene groups constituting the cycloalkane ring may be replaced with a vinylene group.

Each of the above groups in general formula (3U) may have a substituent, and examples of the substituent include the above substituent T.

In general formula (4U), R _U41 and R _U42 each independently represent a hydrogen atom or an organic group. R _U43 and R _U44 each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, or an alkenyl group. Note that R _U43 and R _U44 may be combined with each other to form a ring.
The organic groups represented by R _U41 and R _U42 have the same meaning as the organic groups represented by R _U31 to R _U34 in formula (3U) described above, and preferred embodiments are also the same.
The alkyl group, cycloalkyl group, aryl group, aralkyl group, and alkenyl group represented by R _U43 and R _U44 include the alkyl group represented by R _U24 to R _U26 in the general formula (2U), cyclo Examples include groups similar to alkyl groups, aryl groups, aralkyl groups, and alkenyl groups.
The alkyl group, cycloalkyl group, aryl group, aralkyl group, and alkenyl group represented by R _U43 and R _U44 may have a substituent, for example, the substituent T is Can be mentioned.

The ring formed by bonding R _U43 and R _U44 is preferably a cycloalkyl group. The cycloalkyl group formed by combining R _U43 and R _U44 includes a cyclopentyl group, a monocyclic cycloalkyl group such as a cyclohexyl group, a norbornyl group, a tetracyclodecanyl group, a tetracyclododecanyl group, Alternatively, a polycyclic cycloalkyl group such as an adamantyl group is preferable, and a monocyclic cycloalkyl group having 5 to 6 carbon atoms is more preferable.
The cycloalkyl group formed by combining R _U43 and R _U44 is, for example, a group in which one of the methylene groups constituting the ring has a hetero atom such as an oxygen atom, a hetero atom such as a carbonyl group, or a vinylidene group. May be replaced. Further, in these cycloalkyl groups, one or more of the ethylene groups constituting the cycloalkane ring may be replaced with a vinylene group.

In general formula (5U), R _U51 , R _U52 , and R _U53 each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, a cyano group, or an alkoxycarbonyl group. L _U51 represents a single bond or a divalent linking group. Ar _U51 represents an aromatic ring group. R _U54 to R _U56 each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, or an alkenyl group. Note that R _U55 and R _U56 may be combined with each other to form a ring. Furthermore, Ar _U51 may be combined with R _U53 or R _U54 to form a ring.

R _U51 , R _U52 , R _U53 , and L _U51 have the same meanings as R _U21 , R _U22 , R _U23 , and L _U21 in general formula (2U), and preferred embodiments are also the same.
The aromatic ring group represented by Ar _U51 is not particularly limited, but includes, for example, a benzene ring or a naphthalene ring, with a benzene ring being preferred.
Examples of the alkyl group, cycloalkyl group, aryl group, aralkyl group, and alkenyl group represented by R _U54 to R _U56 include the alkyl group represented by R _U24 to R _U26 in the general formula (2U), cyclo Examples include groups similar to alkyl groups, aryl groups, aralkyl groups, and alkenyl groups.
The alkyl group, cycloalkyl group, aryl group, aralkyl group, and alkenyl group represented by R _U54 to R _U56 may have a substituent, for example, the substituent T is Can be mentioned.

The ring formed by bonding R _U55 and R _U56 , Ar _U51 and R _U53 , and R _U54 and Ar _U51 is preferably a cycloalkyl group. The cycloalkyl group formed by combining R _U55 and R _U56 , Ar _U51 and R _U53 , and R _U54 and Ar _U51 is a monocyclic cycloalkyl group such as a cyclopentyl group or a cyclohexyl group, or a norbornyl group. A polycyclic cycloalkyl group such as , tetracyclodecanyl group, tetracyclododecanyl group, or adamantyl group is preferable, and a monocyclic cycloalkyl group having 5 to 6 carbon atoms is more preferable.
The cycloalkyl group formed by bonding R _U55 and R _U56 , Ar _U51 and R _U53 , and R _U54 and Ar _U51 is, for example, one of the methylene groups constituting the ring, a hetero atom such as an oxygen atom, carbonyl It may be replaced with a group having a heteroatom such as a group, or a vinylidene group. Further, in these cycloalkyl groups, one or more of the ethylene groups constituting the cycloalkane ring may be replaced with a vinylene group.

In general formula (6U), R _U61 , R _U62 , and R _U63 each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, a cyano group, or an alkoxycarbonyl group. L _U61 represents a single bond or a divalent linking group. R _U64 and R _U65 each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, or an alkenyl group. R _U66 represents an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, or an alkenyl group. Note that R _U65 and R _U66 may be combined with each other to form a ring.

R _U61 , R _U62 , R _U63 , and L _U61 have the same meanings as R _U21 , R _U22 , R _U23 , and L _U21 in general formula (2U), and preferred embodiments are also the same.
Examples of the alkyl group, cycloalkyl group, aryl group, aralkyl group, and alkenyl group represented by R _U64 , R _U65 , and R _U66 include the alkyl groups represented by R _U24 to R _U26 in the general formula (2U) above; groups, cycloalkyl groups, aryl groups, aralkyl groups, and alkenyl groups.
The alkyl group, cycloalkyl group, aryl group, aralkyl group, and alkenyl group represented by R _U64 , R _U65 , and R _U66 may have a substituent, and examples of the substituent include the above-mentioned substituents. Substituent T is mentioned.
The ring formed by bonding R _U65 and R _U66 is preferably a cycloalkyl group. The cycloalkyl group formed by combining R _U65 and R _U66 includes a cyclopentyl group, a monocyclic cycloalkyl group such as a cyclohexyl group, a norbornyl group, a tetracyclodecanyl group, a tetracyclododecanyl group, Alternatively, a polycyclic cycloalkyl group such as an adamantyl group is preferable, and a monocyclic cycloalkyl group having 5 to 6 carbon atoms is more preferable.
The cycloalkyl group formed by combining R _U65 and R _U66 is, for example, a group in which one of the methylene groups constituting the ring has a hetero atom such as an oxygen atom, a hetero atom such as a carbonyl group, or a vinylidene group. May be replaced. Further, in these cycloalkyl groups, one or more of the ethylene groups constituting the cycloalkane ring may be replaced with a vinylene group.

The content of the repeating unit having an acid-decomposable group is preferably 5 mol% or more, more preferably 10 mol% or more, and even more preferably 15 mol% or more, based on all the repeating units in the resin (A). Further, the upper limit thereof is preferably 95 mol% or less, more preferably 90 mol% or less, and particularly preferably 85 mol% or less.

Specific examples of the repeating unit having an acid-decomposable group are shown below, but the present invention is not limited thereto. In the formula, Xa ₁ represents any one of H, CH ₃ , CF ₃ , and CH ₂ OH, and Rxa and Rxb each represent a linear or branched alkyl group having 1 to 5 carbon atoms.

The resin (A) may contain repeating units other than the above-mentioned repeating units.
For example, the resin (A) contains at least one repeating unit selected from the group consisting of the following group A, and/or at least one repeating unit selected from the group consisting of the following group B. Good too.
Group A: A group consisting of the following repeating units (20) to (29).
(20) A repeating unit having an acid group, which will be described later. (23) A repeating unit having a photoacid generating group (24) (described later) A repeating unit (25) represented by the general formula (V-1) or the following general formula (V-2) (described later) A repeating unit represented by formula (A) (26) described below, a repeating unit represented by formula (B) (27) described below, a repeating unit represented by formula (C) (28) described below, Repeating unit represented by formula (D) (29) Group B of repeating units represented by formula (E), which will be described later: A group consisting of the following repeating units (30) to (32).
(30) A repeating unit having at least one group selected from a lactone group, a sultone group, a carbonate group, a hydroxyl group, a cyano group, and an alkali-soluble group (31) having an alicyclic hydrocarbon structure as described below , a repeating unit that does not exhibit acid decomposability (32) A repeating unit represented by the general formula (III) that does not have either a hydroxyl group or a cyano group, which will be described later.

When the composition of the present invention is used as an actinic ray-sensitive or radiation-sensitive resin composition for EUV, the resin (A) may have at least one repeating unit selected from the group consisting of the above group A. preferable.
Furthermore, when the composition is used as an actinic ray-sensitive or radiation-sensitive resin composition for EUV, the resin (A) preferably contains at least one of a fluorine atom and an iodine atom, and it is preferable that the resin (A) contain a fluorine atom. More preferred. When the resin (A) contains both a fluorine atom and an iodine atom, the resin (A) may have one repeating unit containing both a fluorine atom and an iodine atom; It may contain two types: a repeating unit having a fluorine atom and a repeating unit containing an iodine atom.
Moreover, when the composition is used as an actinic ray-sensitive or radiation-sensitive resin composition for EUV, it is also preferable that the resin (A) has a repeating unit having an aromatic group.

(Repeating unit with acid group)
The resin (A) may have a repeating unit having an acid group.
As the acid group, as described above, an acid group having a pKa of 13 or less is preferable.
Preferred examples of the acid group include a carboxy group, a phenolic hydroxyl group, a fluorinated alcohol group (preferably a hexafluoroisopropanol group), a sulfonic acid group, a sulfonamide group, or an isopropanol group.
Furthermore, in the hexafluoroisopropanol group, one or more (preferably 1 to 2) fluorine atoms may be substituted with a group other than a fluorine atom (such as an alkoxycarbonyl group). -C(CF ₃ )(OH)-CF ₂ - formed in this way is also preferred as an acid group. Furthermore, one or more of the fluorine atoms may be substituted with a group other than a fluorine atom to form a ring containing -C(CF ₃ )(OH)-CF ₂ -.
The repeating unit having an acid group is a repeating unit having a structure in which a polar group is protected by a leaving group that is eliminated by the action of an acid as described above, and a repeating unit having a lactone group, sultone group, or carbonate group described below. are preferably different repeating units.

The repeating unit having an acid group may have a substituent, and examples of the substituent include the above substituent T.

As the repeating unit having an acid group, a repeating unit represented by formula (B) is preferable.

R ₃ represents a hydrogen atom or a monovalent organic group.
As the monovalent organic group, a group represented by -L ₄ -R ₈ is preferable. L ₄ represents a single bond or an ester group. Examples of R ₈ include an alkyl group, a cycloalkyl group, an aryl group, or a combination thereof.

R ₄ and R ₅ each independently represent a hydrogen atom, a fluorine atom, an iodine atom, or an alkyl group.

L ₂ represents a single bond or an ester group.
L ₃ represents an (n+m+1)-valent aromatic hydrocarbon ring group or an (n+m+1)-valent alicyclic hydrocarbon ring group. Examples of the aromatic hydrocarbon ring group include a benzene ring group and a naphthalene ring group. The alicyclic hydrocarbon ring group may be monocyclic or polycyclic, and includes, for example, a cycloalkyl ring group.
R ₆ represents a hydroxyl group or a fluorinated alcohol group (preferably a hexafluoroisopropanol group). Note that when R ₆ is a hydroxyl group, L ₃ is preferably an (n+m+1)-valent aromatic hydrocarbon ring group.
R ₇ represents a halogen atom. Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.
m represents an integer of 1 or more. m is preferably an integer of 1 to 3, more preferably an integer of 1 to 2.
n represents an integer of 0 or 1 or more. n is preferably an integer of 1 to 4.
Note that (n+m+1) is preferably an integer of 1 to 5.

Each of the above groups in formula (B) may have a substituent, and examples of the substituent include the above substituent T.

As the repeating unit having an acid group, a repeating unit represented by the following general formula (I) is also preferable.

In general formula (I),
R ₄₁ , R ₄₂ and R ₄₃ each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, a cyano group or an alkoxycarbonyl group. However, R ₄₂ may combine with Ar ₄ to form a ring, and in this case R ₄₂ represents a single bond or an alkylene group.
X ₄ represents a single bond, -COO-, or -CONR ₆₄ -, and R ₆₄ represents a hydrogen atom or an alkyl group.
L ₄ represents a single bond or an alkylene group.
Ar ₄ represents an (n+1)-valent aromatic ring group, and when bonded to R ₄₂ to form a ring, represents an (n+2)-valent aromatic ring group.
n represents an integer from 1 to 5.

Examples of the alkyl group for R ₄₁ , R ₄₂ , and R ₄₃ in general formula (I) include methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, sec-butyl group, hexyl group, and 2-ethylhexyl group. , an octyl group, and a dodecyl group are preferable, an alkyl group having 20 or less carbon atoms is preferable, an alkyl group having 8 or less carbon atoms is more preferable, and an alkyl group having 3 or less carbon atoms is even more preferable.

The cycloalkyl groups represented by R ₄₁ , R ₄₂ and R ₄₃ in general formula (I) may be monocyclic or polycyclic. Among these, monocyclic cycloalkyl groups having 3 to 8 carbon atoms such as cyclopropyl group, cyclopentyl group, and cyclohexyl group are preferred.
Examples of the halogen atom for R ₄₁ , R ₄₂ , and R ₄₃ in general formula (I) include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, with a fluorine atom being preferred.
The alkyl group contained in the alkoxycarbonyl group of R ₄₁ , R ₄₂ , and R ₄₃ in general formula (I) is preferably the same as the alkyl group in R ₄₁ , R ₄₂ , and R ₄₃ described above.

Preferred substituents for each of the above groups include, for example, an alkyl group, a cycloalkyl group, an aryl group, an amino group, an amide group, a ureido group, a urethane group, a hydroxyl group, a carboxy group, a halogen atom, an alkoxy group, a thioether group, and an acyl group. , an acyloxy group, an alkoxycarbonyl group, a cyano group, and a nitro group. The number of carbon atoms in the substituent is preferably 8 or less.

Ar ₄ represents an (n+1)-valent aromatic ring group. The divalent aromatic ring group when n is 1 is, for example, an arylene group having 6 to 18 carbon atoms such as a phenylene group, tolylene group, naphthylene group, and anthracenylene group, or a thiophene ring, a furan ring, a pyrrole ring, Divalent aromatic ring groups containing heterocycles such as benzothiophene ring, benzofuran ring, benzopyrrole ring, triazine ring, imidazole ring, benzimidazole ring, triazole ring, thiadiazole ring, and thiazole ring are preferred. In addition, the said aromatic ring group may have a substituent.

Specific examples of (n+1)-valent aromatic ring groups when n is an integer of 2 or more include (n-1) arbitrary hydrogen atoms removed from the above-mentioned specific examples of divalent aromatic ring groups. The following groups are mentioned.
The (n+1)-valent aromatic ring group may further have a substituent.

Examples of substituents that the above-mentioned alkyl group, cycloalkyl group, alkoxycarbonyl group, alkylene group, and (n+1)-valent aromatic ring group may have include R ₄₁ , R ₄₂ , and R in general formula (I). Examples include alkoxy groups such as the alkyl groups listed in _{No. 43} , methoxy groups, ethoxy groups, hydroxyethoxy groups, propoxy groups, hydroxypropoxy groups, and butoxy groups; aryl groups such as phenyl groups; and the like.
The alkyl group of R ₆₄ in -CONR ₆₄ - (R ₆₄ represents a hydrogen atom or an alkyl group) represented by X ₄ includes a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, a sec Examples include alkyl groups having 20 or less carbon atoms such as -butyl group, hexyl group, 2-ethylhexyl group, octyl group, and dodecyl group, with alkyl groups having 8 or less carbon atoms being preferred.
X ₄ is preferably a single bond, -COO-, or -CONH-, and more preferably a single bond or -COO-.

The alkylene group for L ₄ is preferably an alkylene group having 1 to 8 carbon atoms, such as a methylene group, an ethylene group, a propylene group, a butylene group, a hexylene group, and an octylene group.
Ar ₄ is preferably an aromatic ring group having 6 to 18 carbon atoms, and more preferably a benzene ring group, a naphthalene ring group, and a biphenylene ring group.
The repeating unit represented by general formula (I) preferably has a hydroxystyrene structure. That is, Ar ₄ is preferably a benzene ring group.

As the repeating unit represented by the general formula (I), a repeating unit represented by the following general formula (1) is preferable.

In general formula (1),
A represents a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, or a cyano group.
R represents a halogen atom, an alkyl group, a cycloalkyl group, an aryl group, an alkenyl group, an aralkyl group, an alkoxy group, an alkylcarbonyloxy group, an alkylsulfonyloxy group, an alkyloxycarbonyl group, or an aryloxycarbonyl group, and there are a plurality of them. They may be the same or different depending on the case. When a plurality of R's are present, they may cooperate with each other to form a ring. R is preferably a hydrogen atom.
a represents an integer from 1 to 3.
b represents an integer from 0 to (5-a).

Examples of repeating units having an acid group are shown below. In the formula, a represents 1 or 2.

Note that the repeating unit having an acid group is preferably a repeating unit specifically described below. In the formula, R represents a hydrogen atom or a methyl group, and a represents 2 or 3.

The content of the repeating unit having an acid group is preferably 10 mol% or more, more preferably 15 mol% or more, based on all the repeating units in the resin (A). Further, the upper limit thereof is preferably 70 mol% or less, more preferably 65 mol% or less, and even more preferably 60 mol% or less.

(Repeating unit that has a fluorine atom or an iodine atom and does not show acid decomposability)
The resin (A) may have a repeating unit having a fluorine atom or an iodine atom, in addition to the above-mentioned "(repeat unit having an acid-decomposable group)" and "(repeat unit having an acid group)". good. In addition, "(a repeating unit having a fluorine atom or an iodine atom)" herein refers to "(a repeating unit having a lactone group, a sultone group, or a carbonate group)" and "(a repeating unit having a photoacid generating group)" described later. It is preferable that the repeating unit is different from other types of repeating units belonging to Group A, such as "unit)".
In addition, the main chain of the above-mentioned "(repeating unit having a fluorine atom or an iodine atom and not showing acid decomposability)" preferably does not contain a ring member atom (in other words, an atom constituting a ring structure). .

As the repeating unit having a fluorine atom or an iodine atom and not showing acid decomposability, a repeating unit represented by formula (C) is preferable.

L ₅ represents a single bond or an ester group.
R ₉ represents a hydrogen atom or an alkyl group which may have a fluorine atom or an iodine atom.
_R10 may have a hydrogen atom, an alkyl group which may have a fluorine atom or an iodine atom, a cycloalkyl group which may have a fluorine atom or an iodine atom, a fluorine atom or an iodine atom. Represents an aryl group or a group combining these.

Examples of repeating units having a fluorine atom or an iodine atom and not showing acid decomposability are shown below.

The content of repeating units having a fluorine atom or an iodine atom and not showing acid decomposability is preferably 0 mol% or more, more preferably 5 mol% or more, and 10 mol% or more, based on all the repeating units in the resin (A). More preferably mol% or more. Further, the upper limit thereof is preferably 50 mol% or less, more preferably 45 mol% or less, and even more preferably 40 mol% or less.

(Repeat unit having lactone group, sultone group, or carbonate group)
The resin (A) is a repeating unit having at least one type selected from the group consisting of a lactone group, a sultone group, and a carbonate group (hereinafter collectively referred to as "a repeating unit having a lactone group, a sultone group, or a carbonate group"). ).
The repeating unit having a lactone group, sultone group, or carbonate group is preferably one that does not have an acid group such as a hexafluoropropanol group.

The lactone group or sultone group may have a lactone structure or a sultone structure. The lactone structure or sultone structure is preferably a 5- to 7-membered ring lactone structure or a 5- to 7-membered ring sultone structure. Among these, 5- to 7-membered ring lactone structures are fused with other ring structures to form a bicyclo or spiro structure, or 5- to 7-membered sultone structures to form a bicyclo or spiro structure. More preferred is a structure in which another ring structure is condensed.
The resin (A) has a lactone structure represented by any of the following general formulas (LC1-1) to (LC1-21), or a lactone structure represented by any of the following general formulas (SL1-1) to (SL1-3). It is preferable to have a repeating unit having a lactone group or a sultone group formed by abstracting one or more hydrogen atoms from a ring member atom of a sultone structure.
Furthermore, the lactone group or sultone group may be directly bonded to the main chain. For example, ring member atoms of a lactone group or a sultone group may constitute the main chain of the resin (A).

The lactone structure or sultone structure portion may have a substituent (Rb ₂ ). Preferred substituents (Rb ₂ ) include alkyl groups having 1 to 8 carbon atoms, cycloalkyl groups having 4 to 7 carbon atoms, alkoxy groups having 1 to 8 carbon atoms, alkoxycarbonyl groups having 1 to 8 carbon atoms, and carboxy groups. , a halogen atom, a hydroxyl group, a cyano group, and an acid-decomposable group. n ₂ represents an integer from 0 to 4. When n ₂ is 2 or more, a plurality of Rb _2s may be different, or a plurality of Rb _2s may be bonded to each other to form a ring.

Contains a group having a lactone structure represented by any of the general formulas (LC1-1) to (LC1-21) or a sultone structure represented by any of the general formulas (SL1-1) to (SL1-3) Examples of the repeating unit include repeating units represented by the following general formula (AI).

In the general formula (AI), Rb ₀ represents a hydrogen atom, a halogen atom, or an alkyl group having 1 to 4 carbon atoms.
Preferred substituents that the alkyl group of Rb ₀ may have include a hydroxyl group and a halogen atom.
Examples of the halogen atom for Rb ₀ include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. Rb ₀ is preferably a hydrogen atom or a methyl group.
Ab is a single bond, an alkylene group, a divalent linking group having a monocyclic or polycyclic alicyclic hydrocarbon structure, an ether group, an ester group, a carbonyl group, a carboxy group, or a divalent group combining these. represent. Among these, a single bond or a connecting group represented by -Ab ₁ -CO ₂ - is preferred. Ab ₁ is a linear or branched alkylene group, or a monocyclic or polycyclic cycloalkylene group, and is preferably a methylene group, ethylene group, cyclohexylene group, adamantylene group, or norbornylene group.
V is a group obtained by removing one hydrogen atom from a ring member atom of a lactone structure represented by any of the general formulas (LC1-1) to (LC1-21), or SL1-3) represents a group formed by abstracting one hydrogen atom from a ring member atom of a sultone structure represented by any of SL1-3).

When an optical isomer exists in the repeating unit having a lactone group or a sultone group, any optical isomer may be used. Further, one type of optical isomer may be used alone or a plurality of optical isomers may be used in combination. When one type of optical isomer is mainly used, its optical purity (ee) is preferably 90 or more, more preferably 95 or more.

As the carbonate group, a cyclic carbonate group is preferable.
As the repeating unit having a cyclic carbonate group, a repeating unit represented by the following general formula (A-1) is preferable.

In general formula (A-1), R _A ¹ represents a hydrogen atom, a halogen atom, or a monovalent organic group (preferably a methyl group).
n represents an integer of 0 or more.
R _A ² represents a substituent. When n is 2 or more, a plurality of R _A ² 's may be the same or different.
A represents a single bond or a divalent linking group. The divalent linking group mentioned above is an alkylene group, a divalent linking group having a monocyclic or polycyclic alicyclic hydrocarbon structure, an ether group, an ester group, a carbonyl group, a carboxy group, or a combination of these. The group is preferred.
Z represents an atomic group forming a monocyclic or polycyclic ring together with the group represented by -O-CO-O- in the formula.

Examples of repeating units having a lactone group, a sultone group, or a carbonate group are shown below.

The content of repeating units having a lactone group, sultone group, or carbonate group is preferably 1 mol% or more, more preferably 10 mol% or more, based on all the repeating units in the resin (A). The upper limit thereof is preferably 85 mol% or less, more preferably 80 mol% or less, even more preferably 70 mol% or less, and particularly preferably 60 mol% or less.

(Repeating unit with photoacid generating group)
The resin (A) may have, as a repeating unit other than the above, a repeating unit having a group that generates an acid upon irradiation with actinic rays or radiation (hereinafter also referred to as a "photoacid generating group").
In this case, this repeating unit having a photoacid generating group can be considered to correspond to a compound (also referred to as a "photoacid generator") that generates an acid upon irradiation with actinic rays or radiation, which will be described later.
Examples of such repeating units include repeating units represented by the following general formula (4).

R ⁴¹ represents a hydrogen atom or a methyl group. L ⁴¹ represents a single bond or a divalent linking group. L ⁴² represents a divalent linking group. R ⁴⁰ represents a structural moiety that decomposes upon irradiation with actinic rays or radiation to generate an acid in the side chain.

Examples of repeating units having a photoacid generating group are shown below.

In addition, examples of the repeating unit represented by the general formula (4) include repeating units described in paragraphs <0094> to <0105> of JP-A No. 2014-041327.

The content of the repeating unit having a photoacid generating group is preferably 1 mol% or more, more preferably 5 mol% or more, based on all the repeating units in the resin (A). Further, the upper limit thereof is preferably 40 mol% or less, more preferably 35 mol% or less, and even more preferably 30 mol% or less.

(Repeating unit represented by general formula (V-1) or general formula (V-2) below)
The resin (A) may have a repeating unit represented by the following general formula (V-1) or the following general formula (V-2).
The repeating units represented by the following general formula (V-1) and the following general formula (V-2) are preferably repeating units different from the above-mentioned repeating units.

During the ceremony,
R ₆ and R ₇ are each independently a hydrogen atom, a hydroxyl group, an alkyl group, an alkoxy group, an acyloxy group, a cyano group, a nitro group, an amino group, a halogen atom, an ester group (-OCOR or -COOR: R is the number of carbon atoms 1 to 6 alkyl groups or fluorinated alkyl groups), or carboxy groups. The alkyl group is preferably a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms.
n ₃ represents an integer from 0 to 6.
n ₄ represents an integer from 0 to 4.
X ₄ is a methylene group, an oxygen atom, or a sulfur atom.
Examples of repeating units represented by general formula (V-1) or (V-2) are shown below.

(Repeat unit to reduce main chain mobility)
The resin (A) preferably has a high glass transition temperature (Tg) from the viewpoint of suppressing excessive diffusion of generated acid or pattern collapse during development. Tg is preferably greater than 90°C, more preferably greater than 100°C, even more preferably greater than 110°C, and particularly preferably greater than 125°C. In addition, since an excessively high Tg causes a decrease in the rate of dissolution in a developer, the Tg is preferably 400°C or less, more preferably 350°C or less.
In addition, in this specification, the glass transition temperature (Tg) of polymers, such as resin (A), is calculated by the following method. First, the Tg of a homopolymer consisting only of each repeating unit contained in the polymer is calculated by the Bicerano method. Hereinafter, the calculated Tg will be referred to as "Tg of a repeating unit." Next, the mass ratio (%) of each repeating unit to all repeating units in the polymer is calculated. Next, the Tg at each mass ratio is calculated using Fox's formula (described in Materials Letters 62 (2008) 3152, etc.), and these are summed to determine the Tg (° C.) of the polymer.
The Bicerano method is described in Prediction of polymer properties, Marcel Dekker Inc, New York (1993), etc. Calculation of Tg by the Bicerano method can be performed using polymer physical property estimation software MDL Polymer (MDL Information Systems, Inc.).

In order to increase the Tg of the resin (A) (preferably to make the Tg higher than 90° C.), it is preferable to reduce the mobility of the main chain of the resin (A). Examples of methods for reducing the mobility of the main chain of resin (A) include the following methods (a) to (e).
(a) Introduction of a bulky substituent to the main chain (b) Introduction of multiple substituents to the main chain (c) Introduction of a substituent that induces interaction between the resins (A) near the main chain ( d) Main chain formation with a cyclic structure (e) Connection of the cyclic structure to the main chain It is preferable that the resin (A) has a repeating unit whose homopolymer Tg is 130° C. or higher.
The type of repeating unit whose homopolymer Tg is 130°C or higher is not particularly limited, and any repeating unit whose homopolymer Tg calculated by the Bicerano method is 130°C or higher may be used. Note that, depending on the type of functional group in the repeating units represented by formulas (A) to (E) described below, the repeating units correspond to homopolymer Tg of 130° C. or higher.

(Repeating unit represented by formula (A))
An example of a specific means for achieving the above (a) is a method of introducing a repeating unit represented by the formula (A) into the resin (A).

In formula (A), R _A represents a group having a polycyclic structure. R _x represents a hydrogen atom, a methyl group, or an ethyl group. A group having a polycyclic structure is a group having a plurality of ring structures, and the plurality of ring structures may or may not be condensed.
Specific examples of the repeating unit represented by formula (A) include the following repeating units.

In the above formula, R represents a hydrogen atom, a methyl group, or an ethyl group.
Ra is a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, an alkenyl group, a hydroxyl group, an alkoxy group, an acyloxy group, a cyano group, a nitro group, an amino group, a halogen atom, an ester group (-OCOR''' or -COOR''': R''' represents an alkyl group having 1 to 20 carbon atoms or a fluorinated alkyl group), or a carboxy group. Note that each of the alkyl group, cycloalkyl group, aryl group, aralkyl group, and alkenyl group may have a substituent. Further, the hydrogen atom bonded to the carbon atom in the group represented by Ra may be substituted with a fluorine atom or an iodine atom.
Further, R' and R'' each independently represent an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, an alkenyl group, a hydroxyl group, an alkoxy group, an acyloxy group, a cyano group, a nitro group, an amino group, a halogen atom, It represents an ester group (-OCOR''' or -COOR''': R''' is an alkyl group having 1 to 20 carbon atoms or a fluorinated alkyl group) or a carboxy group. Note that each of the alkyl group, cycloalkyl group, aryl group, aralkyl group, and alkenyl group may have a substituent. Further, the hydrogen atoms bonded to carbon atoms in the groups represented by R' and R'' may be substituted with fluorine atoms or iodine atoms.
L represents a single bond or a divalent linking group. Examples of the divalent linking group include -COO-, -CO-, -O-, -S-, -SO-, -SO ₂ -, an alkylene group, a cycloalkylene group, an alkenylene group, and a plurality of these. Examples include linked linking groups.
m and n each independently represent an integer of 0 or more. The upper limits of m and n are not particularly limited, but are often 2 or less, and more often 1 or less.

(Repeating unit represented by formula (B))
An example of a specific means for achieving the above (b) is a method of introducing a repeating unit represented by the formula (B) into the resin (A).

In formula (B), R _b1 to R _b4 each independently represent a hydrogen atom or an organic group, and at least two or more of R _b1 to R _b4 represent an organic group.
Moreover, when at least one of the organic groups is a group in which a ring structure is directly connected to the main chain in the repeating unit, the types of other organic groups are not particularly limited.
In addition, if none of the organic groups is a group in which a ring structure is directly connected to the main chain in the repeating unit, at least two or more of the organic groups have three or more constituent atoms excluding hydrogen atoms. It is a substituent.

Specific examples of the repeating unit represented by formula (B) include the following repeating units.

In the above formula, each R independently represents a hydrogen atom or an organic group. Examples of the organic group include organic groups such as an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, and an alkenyl group, which may have a substituent.
R' each independently represents an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, an alkenyl group, a hydroxyl group, an alkoxy group, an acyloxy group, a cyano group, a nitro group, an amino group, a halogen atom, an ester group (-OCOR''or-COOR'':R'' represents an alkyl group having 1 to 20 carbon atoms or a fluorinated alkyl group), or a carboxy group. Note that each of the alkyl group, cycloalkyl group, aryl group, aralkyl group, and alkenyl group may have a substituent. Further, the hydrogen atom bonded to the carbon atom in the group represented by R' may be substituted with a fluorine atom or an iodine atom.
m represents an integer of 0 or more. The upper limit of m is not particularly limited, but is often 2 or less, more often 1 or less.

(Repeating unit represented by formula (C))
An example of a specific means for achieving the above (c) is a method of introducing a repeating unit represented by the formula (C) into the resin (A).

In formula (C), R _c1 to R _c4 each independently represent a hydrogen atom or an organic group, and at least one of R _c1 to R _c4 has a hydrogen bonding property within 3 atoms from the main chain carbon. It is a group having an atom. Among these, in order to induce interaction between the main chains of the resin (A), it is preferable to have hydrogen atoms capable of hydrogen bonding within 2 atoms (closer to the main chain).

Specific examples of the repeating unit represented by formula (C) include the following repeating units.

In the above formula, R represents an organic group. Examples of organic groups include alkyl groups, cycloalkyl groups, aryl groups, aralkyl groups, alkenyl groups, and ester groups (-OCOR or -COOR: R is an alkyl group having 1 to 20 carbon atoms), which may have a substituent. or fluorinated alkyl group).
R' represents a hydrogen atom or an organic group. Examples of the organic group include organic groups such as an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, and an alkenyl group. Note that the hydrogen atom in the organic group may be substituted with a fluorine atom or an iodine atom.

(Repeating unit represented by formula (D))
An example of a specific means for achieving the above (d) is a method of introducing a repeating unit represented by the formula (D) into the resin (A).

In formula (D), "Cyclic" represents a group forming a main chain with a cyclic structure. The number of atoms constituting the ring is not particularly limited.

Specific examples of the repeating unit represented by formula (D) include the following repeating units.

In the above formula, R is each independently a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, an alkenyl group, a hydroxyl group, an alkoxy group, an acyloxy group, a cyano group, a nitro group, an amino group, a halogen atom, It represents an ester group (-OCOR'' or -COOR'': R'' is an alkyl group having 1 to 20 carbon atoms or a fluorinated alkyl group) or a carboxy group. Note that each of the alkyl group, cycloalkyl group, aryl group, aralkyl group, and alkenyl group may have a substituent. Further, the hydrogen atom bonded to the carbon atom in the group represented by R may be substituted with a fluorine atom or an iodine atom.
In the above formula, R' each independently represents an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, an alkenyl group, a hydroxyl group, an alkoxy group, an acyloxy group, a cyano group, a nitro group, an amino group, a halogen atom, an ester group (-OCOR'' or -COOR'': R'' represents an alkyl group having 1 to 20 carbon atoms or a fluorinated alkyl group), or a carboxy group. Note that each of the alkyl group, cycloalkyl group, aryl group, aralkyl group, and alkenyl group may have a substituent. Further, the hydrogen atom bonded to the carbon atom in the group represented by R' may be substituted with a fluorine atom or an iodine atom.
m represents an integer of 0 or more. The upper limit of m is not particularly limited, but is often 2 or less, more often 1 or less.

(Repeating unit represented by formula (E))
An example of a specific means for achieving the above (e) is a method of introducing a repeating unit represented by the formula (E) into the resin (A).

In formula (E), Re each independently represents a hydrogen atom or an organic group. Examples of the organic group include an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, and an alkenyl group, which may have a substituent.
"Cyclic" is a cyclic group containing backbone carbon atoms. The number of atoms contained in the cyclic group is not particularly limited.

Specific examples of the repeating unit represented by formula (E) include the following repeating units.

Furthermore, as specific examples of the repeating unit represented by formula (E), repeating units derived from the following monomers can also be suitably used.

In the above formula, R is each independently a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, an alkenyl group, a hydroxyl group, an alkoxy group, an acyloxy group, a cyano group, a nitro group, an amino group, or a halogen atom. , an ester group (-OCOR'' or -COOR'': R'' is an alkyl group having 1 to 20 carbon atoms or a fluorinated alkyl group), or a carboxy group. Note that each of the alkyl group, cycloalkyl group, aryl group, aralkyl group, and alkenyl group may have a substituent. Further, the hydrogen atom bonded to the carbon atom in the group represented by R may be substituted with a fluorine atom or an iodine atom.
R' each independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, an alkenyl group, a hydroxyl group, an alkoxy group, an acyloxy group, a cyano group, a nitro group, an amino group, a halogen atom, an ester group (-OCOR'' or -COOR'': R'' represents an alkyl group having 1 to 20 carbon atoms or a fluorinated alkyl group), or a carboxy group. Note that each of the alkyl group, cycloalkyl group, aryl group, aralkyl group, and alkenyl group may have a substituent. Further, the hydrogen atom bonded to the carbon atom in the group represented by R' may be substituted with a fluorine atom or an iodine atom.
m represents an integer of 0 or more. The upper limit of m is not particularly limited, but is often 2 or less, more often 1 or less.
Further, in formula (E-2), formula (E-4), formula (E-6), and formula (E-8), two R may be bonded to each other to form a ring.

The content of the repeating units represented by formulas (A) to (E) is preferably 5 mol% or more, more preferably 10 mol% or more, based on all the repeating units in the resin (A). Further, the upper limit thereof is preferably 60 mol% or less, and more preferably 55 mol% or less.

(Repeating unit having at least one type of group selected from lactone group, sultone group, carbonate group, hydroxyl group, cyano group, and alkali-soluble group)
The resin (A) may have a repeating unit having at least one type of group selected from a lactone group, a sultone group, a carbonate group, a hydroxyl group, a cyano group, and an alkali-soluble group.
Examples of the repeating unit having a lactone group, sultone group, or carbonate group that the resin (A) has include the repeating units described in "(Repeat unit having a lactone group, sultone group, or carbonate group)" above. The preferable content is also as explained in "(repeating unit having lactone group, sultone group, or carbonate group)" above.

The resin (A) may have a repeating unit having a hydroxyl group or a cyano group. This improves substrate adhesion and developer affinity.
The repeating unit having a hydroxyl group or a cyano group is preferably a repeating unit having an alicyclic hydrocarbon structure substituted with a hydroxyl group or a cyano group.
The repeating unit having a hydroxyl group or a cyano group preferably does not have an acid-decomposable group. Examples of the repeating unit having a hydroxyl group or a cyano group include repeating units represented by the following general formulas (AIIa) to (AIId).

In general formulas (AIIa) to (AIId),
R _1c represents a hydrogen atom, a methyl group, a trifluoromethyl group, or a hydroxymethyl group.
R _2c to R _4c each independently represent a hydrogen atom, a hydroxyl group, or a cyano group. However, at least one of R _2c to R _4c represents a hydroxyl group or a cyano group. Preferably, one or two of R _2c to R _4c are hydroxyl groups, and the remainder are hydrogen atoms. More preferably, two of R _2c to R _4c are hydroxyl groups and the remaining are hydrogen atoms.

The content of repeating units having a hydroxyl group or cyano group is preferably 5 mol% or more, more preferably 10 mol% or more, based on all the repeating units in the resin (A). Further, the upper limit thereof is preferably 40 mol% or less, more preferably 35 mol% or less, and even more preferably 30 mol% or less.

Specific examples of repeating units having a hydroxyl group or a cyano group are listed below, but the present invention is not limited thereto.

The resin (A) 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 bisulfonylimide group, and an aliphatic alcohol group substituted with an electron-withdrawing group at the α position (for example, a hexafluoroisopropanol group), A carboxy group is preferred. When the resin (A) contains a repeating unit having an alkali-soluble group, resolution in contact hole applications increases.
Examples of repeating units having an alkali-soluble group include repeating units in which an alkali-soluble group is directly bonded to the main chain of the resin, such as repeating units of acrylic acid and methacrylic acid, or repeating units in which an alkali-soluble group is bonded directly to the main chain of the resin through a linking group. Examples include repeating units to which a soluble group is bonded. Note that the linking group may have a monocyclic or polycyclic cyclic hydrocarbon structure.
The repeating unit having an alkali-soluble group is preferably a repeating unit based on acrylic acid or methacrylic acid.

The content of the repeating unit having an alkali-soluble group is preferably 0 mol% or more, more preferably 3 mol% or more, and even more preferably 5 mol% or more, based on all the repeating units in the resin (A). The upper limit thereof is preferably 20 mol% or less, more preferably 15 mol% or less, and even more preferably 10 mol% or less.

Specific examples of repeating units 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 repeating unit having at least one type of group selected from a lactone group, a hydroxyl group, a cyano group, and an alkali-soluble group is preferably a repeating unit having at least two groups selected from a lactone group, a hydroxyl group, a cyano group, and an alkali-soluble group. , a repeating unit having a cyano group and a lactone group is more preferable, and a repeating unit having a structure in which a lactone structure represented by the general formula (LC1-4) is substituted with a cyano group is even more preferable.

(Repeating unit that has an alicyclic hydrocarbon structure and does not show acid decomposition)
The resin (A) has an alicyclic hydrocarbon structure and may have repeating units that are not acid-decomposable. This can reduce the elution of low molecular weight components from the resist film into the immersion liquid during immersion exposure. Examples of such repeating units include repeating units derived from 1-adamantyl (meth)acrylate, diadamantyl (meth)acrylate, tricyclodecanyl (meth)acrylate, or cyclohexyl (meth)acrylate.

(Repeating unit represented by general formula (III) that does not have either a hydroxyl group or a cyano group)
The resin (A) may have a repeating unit represented by general formula (III) that does not have either a hydroxyl group or a cyano group.

In general formula (III), R ₅ represents a hydrocarbon group having at least one cyclic structure and having neither a hydroxyl group nor a cyano group.
Ra represents a hydrogen atom, an alkyl group, or _two groups of -CH ₂ -O-Ra. In the formula, Ra ₂ represents a hydrogen atom, an alkyl group or an acyl group.

The cyclic structure that R ₅ has includes a monocyclic hydrocarbon group and a polycyclic hydrocarbon group. Examples of the monocyclic hydrocarbon group include a cycloalkyl group having 3 to 12 carbon atoms (more preferably 3 to 7 carbon atoms), or a cycloalkenyl group having 3 to 12 carbon atoms.

Examples of the polycyclic hydrocarbon group include a ring assembly hydrocarbon group and a bridged cyclic hydrocarbon group. Examples of the bridged cyclic hydrocarbon ring include a bicyclic hydrocarbon ring, a tricyclic hydrocarbon ring, and a tetracyclic hydrocarbon ring. The bridged cyclic hydrocarbon ring also includes a condensed ring in which a plurality of 5- to 8-membered cycloalkane rings are condensed.
As the bridged cyclic hydrocarbon group, a norbornyl group, an adamantyl group, a bicyclooctanyl group, or a tricyclo[5,2,1,02,6]decanyl group is preferable, and a norbornyl group or an adamantyl group is more preferable.

The alicyclic hydrocarbon group may have a substituent, and examples of the substituent include a halogen atom, an alkyl group, a hydroxyl group protected with a protecting group, and an amino group protected with a protecting group.
The halogen atom is preferably a bromine atom, a chlorine atom, or a fluorine atom.
The alkyl group is preferably a methyl group, ethyl group, butyl group, or t-butyl group. The above alkyl group may further have a substituent, and examples of the substituent include a halogen atom, an alkyl group, a hydroxyl group protected with a protecting group, or an amino group protected with a protecting group.

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

The content of the repeating unit represented by the general formula (III), which does not have either a hydroxyl group or a cyano group, is preferably 0 to 40 mol%, and 0 to 20% by mole, based on the total repeating units in the resin (A). Mol% is more preferred.
Specific examples of the repeating unit represented by general formula (III) are listed below, but the present invention is not limited thereto. In the formula, Ra represents H, CH ₃ , CH ₂ OH, or CF ₃ .

(Other repeat units)
Furthermore, the resin (A) may have repeating units other than the above-mentioned repeating units.
For example, the resin (A) has a repeating unit selected from the group consisting of a repeating unit having an oxathian ring group, a repeating unit having an oxazolone ring group, a repeating unit having a dioxane ring group, and a repeating unit having a hydantoin ring group. You may do so.
Examples of such repeating units are shown below.

In addition to the above repeating structural units, the resin (A) has various repeating structural units for the purpose of adjusting dry etching resistance, standard developer suitability, substrate adhesion, resist profile, resolution, heat resistance, sensitivity, etc. You may do so.

Resin (A) can be synthesized according to conventional methods (eg, radical polymerization).
The weight average molecular weight of the resin (A) is preferably 1,000 to 200,000, more preferably 2,000 to 30,000, and even more preferably 3,000 to 20,000, as determined by GPC in terms of polystyrene. By setting the weight average molecular weight of the resin (A) to 1,000 to 200,000, deterioration of heat resistance and dry etching resistance can be further suppressed. Further, it is possible to further suppress deterioration of developability and deterioration of film formability due to increase in viscosity.
The dispersity (molecular weight distribution) of the resin (A) is usually 1.0 to 5.0, preferably 1.0 to 3.0, more preferably 1.0 to 2.5, and 1.0 to 2. .0 is more preferable. The smaller the degree of dispersion, the better the resolution and resist shape, the smoother the sidewalls of the resist pattern, and the better the roughness.

In the composition of the present invention, the content of the resin (A) is preferably 50 to 99.9% by mass, more preferably 60 to 99.0% by mass, based on the total solid content of the composition.
Note that the solid content refers to components other than the solvent in the composition, and even if the components are liquid components other than the solvent, they are considered solid components.
Further, the resin (A) may be used alone or in combination.

[(B) A compound that generates an acid upon irradiation with actinic rays or radiation, and is represented by general formula (1)]
As described above, the actinic ray-sensitive or radiation-sensitive resin composition of the present invention is (B) a compound that generates an acid upon irradiation with actinic rays or radiation, and is represented by the following general formula (1). Contains a compound (also referred to as "compound (B)" or "photoacid generator (B)").
Compound (B) is a compound (photoacid generator) that generates an acid upon irradiation with actinic rays or radiation.

<Compound represented by general formula (1)>

一般式（Ｒ－１）中、Ａは単結合又は（ｍ＋１）価の連結基を表す。
Ｙは、それぞれ独立に下記式（Ａ１）～（Ａ６）のいずれかで表される基を表す。
ｍは１以上の整数を表す。
ｍが２以上の整数を表す場合、複数のＹは、それぞれ同一であってもよく、異なっていてもよい。
＊は、ベンゼン環への結合手を表す。

式（Ａ１）～（Ａ６）中、*はＡへの結合手を表す。
式（Ａ２）中、Ｒ_６は、炭素原子を有する置換基を表す。式（Ａ２）のＳＯ_２における硫黄原子は、Ｒ_６中の上記炭素原子と結合する。また、Ｒ_６は、Ａ又はＬと互いに結合して環を形成してもよい。
Ｌは、単結合、カルボニル結合、アルキレン基、又は２価の芳香族基を表す。
式（Ａ３）中、Ｒ_７は、炭素原子を有する置換基を表す。式（Ａ３）のＮ^－は、Ｒ_７中の上記炭素原子と結合する。また、Ｒ_７は、Ａと互いに結合して環を形成してもよい。
式（Ａ４）中、Ｒ_８は、炭素原子を有する置換基を表す。式（Ａ４）のカルボニル結合における炭素原子は、Ｒ_８中の上記炭素原子と結合する。また、Ｒ_８は、Ａと互いに結合して環を形成してもよい。
式（Ａ５）中、Ｒ_９、及びＲ_９’は、それぞれ独立に水素原子又は置換基を表す。Ｒ_９、及びＲ_９’は互いに結合して環を形成してもよい。In general formula (1), R ₁ to R ₅ each independently represent a hydrogen atom or a substituent. At least one of R ₁ to R ₅ represents a group represented by the following general formula (R-1). M ⁿ⁺ represents a cation moiety. n represents an integer of 2 or more.

In the general formula (R-1), A represents a single bond or a (m+1)-valent linking group.
Y each independently represents a group represented by any one of the following formulas (A1) to (A6).
m represents an integer of 1 or more.
When m represents an integer of 2 or more, the plurality of Y's may be the same or different.
* represents a bond to the benzene ring.

In formulas (A1) to (A6), * represents a bond to A.
In formula (A2), R ₆ represents a substituent having a carbon atom. The sulfur atom in SO ₂ of formula (A2) bonds with the carbon atom in R ₆ . Further, R ₆ may be combined with A or L to form a ring.
L represents a single bond, a carbonyl bond, an alkylene group, or a divalent aromatic group.
In formula (A3), R ₇ represents a substituent having a carbon atom. N ⁻ in formula (A3) is bonded to the above carbon atom in R ₇ . Furthermore, R ₇ may combine with A to form a ring.
In formula (A4), R ₈ represents a substituent having a carbon atom. The carbon atom in the carbonyl bond of formula (A4) is bonded to the carbon atom in R ₈ . Moreover, R ₈ may combine with A to form a ring.
In formula (A5), R ₉ and R _9' each independently represent a hydrogen atom or a substituent. R ₉ and R _9' may be combined with each other to form a ring.

In general formula (1), R ₁ to R ₅ each independently represent a hydrogen atom or a substituent.
When R ₁ to R ₅ represent a substituent, the substituent is not particularly limited as long as it is a monovalent substituent, and examples include an alkyl group; an alkenyl group; an aliphatic hydrocarbon ring group; an aryl group; a halogen atom. ; a group containing a heteroatom such as an oxygen atom, a sulfur atom, a nitrogen atom, and a silicon atom; and combinations of two or more thereof.

Examples of the alkyl groups as R ₁ to R ₅ include alkyl groups having 1 to 30 carbon atoms. Preferably, the alkyl group is an alkyl group having 1 to 20 carbon atoms, such as a methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, sec-butyl group, hexyl group, 2-ethylhexyl group, octyl group, or dodecyl group. More preferably, it is an alkyl group having 1 to 8 carbon atoms.

Examples of the alkenyl groups as R ₁ to R ₅ include alkenyl groups having 2 to 30 carbon atoms, and alkenyl groups having 2 to 8 carbon atoms are preferred.

The aliphatic hydrocarbon ring groups as R ₁ to R ₅ may be monocyclic or polycyclic. Examples of the aliphatic hydrocarbon ring group include a cycloalkyl group and a cycloalkenyl group, and the number of carbon atoms in the cycloalkyl group and cycloalkenyl group is not particularly limited, but is preferably 3 to 12.
Preferred examples of the cycloalkyl group include a cyclopentyl group, a cyclohexyl group, a norbornyl group, a tetracyclodecanyl group, a tetracyclododecanyl group, and an adamantyl group.

Examples of the aryl group as R ₁ to R ₅ include aryl groups having 6 to 15 carbon atoms, and specifically, preferred examples include phenyl group, naphthyl group, and anthryl group.

Examples of the halogen atoms as R ₁ to R ₅ include fluorine atoms, chlorine atoms, bromine atoms, and iodine atoms.

Groups containing hetero atoms as R ₁ to R ₅ include, for example, hydroxyl group, carboxyl group, alkoxy group, thiol group, thioether group, nitro group, nitroso group, cyano group, amino group, acyloxy group, acylamido group, Examples include an aromatic heterocyclic group, a heteroaryl group, an ether bond, a carbonyl bond, and a combination of two or more thereof.

The number of carbon atoms in the alkoxy group, acyloxy group and acylamido group is preferably 20 or less, more preferably 8 or less. Examples of the alkoxy group include methoxy group, ethoxy group, propoxy group, isopropoxy group, n-butyloxy group, t-butoxy group and octyloxy group. Among these, methoxy, ethoxy, propoxy, isopropoxy and t-butoxy groups are particularly preferred. In addition, as for the thioether group, the same ones as the alkoxy group can be mentioned, except that a sulfur atom is used instead of an oxygen atom. Examples of the acyloxy group include an acetyloxy group. Examples of the acylamide group include an acetylamide group.
Examples of the non-aromatic heterocyclic group include aliphatic heterocyclic groups having 2 to 15 carbon atoms, with 5- to 10-membered rings being preferred. Specific examples include a tetrahydrofuryl group, a tetrahydrothienyl group, a tetrahydropyrrolyl group, and the like.
Examples of the heteroaryl group include heteroaryl groups having 2 to 15 carbon atoms, with 5- to 10-membered rings being preferred. Specific examples include furyl group, thienyl group, pyrrolyl group, oxazolyl group, pyridyl group, quinolinyl group, carbazolyl group, and the like.

Alkyl groups; alkenyl groups; aliphatic hydrocarbon ring groups; aryl groups as substituents for R ₁ to R ₅ ; You may have one. Examples of further substituents include, in addition to the substituents described above as R ₁ to R ₅ , amide groups, ureido groups, urethane groups, acyl groups, and alkoxycarbonyl groups.
When the substituents R ₁ to R ₅ have a plurality of further substituents, at least two of the plurality of substituents may be bonded to each other to form a ring.

R ₁ to R ₅ are a group containing a polar group as described below, a group containing a group whose polarity increases when decomposed by the action of an acid, or a group which decomposes by the action of an alkaline developer and increases its solubility in the alkaline developer. A group containing a group can be constructed.

In the above general formula (1), from the viewpoint of further reducing development defects, at least one of R ₁ to R ₅ is a group containing a polar group, or a group that decomposes under the action of an acid to increase polarity. A group containing a group, or a group containing a group that is decomposed by the action of an alkaline developer and increases its solubility in the alkaline developer is preferable.

A polar group in a group containing a polar group as R ₁ to R ₅ , a group that decomposes and increases in polarity by the action of an acid in a group containing a group that decomposes and increases in polarity by the action of an acid, and a group that decomposes and increases in polarity by the action of an alkaline developer. Specifically, a group that decomposes and increases its solubility in an alkaline developer by the action of an alkaline developer in a group that decomposes and increases its solubility in an alkaline developer is represented by the general formula ( In the group represented by Ar), as at least one of R ₁₀ to R ₁₄ , a polar group in a group containing a polar group, a group containing a group whose polarity increases when decomposed by the action of an acid, due to the action of an acid. A group that decomposes and increases polarity, and a group that decomposes under the action of an alkaline developer and increases its solubility in the alkaline developer is decomposed by the action of an alkaline developer, and its solubility in the alkaline developer increases. Mention may be made of increasing groups.

In the general formula (1), at least one of R ₁ to R ₅ represents a group represented by the following general formula (R-1).

In the general formula (R-1), A represents a single bond or a (m+1)-valent linking group.
Y each independently represents a group represented by any one of the following formulas (A1) to (A6).
m represents an integer of 1 or more.
When m represents an integer of 2 or more, the plurality of Y's may be the same or different.
* represents a bond to the benzene ring.

In formulas (A1) to (A6), * represents a bond to A.
In formula (A2), R ₆ represents a substituent having a carbon atom. The sulfur atom in SO ₂ of formula (A2) bonds with the carbon atom in R ₆ . Further, R ₆ may be combined with A or L to form a ring.
L represents a single bond, a carbonyl bond, an alkylene group, or a divalent aromatic group.
In formula (A3), R ₇ represents a substituent having a carbon atom. N ⁻ in formula (A3) is bonded to the above carbon atom in R ₇ . Furthermore, R ₇ may combine with A to form a ring.
In formula (A4), R ₈ represents a substituent having a carbon atom. The carbon atom in the carbonyl bond of formula (A4) is bonded to the carbon atom in R ₈ . Moreover, R ₈ may combine with A to form a ring.
In formula (A5), R ₉ and R _9' each independently represent a hydrogen atom or a substituent. R ₉ and R _9' may be combined with each other to form a ring.

As the (m+1)-valent linking group of A, for example, a divalent linking group is described below.
When A represents a divalent linking group, the divalent linking group is not particularly limited, but includes, for example, an alkylene group, an alkenylene group, an alkynylene group, a cycloalkylene group, a divalent aromatic group, -O-, -C(=O)-, or a combination thereof.
The alkylene group is not particularly limited, but a linear or branched alkylene group is preferable, and an alkylene group having 1 to 10 carbon atoms is more preferable.
The alkenylene group is not particularly limited, but an alkenylene group having 2 to 10 carbon atoms is preferred.
The alkynylene group is not particularly limited, but an alkynylene group having 2 to 10 carbon atoms is preferred.

The cycloalkylene group is not particularly limited, but a cycloalkylene group having 3 to 10 carbon atoms is preferred. Note that the carbon atoms constituting the cycloalkylene group may be replaced with -C(=O)-.

The divalent aromatic group may be an aryl group, an aralkyl group, a group obtained by removing one hydrogen atom from a heterocyclic group, or the like. The aryl group is an aryl group having 6 to 15 carbon atoms, and specifically, preferred examples include phenyl group, tolyl group, naphthyl group, and anthryl group. The aralkyl group is preferably an aralkyl group having 6 to 20 carbon atoms, more preferably an aralkyl group having 7 to 12 carbon atoms. Specific examples include benzyl group, phenethyl group, naphthylmethyl group, naphthylethyl group, and the like. The heterocyclic group is preferably a heterocyclic group having 6 to 20 carbon atoms, more preferably a heterocyclic group having 6 to 12 carbon atoms. Examples include thienyl group, furanyl group, pyridinyl group, and benzofuranyl group.

The above divalent linking group may further have a substituent. Specific examples of further substituents include, for example, alkyl groups, alkenyl groups, cycloalkyl groups, aryl groups, amino groups, amide groups, ureido groups, urethane groups, hydroxy groups, carboxy groups, halogen atoms, alkoxy groups, and thioether groups. , an acyl group, an acyloxy group, an alkoxycarbonyl group, a cyano group, a nitro group, a group obtained by removing one of R ₁ to R ₅ of the anion moiety in the above general formula (1), and two types thereof. Combinations of the above may be mentioned.
Examples of the (m+1)-valent linking group of A include a group obtained by removing (m-1) hydrogen atoms from a divalent linking group.

More preferably, A is a divalent aromatic group.

In formula (A2), R ₆ represents a substituent having a carbon atom.
Examples of the substituent having a carbon atom represented by R ₆ include an alkyl group, an alkenyl group, an alkynyl group, a cycloalkyl group, and an aromatic group.
The alkyl group represented by R ₆ is preferably a linear or branched alkyl group, more preferably an alkyl group having 1 to 10 carbon atoms, and even more preferably an alkyl group having 1 to 3 carbon atoms.
The alkenyl group represented by R ₆ is preferably an alkenyl group having 2 to 10 carbon atoms.
The alkynyl group represented by R ₆ is preferably an alkynyl group having 2 to 10 carbon atoms.
The cycloalkyl group represented by R ₆ is preferably a cycloalkyl group having 3 to 10 carbon atoms, and more preferably a cyclohexyl group.
Examples of the aromatic group represented by R ₆ include an aryl group, an aralkyl group, and a heterocyclic group, with an aryl group being preferred. The aryl group is preferably an aryl group having 6 to 15 carbon atoms, more preferably a phenyl group or a naphthyl group.
The substituent having a carbon atom represented by R ₆ may further have a substituent. The further substituent is not particularly limited, but a halogen atom is preferable, and a fluorine atom and a chlorine atom are more preferable.
R ₆ is preferably an alkyl group, a cycloalkyl group, or an aryl group, and more preferably an alkyl group or an aryl group.

R ₆ may be combined with A or L to form a ring.
The ring formed by R ₆ bonding with A or L is not particularly limited, but examples include 5- to 10-membered rings, with 5- or 6-membered rings being more preferred.

In formula (A2), L represents a single bond, a carbonyl bond, an alkylene group, or a divalent aromatic group.
Preferred examples of the alkylene group and divalent aromatic group represented by L include the alkylene group and divalent aromatic group represented by A.

In addition, when Y in general formula (R-1) is represented by the above formula (A2) and L is a single bond, nitrogen in formula (A2) in A in general formula (R-1) The group linked to the atom is not -S(=O) ₂ -.

In formula (A3), R ₇ represents a substituent having a carbon atom.
Examples of the substituent having a carbon atom represented by R ₇ include an alkyl group, an alkenyl group, an alkynyl group, a cycloalkyl group, or an aromatic group, and the alkyl group, alkenyl group, alkynyl group represented by R ₆ above, Preferred examples include cycloalkyl groups and aromatic groups.
The substituent having a carbon atom represented by R ₇ may further have a substituent. The further substituent is not particularly limited, but a halogen atom is preferable, and a fluorine atom and a chlorine atom are more preferable.
R ₇ is preferably an alkyl group, a cycloalkyl group, or an aryl group, and more preferably an alkyl group.

R ₇ may combine with A to form a ring.
The ring formed by R ₇ bonding with A is not particularly limited, but examples include 5- to 10-membered rings, with 5- or 6-membered rings being more preferred.

In formula (A4), R ₈ represents a substituent having a carbon atom.
_Examples of the substituent having a carbon atom represented by R ₈ include an alkyl group, an alkenyl group, an alkynyl group, a cycloalkyl group, or an aromatic group; Preferred examples include alkyl groups and aromatic groups.
The substituent having a carbon atom represented by R ₈ may further have a substituent. The further substituent is not particularly limited, but a halogen atom is preferable, and a fluorine atom and a chlorine atom are more preferable.
R ₈ is preferably an alkyl group, a cycloalkyl group, or an aryl group.

R ₈ may combine with A to form a ring.
The ring formed by bonding R ₈ with A is not particularly limited, but examples include 6- to 10-membered rings, with 6-membered rings being preferred.

In formula (A5), R ₉ and R _9' each independently represent a hydrogen atom or a substituent.
Examples of the substituent represented by R ₉ and R _9' include an alkyl group, a cycloalkyl group, or an aryl group, and preferably an alkyl group, a cycloalkyl group, and an aryl group represented by R ₆ .
The substituents represented by R ₉ and R _9' may further have a substituent. The further substituent is not particularly limited, but a halogen atom is preferable, and a fluorine atom and a chlorine atom are more preferable.
R ₉ and R _9' are preferably a hydrogen atom or an alkyl group, more preferably a hydrogen atom or a methyl group.

R ₉ and R _9' may be combined with each other to form a ring.
The ring formed by R ₉ and R _9' bonding to each other is not particularly limited, but includes a 3- to 10-membered ring, preferably a 4- to 8-membered ring, and a 5- or 6-membered ring. More preferred.

Y is more preferably a group represented by any of the above formulas (A1) to (A4), particularly preferably a group represented by formula (A1) or formula (A6).

m represents an integer of 1 or more. The upper limit of m is not particularly limited, but is, for example, 5.
m is preferably an integer of 1 to 3, more preferably an integer of 1 to 2, and even more preferably 1.

Here, the number of anionic groups in the anion part of general formula (1) is the number of Y plus 1, which is 2 or more. The number of anionic groups in the anion moiety represents the valence of the anion moiety of the compound represented by general formula (1).
The upper limit of the number of anionic groups in the anion part of general formula (1) is not particularly limited, but is, for example, 6.
The number of anionic groups (the valence of the anion moiety) is preferably an integer of 2 to 4, more preferably an integer of 2 to 3, and even more preferably 2.

In general formula (1), M ⁿ⁺ represents a cation moiety.
The cation part of general formula (1), ie, n in M ⁿ⁺ , represents the valence of the cation part of the compound represented by general formula (1).
The valence of the anion moiety and the cation moiety are the same number.
The cation moiety of general formula (1) may be composed of only one type of cation, or may be composed of two or more types of cations, as long as it is n-valent. For example, when n is 4, M ⁿ⁺ may include one tetravalent cation or four monovalent cations. In any case, M ⁿ⁺ as a whole may be n-valent.

n represents an integer of 2 or more. The upper limit of n is not particularly limited, but is, for example, 6.
n is preferably an integer of 2 to 4, more preferably an integer of 2 to 3, and even more preferably 2.

M ⁿ⁺ is not particularly limited, but is preferably a cation represented by (M ⁺ )n. That is, it is preferable to have n monovalent cations. At this time, the plurality of M ⁺ may be the same or different.
In another preferred embodiment, it is also preferable that a plurality of M ⁺ be a divalent or higher cation formed by bonding via a single bond or a linking group.

The cation as M ⁺ in (M ⁺ )n is not particularly limited, but an onium cation is preferable, and a cation represented by the following general formula (ZIA) or general formula (ZIIA) is preferable.

In the above general formula (ZIA),
R ₂₀₁ , R ₂₀₂ and R ₂₀₃ each independently represent a hydrogen atom or a substituent.
The substituents for R ₂₀₁ , R ₂₀₂ and R ₂₀₃ are preferably organic groups, and the organic group generally has 1 to 30 carbon atoms, preferably 1 to 20 carbon atoms.
Furthermore, two of R ₂₀₁ to R ₂₀₃ may be bonded to each other to form a ring (also referred to as a ring structure), and the ring may contain an oxygen atom, a sulfur atom, an ester bond, an amide bond, or a carbonyl group. You can stay there. Examples of the group formed by two of R ₂₀₁ to R ₂₀₃ bonding to each other include an alkylene group (e.g., butylene group, pentylene group) and -CH ₂ -CH ₂ -O-CH ₂ -CH ₂ - .

Preferred embodiments of the cation as general formula (ZIA) include cation (ZI-11), cation (ZI-12), and cation (cation (ZI-13)) represented by general formula (ZI-13), which will be described later. ) and a cation (cation (ZI-14)) represented by the general formula (ZI-14).
The divalent or higher cation in the case where n is 2 or more may be a cation having a plurality of structures represented by the general formula (ZIA). Such cations include, for example, at least one of the cations R ₂₀₁ to R 203 represented by the general formula (ZIA) and at least one of R ₂₀₁ to _{R 203 of} the other cation represented by the general formula (ZIA). Examples include divalent cations having a structure in which at least one of them is bonded via a single bond or a linking group.

First, the cation (ZI-11) will be explained.
The cation (ZI-11) is a cation in which at least one of R ₂₀₁ to R ₂₀₃ in the above general formula (ZIA) is an aryl group, that is, an arylsulfonium cation.
In the arylsulfonium cation, all of R ₂₀₁ to R ₂₀₃ may be an aryl group, or some of R ₂₀₁ to R ₂₀₃ may be an aryl group, and the remainder may be an alkyl group or a cycloalkyl group.
Examples of the arylsulfonium cation include triarylsulfonium cation, diarylalkylsulfonium cation, aryldialkylsulfonium cation, diarylcycloalkylsulfonium cation, and aryldicycloalkylsulfonium cation.

The aryl group contained in the arylsulfonium cation is preferably a phenyl group or a naphthyl group, and more preferably a phenyl group. The aryl group may be an aryl group having a heterocyclic structure containing an oxygen atom, a nitrogen atom, a sulfur atom, or the like. Examples of the heterocyclic structure include pyrrole residue, furan residue, thiophene residue, indole residue, benzofuran residue, and benzothiophene residue. When the arylsulfonium cation has two or more aryl groups, the two or more aryl groups may be the same or different.
The alkyl group or cycloalkyl group that the arylsulfonium cation has as necessary is a linear alkyl group having 1 to 15 carbon atoms, a branched alkyl group having 3 to 15 carbon atoms, or a branched alkyl group having 3 to 15 carbon atoms. Preferred are cycloalkyl groups such as methyl group, ethyl group, propyl group, n-butyl group, sec-butyl group, t-butyl group, cyclopropyl group, cyclobutyl group, and cyclohexyl group.

The aryl group, alkyl group, and cycloalkyl group of R ₂₀₁ to R ₂₀₃ each independently represent an alkyl group (for example, carbon number 1 to 15), a cycloalkyl group (for example, carbon number 3 to 15), an aryl group (for example, carbon number 6 to 14), an alkoxy group (eg, carbon number 1 to 15), a halogen atom, a hydroxyl group, a lactone ring group, or a phenylthio group as a substituent.
Examples of the lactone ring group include groups obtained by removing a hydrogen atom from a structure represented by any of (KA-1-1) to (KA-1-17) described below.

Next, the cation (ZI-12) will be explained.
The cation (ZI-12) is a compound in which R ₂₀₁ to R ₂₀₃ in formula (ZIA) each independently represent an organic group having no aromatic ring. Here, the aromatic ring includes an aromatic ring containing a hetero atom.
The organic group having no aromatic ring as R ₂₀₁ to R ₂₀₃ generally has 1 to 30 carbon atoms, preferably 1 to 20 carbon atoms.
R ₂₀₁ to R ₂₀₃ are each independently preferably an alkyl group, a cycloalkyl group, an allyl group, or a vinyl group, more preferably a linear or branched 2-oxoalkyl group, a 2-oxocyclo An alkyl group or an alkoxycarbonylmethyl group, more preferably a linear or branched 2-oxoalkyl group.

The alkyl group and cycloalkyl group of R ₂₀₁ to R ₂₀₃ are preferably a linear alkyl group having 1 to 10 carbon atoms or a branched alkyl group having 3 to 10 carbon atoms (for example, a methyl group, an ethyl group, (propyl group, butyl group, pentyl group), and cycloalkyl groups having 3 to 10 carbon atoms (eg, cyclopentyl group, cyclohexyl group, and norbornyl group).
R ₂₀₁ to R ₂₀₃ may be further substituted with a halogen atom, an alkoxy group (eg, having 1 to 5 carbon atoms), a hydroxyl group, a cyano group, or a nitro group.

Next, the cation (ZI-13) will be explained.

In general formula (ZI-13), M represents an alkyl group, a cycloalkyl group, or an aryl group, and when it has a ring structure, the ring structure includes an oxygen atom, a sulfur atom, an ester bond, an amide bond, and a carbon - May contain at least one carbon double bond. R _1c and R _2c each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, a cyano group, or an aryl group. R _1c and R _2c may be combined to form a ring. R _x and R _y each independently represent an alkyl group, a cycloalkyl group, or an alkenyl group. R _x and R _y may be combined to form a ring. Furthermore, at least two selected from M, R _1c and R _2c may be combined to form a ring structure, and the ring structure may include a carbon-carbon double bond.

In the general formula (ZI-13), the alkyl group and cycloalkyl group represented by M include a linear alkyl group having 1 to 15 carbon atoms (preferably 1 to 10 carbon atoms), a linear alkyl group having 3 to 15 carbon atoms ( Preferably a branched alkyl group having 3 to 10 carbon atoms, or a cycloalkyl group having 3 to 15 carbon atoms (preferably 1 to 10 carbon atoms), specifically a methyl group, an ethyl group, a propyl group. , n-butyl group, sec-butyl group, t-butyl group, cyclopropyl group, cyclobutyl group, cyclohexyl group, and norbornyl group.
The aryl group represented by M is preferably a phenyl group or a naphthyl group, and more preferably a phenyl group. The aryl group may be an aryl group having a heterocyclic structure having an oxygen atom, a sulfur atom, or the like. Examples of the heterocyclic structure include a furan ring, a thiophene ring, a benzofuran ring, and a benzothiophene ring.

The above M may further have a substituent. In this embodiment, for example, M may be a benzyl group.
Note that when M has a ring structure, the ring structure may include at least one of an oxygen atom, a sulfur atom, an ester bond, an amide bond, and a carbon-carbon double bond.

As the alkyl group, cycloalkyl group, and aryl group represented by R _1c and R _2c , the same ones as M mentioned above can be mentioned, and the preferred embodiments thereof are also the same. Furthermore, R _1c and R _2c may be combined to form a ring.
Examples of the halogen atom represented by R _1c and R _2c include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

As the alkyl group and cycloalkyl group represented by R _x and R _y , the same ones as M mentioned above can be mentioned, and the preferred embodiments thereof are also the same.
The alkenyl group represented by R _x and R _y is preferably an allyl group or a vinyl group.
The above R _x and R _y may further have a substituent. Examples of this embodiment include a 2-oxoalkyl group or an alkoxycarbonylalkyl group as R _x and R _y .
Examples of the 2-oxoalkyl group represented by R _x and R _y include those having 1 to 15 carbon atoms (preferably 1 to 10 carbon atoms), and specifically, 2-oxopropyl group, and 2-oxobutyl group.
Examples of the alkoxycarbonylalkyl group represented by R _x and R _y include those having 1 to 15 carbon atoms (preferably 1 to 10 carbon atoms). Furthermore, R _x and R _y may be combined to form a ring.
The ring structure formed by connecting R _x and R _y to each other may contain an oxygen atom, a sulfur atom, an ester bond, an amide bond, or a carbon-carbon double bond.

In general formula (ZI-13), M and R _1c may be combined to form a ring structure, and the formed ring structure may contain a carbon-carbon double bond.

Among others, the cation (ZI-13) is preferably a cation (ZI-13A).
The cation (ZI-13A) is a phenacylsulfonium cation represented by the following general formula (ZI-13A).

In the general formula (ZI-13A),
R _1c to R _5c each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an alkoxy group, an aryloxy group, an alkoxycarbonyl group, an alkylcarbonyloxy group, a cycloalkylcarbonyloxy group, a halogen atom, and a hydroxyl group. , represents a nitro group, an alkylthio group or an arylthio group.
R _6c and R _7c have the same meanings as R _1c and R _2c in the above-mentioned general formula (ZI-13), and their preferred embodiments are also the same.
R _x and R _y have the same meanings as R _x and R _y in the above-mentioned general formula (ZI-13), and their preferred embodiments are also the same.

Any two or more of R _1c to R _5c , R _x and R _y , may be bonded to each other to form a ring structure, and this ring structure may each independently contain an oxygen atom, a sulfur atom, an ester bond, It may contain an amide bond or a carbon-carbon double bond. Further, R _5c and R _6c , R _5c and R _x may each be combined to form a ring structure, and this ring structure may each independently contain a carbon-carbon double bond. Further, R _6c and R _7c may be bonded to each other to form a ring structure.
Examples of the ring structure include aromatic or non-aromatic hydrocarbon rings, aromatic or non-aromatic heterocycles, and polycyclic condensed rings formed by combining two or more of these rings. The ring structure includes a 3- to 10-membered ring, preferably a 4- to 8-membered ring, and more preferably a 5- or 6-membered ring.

Examples of the group formed by combining any two or more of R _1c to R _5c , R _6c and R _7c , and R _x and R _y include a butylene group, a pentylene group, and the like.
The group formed by bonding R _5c and R _6c and R _5c and R _x is preferably a single bond or an alkylene group. Examples of the alkylene group include a methylene group and an ethylene group.

Next, the cation (ZI-14) will be explained.
The cation (ZI-14) is represented by the following general formula (ZI-14).

In general formula (ZI-14),
l represents an integer from 0 to 2.
r represents an integer from 0 to 8.
R ₁₃ represents a hydrogen atom, a fluorine atom, a hydroxyl group, an alkyl group, a cycloalkyl group, an alkoxy group, an alkoxycarbonyl group, or a group having a monocyclic or polycyclic cycloalkyl skeleton. These groups may have substituents.
When multiple _R14s exist, each independently represents an alkyl group, a cycloalkyl group, an alkoxy group, an alkylsulfonyl group, a cycloalkylsulfonyl group, an alkylcarbonyl group, an alkoxycarbonyl group, or a monocyclic or polycyclic cycloalkyl group. Represents an alkoxy group having a skeleton. These groups may have substituents.
Each R ₁₅ independently represents an alkyl group, a cycloalkyl group, or a naphthyl group. These groups may have substituents. Two R _15s may be bonded to each other to form a ring. When two R _15s combine with each other to form a ring, the ring skeleton may contain a heteroatom such as an oxygen atom or a nitrogen atom. In one embodiment, two R _15s are alkylene groups and are preferably bonded to each other to form a ring structure.

In general formula (ZI-14), the alkyl groups of R ₁₃ , R ₁₄ and R ₁₅ are linear or branched. The number of carbon atoms in the alkyl group is preferably 1 to 10. As the alkyl group, a methyl group, ethyl group, n-butyl group, or t-butyl group is more preferable.

Next, general formula (ZIIA) will be explained.
In general formula (ZIIA), R ₂₀₄ and R ₂₀₅ each independently represent an aryl group, an alkyl group, or a cycloalkyl group.
The aryl group for R ₂₀₄ and R ₂₀₅ is preferably a phenyl group or a naphthyl group, and more preferably a phenyl group. The aryl group of R ₂₀₄ and R ₂₀₅ may be an aryl group having a heterocyclic structure containing an oxygen atom, a nitrogen atom, a sulfur atom, or the like. Examples of the skeleton of the aryl group having a heterocyclic structure include pyrrole, furan, thiophene, indole, benzofuran, and benzothiophene.
The alkyl group and cycloalkyl group of R ₂₀₄ and R ₂₀₅ include a linear alkyl group having 1 to 10 carbon atoms or a branched alkyl group having 3 to 10 carbon atoms (for example, a methyl group, an ethyl group, a propyl group, butyl group, pentyl group), or a cycloalkyl group having 3 to 10 carbon atoms (eg, cyclopentyl group, cyclohexyl group, and norbornyl group).

The aryl group, alkyl group, and cycloalkyl group of R ₂₀₄ and R ₂₀₅ may each independently have a substituent. Examples of substituents that the aryl group, alkyl group, and cycloalkyl group of R ₂₀₄ to R ₂₀₇ may have include an alkyl group (for example, having 1 to 15 carbon atoms), a cycloalkyl group (for example, having 3 to 15 carbon atoms), 15), an aryl group (for example, having 6 to 15 carbon atoms), an alkoxy group (for example, having 1 to 15 carbon atoms), a halogen atom, a hydroxyl group, a lactone ring group, and a phenylthio group.
Examples of the lactone ring group include groups obtained by removing a hydrogen atom from a structure represented by any of (KA-1-1) to (KA-1-17) described below.

Preferred examples of the cation as M ⁺ in (M ⁺ )n are shown below, but the present invention is not limited thereto. Me represents a methyl group.

<Compound represented by general formula (2)>
The compound represented by the above general formula (1) is preferably a compound represented by the following general formula (2).

In general formula (2), R ₁ to R ₅ each independently represent a hydrogen atom or a substituent. At least one of R ₁ to R ₅ represents a group represented by the above general formula (R-1).
R ₁₀₁ to R ₁₀₃ each independently represent a hydrogen atom or a substituent. Two of R ₁₀₁ to R ₁₀₃ may be bonded to each other to form a ring.
n represents an integer of 2 or more, and R ₁₀₁ s, R ₁₀₂ s, and R _103s may be the same or different.

R ₁ to R ₅ in general formula (2) have the same meanings as R ₁ to R ₅ in general formula (1) above, and preferred examples are also the same.

R ₁₀₁ to R ₁₀₃ in general formula (2) have the same meanings as R ₂₀₁ to R ₂₀₃ in general formula (ZIA) above, and preferred examples are also the same.

n in general formula (2) has the same meaning as n in general formula (1), and the preferred numerical range is also the same.

<Compound represented by general formula (3)>
The compound represented by the above general formula (2) is preferably a compound represented by the following general formula (3).

In general formula (3), Q ₁ and Q ₂ each independently represent a substituent.
R ₃ to R ₅ each independently represent a hydrogen atom or a substituent. At least one of R ₃ to R ₅ represents a group represented by the above general formula (R-1).
R ₁₀₁ to R ₁₀₃ each independently represent a hydrogen atom or a substituent. Two of R ₁₀₁ to R ₁₀₃ may be bonded to each other to form a ring.
n represents an integer of 2 or more, and R ₁₀₁ s, R ₁₀₂ s, and R _103s may be the same or different.

In general formula (3), R ₃ to R ₅ , R ₁₀₁ to R ₁₀₃ , and n have the same meanings as R ₃ to R ₅ , R ₁₀₁ to R ₁₀₃ , and n in general formula (2), and are preferred examples. The same is true.

In general formula (3), Q ₁ and Q ₂ each independently represent a substituent.
Examples of the substituents represented by Q ₁ and Q ₂ include the substituents represented by R ₁ to R ₅ in the above general formula (1), and Q ₁ and Q ₂ each independently represent an aliphatic hydrocarbon ring group, an aryl or a heteroaryl group, and more preferably an aryl group.

Specifically, the aliphatic hydrocarbon ring group, aryl group, and heteroaryl group represented by Q ₁ and Q ₂ include the aliphatic hydrocarbon ring group, aryl group, and heteroaryl group as R ₁ to R ₅ above. Groups may be mentioned, and preferred examples are also the same.

In general formula (3), Q ₁ and Q ₂ are at the 2nd and 6th positions, respectively, based on the carbon atom bonded to the sulfonate anion, and therefore can be said to be adjacent positions to the sulfonate anion. Therefore, it is considered that when bulky substituents are used as Q ₁ and Q ₂ , they can function as a steric hindrance group for the sulfonic acid anion. As a result, the acid generated by the compound (B) having such a sulfonic acid anion in the exposed area becomes difficult to diffuse excessively into the unexposed area, and it is presumed that the resolution is further improved.

The substituents represented by Q ₁ and Q ₂ are also preferably groups represented by the following general formulas (QR-1) to (QR-3).

In the general formulas (QR-1) to (QR-3), R _Q6 to R _Q27 each independently represent a hydrogen atom or a substituent.
In general formula (QR-1), at least two of R _Q6 to R _Q13 may be bonded to each other to form a ring.
In general formula (QR-2), at least two of R _Q14 to R _Q18 may be bonded to each other to form a ring.
In general formula (QR-3), at least two of R _Q19 to R _Q27 may be bonded to each other to form a ring. * represents a bond with the benzene ring in general formula (3).

The substituents for R _Q6 to R _Q27 are not particularly limited as long as they are monovalent substituents, but include, for example, an alkyl group; an alkenyl group; a cycloalkyl group; an aryl group; a halogen atom; an oxygen atom, a sulfur atom, and a nitrogen atom. Examples include groups containing atoms and heteroatoms such as silicon atoms; and combinations of two or more thereof.

Examples of the alkyl groups as R _Q6 to R _Q27 include alkyl groups having 1 to 30 carbon atoms. Preferably, the alkyl group is an alkyl group having 1 to 20 carbon atoms, such as a methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, sec-butyl group, hexyl group, 2-ethylhexyl group, octyl group, or dodecyl group. More preferably, it is an alkyl group having 1 to 8 carbon atoms.

Examples of the alkenyl groups as R _Q6 to R _Q27 include alkenyl groups having 1 to 20 carbon atoms, and alkenyl groups having 1 to 8 carbon atoms are preferable.
The cycloalkyl groups as R _Q6 to R _Q27 may be monocyclic or polycyclic. The number of carbon atoms in this cycloalkyl group is not particularly limited, but is preferably 3 to 8.

Examples of the aryl group as R _Q6 to R _Q27 include aryl groups having 6 to 15 carbon atoms, and specifically, preferred examples include phenyl group, naphthyl group, anthryl group, etc. can.
Examples of the halogen atom as R _Q6 to R _Q27 include a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, and the like.

Examples of groups containing a hetero atom as R _Q6 to R _Q27 include hydroxyl group, carboxyl group, alkoxy group, thiol group, thioether group, nitro group, nitroso group, cyano group, amino group, acyloxy group, acylamido group, and ether group. Examples include bonds, carbonyl bonds, and combinations of two or more thereof.

The number of carbon atoms in the alkoxy group, acyloxy group and acylamido group is preferably 20 or less, more preferably 8 or less. Examples of the alkoxy group include methoxy group, ethoxy group, propoxy group, isopropoxy group, n-butyloxy group, t-butoxy group and octyloxy group. Among these, methoxy, ethoxy, propoxy, isopropoxy and t-butoxy groups are particularly preferred. In addition, as for the thioether group, the same ones as the alkoxy group can be mentioned, except that a sulfur atom is used instead of an oxygen atom. Examples of the acyloxy group include an acetyloxy group. Examples of the acylamide group include an acetylamide group.

Alkyl groups; alkenyl groups; cycloalkyl groups; aryl groups; groups containing heteroatoms such as oxygen atoms, sulfur atoms, nitrogen atoms, and silicon atoms as substituents for R _Q6 to R _Q27 further have a substituent. It's okay. Additional substituents include, for example, alkyl groups, alkenyl groups, cycloalkyl groups, aryl groups, amino groups, amido groups, ureido groups, urethane groups, hydroxy groups, carboxy groups, halogen atoms, alkoxy groups, thioether groups, acyl groups, etc. group, an acyloxy group, an alkoxycarbonyl group, a cyano group, a nitro group, and a combination of two or more thereof.

In general formula (QR-1), at least two of R _Q6 to R _Q13 may be combined to form a ring. In general formula (QR-2), at least two of R _Q14 to R _Q18 may be combined to form a ring. Furthermore, in general formula (QR-3), at least two of R _Q19 to R _Q27 may be combined to form a ring.

In the above general formula (QR-1), at least two of R _Q6 to R _Q13 are bonded to form a ring, and in the above general formula (QR-2), at least two of R _Q14 to R _Q18 are a bond and in the general formula (QR-3), at least two of R _Q19 to R _Q27 are aromatic or non-aromatic, although the ring formed by combining is not particularly limited. Examples include a hydrocarbon ring of a group (eg, aliphatic), an aromatic or non-aromatic heterocycle, and a polycyclic condensed ring formed by combining two or more of these rings. The ring structure (in the case of a polycyclic condensed ring, the monocyclic ring structure constituting it) includes a 3- to 10-membered ring, preferably a 4- to 8-membered ring, and more preferably a 5- or 6-membered ring.

At least one of the above R _Q6 to R _Q27 is a group containing a polar group, a group containing a group that decomposes under the action of an acid and increases in polarity, or a group that decomposes under the action of an alkaline developer and is A group containing a group that increases solubility is preferred.
A polar group in a group containing a polar group as R _Q6 to R _Q27 , a group that decomposes and increases polarity by the action of an acid in a group containing a group that decomposes and increases polarity by the action of an acid, and a group that decomposes and increases polarity by the action of an alkaline developer. Specifically, a group that decomposes and increases its solubility in an alkaline developer by the action of an alkaline developer in a group that decomposes and increases its solubility in an alkaline developer is represented by the general formula ( In the group represented by Ar), as at least one of R ₁₀ to R ₁₄ , a polar group in a group containing a polar group, a group containing a group whose polarity increases when decomposed by the action of an acid, due to the action of an acid. A group that decomposes and increases polarity, and a group that decomposes under the action of an alkaline developer and increases its solubility in the alkaline developer is decomposed by the action of an alkaline developer, and its solubility in the alkaline developer increases. Mention may be made of increasing groups.

In the above general formula (3), it is preferable that Q ₁ and Q ₂ are groups each represented by the following general formula (Ar).

In the general formula (Ar), R ₁₀ to R ₁₄ each independently represent a hydrogen atom or a substituent. At least one of R ₁₀ to R ₁₄ is a group containing a polar group, a group containing a group whose polarity increases when decomposed by the action of an acid, or a group which decomposes by the action of an alkaline developer and has solubility in the alkaline developer. It is a group containing a group in which .
* represents a bond to the benzene ring in general formula (3).

In the general formula (Ar), R ₁₀ to R ₁₄ each independently represent a hydrogen atom or a substituent.
When R ₁₀ to R ₁₄ represent a substituent, examples of the substituent include an alkyl group; an alkenyl group; an aliphatic hydrocarbon ring group; an aryl group; a halogen atom; an oxygen atom, a sulfur atom, a nitrogen atom, a silicon atom, etc. and combinations of two or more of these; specifically, alkyl groups as R ₁ to R ₅ in general formula (1); alkenyl groups; aliphatic hydrocarbon ring groups; ; an aryl group; a halogen atom; a group containing a heteroatom such as an oxygen atom, a sulfur atom, a nitrogen atom, and a silicon atom; and combinations of two or more thereof.
R ₁₀ to R ₁₄ are preferably groups containing a hydrogen atom or a hetero atom, a group containing a polar group, a group containing a group whose polarity increases when decomposed by the action of an acid, and a group which decomposes by the action of an alkaline developer, It is preferable that the group other than the group containing the group that increases solubility in an alkaline developer is a hydrogen atom.

In the above general formula (Ar), at least one of R ₁₀ to R ₁₄ is a group containing a polar group, a group containing a group whose polarity increases when decomposed by the action of an acid, or a group which decomposes by the action of an alkaline developer. , a group containing a group that increases solubility in an alkaline developer. By using the above groups, development defects can be further reduced.

(Group containing polar group)
Examples of the polar group in the group containing a polar group as at least one of R ₁₀ to R ₁₄ include a carboxyl group, a phenolic hydroxyl group, a fluorinated alcohol group, a sulfonamide group, a sulfonylimide group, and an (alkylsulfonyl) group. (alkylcarbonyl)methylene group, (alkylsulfonyl)(alkylcarbonyl)imide group, bis(alkylcarbonyl)methylene group, bis(alkylcarbonyl)imide group, bis(alkylsulfonyl)methylene group, bis(alkylsulfonyl)imide group, Examples include acidic groups such as a tris(alkylcarbonyl)methylene group and a tris(alkylsulfonyl)methylene group, and alcoholic hydroxyl groups.

In addition, alcoholic hydroxyl group refers to a hydroxyl group bonded to a hydrocarbon group other than a hydroxyl group directly bonded to an aromatic ring (phenolic hydroxyl group), and the hydroxyl group is an electron-withdrawing group such as a fluorine atom at the α position of the hydroxyl group. Excludes aliphatic alcohols substituted with functional groups (for example, hexafluoroisopropanol groups, etc.). The alcoholic hydroxyl group is preferably a hydroxyl group having a pKa (acid dissociation constant) of 12 or more and 20 or less.
Among these, as the polar group, a carboxyl group, a phenolic hydroxyl group, or a fluorinated alcohol group (preferably a hexafluoroisopropanol group) is preferable.

Examples of the group containing a polar group include a group having a carbonyl bond.
Examples of the group having a carbonyl bond include an alkylcarbonyl group and an arylcarbonyl group.
Examples of the alkyl group include the same alkyl groups as R ₁ to R ₅ .
Examples of the aryl group include the same aryl groups as R ₁ to R ₅ .
A group having a carbonyl bond is a group in which a carbonyl bond and an ether bond are not bonded adjacently.

The alkylcarbonyl group and arylcarbonyl group as a group having a carbonyl bond may further have a substituent.
Further substituents include, for example, alkyl groups; alkenyl groups; cycloalkyl groups; aryl groups; halogen atoms; groups containing heteroatoms such as oxygen atoms, sulfur atoms, nitrogen atoms, and silicon atoms; and two or more of these. A combination of these can be mentioned.
Alkyl group; alkenyl group; cycloalkyl group; aryl group; halogen atom; group _containing heteroatoms such as oxygen atom, sulfur atom, nitrogen atom and silicon atom; In specific examples of the substituent as _R5 , alkyl groups; alkenyl groups; cycloalkyl groups; aryl groups; halogen atoms; groups containing heteroatoms such as oxygen atoms, sulfur atoms, nitrogen atoms, and silicon atoms; and 2 of these It is the same as a combination of more than one species.

Examples of the group containing a polar group include, but are not particularly limited to, organic groups containing a polar group. Examples of organic groups containing polar groups include alkyl groups; alkenyl groups; cycloalkyl groups; aryl groups; halogen atoms; groups containing heteroatoms such as oxygen atoms, sulfur atoms, nitrogen atoms, and silicon atoms; Examples include a combination of more than one species and a group having a polar group.
Alkyl group; alkenyl group; cycloalkyl group; aryl group; halogen atom; group _containing heteroatoms such as oxygen atom, sulfur atom, nitrogen atom and silicon atom; In specific examples of the substituent as _R5 , alkyl groups; alkenyl groups; cycloalkyl groups; aryl groups; halogen atoms; groups containing heteroatoms such as oxygen atoms, sulfur atoms, nitrogen atoms, and silicon atoms; and 2 of these It is the same as a combination of more than one species.

Examples of the group containing a polar group include an alkyl group containing a polar group and an aryl group containing a polar group.
Examples of the alkyl group in the alkyl group containing a polar group include the same alkyl groups as R ₁ to R ₅ .
Examples of the aryl group in the aryl group containing a polar group include the same aryl groups as R ₁ to R ₅ .
Further, the group containing a polar group may be the polar group itself.

(Group containing a group that decomposes and increases polarity by the action of acid)
At least one of R ₁₀ to R ₁₄ is a group that decomposes and increases in polarity due to the action of an acid in a group that decomposes and increases in polarity due to the action of an acid (hereinafter also referred to as an "acid-decomposable group") ) preferably has a structure in which the polar group is protected by a group (leaving group) that decomposes and leaves under the action of an acid.
Examples of the polar group include the same polar groups as in the group containing a polar group as at least one of R ₁₀ to R ₁₄ .

Examples of groups that decompose and leave by the action of acids (leaving groups) include groups represented by formulas (Y1) to (Y4).
Formula (Y1): -C(Rx ₁ )(Rx ₂ )(Rx ₃ )
Formula (Y2): -C(=O)OC(Rx ₁ )(Rx ₂ )(Rx ₃ )
Formula (Y3): -C(R ₃₆ )(R ₃₇ )(OR ₃₈ )
Formula (Y4): -C(Rn)(H)(Ar)

In formulas (Y1) and (Y2), Rx ₁ to Rx ₃ each independently represent an alkyl group (linear or branched) or a cycloalkyl group (monocyclic or polycyclic). Note that when all of Rx ₁ to Rx ₃ are alkyl groups (linear or branched), it is preferable that at least two of Rx ₁ to Rx ₃ are methyl groups.
Among these, it is preferable that Rx ₁ to Rx ₃ each independently represent a linear or branched alkyl group, and Rx ₁ to Rx ₃ each independently represent a linear alkyl group. is more preferable.
Two of Rx ₁ to Rx ₃ may be combined to form a monocyclic ring or a polycyclic ring.
Examples of the alkyl groups of Rx ₁ to Rx ₃ include alkyl groups 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. preferable.
Examples of the cycloalkyl group for Rx ₁ to Rx ₃ include monocyclic cycloalkyl groups such as a cyclopentyl group and a cyclohexyl group, a norbornyl group, a tetracyclodecanyl group, a tetracyclododecanyl group, and an adamantyl group. A polycyclic cycloalkyl group is preferred.
The cycloalkyl group formed by bonding two of Rx ₁ to Rx ₃ includes monocyclic cycloalkyl groups such as cyclopentyl group and cyclohexyl group, norbornyl group, tetracyclodecanyl group, and tetracyclododecanyl group. Polycyclic cycloalkyl groups such as nyl group and adamantyl group are preferred, and monocyclic cycloalkyl groups having 5 to 6 carbon atoms are more preferred.
The cycloalkyl group formed by bonding two of Rx ₁ to Rx ₃ is, for example, a group in which one of the methylene groups constituting the ring has a hetero atom such as an oxygen atom or a hetero atom such as a carbonyl group. May be replaced.
The group represented by formula (Y1) or formula (Y2) is, for example, an embodiment in which Rx ₁ is a methyl group or an ethyl group, and Rx ₂ and Rx ₃ are bonded to form the above-mentioned cycloalkyl group. is preferred.

In formula (Y3), R ₃₆ to R ₃₈ each independently represent a hydrogen atom or a monovalent organic group. R ₃₇ and R ₃₈ may be combined with each other to form a ring. Examples of the monovalent organic group include an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, and an alkenyl group. It is also preferable that R ₃₆ is a hydrogen atom.

As formula (Y3), a group represented by the following formula (Y3-1) is preferable.

Here, L ₁ and L ₂ each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, or a group combining these (for example, a group combining an alkyl group and an aryl group). .
M represents a single bond or a divalent linking group.
Q is an alkyl group that may contain a hetero atom, a cycloalkyl group that may contain a hetero atom, an aryl group that may contain a hetero atom, an amino group, an ammonium group, a mercapto group, a cyano group, an aldehyde represents a group or a group combining these (for example, a group combining an alkyl group and a cycloalkyl group).
In the alkyl group and cycloalkyl group, for example, one of the methylene groups may be replaced with a hetero atom such as an oxygen atom, or a group having a hetero atom such as a carbonyl group.
It is preferable that one of L ₁ and L ₂ is a hydrogen atom, and the other is an alkyl group, a cycloalkyl group, an aryl group, or a combination of an alkylene group and an aryl group.
At least two of Q, M, and L ₁ may be combined to form a ring (preferably a 5-membered or 6-membered ring).
In terms of pattern refinement, _L2 is preferably a secondary or tertiary alkyl group, more preferably a tertiary alkyl group. Examples of the secondary alkyl group include an isopropyl group, cyclohexyl group, or norbornyl group, and examples of the tertiary alkyl group include a tert-butyl group or an adamantane group. In these embodiments, Tg (glass transition temperature) and activation energy are increased, so that in addition to ensuring film strength, fogging can be suppressed.

In formula (Y4), Ar represents an aromatic ring group. Rn represents an alkyl group, a cycloalkyl group or an aryl group. Rn and Ar may be bonded to each other to form a non-aromatic ring. Ar is more preferably an aryl group.

The acid-decomposable group preferably has an acetal structure. The acetal structure is a structure in which a polar group such as a carboxyl group, a phenolic hydroxyl group, or a fluorinated alcohol group is protected with a group represented by the above formula (Y3).

The group containing an acid-decomposable group is not particularly limited as long as it is a group containing an acid-decomposable group, and examples include organic groups containing an acid-decomposable group. Examples of organic groups containing acid-decomposable groups include alkyl groups; alkenyl groups; cycloalkyl groups; aryl groups; halogen atoms; groups containing heteroatoms such as oxygen atoms, sulfur atoms, nitrogen atoms, and silicon atoms; Examples include a combination of two or more of the following, which has an acid-decomposable group.
Alkyl group; alkenyl group; cycloalkyl group; aryl group; halogen atom; group _containing heteroatoms such as oxygen atom, sulfur atom, nitrogen atom and silicon atom; In specific examples of the substituent as _R5 , alkyl groups; alkenyl groups; cycloalkyl groups; aryl groups; halogen atoms; groups containing heteroatoms such as oxygen atoms, sulfur atoms, nitrogen atoms, and silicon atoms; and 2 of these It is the same as a combination of more than one species.

Examples of the group containing an acid-decomposable group include an alkyl group containing an acid-decomposable group and an aryl group containing an acid-decomposable group.
Examples of the alkyl group in the alkyl group containing an acid-decomposable group include the same alkyl groups as R ₁ to R ₅ .
Examples of the aryl group in the aryl group containing an acid-decomposable group include the same aryl groups as R ₁ to R ₅ .
Further, the group containing an acid-decomposable group may be the acid-decomposable group itself.

Among groups containing groups that decompose and increase polarity by the action of an acid, the group that decomposes and increases the polarity by the action of an acid is a group represented by the following general formula (T-1) and a group represented by the following general formula (T-2). ) is also preferable, and a group represented by the following general formula (T-1) is more preferable. It is thought that the group represented by the general formula (T-1) has high reactivity with acids and the reaction tends to proceed uniformly, resulting in particularly good LWR performance.

In general formula (T-1),
R _T11 represents a hydrogen atom or an alkyl group.
R _T12 represents a hydrogen atom, an alkyl group, a cycloalkyl group, or an aryl group, and the alkyl group and cycloalkyl group may contain an ether bond or a carbonyl bond.
R _T13 represents an alkyl group, a cycloalkyl group, or an aryl group, and the alkyl group and cycloalkyl group may contain an ether bond or a carbonyl bond.
R _T11 and R _T12 may be bonded to each other to form a ring.
R _T12 and R _T13 may be bonded to each other to form a ring.
* represents a bond.
In general formula (T-2),
R _T21 , R _T22 and R _T23 each independently represent an alkyl group.
Two of R _T21 to R _T23 may be bonded to each other to form a ring.
* represents a bond.

In general formula (T-1), R _T11 represents a hydrogen atom or an alkyl group.
When R _T11 represents an alkyl group, the alkyl group may be linear or branched, and preferably has 1 to 10 carbon atoms, more preferably 1 to 5 carbon atoms, and even more preferably 1 to 3 carbon atoms. It is the basis. Examples of the alkyl group include methyl group, ethyl group, propyl group, n-butyl group, sec-butyl group, hexyl group, and octyl group.
The above alkyl group may have a substituent, and examples of the substituent include further substituents that the substituents R ₁ to R ₅ above may have.
R _T11 is preferably a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and more preferably a hydrogen atom.

In general formula (T-1), R _T12 represents a hydrogen atom, an alkyl group, a cycloalkyl group, or an aryl group.
When R _T12 represents an alkyl group, the alkyl group may be linear or branched, preferably having 1 to 10 carbon atoms, more preferably 1 to 5 carbon atoms. Examples of the alkyl group include methyl group, ethyl group, propyl group, n-butyl group, sec-butyl group, hexyl group, and octyl group.
The above alkyl group may have a substituent, and examples of the substituent include further substituents that the substituents R ₁ to R ₅ above may have.
The alkyl group may contain an ether bond or a carbonyl bond.

When R _T12 represents a cycloalkyl group, the cycloalkyl group may be monocyclic or polycyclic, preferably having 3 to 20 carbon atoms, more preferably 5 to 15 carbon atoms, even more preferably 5 to 10 carbon atoms. It is a cycloalkyl group. Examples of the cycloalkyl group include cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cyclooctyl group, adamantyl group, norbornyl group, isobornyl group, camphanyl group, dicyclopentyl group, α-pinel group, tricyclo Examples include decanyl group, tetracyclododecyl group, androstannyl group, and the like.
The above cycloalkyl group may have a substituent, and examples of the substituent include further substituents that the substituents as R ₁ to R ₅ above may have.
The cycloalkyl group may contain an ether bond or a carbonyl bond.

When R _T12 represents an aryl group, the aryl group preferably has 6 to 20 carbon atoms, more preferably 6 to 15 carbon atoms, and still more preferably 6 to 10 carbon atoms. Examples of the aryl group include phenyl group and naphthyl group.
The above aryl group may have a substituent, and examples of the substituent include further substituents that the substituents R ₁ to R ₅ above may have.

It is preferable that R _T12 is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms.

In general formula (T-1), R _T13 represents an alkyl group, a cycloalkyl group, or an aryl group.
The alkyl group, cycloalkyl group, or aryl group represented by _RT13 is the same as the alkyl group, cycloalkyl group, or aryl group described as represented by _RT12 above.
R _T13 is preferably an alkyl group having 1 to 5 carbon atoms.

R _T11 and R _T12 may be bonded to each other to form a ring.
The ring formed by bonding R _T11 and R _T12 to each other is preferably an aliphatic ring.
The aliphatic ring is preferably a cycloalkane having 3 to 20 carbon atoms, more preferably a cycloalkane having 5 to 15 carbon atoms. The above cycloalkane may be monocyclic or polycyclic.
The above aliphatic ring may have a substituent, and examples of the substituent include further substituents that the substituents R ₁ to R ₅ above may have.
The aliphatic ring may have a heteroatom (eg, sulfur atom, oxygen atom, nitrogen atom, etc.) between carbon atoms.

R _T12 and R _T13 may be bonded to each other to form a ring.
The ring formed by bonding R _T12 and R _T13 to each other is preferably an aliphatic ring containing an oxygen atom as a ring member.
The aliphatic ring preferably has 3 to 20 carbon atoms, more preferably 5 to 15 carbon atoms. The aliphatic ring may be monocyclic or polycyclic.
The above aliphatic ring may have a substituent, and examples of the substituent include further substituents that the substituents R ₁ to R ₅ above may have.
The aliphatic ring may have a heteroatom other than an oxygen atom (eg, a sulfur atom, a nitrogen atom, etc.) between carbon atoms.

In the general formula (T-1), an embodiment in which R _T11 and R _T12 are not bonded to each other, and R _T12 and R _T13 are bonded to each other to form a ring is one of the preferred embodiments of the present invention. It is.

In general formula (T-2), R _T21 , R _T22 and R _T23 each independently represent an alkyl group.
When R _T21 , R _T22 and R _T23 represent an alkyl group, the alkyl group is not particularly limited and may be linear or branched. The alkyl group is preferably an alkyl group having 1 to 4 carbon atoms, such as a methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, or t-butyl group.
The above alkyl group may have a substituent. Examples of the substituent include an aryl group (for example, 6 to 15 carbon atoms), a halogen atom, a hydroxyl group, an alkoxy group (for example, 1 to 4 carbon atoms), a carboxy group, an alkoxycarbonyl group (for example, 2 to 6 carbon atoms), etc. Can be mentioned. The number of carbon atoms in the substituent is preferably 8 or less.

Two of R _T21 to R _T23 may be bonded to each other to form a ring.
When two of R _T21 to R _T23 bond to each other to form a ring, it is preferable that two of R _T21 to R _T23 bond to each other to form a cycloalkyl group. The above-mentioned cycloalkyl group may be a monocyclic cycloalkyl group such as a cyclopentyl group or a cyclohexyl group, or a polycyclic cycloalkyl group such as a norbornyl group, a tetracyclodecanyl group, a tetracyclododecanyl group, or an adamantyl group. good. Among these, monocyclic cycloalkyl groups having 5 to 6 carbon atoms are preferred.
In the above cycloalkyl group, for example, one of the methylene groups constituting the ring may be replaced with a hetero atom such as an oxygen atom, or a group having a hetero atom such as a carbonyl group.

(Group containing a group that decomposes by the action of an alkaline developer and increases its solubility in the alkaline developer)
At least one of R ₁₀ to R ₁₄ contains a group that decomposes under the action of an alkaline developer and increases its solubility in the alkaline developer. A group that increases the solubility in is also called a "polar conversion group", and specific examples include a lactone group, a carboxylic acid ester group (-COO-), an acid anhydride group (-C(O)OC(O) -), acid imide group (-NHCONH-), carboxylic acid thioester group (-COS-), carbonate ester group (-OC(O)O-), sulfuric acid ester group (-OSO ₂ O-), sulfonic acid ester group (-SO ₂ O-) and the like.

Examples of the group containing a polarity converting group include an acyloxy group, an alkoxycarbonyloxy group, an aryloxycarbonyloxy group, an aryloxycarbonyl group, an alkoxycarbonyl group, a carbamoyl group, and an imido group.

The number of carbon atoms in the acyl group in the acyloxy group is preferably 1 to 30, more preferably 1 to 8.
The number of carbon atoms in the alkoxy group in the alkoxycarbonyloxy group is preferably 1 to 30, more preferably 1 to 8.

The number of carbon atoms in the aryl group in the aryloxycarbonyloxy group is preferably 6 to 14, more preferably 6 to 10.
The number of carbon atoms in the aryl group in the aryloxycarbonyl group is preferably 6 to 14, more preferably 6 to 10.
The number of carbon atoms in the alkoxy group in the alkoxycarbonyl group is preferably 1 to 30, more preferably 1 to 8.
An imide group is a group obtained by removing one hydrogen atom from imide.

The acyloxy group, alkoxycarbonyloxy group, aryloxycarbonyloxy group, aryloxycarbonyl group, alkoxycarbonyl group, carbamoyl group, and imide group may further have a substituent.
As further substituents, the above-mentioned groups can be mentioned as specific examples of the substituents that R ₁ to R ₅ mentioned above may further have, preferably a halogen atom, and a fluorine atom. It is more preferable.

In one preferred embodiment of the present invention, the polarity converting group is a group represented by X in the partial structure represented by 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-, sulfuric acid ester group: -OSO ₂ O-, sulfonic acid ester group: -SO ₂ O-.
Y ¹ and Y ² may be the same or different, and each represents an electron-withdrawing group.
In addition, as one preferable embodiment of the present invention, the compound (B) has a group having a partial structure represented by general formula (KA-1) or (KB-1) as a group containing a polarity converting group. , 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, the above partial structure has a bond. When the group does not have the above partial structure, the group having the above partial structure is a group having a monovalent or higher valence from which at least one arbitrary hydrogen atom in the above partial structure is removed.

The partial structure represented by general formula (KA-1) is a structure that forms a ring structure together with the group as X.
X in general formula (KA-1) is preferably a carboxylic ester group (ie, when KA-1 forms a lactone ring structure), an acid anhydride group, or a carbonate ester group. More preferred is a carboxylic acid ester group.
The ring structure represented by the general formula (KA-1) may have a substituent, for example, it may have nka number of substituents Z _ka1 .
When there is a plurality of Z _ka1 , each independently represents an alkyl group, a cycloalkyl group, an ether group, a hydroxyl group, an amide group, an aryl group, a lactone ring group, or an electron-withdrawing group.
Z _ka1 may be connected to each other to form a ring. Examples of the ring formed by connecting Z _ka1 to each other include a cycloalkyl ring and a hetero ring (cyclic ether ring, lactone ring, etc.).
nka represents an integer from 0 to 10. It is preferably an integer of 0 to 8, more preferably an integer of 0 to 5, even 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 below, which are represented by a halogen atom.
Note that 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. The ether group is preferably one substituted with an alkyl group or a cycloalkyl group, that is, an alkyl ether group. Preferable examples of the electron-withdrawing group are the same as the electron-withdrawing groups as Y ¹ and Y ² described below.
Examples of the halogen atom as Z _ka1 include a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, and the like, with a fluorine atom being preferred.
The alkyl group as Z _ka1 may have a substituent and may be either linear or branched. The straight chain alkyl group preferably has 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, such as methyl group, ethyl group, n-propyl group, n-butyl group, sec-butyl group, t-butyl group. group, n-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, n-nonyl group, n-decanyl group and the like. The branched alkyl group preferably has 3 to 30 carbon atoms, more preferably 3 to 20 carbon atoms, and includes, for example, an i-propyl group, an i-butyl group, a t-butyl group, an i-pentyl group, a t-pentyl group, Examples include i-hexyl group, t-hexyl group, i-heptyl group, t-heptyl group, i-octyl group, t-octyl group, i-nonyl group, and t-decanoyl group. Those having 1 to 4 carbon atoms such as methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, i-butyl group, and t-butyl group are preferable.
The cycloalkyl group as Z _ka1 may have a substituent, and may be monocyclic, polycyclic, or bridged. For example, a cycloalkyl group may have a bridged structure. As the monocyclic type, a cycloalkyl group having 3 to 8 carbon atoms is preferable, and examples thereof include a cyclopropyl group, a cyclopentyl group, a cyclohexyl group, a cyclobutyl group, a cyclooctyl group, and the like. Examples of the polycyclic type include groups having a bicyclo, tricyclo, and tetracyclo structure having 5 or more carbon atoms, and preferably a cycloalkyl group having 6 to 20 carbon atoms, such as an adamantyl group, a norbornyl group, an isobornyl group, Examples include camphanyl group, dicyclopentyl group, α-pinel group, tricyclodecanyl group, tetracyclododecyl group, androstannyl group, and the like. The following structures are also preferable as the cycloalkyl group. Note that some of the carbon atoms in the cycloalkyl group may be substituted with heteroatoms such as oxygen atoms.

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

Examples of the lactone ring group of Z _ka1 include groups obtained by removing a hydrogen atom from a structure represented by any of (KA-1-1) to (KA-1-17) described below.

Examples of the aryl group of Z _ka1 include a phenyl group and a naphthyl group.

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

X in general formula (KA-1) is a carboxylic acid ester group, and the partial structure represented by general formula (KA-1) is preferably a lactone ring, preferably a 5- to 7-membered lactone ring.
In addition, as shown in (KA-1-1) to (KA-1-17) below, the 5- to 7-membered lactone ring as a partial structure represented by the general formula (KA-1) has a bicyclo structure and a spiro structure. It is preferable that other ring structures are condensed to form a structure.
Regarding the surrounding ring structures to which the ring structure represented by general formula (KA-1) may be bonded, for example, those in (KA-1-1) to (KA-1-17) below or to this I can list things that are similar.

As the structure containing a lactone ring structure represented by general formula (KA-1), structures represented by any of the following (KA-1-1) to (KA-1-17) are more preferable. Note that 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), (KA-1-17).

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

Although some lactone structures have optically active forms, any optically active form may be used. Further, one type of optically active substance may be used alone, or a plurality of optically active substances may be used in combination. When one kind of optically active substance is mainly used, its optical purity (ee) is preferably 90% or more, more preferably 95% or more, and most preferably 98% or more.

Preferably, X in the general formula (KB-1) is a carboxylic acid ester group (-COO-).

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

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

In the formula (EW),
_new is the repeating number of the linking group represented by -C(R _ew1 )(R _ew2 )-, and represents an integer of 0 or 1. When _new is 0, it represents a single bond and indicates that Y _ew1 is directly bonded.
Y _ew1 is a halogen atom, a cyano group, a nitrile group, a nitro group, a halo(cyclo)alkyl group represented by -C(R _f1 )(R _f2 )-R _f3 described below, a haloaryl group, an oxy group, a carbonyl group , a sulfonyl group, a sulfinyl group, and a combination thereof, and the electron-withdrawing group may have the following structure, for example. Note that the term "halo(cyclo)alkyl group" refers to an alkyl group and a cycloalkyl group in which at least a portion thereof is halogenated. R _ew3 and R _ew4 each independently represent an arbitrary structure. No matter what structure R _ew3 and R _ew4 have, the partial structure represented by formula (EW) has electron-withdrawing properties, and is preferably an alkyl group, a cycloalkyl group, or a fluorinated alkyl group.

When Y _ew1 is a divalent or higher group, the remaining bond forms a bond with any atom or substituent.
Y _ew1 is preferably a halogen atom, or a halo(cyclo)alkyl group or haloaryl group represented by -C(R _f1 )(R _f2 )-R _f3 .
R _ew1 and R _ew2 each independently represent an arbitrary substituent, such as a hydrogen atom, an alkyl group, a cycloalkyl group, or an aryl group.
At least two of R _ew1 , R _ew2 and Y _ew1 may be linked 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, and even more preferably a fluorine atom or a trifluoroaryl 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 connected to form a ring. Examples of the organic group include an alkyl group, a cycloalkyl group, and an alkoxy group, which may be substituted with a halogen atom (preferably a fluorine atom). More preferably, R _f2 and R _f3 are (halo) It is an alkyl group. It is more preferable that R _f2 represents a group similar to R _f1 or is linked to R _f3 to form a ring.
R _f1 and R _f3 may be connected 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 halogenated structure thereof.
As the (per)halocycloalkyl group and (per)haloaryl group in R _f1 to R _f3 or in the ring formed by connecting R _f2 and R _f3 , for example, the cycloalkyl group in Z _ka1 described above is a halogen group. structure, more preferably a fluorocycloalkyl group represented by -C _(n) F _(2n-2) H, and a perfluoroaryl group represented by -C _(n) F _(n-1). Can be mentioned. Here, the number n of carbon atoms is not particularly limited, but is preferably 5 to 13, and more preferably 6.

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

In addition, in the above compound (B), there may be 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 plurality of partial structures represented by the general formula (KB-1). ) and the general formula (KB-1).
Note that part or all of the partial structure of general formula (KA-1) may also serve as an electron-withdrawing group as Y ¹ or Y ² in general formula (KB-1). For example, when X in general formula (KA-1) is a carboxylic ester group, the carboxylic ester group functions as an electron-withdrawing group as Y ¹ or Y ² in general formula (KB-1). It is also possible.

Examples of the group containing a polarity converting group include, but are not particularly limited to, organic groups containing a polarity converting group. Examples of organic groups containing polarity converting groups include alkyl groups; alkenyl groups; cycloalkyl groups; aryl groups; halogen atoms; groups containing heteroatoms such as oxygen atoms, sulfur atoms, nitrogen atoms, and silicon atoms; Examples include groups that are a combination of two or more types and have a polarity converting group.
Alkyl group; alkenyl group; cycloalkyl group; aryl group; halogen atom; group _containing heteroatoms such as oxygen atom, sulfur atom, nitrogen atom and silicon atom; In specific examples of the substituent as _R5 , alkyl groups; alkenyl groups; cycloalkyl groups; aryl groups; halogen atoms; groups containing heteroatoms such as oxygen atoms, sulfur atoms, nitrogen atoms, and silicon atoms; and 2 of these It is the same as a combination of more than one species.

Examples of the group containing a polarity converting group include an alkyl group containing a polarity converting group, an aryl group containing a polarity converting group, and the like.
Examples of the alkyl group in the alkyl group containing a polarity converting group include the same alkyl groups as R ₁ to R ₅ .
Examples of the aryl group in the aryl group containing a polarity converting group include the same aryl groups as R ₁ to R ₅ .

In the general formula (Ar), at least one of R ₁₀ to R ₁₄ is a group containing the above polar group, a group containing a group whose polarity increases when decomposed by the action of an acid, or a group decomposed by the action of an alkaline developer, Any group may be used as long as it includes a group that increases solubility in an alkaline developer.
One or two of R ₁₀ to R ₁₄ is a group containing the above-mentioned polar group, a group containing a group whose polarity increases when decomposed by the action of an acid, or a group that decomposes by the action of an alkaline developer and is dissolved in an alkaline developer. It is preferable that one of R 10 to R 14 be a group containing a group that increases the solubility of the group, and one of R ₁₀ to R ₁₄ is a group containing the above-mentioned polar group, a group containing a group that increases polarity when decomposed by the action of an acid, or a group that includes a group that increases polarity when decomposed by the action of an acid. More preferably, it is a group containing a group that decomposes under the action of a solution and increases its solubility in an alkaline developer.

In the above general formula (3), it is also preferable that Q ₁ and Q ₂ are groups each represented by the following general formula (Ar1).

In the general formula (Ar1), R ₁₅ to R ₁₉ each independently represent a hydrogen atom or a substituent. At least one of R ₁₅ to R ₁₉ represents the following substituent X.
* represents a bond to the benzene ring in general formula (3).
Substituent X: hydroxy group, carboxyl group, group having a carbonyl bond, alkoxy group, acyloxy group, alkoxycarbonyloxy group, aryloxycarbonyloxy group, aryloxycarbonyl group, alkoxycarbonyl group, aryloxyalkyloxy group, alkoxyalkyl Oxy group, carbamoyl group, or imide group

In the general formula (Ar1), R ₁₅ to R ₁₉ each independently represent a hydrogen atom or a substituent.
When R ₁₅ to R ₁₉ represent a substituent, examples of the substituent include an alkyl group; an alkenyl group; an aliphatic hydrocarbon ring group; an aryl group; a halogen atom; an oxygen atom, a sulfur atom, a nitrogen atom, a silicon atom, etc. and combinations of two or more of these; specifically, alkyl groups as R ₁ to R ₅ in general formula (1); alkenyl groups; aliphatic hydrocarbon ring groups; ; an aryl group; a halogen atom; a group containing a heteroatom such as an oxygen atom, a sulfur atom, a nitrogen atom, and a silicon atom; and combinations of two or more thereof.
R ₁₅ to R ₁₉ are preferably a hydrogen atom or a group containing a hetero atom, and it is more preferable that the group other than the group representing the substituent X is a hydrogen atom.

At least one of R ₁₅ to R ₁₉ represents the above substituent X.

Specific examples of the group having a carbonyl bond as the substituent X are the same as the above-mentioned specific examples of the group having a carbonyl bond as the group having a polar group.
The alkoxy group as the substituent X is preferably an alkoxy group having 1 to 30 carbon atoms, more preferably an alkoxy group having 1 to 8 carbon atoms.
The number of carbon atoms in the acyl group in the acyloxy group as the substituent X is preferably 1 to 30, more preferably 1 to 8.
The number of carbon atoms in the alkoxy group in the alkoxycarbonyloxy group as the substituent X is preferably 1 to 30, more preferably 1 to 8.
The number of carbon atoms in the aryl group in the aryloxycarbonyloxy group as the substituent X is preferably 6 to 14, more preferably 6 to 10.
The number of carbon atoms in the aryl group in the aryloxycarbonyl group as the substituent X is preferably 6 to 14, more preferably 6 to 10.
The number of carbon atoms in the alkoxy group in the alkoxycarbonyl group as the substituent X is preferably 1 to 30, more preferably 1 to 8.
The number of carbon atoms in the aryl group in the aryloxyalkyloxy group as the substituent X is preferably 6 to 14, more preferably 6 to 10. The number of carbon atoms in the alkyl group in the aryloxyalkyloxy group is preferably 1 to 30, more preferably 1 to 8.
The number of carbon atoms in the alkoxy group in the alkoxyalkyloxy group as the substituent X is preferably 1 to 30, more preferably 1 to 8. The number of carbon atoms in the alkyl group in the alkoxyalkyloxy group (excluding the alkyl group in the alkoxyalkoxy group in the alkoxyalkyloxy group) is preferably 1 to 30, more preferably 1 to 8.
The imide group as the substituent X is a group obtained by removing one hydrogen atom from imide.

As the substituent X, a group having a carbonyl bond, an alkoxy group, an acyloxy group, an alkoxycarbonyloxy group, an aryloxycarbonyloxy group, an aryloxycarbonyl group, an alkoxycarbonyl group, an aryloxyalkyloxy group, an alkoxyalkyloxy group, and an imide The group may further have a substituent.
As further substituents, the above-mentioned groups can be mentioned as specific examples of the substituents that R ₁ to R ₅ mentioned above may further have.

In general formula (Ar1), at least one of R ₁₅ to R ₁₉ may represent the above substituent X.
One or two of R ₁₅ to R ₁₉ preferably represent the above substituent X, and more preferably one of R ₁₅ to R ₁₉ represents the above substituent X.

<Compound represented by general formula (4)>
The compound represented by the above general formula (3) is preferably a compound represented by the following general formula (4).

In general formula (4), R ₃ and R ₅ each independently represent a hydrogen atom or a substituent.
A represents a single bond or a (m+1)-valent linking group.
Y each independently represents a group represented by any one of the above formulas (A1) to (A6).
m represents an integer of 1 or more.
When m represents an integer of 2 or more, the plurality of Y's may be the same or different.
R ₂₀ to R ₂₄ each independently represent a hydrogen atom or a substituent. At least one of R ₂₀ to R ₂₄ represents the following substituent X.
R ₂₅ to R ₂₉ each independently represent a hydrogen atom or a substituent. At least one of R ₂₅ to R ₂₉ represents the following substituent X.
R ₁₀₁ to R ₁₀₃ each independently represent a hydrogen atom or a substituent. Two of R ₁₀₁ to R ₁₀₃ may be bonded to each other to form a ring.
n represents an integer of 2 or more, and R ₁₀₁ s, R ₁₀₂ s, and R _103s may be the same or different.
Substituent X: hydroxy group, carboxyl group, group having a carbonyl bond, alkoxy group, acyloxy group, alkoxycarbonyloxy group, aryloxycarbonyloxy group, aryloxycarbonyl group, alkoxycarbonyl group, aryloxyalkyloxy group, alkoxyalkyl Oxy group, carbamoyl group, or imide group

In general formula (4), R ₃ and R ₅ have the same meanings as R ₃ and R ₅ in general formula (3).
In general formula (4), R ₃ and R ₅ are preferably hydrogen atoms.
In general formula (4), R ₁₀₁ to R ₁₀₃ and n have the same meanings as R ₁₀₁ to R ₁₀₃ and n in general formula (3), and preferred examples are also the same.
In general formula (4), A, Y, and m have the same meanings as A, Y, and m in general formula (R-1) above, and preferred examples are also the same.
In general formula (4), R ₂₀ to R ₂₄ and R ₂₅ to R ₂₉ have the same meanings as R ₁₅ to R ₁₉ in general formula (Ar1), respectively, and preferred examples are also the same.

As described in the group represented by general formula (R-1) above, A in general formula (R-1) is preferably an aromatic group. That is, A in the general formula (R-1) and A in the general formula (4) in the compounds represented by the general formulas (1) to (3) are preferably divalent aromatic groups. , more preferably a phenylene group.

<Compound represented by general formula (4')>
The compound represented by the above general formula (3) is also preferably a compound represented by the following general formula (4').

In general formula (4'), R ₃ and R ₅ each independently represent a hydrogen atom or a substituent.
A represents a single bond or a (m+1)-valent linking group.
Y each independently represents a group represented by any one of the above formulas (A1) to (A6).
m represents an integer of 1 or more.
When m represents an integer of 2 or more, the plurality of Y's may be the same or different.
R _20' to R _24' each independently represent a hydrogen atom or a substituent. At least one of R _20' to R _24' represents a group containing a group that is decomposed by the action of an acid and increases in polarity.
R _25' to R _29' each independently represent a hydrogen atom or a substituent. At least one of R _25' to R _29' represents a group containing a group that is decomposed by the action of an acid and increases in polarity.
R ₁₀₁ to R ₁₀₃ each independently represent a hydrogen atom or a substituent. Two of R ₁₀₁ to R ₁₀₃ may be bonded to each other to form a ring.
n represents an integer of 2 or more, and R ₁₀₁ s, R ₁₀₂ s, and R _103s may be the same or different.

In general formula (4'), R ₃ and R ₅ have the same meanings as R ₃ and R ₅ in general formula (3).
In general formula (4'), R ₃ and R ₅ are preferably hydrogen atoms.
In general formula (4'), R ₁₀₁ to R ₁₀₃ and n have the same meanings as R ₁₀₁ to R ₁₀₃ and n in general formula (3), and preferred examples are also the same.
In general formula (4'), A, Y, and m have the same meanings as A, Y, and m in general formula (R-1) above, and preferred examples are also the same.
In the general formula (4'), the substituents as R _20' to R _24' and R _25' to R _29' have the same meaning as the substituents as R ₁₀ to R ₁₄ in the above general formula (Ar), respectively. The same applies to preferred examples.

At least one of R _20' to R _24' and at least one of R _25' to R _29' represent a group containing a group whose polarity increases when decomposed by the action of an acid. Specifically, a group containing a group that decomposes and increases polarity by the action of an acid is a group that decomposes and increases polarity by the action of an acid, as at least one of R ₁₀ to R ₁₄ in the above general formula (Ar). Examples include groups containing a group, and preferred examples are also the same.

As described in the group represented by general formula (R-1) above, A in general formula (R-1) is preferably an aromatic group. That is, A in the general formula (R-1) and A in the general formula (4') in the compounds represented by the general formulas (1) to (3) are divalent aromatic groups. Preferably, a phenylene group is more preferable.

<Compound represented by general formula (5)>
The compound represented by the above general formula (4) is preferably a compound represented by the following general formula (5).

In general formula (5), R ₃ and R ₅ each independently represent a hydrogen atom or a substituent.
R ₂₀ to R ₂₄ each independently represent a hydrogen atom or a substituent. At least one of R ₂₀ to R ₂₄ represents the following substituent X.
R ₂₅ to R ₂₉ each independently represent a hydrogen atom or a substituent. At least one of R ₂₅ to R ₂₉ represents the following substituent X.
R ₃₀ to R ₃₄ each independently represent a hydrogen atom or a substituent. At least one of R ₃₀ to R ₃₄ represents a group represented by the following general formula (R-2).
R ₁₀₁ to R ₁₀₃ each independently represent a hydrogen atom or a substituent. Two of R ₁₀₁ to R ₁₀₃ may be bonded to each other to form a ring.
n represents an integer of 2 or more, and R ₁₀₁ s, R ₁₀₂ s, and R _103s may be the same or different.
Substituent X: hydroxy group, carboxyl group, group having a carbonyl bond, alkoxy group, acyloxy group, alkoxycarbonyloxy group, aryloxycarbonyloxy group, aryloxycarbonyl group, alkoxycarbonyl group, aryloxyalkyloxy group, alkoxyalkyl Oxy group, carbamoyl group, or imide group

In the general formula (R-2), A' represents a single bond or a (m1+1)-valent linking group.
Y each independently represents a group represented by any one of the above formulas (A1) to (A6).
m1 represents an integer of 1 or more.
When m1 represents an integer of 2 or more, the plurality of Y's may be the same or different.
* represents a bond to the benzene ring in general formula (5).

In general formula (5), R ₃ , R ₅ , R ₁₀₁ to R ₁₀₃ , and n have the same meanings as R ₃ , R ₅ , R ₁₀₁ to R ₁₀₃ , and n in general formula (4), and are preferred examples. The same is true.
In general formula (5), R ₂₀ to R ₂₄ and R ₂₅ to R ₂₉ have the same meanings as R ₂₀ to R ₂₄ and R ₂₅ to R ₂₉ in general formula (4), respectively, and preferred examples are also the same. be.

In general formula (5), R ₃₀ to R ₃₄ each independently represent a hydrogen atom or a substituent.
When R ₃₀ to R ₃₄ represent a substituent, examples of the substituent include an alkyl group, an alkenyl group, a cycloalkyl group, an aryl group, an amino group, an amide group, a ureido group, a urethane group, a hydroxy group, a carboxy group, Examples include a halogen atom, an alkoxy group, a thioether group, an acyl group, an acyloxy group, an alkoxycarbonyl group, a cyano group, a nitro group, and a combination of two or more thereof.
R ₃₀ to R ₃₄ are preferably hydrogen atoms, except for the group represented by general formula (R-2).

In the general formula (5), at least one of R ₃₀ to R ₃₄ represents a group represented by the above general formula (R-2).
A' in general formula (R-2) represents a single bond or a (m1+1)-valent linking group.
As the (m1+1)-valent linking group of A', for example, a divalent linking group will be described below.
When A' represents a divalent linking group, the divalent linking group is not particularly limited, but includes, for example, an alkylene group, an alkenylene group, an alkynylene group, a cycloalkylene group, -O-, -C(=O) - or a combination thereof.
Specific examples of the above alkylene group, alkenylene group, alkynylene group, and cycloalkylene group include the alkylene group, alkenylene group, alkynylene group, and cycloalkylene group as A in the above general formula (R-1). .
Examples of the (m1+1)-valent linking group of A' include a group obtained by removing (m1-1) hydrogen atoms from a divalent linking group.
A' is preferably a single bond or a methylene group.

Y and m1 in the general formula (R-2) have the same meanings as Y and m in the above general formula (R-1), and preferred examples are also the same.

<Compound represented by general formula (5')>
The compound represented by the above general formula (4) is preferably a compound represented by the following general formula (5').

In general formula (5'), R ₃ and R ₅ each independently represent a hydrogen atom or a substituent.
R _20' to R _24' each independently represent a hydrogen atom or a substituent. At least one of R _20' to R _24' represents a group containing a group that is decomposed by the action of an acid and increases in polarity.
R _25' to R _29' each independently represent a hydrogen atom or a substituent. At least one of R _25' to R _29' represents a group containing a group that is decomposed by the action of an acid and increases in polarity.
R ₃₀ to R ₃₄ each independently represent a hydrogen atom or a substituent. At least one of R ₃₀ to R ₃₄ represents a group represented by the following general formula (R-2).
R ₁₀₁ to R ₁₀₃ each independently represent a hydrogen atom or a substituent. Two of R ₁₀₁ to R ₁₀₃ may be bonded to each other to form a ring.
n represents an integer of 2 or more, and R ₁₀₁ s, R ₁₀₂ s, and R _103s may be the same or different.

In the general formula (R-2), A' represents a single bond or a (m1+1)-valent linking group.
Y each independently represents a group represented by any one of the above formulas (A1) to (A6).
m1 represents an integer of 1 or more.
When m1 represents an integer of 2 or more, the plurality of Y's may be the same or different.
* represents a bond to the benzene ring in general formula (5').

In general formula (5′), R ₃ , R ₅ , R ₁₀₁ to R ₁₀₃ , and n have the same meanings as R ₃ , R ₅ , R ₁₀₁ to R ₁₀₃ , and n in general formula (4′), The same applies to preferred examples.
In general formula (5'), R _20' to R _24' and R ₂₅ ' to R _29' are respectively R _20' to R ₂₄ ' and R _25' to R ₂₉ in general formula (4'). _' , and preferred examples are also the same.

At least one of R _20' to R _24' and at least one of R _25' to R _29' represent a group containing a group whose polarity increases when decomposed by the action of an acid. Specifically, a group containing a group that decomposes and increases polarity by the action of an acid is a group that decomposes and increases polarity by the action of an acid, as at least one of R ₁₀ to R ₁₄ in the above general formula (Ar). Examples include groups containing a group, and preferred examples are also the same.

In general formula (5'), R ₃₀ to R ₃₄ each independently represent a hydrogen atom or a substituent.
When R ₃₀ to R ₃₄ represent a substituent, examples of the substituent include an alkyl group, an alkenyl group, a cycloalkyl group, an aryl group, an amino group, an amide group, a ureido group, a urethane group, a hydroxy group, a carboxy group, Examples include a halogen atom, an alkoxy group, a thioether group, an acyl group, an acyloxy group, an alkoxycarbonyl group, a cyano group, a nitro group, and a combination of two or more thereof.
R ₃₀ to R ₃₄ are preferably hydrogen atoms, except for the group represented by general formula (R-2).

In the general formula (5'), at least one of R ₃₀ to R ₃₄ represents a group represented by the above general formula (R-2).
A' in general formula (R-2) represents a single bond or a (m1+1)-valent linking group.
As the (m1+1)-valent linking group of A', for example, a divalent linking group will be described below.
When A' represents a divalent linking group, the divalent linking group is not particularly limited, but includes, for example, an alkylene group, an alkenylene group, an alkynylene group, a cycloalkylene group, -O-, -C(=O) - or a combination thereof.
Specific examples of the above alkylene group, alkenylene group, alkynylene group, and cycloalkylene group include the alkylene group, alkenylene group, alkynylene group, and cycloalkylene group as A in the above general formula (R-1). .
Examples of the (m1+1)-valent linking group of A' include a group obtained by removing (m1-1) hydrogen atoms from a divalent linking group.
A' is preferably a single bond or a methylene group.

Y and m1 in the general formula (R-2) have the same meanings as Y and m in the above general formula (R-1), and preferred examples are also the same.

In the above general formulas (1) to (3), (4), (4'), (5), and (5'), n is most preferably 2.

It is preferable that the pKa of the acid generated by the compound (B) when irradiated with actinic rays or radiation is -10 or more and 5 or less.

In this specification, acid dissociation constant (pKa) refers to pKa in an aqueous solution, and specifically, using the following software package 1, a value based on Hammett's substituent constant and a database of known literature values is calculated. , is a value obtained by calculation. All pKa values described herein are values calculated using this software package.

Software package 1: Advanced Chemistry Development (ACD/Labs) Software V8.14 for Solaris (1994-2007 ACD/Labs).

On the other hand, pKa can also be determined by molecular orbital calculation method. A specific method for this includes a method of calculating H 2 ⁺ dissociation free energy in an aqueous solution based on a thermodynamic cycle. The H ⁺ dissociation free energy can be calculated, for example, by DFT (density functional theory), but various other methods have been reported in the literature, and the method is not limited to this. . Note that there is a plurality of software that can perform DFT, and one example is Gaussian 16.

As mentioned above, pKa in this specification refers to a value obtained by calculating a value based on Hammett's substituent constant and a database of known literature values using software package 1. If calculation is not possible, a value obtained by Gaussian 16 based on DFT (density functional theory) is adopted.
In addition, pKa in this specification refers to "pKa in an aqueous solution" as described above, but if pKa in an aqueous solution cannot be calculated, "pKa in a dimethyl sulfoxide (DMSO) solution" is adopted. It shall be.

Preferred examples of the anion moiety in the compound represented by general formula (1) are shown below, but the present invention is not limited thereto. Me represents a methyl group, and tBu represents a t-butyl group.

A preferable example of the compound (B) is a compound that is a combination of the above-mentioned anion and the above-mentioned cation.
Compounds (B-1) to (B-21) used in Examples can also be preferably used.

Compound (B) can be synthesized, for example, by a method using sequential coupling reactions.

Examples of the coupling reaction include the following. The counter cation can be converted into the desired cation M ⁺ by a known anion exchange method or a conversion method using an ion exchange resin, for example, as described in JP-A-6-184170.

X ₁ and X ₂ each independently represent a halogen atom, and Ak represents an alkyl group. R represents a substituent. A represents a single bond or a connecting group.
Y' represents a group represented by any of the above formulas (A1) to (A6) into which a protecting group has been introduced.
Y represents a group represented by any of the above formulas (A1) to (A6).
Z ⁺ represents a cation, and M ⁺ represents a cation.

Compound (B) may be used alone or in combination of two or more.
In the composition of the present invention, the content of compound (B) (the total amount when there are multiple types) is preferably 0.1 to 35% by mass, and 0.5 to 35% by mass, based on the total solid content of the composition. It is more preferably 25% by weight, even more preferably 1 to 20% by weight, and particularly preferably 5 to 20% by weight.

[(B') A compound other than the above compound (B) that generates an acid upon irradiation with actinic rays or radiation]
The composition of the present invention may contain a compound other than compound (B) that generates an acid upon irradiation with actinic rays or radiation, as long as the effects of the present invention are not impaired.

[Acid diffusion control agent]
The composition of the present invention preferably contains an acid diffusion control agent. The acid diffusion control agent traps the acid generated from the photoacid generator and the like during exposure, and acts as a quencher to suppress the reaction of the acid-decomposable resin in the unexposed area due to the excess generated acid.
Examples of acid diffusion control agents include basic compounds (DA), basic compounds (DB) whose basicity decreases or disappears when irradiated with actinic rays or radiation, and onium which becomes a weak acid relative to the acid generator. Salts (DC), low-molecular compounds (DD) that have a nitrogen atom and a group that can be eliminated by the action of an acid, or onium salt compounds (DE) that have a nitrogen atom in the cation moiety are used as acid diffusion control agents. can. In the composition of the present invention, known acid diffusion control agents can be used as appropriate. For example, paragraphs [0627] to [0664] of US Patent Application Publication No. 2016/0070167A1, paragraphs [0095] to [0187] of US Patent Application Publication No. 2015/0004544A1, and US Patent Application Publication No. 2016/0237190A1. Known compounds disclosed in paragraphs [0403] to [0423] of the specification and paragraphs [0259] to [0328] of US Patent Application Publication No. 2016/0274458A1 can be suitably used as acid diffusion control agents. .

As the basic compound (DA), compounds having structures represented by the following general formulas (A) to (E) are preferred.

In general formulas (A) and (E),
R ²⁰⁰ , R ²⁰¹ and R ²⁰² may be the same or different, and each independently represents 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. Represents a group (having 6 to 20 carbon atoms). R ²⁰¹ and R ²⁰² may be combined with each other to form a ring.
R ²⁰³ , R ²⁰⁴ , R ²⁰⁵ and R ²⁰⁶ may be the same or different and each independently represents an alkyl group having 1 to 20 carbon atoms.

The alkyl groups in general formulas (A) and (E) may have a substituent or may be unsubstituted.
Regarding the above alkyl group, the alkyl group having a substituent is preferably an aminoalkyl group having 1 to 20 carbon atoms, a hydroxyalkyl group having 1 to 20 carbon atoms, or a cyanoalkyl group having 1 to 20 carbon atoms.
The alkyl groups in general formulas (A) and (E) are more preferably unsubstituted.

As the basic compound (DA), thiazole, benzothiazole, oxazole, benzoxazole, guanidine, aminopyrrolidine, pyrazole, pyrazoline, piperazine, aminomorpholine, aminoalkylmorpholine, piperidine, or compounds having these structures are preferred, Compounds having a thiazole structure, benzothiazole structure, oxazole structure, benzoxazole structure, imidazole structure, diazabicyclo structure, onium hydroxide structure, onium carboxylate structure, trialkylamine structure, aniline structure or pyridine structure, hydroxyl group and/or ether bond or aniline derivatives having a hydroxyl group and/or ether bond are more preferred.

A basic compound (DB) whose basicity decreases or disappears upon irradiation with actinic rays or radiation (hereinafter also referred to as "compound (DB)") has a proton acceptor functional group and is resistant to actinic rays or radiation. It is a compound whose proton acceptor property decreases, disappears, or changes from proton acceptor property to acidic property when it is decomposed by irradiation with radiation.

A proton acceptor functional group is a group capable of electrostatic interaction with protons or a functional group having electrons, such as a functional group having a macrocyclic structure such as a cyclic polyether, or a π-conjugated functional group. A functional group having a nitrogen atom with a lone pair of electrons that does not contribute to A nitrogen atom having a lone pair of electrons that does not contribute to π conjugation is, for example, a nitrogen atom having a partial structure shown in the following formula.

Preferred partial structures of the proton acceptor functional group include, for example, a crown ether structure, an aza crown ether structure, a primary to tertiary amine structure, a pyridine structure, an imidazole structure, and a pyrazine structure.

The compound (DB) is decomposed by irradiation with actinic rays or radiation, and its proton acceptor property decreases or disappears, or a compound whose proton acceptor property changes to acidicity is generated. Here, the decrease or disappearance of proton acceptor property, or the change from proton acceptor property to acidity, refers to a change in proton acceptor property due to the addition of a proton to a proton acceptor functional group. means that when a proton adduct is generated from a compound (DB) having a proton acceptor functional group and a proton, the equilibrium constant in its chemical equilibrium decreases.
Proton acceptor properties can be confirmed by pH measurement.

The acid dissociation constant pKa of the compound (DB) generated when the compound (DB) is decomposed by irradiation with actinic light or radiation preferably satisfies pKa<-1, more preferably satisfies -13<pKa<-1, and - It is more preferable to satisfy 13<pKa<-3.

In the composition of the present invention, an onium salt (DC) that is a relatively weak acid relative to the photoacid generator can be used as an acid diffusion control agent.
When a photoacid generator is used in combination with an onium salt that generates an acid that is weaker than the acid generated from the photoacid generator, the photoacid generator may When the resulting acid collides with an onium salt having an unreacted weak acid anion, the weak acid is released through salt exchange to produce an onium salt having a strong acid anion. In this process, the strong acid is exchanged with a weak acid with lower catalytic ability, so the acid appears to be deactivated and acid diffusion can be controlled.

As onium salts that are relatively weak acids with respect to photoacid generators, compounds represented by the following general formulas (d1-1) to (d1-3) are preferred.

In the formula, R ⁵¹ is a hydrocarbon group that may have a substituent, and Z ^2c is a hydrocarbon group having 1 to 30 carbon atoms that may have a substituent (provided that the carbon adjacent to S ), ^R52 is an organic group, ^Y3 is a linear, branched or cyclic alkylene group or arylene group, and Rf is a fluorine atom. and each M ⁺ is independently an ammonium cation, a sulfonium cation, or an iodonium cation.

Preferred examples of the sulfonium cation or iodonium cation represented by M ⁺ include the sulfonium cation exemplified by the general formula (ZIA) and the iodonium cation exemplified by the general formula (ZIIA).

Onium salts (DC), which are weak acids relative to photoacid generators, are compounds that have a cationic site and an anionic site within the same molecule, and the cationic site and anionic site are linked by a covalent bond ( (hereinafter also referred to as "compound (DCA)").
As the compound (DCA), compounds represented by any of the following general formulas (C-1) to (C-3) are preferred.

In general formulas (C-1) to (C-3),
R ₁ , R ₂ and R ₃ each independently represent a substituent having 1 or more carbon atoms.
L ₁ represents a divalent linking group or a single bond that connects the cation site and the anion site.
^-X- represents an anion moiety selected from ^-COO- , _-SO3- ^, _-SO2- ^, and -N ^-- _R4 . R ₄ has a carbonyl group (-C(=O)-), a sulfonyl group (-S(=O) ₂ -), and a sulfinyl group (-S(=O)- ) represents a monovalent substituent having at least one of the following.
R ₁ , R ₂ , R ₃ , R ₄ , and L ₁ may be bonded to each other to form a ring structure. Further, in the general formula (C-3), two of R ₁ to R ₃ may collectively represent one divalent substituent, and may be bonded to the N atom through a double bond.

Substituents having 1 or more carbon atoms in R ₁ to R ₃ include alkyl groups, cycloalkyl groups, aryl groups, alkyloxycarbonyl groups, cycloalkyloxycarbonyl groups, aryloxycarbonyl groups, alkylaminocarbonyl groups, and cycloalkylamino groups. Examples include carbonyl group and arylaminocarbonyl group. Preferably, it is an alkyl group, a cycloalkyl group, or an aryl group.

L ₁ as a divalent linking group is a linear or branched alkylene group, a cycloalkylene group, an arylene group, a carbonyl group, an ether bond, an ester bond, an amide bond, a urethane bond, a urea bond, and two of these. Examples include groups formed by combining more than one species. L ₁ is preferably an alkylene group, an arylene group, an ether bond, an ester bond, or a combination of two or more thereof.

A low-molecular compound (DD) that has a nitrogen atom and a group that can be eliminated by the action of an acid (hereinafter also referred to as a "compound (DD)") has a group that can be eliminated by the action of an acid on the nitrogen atom. It is preferable that the amine derivative has the following.
As the group that is eliminated by the action of an acid, an acetal group, a carbonate group, a carbamate group, a tertiary ester group, a tertiary hydroxyl group, or a hemiaminal ether group is preferable, and a carbamate group or a hemiaminal ether group is more preferable. .
The molecular weight of the compound (DD) is preferably from 100 to 1,000, more preferably from 100 to 700, even more preferably from 100 to 500.
Compound (DD) may have a carbamate group having a protective group on the nitrogen atom. The protecting group constituting the carbamate group is represented by the following general formula (d-1).

In general formula (d-1),
Rb each independently represents a hydrogen atom, an alkyl group (preferably having 1 to 10 carbon atoms), a cycloalkyl group (preferably having 3 to 30 carbon atoms), an aryl group (preferably having 3 to 30 carbon atoms), an aralkyl group (preferably having 3 to 30 carbon atoms), (preferably 1 to 10 carbon atoms) or an alkoxyalkyl group (preferably 1 to 10 carbon atoms). Rb may be bonded to each other to form a ring.
The alkyl group, cycloalkyl group, aryl group, and aralkyl group represented by Rb are each independently a functional group such as a hydroxyl group, a cyano group, an amino group, a pyrrolidino group, a piperidino group, a morpholino group, an oxo group, an alkoxy group, or It may be substituted with a halogen atom. The same applies to the alkoxyalkyl group represented by Rb.

Rb is preferably a linear or branched alkyl group, a cycloalkyl group, or an aryl group, and more preferably a linear or branched alkyl group or a cycloalkyl group.
Examples of the ring formed by mutually connecting two Rb's include alicyclic hydrocarbons, aromatic hydrocarbons, heterocyclic hydrocarbons, and derivatives thereof.
Specific structures of the group represented by general formula (d-1) include, but are not limited to, the structure disclosed in paragraph [0466] of US Patent Publication US2012/0135348A1.

It is preferable that the compound (DD) has a structure represented by the following general formula (6).

In general formula (6),
l represents an integer from 0 to 2, m represents an integer from 1 to 3, and l+m=3 is satisfied.
Ra represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, or an aralkyl group. When l is 2, the two Ra's may be the same or different, and the two Ra's may be interconnected to form a heterocycle with the nitrogen atom in the formula. This heterocycle may contain a heteroatom other than the nitrogen atom in the formula.
Rb has the same meaning as Rb in the above general formula (d-1), and preferred examples are also the same.
In general formula (6), the alkyl group, cycloalkyl group, aryl group, and aralkyl group as Ra may be independently substituted with the alkyl group, cycloalkyl group, aryl group, and aralkyl group as Rb. It may be substituted with the same groups as those mentioned above as good groups.

Specific examples of the alkyl group, cycloalkyl group, aryl group, and aralkyl group (these groups may be substituted with the above group) for Ra include the same groups as mentioned above for Rb. It will be done.
Specific examples of particularly preferred compounds (DD) in the present invention include, but are not limited to, the compounds disclosed in paragraph [0475] of US Patent Application Publication No. 2012/0135348A1.

The onium salt compound (DE) having a nitrogen atom in the cation moiety (hereinafter also referred to as "compound (DE)") is preferably a compound having a basic moiety containing a nitrogen atom in the cation moiety. The basic moiety is preferably an amino group, more preferably an aliphatic amino group. It is further preferred that all atoms adjacent to the nitrogen atom in the basic site are hydrogen atoms or carbon atoms. Further, 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 bonded to the nitrogen atom.
Preferred specific examples of the compound (DE) include, but are not limited to, the compounds disclosed in paragraph [0203] of US Patent Application Publication No. 2015/0309408A1.

Preferred examples of the acid diffusion control agent are shown below, but the present invention is not limited thereto. Me represents a methyl group.

In the composition of the present invention, one type of acid diffusion control agent may be used alone, or two or more types may be used in combination.
The content of the acid diffusion control agent in the composition of the present invention (if there are multiple types, the total thereof) is preferably 0.001 to 20% by mass, and 0.01 to 20% by mass based on the total solid content of the composition. 5% by mass is more preferred.

[solvent]
The composition of the present invention preferably contains a solvent.
In the composition of the present invention, any known resist solvent can be used as appropriate. For example, paragraphs [0665] to [0670] of US Patent Application Publication No. 2016/0070167A1, paragraphs [0210] to [0235] of US Patent Application Publication No. 2015/0004544A1, and US Patent Application Publication No. 2016/0237190A1. Known solvents disclosed in paragraphs [0424] to [0426] of the specification and paragraphs [0357] to [0366] of US Patent Application Publication No. 2016/0274458A1 can be suitably used.
Examples of solvents that can be used in preparing the composition include alkylene glycol monoalkyl ether carboxylates, alkylene glycol monoalkyl ethers, lactic acid alkyl esters, alkyl alkoxypropionates, cyclic lactones (preferably having 4 to 10 carbon atoms), Examples include organic solvents such as monoketone compounds which may have a ring (preferably having 4 to 10 carbon atoms), alkylene carbonates, alkyl alkoxyacetates, and alkyl pyruvates.

As the organic solvent, a mixed solvent obtained by mixing a solvent having a hydroxyl group in its structure and a solvent not having a hydroxyl group may be used.
As the solvent having a hydroxyl group and the solvent not having a hydroxyl group, the above-mentioned exemplified compounds can be selected as appropriate.As the solvent containing a hydroxyl group, alkylene glycol monoalkyl ether, alkyl lactate, etc. are preferable, and propylene glycol monomethyl ether ( PGME), propylene glycol monoethyl ether (PGEE), methyl 2-hydroxyisobutyrate, or ethyl lactate are more preferred. Further, as the solvent having no hydroxyl group, alkylene glycol monoalkyl ether acetate, alkyl alkoxypropionate, monoketone compound which may have a ring, cyclic lactone, or alkyl acetate are preferable, and among these, propylene Glycol monomethyl ether acetate (PGMEA), ethyl ethoxypropionate, 2-heptanone, γ-butyrolactone, cyclohexanone, cyclopentanone or butyl acetate are more preferred, propylene glycol monomethyl ether acetate, γ-butyrolactone, ethyl ethoxypropionate, More preferred are cyclohexanone, cyclopentanone or 2-heptanone. Propylene carbonate is also preferred as the solvent having no hydroxyl group.
The mixing ratio (mass ratio) of the solvent having a hydroxyl group and the solvent not having a hydroxyl group is 1/99 to 99/1, preferably 10/90 to 90/10, and more preferably 20/80 to 60/40. preferable. A mixed solvent containing 50% by mass or more of a solvent that does not have a hydroxyl group is preferable in terms of coating uniformity.
The solvent preferably contains propylene glycol monomethyl ether acetate, and may be a single solvent of propylene glycol monomethyl ether acetate or a mixed solvent of two or more types containing propylene glycol monomethyl ether acetate.

[Surfactant]
The composition of the present invention may further contain a surfactant. By containing a surfactant, when using an exposure light source with a wavelength of 250 nm or less, especially 220 nm or less, it is possible to form a pattern with good sensitivity and resolution, better adhesion, and fewer development defects. Become.
As the surfactant, it is particularly preferable to use a fluorine-based and/or silicon-based surfactant.
Examples of the fluorine-based and/or silicon-based surfactants include the surfactants described in [0276] of US Patent Application Publication No. 2008/0248425. Additionally, FTOP EF301 or EF303 (manufactured by Shin-Akita Kasei Co., Ltd.); Florado FC430, 431 or 4430 (manufactured by Sumitomo 3M Co., Ltd.); Megafac F171, F173, F176, F189, F113, F110, F177, F120 or R08 (manufactured by DIC Corporation); Surflon S-382, SC101, 102, 103, 104, 105 or 106 (manufactured by Asahi Glass Co., Ltd.); Troysol S-366 (manufactured by Troy Chemical Corporation); GF-300 or GF-150 (manufactured by Toagosei Kagaku Co., Ltd.), Surflon S-393 (manufactured by Seimi Chemical Co., Ltd.); Gemco Co., Ltd.); PF636, PF656, PF6320 or PF6520 (OMNOVA Co., Ltd.); It's okay. Note that polysiloxane polymer KP-341 (manufactured by Shin-Etsu Chemical Co., Ltd.) can also be used as the silicone surfactant.

In addition to the known surfactants listed above, surfactants may also be prepared using fluoroaliphatic compounds produced by the telomerization method (also called the telomer method) or the oligomerization method (also called the oligomer method). May be synthesized. Specifically, a polymer having a fluoroaliphatic group derived from this fluoroaliphatic compound may be used as a surfactant. This fluoroaliphatic compound can be synthesized, for example, by the method described in JP-A No. 2002-90991.
Further, surfactants other than the fluorine-based and/or silicon-based surfactants described in [0280] of US Patent Application Publication No. 2008/0248425 may be used.

These surfactants may be used alone or in combination of two or more.

When the composition of the present invention contains a surfactant, its content is preferably 0 to 2% by mass, more preferably 0.0001 to 2% by mass, and more preferably 0.0001 to 2% by mass, based on the total solid content of the composition. Preferably it is 0.0005 to 1% by mass.

[Other additives]
In addition to the components described above, the composition of the present invention also contains carboxylic acids, carboxylic acid onium salts, dissolution-inhibiting compounds with a molecular weight of 3000 or less as described in Proceedings of SPIE, 2724, 355 (1996), dyes, and plasticizers. , a photosensitizer, a light absorber, an antioxidant, etc. may be contained as appropriate.

In particular, carboxylic acids can also be suitably used to improve performance. As the carboxylic acid, aromatic carboxylic acids such as benzoic acid and naphthoic acid are preferred.

When the composition of the present invention contains a carboxylic acid, the content of the carboxylic acid is preferably 0.01 to 10% by mass, more preferably 0.01 to 5% by mass, and even more preferably 0.01 to 5% by mass based on the total solid content of the composition. Preferably it is 0.01 to 3% by mass.

The actinic ray-sensitive or radiation-sensitive resin composition of the present invention is preferably used in a film thickness of 10 to 250 nm, more preferably in a film thickness of 20 to 200 nm, from the viewpoint of improving resolution. Preferably, the wavelength is more preferably 30 to 100 nm. Such a film thickness can be achieved by setting the solid content concentration in the composition within an appropriate range to provide an appropriate viscosity and improving coating properties and film forming properties.

The solid content concentration of the actinic ray-sensitive or radiation-sensitive resin composition in the present invention is usually 1.0 to 10% by mass, preferably 1.5 to 5.7% by mass, and more preferably 1.8% by mass. ~5.3% by mass. By setting the solid content concentration within the above range, the resist solution can be uniformly applied onto the substrate, and furthermore, it becomes possible to form a resist pattern with excellent line width roughness.
The solid content concentration is the mass percentage of the mass of other components excluding the solvent with respect to the total mass of the actinic ray-sensitive or radiation-sensitive resin composition.

[Application]
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 composition of the present invention can be used in semiconductor manufacturing processes such as IC (Integrated Circuit), manufacturing of circuit boards such as liquid crystal or thermal heads, manufacturing of imprint mold structures, other photofabrication processes, or The present invention relates to actinic ray-sensitive or radiation-sensitive resin compositions used in the production of lithographic printing plates or acid-curable compositions. The pattern formed in the present invention can be used in an etching process, an ion implantation process, a bump electrode formation process, a rewiring formation process, MEMS (Micro Electro Mechanical Systems), and the like.
The present invention also relates to an actinic ray-sensitive or radiation-sensitive resin composition for producing a photomask.

[Actinic ray-sensitive or radiation-sensitive film]
The present invention also relates to an actinic ray- or radiation-sensitive film (preferably a resist film) formed from the actinic ray- or radiation-sensitive composition of the present invention. Such a film is formed, for example, by applying the composition of the present invention onto a support such as a substrate. The thickness of this film is preferably 0.02 to 0.1 μm. The coating is applied onto the substrate by any suitable coating method such as spin coating, roll coating, flow coating, dip coating, spray coating, doctor coating, etc., but spin coating is preferable, and the rotation speed is 1000 to 3000 rpm (rotations per minute) is preferred. The coating film is prebaked at 60 to 150°C for 1 to 20 minutes, preferably at 80 to 120°C for 1 to 10 minutes to form a thin film.
For example, in the case of a semiconductor wafer, a silicon wafer can be used as the material constituting the substrate to be processed and its outermost layer, and examples of the material forming the outermost layer include Si, SiO ₂ , SiN, SiON, TiN, Examples include WSi, BPSG, SOG, and organic antireflection film.

Before forming the resist film, an antireflection film may be applied on the substrate in advance.
As the antireflection film, either an inorganic film type made of titanium, titanium dioxide, titanium nitride, chromium oxide, carbon, amorphous silicon, etc., or an organic film type made of a light absorbing agent and a polymer material can be used. In addition, commercially available organic anti-reflection films such as the DUV30 series and DUV-40 series manufactured by Brewer Sciences, and AR-2, AR-3, and AR-5 manufactured by Shipley may be used as the organic anti-reflection film. can.

In addition, in the pattern forming method of the present invention, a top coat may be formed on the upper layer of the resist film. Preferably, the top coat does not mix with the resist film and can be applied uniformly to the upper layer of the resist film.
The top coat is not particularly limited, and a conventionally known top coat can be formed by a conventionally known method, for example, a top coat can be formed based on the description in paragraphs 0072 to 0082 of JP 2014-059543A.
For example, it is preferable to form a top coat containing a basic compound on the resist film as described in JP-A-2013-61648. Specific examples of basic compounds that the top coat may contain are the same as the acid diffusion inhibitors described above.
Further, the top coat preferably contains a compound containing at least one group or bond selected from the group consisting of an ether bond, a thioether bond, a hydroxyl group, a thiol group, a carbonyl bond, and an ester bond.

Moreover, it is preferable that the top coat contains resin. The resin that can be contained in the top coat is not particularly limited, but the same resins as hydrophobic resins that can be included in actinic ray-sensitive or radiation-sensitive compositions can be used.
Regarding hydrophobic resins, [0017] to [0023] of JP2013-61647A (corresponding [0017] to [0023] of U.S. Patent Publication No. 2013/244438), and JP2014-56194A The descriptions in [0016] to [0165] can be referred to, and the contents thereof are incorporated into the present specification.
It is preferable that the top coat contains a resin containing a repeating unit having an aromatic ring. By containing a repeating unit having an aromatic ring, the generation efficiency of secondary electrons and the efficiency of acid generation from compounds that generate acid due to actinic light or radiation are increased, especially during electron beam or EUV exposure, and the pattern The effects of higher sensitivity and higher resolution can be expected during formation.

When the top coat contains a plurality of resins, it is preferable to contain at least one resin (XA) having a fluorine atom and/or a silicon atom. The top coat composition may include at least one resin (XA) having a fluorine atom and/or a silicon atom, and a resin (XB) having a lower content of fluorine atoms and/or silicon atoms than the resin (XA). More preferred. Thereby, when the top coat film is formed, the resin (XA) is unevenly distributed on the surface of the top coat film, so that performance such as development characteristics and immersion liquid followability can be improved.

Further, the top coat may contain an acid generator and a crosslinking agent.

Topcoats are typically formed from topcoat-forming compositions.
In the top coat forming composition, each component is preferably dissolved in a solvent and then filtered. The filter is preferably made of polytetrafluoroethylene, polyethylene, or nylon and has a pore size of 0.1 μm or less, more preferably 0.05 μm or less, and still more preferably 0.03 μm or less. Further, when the solid content concentration of the composition is high (for example, 25% by mass or more), the pore size of the filter used for filter filtration is preferably 3 μm or less, more preferably 0.5 μm or less, and even more preferably 0.3 μm or less. This filter is preferably made of polytetrafluoroethylene, polyethylene, or nylon. In filter filtration, for example, as disclosed in Japanese Patent Application Publication No. 2002-62667, cyclic filtration may be performed, and multiple types of filters may be connected in series or in parallel. You may connect it to perform filtration. The composition may also be filtered multiple times. Furthermore, the composition may be subjected to deaeration treatment or the like before or after filter filtration.
The composition for forming a top coat preferably does not contain impurities such as metals. The content of metal components contained in these materials is preferably 10 ppm or less, more preferably 5 ppm or less, even more preferably 1 ppm or less, and it is especially preferable that they are substantially free (below the detection limit of the measuring device). .
It is also possible to partially or completely glass line the inside of the equipment used in the manufacturing process (process for synthesizing raw materials, etc.) of the raw materials (resin, photoacid generator, etc.) of the resist composition. This is preferable in order to reduce the content of impurities to a small amount (for example, on the order of ppm by mass). Such a method is described in, for example, Kagaku Kogyo Nippo dated December 21, 2017.

When the exposure described below is immersion exposure, the top coat is placed between the resist film and the immersion liquid, and also functions as a layer that does not bring the resist film into direct contact with the immersion liquid. In this case, the properties that the top coat (top coat forming composition) preferably has include suitability for coating on resist films, transparency to radiation, especially 193 nm, and low solubility to immersion liquid (preferably water). . Further, it is preferable that the top coat is not mixed with the resist film and can be applied uniformly to the surface of the resist film.
Note that in order to uniformly apply the top coat forming composition to the surface of the resist film without dissolving the resist film, the top coat forming composition preferably contains a solvent that does not dissolve the resist film. . As the solvent that does not dissolve the resist film, it is more preferable to use a solvent having a different component from a developer containing an organic solvent (organic developer), which will be described in detail later.

The method for applying the top coat-forming composition is not particularly limited, and conventionally known spin coating methods, spray methods, roller coating methods, dipping methods, etc. can be used.

The thickness of the top coat is not particularly limited, but from the viewpoint of transparency to the exposure light source, it is usually formed with a thickness of 5 nm to 300 nm, preferably 10 nm to 300 nm, more preferably 20 nm to 200 nm, even more preferably 30 nm to 100 nm. .
After forming the top coat, the substrate is heated (PB) if necessary.
The refractive index of the top coat is preferably close to the refractive index of the resist film from the viewpoint of resolution.
Preferably, the topcoat is insoluble in the immersion liquid, more preferably insoluble in water.
The receding contact angle of the top coat is preferably 50 to 100 degrees, and preferably 80 to 100 degrees, from the viewpoint of immersion liquid followability. More preferred.
In immersion exposure, the immersion liquid must move over the wafer to follow the movement of the exposure head as it scans the wafer at high speed and forms the exposure pattern. The contact angle of the immersion liquid with respect to the immersion liquid is important, and in order to obtain better resist performance, it is preferable to have a receding contact angle within the above range.

When removing the top coat, an organic developer may be used, or a separate release agent may be used. As the stripping agent, it is preferable to use a solvent that has low penetration into the resist film. In that the top coat can be removed simultaneously with the development of the resist film, it is preferable that the top coat can be removed using an organic developer. The organic developer used for stripping is not particularly limited as long as it can dissolve and remove the low exposure areas of the resist film.

From the viewpoint of peeling with an organic developer, the dissolution rate of the top coat in the organic developer is preferably 1 to 300 nm/sec, more preferably 10 to 100 nm/sec.
Here, the dissolution rate of the top coat in an organic developer is the rate of decrease in film thickness when the top coat is exposed to the developer after being formed. The actual speed.
Setting the dissolution rate of the top coat in the organic developer to 1/sec or more, preferably 10 nm/sec or more has the effect of reducing the occurrence of development defects after the resist film is developed. Furthermore, by setting the speed to 300 nm/sec or less, preferably 100 nm/sec, the line edge roughness of the pattern after developing the resist film becomes better, probably due to the effect of reducing exposure unevenness during immersion exposure. effective.
The top coat may be removed using other known developers, such as aqueous alkaline solutions. A specific example of the alkaline aqueous solution that can be used is an aqueous solution of tetramethylammonium hydroxide.

[Pattern formation method]
The present invention includes a resist film forming step of forming a resist film using the actinic ray-sensitive or radiation-sensitive resin composition of the present invention, an exposure step of exposing the resist film, and a developing solution for the exposed resist film. It also relates to a pattern forming method including a developing step of developing using.
In the present invention, the exposure is preferably performed using an electron beam, an ArF excimer laser, or extreme ultraviolet rays, and more preferably performed using an electron beam or extreme ultraviolet rays.

In the production of precision integrated circuit elements, etc., the exposure on the resist film (pattern formation step) can be performed by first irradiating the resist film of the present invention with ArF excimer laser, electron beam, or extreme ultraviolet (EUV) in a pattern. preferable. In the case of ArF excimer laser, the exposure amount is about 1 to 100 mJ/ ^cm2 , preferably about 20 to 60 mJ/ ^cm2 , and in the case of electron beam, about 0.1 to 20 μC/ ^cm2 , preferably 3 to 10 μC/cm2. In the case of extreme ultraviolet rays, exposure is carried out at an amount of about 0.1 to 20 mJ/cm ² , preferably about 3 ^to 15 mJ/cm ² .
Next, post-exposure heating is performed on a hot plate, preferably at 60 to 150°C for 5 seconds to 20 minutes, more preferably at 80 to 120°C for 15 seconds to 10 minutes, even more preferably at 80 to 120°C for 1 to 10 minutes. (post-exposure baking), then development, rinsing, and drying to form a pattern. Here, the post-exposure heating is appropriately adjusted depending on the acid decomposability of the repeating unit having an acid decomposable group in the resin (A). When acid decomposability is low, it is also preferable that the temperature of post-exposure heating is 110° C. or more and the heating time is 45 seconds or more.
Although the developer is appropriately selected, it is preferable to use an alkaline developer (typically an alkaline aqueous solution) or a developer containing an organic solvent (also referred to as an organic developer). When the developer is an aqueous alkaline solution, an aqueous alkaline solution of 0.1 to 5% by mass, preferably 2 to 3% by mass, such as tetramethylammonium hydroxide (TMAH) or tetrabutylammonium hydroxide (TBAH), Developing is carried out for 0.1 to 3 minutes, preferably for 0.5 to 2 minutes, by a conventional method such as a dip method, a puddle method, or a spray method. An appropriate amount of alcohol and/or surfactant may be added to the alkaline developer. In this way, in the formation of a negative pattern, the film in the unexposed part dissolves, and the exposed part is difficult to dissolve in the developer, and in the formation of a positive pattern, the film in the exposed part dissolves. The target pattern is formed on the substrate because the unexposed portion of the film is difficult to dissolve in the developing solution.

When the pattern forming method of the present invention has a step of developing using an alkaline developer, examples of the alkaline developer include sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, and aqueous ammonia. Inorganic alkalis such as, primary amines such as ethylamine and n-propylamine, secondary amines such as diethylamine and di-n-butylamine, tertiary amines such as triethylamine and methyldiethylamine, dimethylethanolamine and triethanol. Alcohol amines such as amines, tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, tetrapentylammonium hydroxide, tetrahexylammonium hydroxide, tetraoctylammonium hydroxide, ethyl Tetraalkylammonium hydroxide such as trimethylammonium hydroxide, butyltrimethylammonium hydroxide, methyltriamylammonium hydroxide, dibutyl dipentylammonium hydroxide, trimethylphenylammonium hydroxide, trimethylbenzylammonium hydroxide, triethylbenzylammonium hydroxide, dimethyl Alkaline aqueous solutions of quaternary ammonium salts such as bis(2-hydroxytetyl) ammonium hydroxide and cyclic amines such as pyrrole and pyheridine can be used.
Furthermore, appropriate amounts of alcohols and surfactants may be added to the alkaline aqueous solution.
The alkaline concentration of the alkaline developer is usually 0.1 to 20% by mass.
The pH of the alkaline developer is usually 10.0 to 15.0.
Particularly desirable is a 2.38% by weight aqueous solution of tetramethylammonium hydroxide.

As a rinsing liquid in the rinsing treatment performed after alkaline development, pure water may be used, and an appropriate amount of surfactant may be added thereto.
Furthermore, after the development process or the rinsing process, a process can be performed in which the developing solution or rinsing solution adhering to the pattern is removed using a supercritical fluid.

When the pattern forming method of the present invention has a step of developing using a developer containing an organic solvent, the developer in the step (hereinafter also referred to as an organic developer) may be a ketone solvent, an ester-based Solvents, polar solvents such as alcohol solvents, amide solvents, ether solvents, and hydrocarbon solvents can be used.

In the present invention, an ester solvent is a solvent that has an ester group in its molecule, a ketone solvent is a solvent that has a ketone group in its molecule, and an alcohol solvent is a solvent that has an alcoholic group in its molecule. A solvent having a hydroxyl group, an amide solvent having an amide group in the molecule, and an ether solvent having an ether bond in the molecule. Some of these solvents have multiple types of the above-mentioned functional groups in one molecule, but in that case, the term applies to any type of solvent that contains the functional groups that the solvent has. For example, diethylene glycol monomethyl ether is applicable to both alcohol solvents and ether solvents in the above classification. Moreover, a hydrocarbon solvent is a hydrocarbon solvent that does not have a substituent.
In particular, it is preferable that the developing solution contains at least one type of solvent selected from ketone solvents, ester solvents, alcohol solvents, and ether solvents.

The developer has a carbon atom number of 7 or more (preferably 7 to 14, more preferably 7 to 12, and even more preferably 7 to 10) and a heteroatom number of 2 or less, in order to suppress swelling of the resist film. It is preferable to use an ester solvent of
The heteroatom of the above-mentioned ester solvent is an atom other than a carbon atom or a hydrogen atom, and includes, for example, an oxygen atom, a nitrogen atom, a sulfur atom, and the like. The number of heteroatoms is preferably 2 or less.
Preferred examples of ester solvents having 7 or more carbon atoms and 2 or less heteroatoms include amyl acetate, isoamyl acetate, 2-methylbutyl acetate, 1-methylbutyl acetate, hexyl acetate, pentyl propionate, hexyl propionate, Examples include heptyl propionate, butyl butanoate, isobutyl isobutanoate, and it is particularly preferable to use isoamyl acetate or isobutyl isobutanoate.

Instead of the above-mentioned ester solvent having 7 or more carbon atoms and 2 or less heteroatoms, the developer may be a mixed solvent of the above-mentioned ester solvent and the above-mentioned hydrocarbon solvent, or the above-mentioned ketone solvent and the above-mentioned carbonized solvent. A mixed solvent of hydrogen solvents may also be used. In this case as well, it is effective in suppressing swelling of the resist film.
When using a combination of an ester solvent and a hydrocarbon solvent, it is preferable to use isoamyl acetate as the ester solvent. Further, as the hydrocarbon solvent, from the viewpoint of adjusting the solubility of the resist film, it is preferable to use a saturated hydrocarbon solvent (eg, octane, nonane, decane, dodecane, undecane, hexadecane, etc.).
Examples of ketone solvents include 1-octanone, 2-octanone, 1-nonanone, 2-nonanone, acetone, 2-heptanone (methyl amyl ketone), 4-heptanone, 1-hexanone, 2-hexanone, diisobutyl ketone, 2,5-dimethyl-4-hexanone, diisobutyl ketone, cyclohexanone, methylcyclohexanone, phenylacetone, methyl ethyl ketone, methyl isobutyl ketone, acetylacetone, acetonylacetone, ionone, diacetonyl alcohol, acetyl carbinol, acetophenone, methyl naphthyl ketone, Examples include isophorone, propylene carbonate, etc., and it is particularly preferable to use diisobutyl ketone and 2,5-dimethyl-4-hexanone.
Examples of ester solvents include methyl acetate, butyl acetate, ethyl acetate, isopropyl acetate, pentyl acetate, isoamyl 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, butyric acid Examples include butyl, methyl 2-hydroxyisobutyrate, and the like.
Examples of alcoholic solvents include methyl alcohol, ethyl alcohol, n-propyl alcohol, isopropyl alcohol, n-butyl alcohol, sec-butyl alcohol, 4-methyl-2-pentanol, tert-butyl alcohol, isobutyl alcohol, n-butyl alcohol, and n-butyl alcohol. - Alcohols such as hexyl alcohol, n-heptyl alcohol, n-octyl alcohol, and n-decanol, glycol solvents such as ethylene glycol, diethylene glycol, and triethylene glycol, and ethylene glycol monomethyl ether, propylene glycol monomethyl ether, and ethylene glycol monomethyl ether. Examples include glycol ether solvents such as ethyl ether, propylene glycol monoethyl ether, diethylene glycol monomethyl ether, triethylene glycol monoethyl ether, and methoxymethylbutanol.
Examples of the ether solvents include anisole, dioxane, tetrahydrofuran, and the like, in addition to the above-mentioned glycol ether solvents.
Examples of amide solvents include N-methyl-2-pyrrolidone, N,N-dimethylacetamide, N,N-dimethylformamide, hexamethylphosphoric triamide, and 1,3-dimethyl-2-imidazolidinone. Can be used.
Examples of the hydrocarbon solvent include aromatic hydrocarbon solvents such as toluene and xylene, and aliphatic hydrocarbon solvents such as pentane, hexane, octane, decane, and undecane.
Note that the aliphatic hydrocarbon solvent, which is a hydrocarbon solvent, may be a mixture of compounds having the same number of carbon atoms and different structures. For example, when decane is used as an aliphatic hydrocarbon solvent, compounds with the same number of carbon atoms but different structures such as 2-methylnonane, 2,2-dimethyloctane, 4-ethyl octane, and isooctane are used as aliphatic hydrocarbon solvents. may be included in
In addition, the compounds having the same number of carbon atoms and different structures may contain only one kind, or may contain a plurality of kinds as described above.
A plurality of the above-mentioned solvents may be mixed together, or may be used in combination with a solvent other than the above-mentioned solvents 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 contains substantially no water.
The concentration of the organic solvent (in the case of a mixture of multiple organic solvents, the total) in the organic developer is preferably 50% by mass or more, more preferably 50 to 100% by mass, even more preferably 85 to 100% by mass, and even more preferably 90 to 100% by mass. It is 100% by weight, particularly preferably 95-100% by weight. Most preferably, it consists essentially only of an organic solvent. In addition, the case where it consists essentially only of an organic solvent shall include the case where it contains trace amounts of surfactants, antioxidants, stabilizers, antifoaming agents, and the like.
In particular, the organic developer preferably contains 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, particularly preferably 2 kPa or less at 20°C. By reducing the vapor pressure of the organic developer to 5 kPa or less, evaporation of the developer on the substrate or in the developing cup is suppressed, improving temperature uniformity within the wafer surface, resulting in uniform dimensions within the wafer surface. Sexuality improves.
Specific examples having a vapor pressure of 5 kPa or less include 1-octanone, 2-octanone, 1-nonanone, 2-nonanone, 2-heptanone (methyl amyl ketone), 4-heptanone, 2-hexanone, diisobutyl ketone, Ketone solvents such as cyclohexanone, methylcyclohexanone, phenylacetone, methyl isobutyl ketone, butyl acetate, pentyl acetate, isoamyl acetate, amyl acetate, propylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, diethylene glycol monoethyl Ester solvents such as ether acetate, ethyl-3-ethoxypropionate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, butyl formate, propyl formate, ethyl lactate, butyl lactate, propyl lactate, n- Alcohol solvents such as propyl alcohol, isopropyl alcohol, n-butyl alcohol, sec-butyl alcohol, tert-butyl alcohol, isobutyl alcohol, n-hexyl alcohol, n-heptyl alcohol, n-octyl alcohol, n-decanol, ethylene glycol , diethylene glycol, triethylene glycol, and other glycol solvents, 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 butanol, etc. glycol ether solvents, ether solvents such as tetrahydrofuran, amide solvents such as N-methyl-2-pyrrolidone, N,N-dimethylacetamide, N,N-dimethylformamide, aromatic hydrocarbon solvents such as toluene and xylene. , octane, decane, and other aliphatic hydrocarbon solvents.
Specific examples having a vapor pressure of 2 kPa or less, which is a particularly preferable range, include 1-octanone, 2-octanone, 1-nonanone, 2-nonanone, 2-heptanone, 4-heptanone, 2-hexanone, diisobutyl ketone, Ketone solvents such as cyclohexanone, methylcyclohexanone, phenylacetone, butyl 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-ethoxypropio ester solvents such as ester, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, ethyl lactate, butyl lactate, propyl lactate, n-butyl alcohol, sec-butyl alcohol, tert-butyl alcohol, isobutyl alcohol, Alcohol solvents such as n-hexyl alcohol, n-heptyl alcohol, 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, and ethylene. Glycol ether solvents such as glycol monoethyl ether, propylene glycol monoethyl ether, diethylene glycol monomethyl ether, triethylene glycol monoethyl ether, methoxymethyl butanol, N-methyl-2-pyrrolidone, N,N-dimethylacetamide, N,N -Amide solvents such as dimethylformamide, aromatic hydrocarbon solvents such as xylene, and aliphatic hydrocarbon solvents such as octane, decane, and undecane.

The organic developer may contain a basic compound. Specific examples and preferred examples of the basic compound that can be included in the developer used in the present invention are the same as those for the basic compound that can be included in the actinic ray- or radiation-sensitive composition described above.

An appropriate amount of a surfactant can be added to the organic developer, if necessary.
Although the surfactant is not particularly limited, for example, ionic or nonionic fluorine-based and/or silicon-based surfactants can be used. As these fluorine and/or silicone surfactants, for example, JP-A-62-36663, JP-A-61-226746, JP-A-61-226745, JP-A-62-170950, JP-A-63-34540, JP-A-7-230165, JP-A-8-62834, JP-A-9-54432, JP-A-9-5988, US Pat. No. 5,405,720, Examples include the surfactants described in No. 5360692, No. 5529881, No. 5296330, No. 5436098, No. 5576143, No. 5294511, and No. 5824451. , preferably a nonionic surfactant. The nonionic surfactant is not particularly limited, but it is more preferable to use a fluorine-based surfactant or a silicon-based surfactant.
The amount of surfactant used is preferably 0.0001 to 2% by mass, more preferably 0.0001 to 1% by mass, particularly preferably 0.0001 to 0.1% by mass, based on the total amount of the developer. .

Development methods include, for example, a method in which the 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 then developed by standing still for a certain period of time (paddle method). method), a method in which the developer is sprayed onto the substrate surface (spray method), and a method in which the developer is continuously discharged while scanning the developer discharge nozzle at a constant speed onto a rotating substrate (dynamic dispensing method). etc. can be applied.
When the various developing methods described above include a step of discharging a developer toward the resist film from a developing nozzle of a developing device, the discharge pressure of the discharged developer (flow rate per unit area of the discharged developer) is Preferably it is 2 mL/sec/mm ² or less, more preferably 1.5 mL/sec/mm ² or less, still more preferably 1 mL/sec/mm ² or less. There is no particular lower limit to the flow rate, but in consideration of throughput, it is preferably 0.2 mL/sec/mm ² or more.
By setting the discharge pressure of the developer to be discharged within the above range, pattern defects resulting from resist residue after development can be significantly reduced.
Although the details of this mechanism are not clear, it is likely that by setting the discharge pressure within the above range, the pressure exerted by the developer on the resist film is reduced, which prevents the resist film and pattern from being inadvertently scraped or destroyed. This is thought to be because it is suppressed.
Note that the discharge pressure (mL/sec/mm ² ) of the developer is the value at the exit of the developing nozzle in the developing device.

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

Further, after the step of developing using a developer containing an organic solvent, a step of stopping the development may be performed while substituting another solvent.

After the developing process using a developer containing an organic solvent, a cleaning process using a rinsing liquid may be included, but from the viewpoint of throughput (productivity), amount of rinsing liquid used, etc. It is not necessary to include the step of using and washing.

There is no particular restriction on the rinsing liquid used in the rinsing process after the developing process using a developer containing an organic solvent, as long as it does not dissolve the resist pattern, and a solution containing a general organic solvent can be used. . As the rinsing liquid, 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 is used. It is preferable.
Specific examples of hydrocarbon solvents, ketone solvents, ester solvents, alcohol solvents, amide solvents, and ether solvents include those similar to those explained for the developer containing an organic solvent. Particularly preferred are butyl acetate and methylisobutylcarbinol.
After the step of developing using a developer containing an organic solvent, more preferably a rinsing solution containing at least one organic solvent selected from the group consisting of ester solvents, alcohol solvents, and hydrocarbon solvents is used. It is more preferable to perform a cleaning step using a rinsing liquid containing an alcohol-based solvent or a hydrocarbon-based solvent.

As the organic solvent contained in the rinsing liquid, it is also preferable to use a hydrocarbon solvent among organic solvents, and it is more preferable to use an aliphatic hydrocarbon solvent. As the aliphatic hydrocarbon solvent used in the rinse liquid, from the viewpoint of further improving its effect, aliphatic hydrocarbon solvents having 5 or more carbon atoms (for example, pentane, hexane, octane, decane, undecane, dodecane, (hexadecane, etc.) are preferred, aliphatic hydrocarbon solvents having 8 or more carbon atoms are preferred, and aliphatic hydrocarbon solvents having 10 or more carbon atoms are more preferred.
The upper limit of the number of carbon atoms in the aliphatic hydrocarbon solvent is not particularly limited, but may be, for example, 16 or less, preferably 14 or less, and more preferably 12 or less.
Among the above fatty hydrocarbon solvents, decane, undecane, and dodecane are particularly preferred, and undecane is most preferred.
By using a hydrocarbon solvent (especially an aliphatic hydrocarbon solvent) as the organic solvent contained in the rinse solution, the slight amount of developer that has soaked into the resist film after development is washed away, further suppressing swelling. Therefore, the effect of suppressing pattern collapse is further exhibited.

A plurality of the above-mentioned components may be mixed together, or may be used in combination with an organic solvent other than those mentioned above.

The water content in the rinse liquid is preferably 10% by mass or less, more preferably 5% by mass or less, particularly preferably 3% by mass or less. By controlling the water content to 10% by mass or less, good development characteristics can be obtained.

The vapor pressure of the rinsing liquid used after the step of developing using a developer containing an organic solvent is preferably 0.05 kPa or more and 5 kPa or less, more preferably 0.1 kPa or more and 5 kPa or less, and 0.05 kPa or more and 5 kPa or less at 20°C. Most preferably, the pressure is 12 kPa or more and 3 kPa or less. By controlling the vapor pressure of the rinsing liquid to 0.05 kPa or more and 5 kPa or less, temperature uniformity within the wafer surface is improved, and swelling caused by penetration of the rinsing liquid is suppressed, thereby improving dimensional uniformity within the wafer surface. improves.

An appropriate amount of a surfactant can also be added to the rinsing liquid.

In the rinsing step, the wafer that has been developed using a developer containing an organic solvent is cleaned using the above-mentioned rinsing solution containing an organic solvent. The method of cleaning treatment is not particularly limited, but examples include a method of continuously discharging a rinsing liquid onto a substrate rotating at a constant speed (rotary coating method), and a method of immersing a substrate in a tank filled with a rinsing liquid for a certain period of time. (dip method), a method of spraying a rinsing liquid onto the substrate surface (spray method), etc. Among these, the cleaning treatment is performed using a spin coating method, and after cleaning, the substrate is rotated at a rotation speed of 2000 rpm to 4000 rpm. Preferably, the rinsing liquid is removed from the substrate by rotation. Moreover, it is also preferable to include a heating process (PostBake) after the rinsing process. By baking, the developer and rinse solution remaining between patterns and inside the patterns are removed. The heating step after the rinsing step is usually carried out at 40 to 160°C, preferably 70 to 95°C, for usually 10 seconds to 3 minutes, preferably 30 seconds to 90 seconds.

In the case where there is no step of cleaning using a rinsing liquid, for example, the development processing method described in paragraphs [0014] to [0086] of JP-A-2015-216403 can be adopted.

Further, the pattern forming method of the present invention may include a developing step using an organic developer and a developing step using an alkaline developer. Portions with weak exposure intensity are removed by development using an organic developer, and areas with high exposure intensity are also removed by development with an alkaline developer. By using this multiple development process in which development is performed multiple times, patterns can be formed without dissolving only the regions of intermediate exposure intensity, so it is possible to form finer patterns than usual (paragraph 1 of JP-A-2008-292975). mechanism similar to [0077]).

The actinic ray- or radiation-sensitive composition of the present invention, and various materials used in the pattern forming method of the present invention (e.g., resist solvent, developer, rinsing liquid, composition for forming an antireflective film, top coat forming It is preferable that the composition (for example, a composition for use in a pharmaceutical composition) does not contain impurities such as a metal, a metal salt containing a halogen, an acid, an alkali, a component containing a sulfur atom, or a phosphorus atom. Here, examples of impurities containing metal atoms include Na, K, Ca, Fe, Cu, Mn, Mg, Al, Cr, Ni, Zn, Ag, Sn, Pb, Li, or salts thereof. can.
The content of impurities contained in these materials is preferably 1 ppm or less, more preferably 1 ppb or less, even more preferably 100 ppt (parts per trillion) or less, particularly preferably 10 ppt or less, and substantially free of impurities (parts per trillion). most preferably below the detection limit).
Examples of methods for removing impurities such as metals from various materials include filtration using a filter. The pore size of the filter is preferably 10 nm or less, more preferably 5 nm or less, and even more preferably 3 nm or less. As the material of the filter, a filter made of polytetrafluoroethylene, polyethylene, or nylon is preferable. The filter may be a composite material made of a combination of these materials and ion exchange media. The filter may be washed in advance with an organic solvent. In the filter filtration step, a plurality of types of filters may be used by connecting them in series or in parallel. When using multiple types of filters, filters with different pore sizes and/or materials may be used in combination. Moreover, various materials may be filtered multiple times, and the process of filtering multiple times may be a circulating filtration process.
In addition, methods for reducing impurities such as metals contained in various materials include selecting raw materials with low metal content as raw materials constituting various materials, filtering raw materials constituting various materials, and using equipment to reduce impurities such as metals contained in various materials. Examples of methods include performing distillation under conditions where contamination is suppressed as much as possible by lining the inside with Teflon (registered trademark). Preferable conditions for filtering raw materials constituting various materials are the same as those described above.
In addition to filter filtration, impurities may be removed using an adsorbent, or a combination of filter filtration and adsorbent may be used. As the adsorbent, a known adsorbent can be used, and for example, an inorganic adsorbent such as silica gel or zeolite, or an organic adsorbent such as activated carbon can be used.
In addition, methods for reducing impurities such as metals contained in the organic treatment liquid of the present invention include selecting raw materials with low metal content as raw materials constituting various materials, and filtering raw materials constituting various materials. Examples of methods include filtration, lining the inside of the apparatus with Teflon (registered trademark), and performing distillation under conditions that suppress contamination as much as possible. Preferable conditions for filtering raw materials constituting various materials are the same as those described above.
In addition to filter filtration, impurities may be removed using an adsorbent, or a combination of filter filtration and adsorbent may be used. As the adsorbent, a known adsorbent can be used, and for example, an inorganic adsorbent such as silica gel or zeolite, or an organic adsorbent such as activated carbon can be used.

[Storage container]
Organic solvents (also referred to as "organic processing liquids") that can be used in developing solutions and rinsing solutions include storage containers for organic processing solutions for patterning chemically amplified or non-chemically amplified resist films, which have a storage section. It is preferable to use preserved ones. For example, the storage container may be made of a resin different from polyethylene resin, polypropylene resin, or polyethylene-polypropylene resin, or treated with anti-rust/metal elution prevention treatment on the inner wall of the storage portion that comes into contact with the organic treatment liquid. It is preferable that the container is made of a coated metal and contains an organic treatment liquid for patterning a resist film. An organic solvent to be used as an organic processing liquid for patterning a resist film can be stored in the storage part of the storage container, and the solvent discharged from the storage part can be used when patterning a resist film. .

When the above-mentioned storage container further has a seal part for sealing the above-mentioned storage part, this seal part is also selected from the group consisting of polyethylene resin, polypropylene resin, and polyethylene-polypropylene resin. It is preferably formed from a resin different from the one or more resins, or a metal treated to prevent rust and prevent metal elution.

Here, the seal section means a member that can isolate the housing section from the outside air, and suitable examples include packing, O-rings, and the like.

The resin different from the one or more resins selected from the group consisting of polyethylene resin, polypropylene resin, and polyethylene-polypropylene resin is preferably a perfluoro resin.

Perfluoro resins include tetrafluoroethylene resin (PTFE), tetrafluoroethylene/perfluoroalkyl vinyl ether copolymer (PFA), tetrafluoroethylene-hexafluoropropylene copolymer resin (FEP), and tetrafluoroethylene Ethylene-ethylene copolymer resin (ETFE), trifluorochloroethylene-ethylene copolymer resin (ECTFE), vinylidene fluoride resin (PVDF), trifluorochloride ethylene copolymer resin (PCTFE), vinyl fluoride resin ( PVF), etc.

Particularly preferred perfluoro resins include tetrafluoroethylene resin, tetrafluoroethylene/perfluoroalkyl vinyl ether copolymer, and tetrafluoroethylene/hexafluoropropylene copolymer resin.

Examples of metals subjected to rust prevention/metal elution prevention treatment include carbon steel, alloy steel, nickel chromium steel, nickel chromium molybdenum steel, chromium steel, chrome molybdenum steel, manganese steel, and the like.

It is preferable to apply film technology as the rust prevention/metal elution prevention treatment.

Film technologies are broadly divided into three types: metal coatings (various platings), inorganic coatings (various chemical conversion treatments, glass, concrete, ceramics, etc.), and organic coatings (rust preventive oils, paints, rubber, plastics). .

Preferred coating techniques include surface treatment with rust inhibiting oils, rust inhibitors, corrosion inhibitors, chelating compounds, strippable plastics, and lining agents.

Among them, various chromates, nitrites, silicates, phosphates, carboxylic acids such as oleic acid, dimer acid, and naphthenic acid, carboxylic acid metal soaps, sulfonates, amine salts, and esters (glycerin esters of higher fatty acids). Corrosion inhibitors such as ethylene diantetraacetic acid, gluconic acid, nitrilotriacetic acid, chelate compounds such as hydroxyethyl ethylene diane diamine triacic acid, diethylene triamine pentalic acid, and fluororesin linings are preferred. Particularly preferred are phosphate treatments and fluoropolymer linings.

In addition, compared to direct coating treatment, "pretreatment" is a treatment method that does not directly prevent rust, but can extend the rust prevention period by coating treatment, which is a step before rust prevention treatment. It is also preferable to adopt

As a specific example of such pre-treatment, a suitable treatment may be mentioned in which various corrosive factors such as chlorides and sulfates present on the metal surface are removed by cleaning or polishing.

Specific examples of the storage container include the following.

・Entegris FluoroPure PFA composite drum (wetted inner surface; PFA resin lining)
・JFE steel drum (inner surface in contact with liquid; zinc phosphate film)

Further, examples of storage containers that can be used in the present invention include containers described in JP-A-11-021393 [0013] to [0030] and JP-A-10-45961 [0012] to [0024]. be able to.

The organic treatment liquid of the present invention may contain a conductive compound in order to prevent damage to chemical piping and various parts (filters, O-rings, tubes, etc.) due to static electricity charging and subsequent electrostatic discharge. good. The conductive compound is not particularly limited, but includes, for example, methanol. The amount of addition is not particularly limited, but from the viewpoint of maintaining preferable development characteristics, the amount is preferably 10% by mass or less, more preferably 5% by mass or less. Regarding the parts of the chemical piping, various types of piping coated with SUS (stainless steel), polyethylene or polypropylene treated with antistatic treatment, or fluororesin (polytetrafluoroethylene, perfluoroalkoxy resin, etc.) can be used. can. Similarly, for the filter and O-ring, antistatically treated polyethylene, polypropylene, or fluororesin (polytetrafluoroethylene, perfluoroalkoxy resin, etc.) can be used.

Note that, generally, the developer and the rinse liquid are stored in a waste liquid tank through piping after use. At that time, if a hydrocarbon solvent is used as a rinsing liquid, the resist dissolved in the developing solution will precipitate, and in order to prevent it from adhering to the back of the wafer or the side of the piping, apply the solvent that dissolves the resist to the piping again. There is a way to get through it. There are two ways to pass the substrate through the piping: after cleaning with a rinse solution, the back and side surfaces of the board are washed with a solvent that dissolves the resist, and another method is to run a solvent that dissolves the resist through the piping without contacting the resist. One example is the method of flushing.
The solvent to be passed through the piping is not particularly limited as long as it can dissolve the resist, and examples include the above-mentioned organic solvents, such as propylene glycol monomethyl ether acetate (PGMEA), propylene glycol monoethyl ether acetate, propylene glycol monopropyl Ether acetate, propylene glycol monobutyl ether acetate, propylene glycol monomethyl ether propionate, propylene glycol monoethyl ether propionate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether (PGME), propylene glycol mono Ethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, 2-heptanone, ethyl lactate, 1-propanol, acetone, etc. can be used. Among them, PGMEA, PGME, and cyclohexanone can be preferably used.

[Photomask]
The present invention also relates to a photomask produced using the above-described pattern forming method. A photomask created using the above-described pattern forming method may be a light-transmissive mask used in ArF excimer laser or the like, or a light-reflective mask used in reflective lithography using EUV light as a light source. Good too.

[Manufacturing method of electronic device]
The present invention also relates to a method for manufacturing an electronic device, including the above-described pattern forming method. The electronic device manufactured by the electronic device manufacturing method of the present invention can be suitably installed in electrical and electronic equipment (e.g., home appliances, OA (Office Automation)-related equipment, media-related equipment, optical equipment, communication equipment, etc.). be done.

[Compound]
The present invention also relates to a compound represented by the following general formula (3).

In general formula (3), Q ₁ and Q ₂ each independently represent a substituent.
R ₃ to R ₅ each independently represent a hydrogen atom or a substituent. At least one of R ₃ to R ₅ represents a group represented by the following general formula (R-1).
R ₁₀₁ to R ₁₀₃ each independently represent a hydrogen atom or a substituent. Two of R ₁₀₁ to R ₁₀₃ may be bonded to each other to form a ring.
n represents an integer of 2 or more, and R ₁₀₁ s, R ₁₀₂ s, and R _103s may be the same or different.

In the general formula (R-1), A represents a single bond or a (m+1)-valent linking group.
Y each independently represents a group represented by any one of the following formulas (A1) to (A6).
m represents an integer of 1 or more.
When m represents an integer of 2 or more, the plurality of Y's may be the same or different.
* represents a bond to the benzene ring.

In formulas (A1) to (A6), * represents a bond to A.
In formula (A2), R ₆ represents a substituent having a carbon atom. The sulfur atom in SO ₂ of formula (A2) bonds with the carbon atom in R ₆ . Further, R ₆ may be combined with A or L to form a ring.
L represents a single bond, a carbonyl bond, an alkylene group, or a divalent aromatic group.
In formula (A3), R ₇ represents a substituent having a carbon atom. N ⁻ in formula (A3) is bonded to the above carbon atom in R ₇ . Furthermore, R ₇ may combine with A to form a ring.
In formula (A4), R ₈ represents a substituent having a carbon atom. The carbon atom in the carbonyl bond of formula (A4) is bonded to the carbon atom in R ₈ . Moreover, R ₈ may combine with A to form a ring.
In formula (A5), R ₉ and R _9' each independently represent a hydrogen atom or a substituent. R ₉ and R _9' may be combined with each other to form a ring.

Q ₁ , Q ₂ , R ₃ to R ₅ , R ₁₀₁ to R ₁₀₃ , and n in general formula (3) are Q ₁ , Q ₂ , R ₃ in general formula (3) in the above compound (B). ~R ₅ , R ₁₀₁ ~R ₁₀₃ , and n, respectively.
A, Y, and m in the general formula (R-1) are the same as A, Y, and m in the group represented by the above general formula (R-1) in the above compound (B).
Each group in formulas (A1) to (A6) is the same as each group in the above formulas (A1) to (A6) in the above compound (B).

The present invention also relates to a compound in which Q ₁ and Q ₂ in the general formula (3) are each independently an aliphatic hydrocarbon ring group, an aryl group, or a heteroaryl group.
The aliphatic hydrocarbon ring group, aryl group, and heteroaryl group represented by _{Q 1 and} Q ₂ in the general formula (3 ₎ are The same applies to the aliphatic hydrocarbon ring group, aryl group, and heteroaryl group represented.

The present invention will be explained in more detail below based on Examples. The materials, usage amounts, proportions, processing details, processing procedures, etc. shown in the following examples can be changed as appropriate without departing from the spirit of the present invention. Therefore, the scope of the present invention should not be construed as being limited by the Examples shown below.

<Resin (A)>
The structure of the repeating unit of the resin (A) used, its content (molar ratio), weight average molecular weight (Mw), and degree of dispersion (Mw/Mn) are shown below.

The number attached to the leftmost repeating unit in Resin (A-20) to Resin (A-25) represents the content (molar ratio) of the repeating unit.
The numbers attached to each repeating unit in resin (A-26) and resin (A-27) represent the content (molar ratio).
The numbers attached to the repeating units on the right side of resins (A-28) to resins (A-30) represent the content (molar ratio) of the repeating units.
The numbers attached to each repeating unit in resin (A-31) and resin (A-32) represent the content (molar ratio).

<Photoacid generator (B)>
<Synthesis Example 1: Synthesis of photoacid generator (B-3)>

(1) (Synthesis of B-3-1)
75.0 g of 4-bromo-2,6-trichlorobenzenesulfonyl chloride and 1.41 g of N,N-dimethyl-4-aminopyridine were dissolved in 267 g of tetrahydrofuran, and after cooling to 0°C, 25.7 g of isobutyl alcohol and 39 g of triethylamine were dissolved. .8 g was added dropwise, and the mixture was stirred at room temperature (20° C.) for 3 hours. 1N hydrochloric acid was added to the reaction mixture to separate the layers, and the organic layer was washed with 1N hydrochloric acid, saturated aqueous sodium bicarbonate, and saturated brine, and then dried by adding anhydrous magnesium sulfate. After filtration, the solvent in the filtrate was distilled off under reduced pressure, and after vacuum drying, 74.2 g of compound (B-3-1) was obtained.

(2) (Synthesis of B-3-2)
30.0 g of compound (B-3-1), 19.4 g of 4-(methoxycarbonyl)phenylboronic acid, 22.9 g of potassium carbonate, 261 g of 1,2-dimethoxyethane, and 100 g of pure water were charged and degassed. Next, 1.69 g of [1,1'-bis(diphenylphosphino)ferrocene]palladium(II) dichloride dichloromethane adduct was added, and the mixture was stirred at 80°C for 10 hours. Ethyl acetate was added to the reaction mixture to separate the layers, and the organic layer was washed with saturated brine and dried by adding anhydrous magnesium sulfate. After evaporating the solvent under reduced pressure, the concentrated residue was purified by silica gel column chromatography (ethyl acetate/hexane = 3/1) to obtain 25.0 g of compound (B-3-2) as white crystals.

(3) (Synthesis of B-3-3)
9.0 g of compound (B-3-2), 11.0 g of 4-(tetrahydro-2H-pyran-2-yloxy)phenylboronic acid, 18.3 g of tripotassium phosphate, 0.885 g of S-Phos, 178 g of tetrahydrofuran, 100g of pure water was charged and degassed. Then, 0.242 g of palladium acetate was added, and the mixture was stirred at 80° C. for 10 hours. Ethyl acetate was added to the reaction mixture to separate the layers, and the organic layer was washed with saturated brine and dried by adding anhydrous magnesium sulfate. After distilling off the solvent under reduced pressure, the concentrated residue was purified by silica gel column chromatography (ethyl acetate/hexane = 3/1) to obtain 9.52 g of compound (B-3-2) as white crystals.

(3) (Synthesis of B-3-3)
9.00 g of compound (B-3-3), 40 g of acetonitrile, and 2.12 g of sodium iodide were charged and stirred at 80° C. for 8 hours. The solid was filtered off and washed with acetone and hexane. After vacuum drying, 8.02 g of compound (B-3-3) was obtained.

(4) (Synthesis of B-3)
2.00 g of compound (B-3-3), 28 g of a 2.38% by mass aqueous tetramethylammonium hydroxide solution, and 22.5 g of tetrahydrofuran were charged and stirred at 60° C. for 1 hour. Water and the solvent were removed by vacuum concentration. 2.01 g of triphenylsulfonium bromide, 15.0 g of methylene chloride, and 10 g of pure water were added to the concentrated residue, and the mixture was stirred at room temperature for 3 hours. After washing the organic phase with pure water, the solvent was distilled off under reduced pressure, and the mixture was azeotroped with isopropyl ether. The obtained crude product was recrystallized from ethyl acetate/isopropyl ether, and after vacuum drying, compound (B-3) (2.23 g) was obtained.
The ¹ H-NMR spectrum (400 MHz, DMSO-d6) of compound (B-3) shows that δ=7.91-7.7.73 (m, 32H), 7.53 (d, J=8. 0Hz, 2H), 7.49 (d, J = 8.7Hz, 4H), 7.27 (s, 2H), 6.93 (d, J = 8.7Hz, 4H), 5.49-5. 42 (m, 2H), 3.89-4.81 (m, 2H), 3.63-3.50 (m, 2H), 1.98-1.46 (m, 12H).

Compounds (B-1), (B-2), and (B-4) to (B-21) were synthesized using the same method below. Note that Me represents a methyl group.
Compounds (B-1), (B-2), (B-4) to (B-21) are formed by combining the cations listed in Table 1 and the anions listed in Table 1. Regarding cations, the number of cations contained in the compound is also listed.

The following compounds (B'-1) to (B'-4) were used in comparative examples.

The structures of the cations listed in Table 1 are shown below. Me represents a methyl group, and Bu represents an n-butyl group.

The structures of the anions listed in Table 1 are shown below. Me represents a methyl group, and tBu represents a t-butyl group.

<Acid diffusion control agent>
The structure of the acid diffusion control agent used is shown below.

<Surfactant>
As surfactants, the following W-1 to W-4 were used.
W-1: Megafac R08 (manufactured by Dainippon Ink and Chemicals Co., Ltd.; fluorine and silicone-based)
W-2: Polysiloxane polymer KP-341 (manufactured by Shin-Etsu Chemical Co., Ltd.; silicone-based)
W-3: Troil S-366 (manufactured by Troy Chemical Co., Ltd.; fluorine-based)
W-4: PF6320 (manufactured by OMNOVA; fluorine-based)

<Solvent>
The solvents used are shown below.
S-1: Propylene glycol monomethyl ether acetate (PGMEA)
S-2: Propylene glycol monomethyl ether (PGME)
S-3: Ethyl lactate (EL)
S-4: Ethyl 3-ethoxypropionate (EEP)
S-5: 2-heptanone (MAK)
S-6: Methyl 3-methoxypropionate (MMP)
S-7: 3-methoxybutyl acetate S-8: γ-butyrolactone

[Preparation and application of coating solution of resist composition]
(1) Preparation of Support An 8-inch wafer on which Cr oxynitride was vapor-deposited (treated with a shielding film used in ordinary photomask blanks) was prepared.
(2) Preparation of resist composition The components shown in Table 2 were dissolved in the solvent shown in the same table to prepare a solution, and this was filtered through a polyethylene filter having a pore size of 0.03 μm to prepare a resist composition.
(3) Preparation of resist film A resist composition was applied onto the 8-inch wafer using a spin coater Mark8 manufactured by Tokyo Electron, and dried on a hot plate at 120°C for 600 seconds to obtain a resist film with a thickness of 100 nm. Ta. That is, a resist-coated wafer was obtained.

[EB exposure and development]
(4) Preparation of resist pattern Pattern irradiation was performed on the resist film obtained in the above (3) using an electron beam drawing device (manufactured by Advantest Corporation; F7000S, acceleration voltage 50 KeV). After irradiation, it was heated on a hot plate at 100° C. for 600 seconds, immersed in a 2.38% by mass tetramethylammonium hydroxide (TMAH) aqueous solution for 60 seconds, and then rinsed with water for 30 seconds and dried.

[evaluation]
(5) Evaluation of resist pattern The obtained pattern was evaluated for resolution, roughness performance, and development defects using the following methods. The results are shown in Table 3 below.

The irradiation energy used to resolve a 1:1 line-and-space pattern with a line width of 50 nm was defined as the sensitivity (Eop).

<L/S resolution>
The critical resolving power (minimum line width at which lines and spaces (line:space=1:1) are separated and resolved) at the exposure amount showing the above sensitivity (Eop) was defined as the resolving power (nm).

<Isolated space pattern (IS) resolution>
The critical resolution (minimum space width at which lines and spaces can be separated and resolved) of an isolated space (line:space=100:1) at the above sensitivity (Eop) was determined. This value was defined as "isolated space pattern resolution (nm)". The smaller this value is, the better the performance is.

<Roughness performance (LWR)>
A 20 nm (1:1) line-and-space pattern resolved at the optimum exposure dose for resolving a line pattern with an average line width of 30 nm was examined using a length-measuring scanning electron microscope (SEM Co., Ltd.). When observing from above the pattern using Hitachi S-9380II)), the line width was observed at arbitrary points, and the measurement variation was evaluated in 3σ (nm). The smaller the value, the better the performance.

<Development defects>
A 1:1 line and space pattern with a line width of 50 nm formed at the above sensitivity (Eop) was measured using a defect inspection device KLA2360 (trade name) manufactured by KLA-Tencor Co., Ltd., and the pixel size of the defect inspection device was set to 0. 16 μm and the threshold value is set to 20, detect the defects (number/cm ² ) extracted from the difference caused by superimposing the comparison image and pixel by pixel, and calculate the number of defects per unit area (number/cm ^{2 )} . ) was calculated. Thereafter, by conducting a defect review, development defects were classified and extracted from all the defects, and the number of development defects per unit area (pieces/cm ² ) was calculated. AA for values less than 0.25, A for 0.25 or more and less than 0.5, B for 0.5 or more and less than 1.0, C for 1.0 or more and less than 5.0. Those with a score of 5.0 or higher were rated D. The smaller the value, the better the performance.

In addition, in Table 2 below, the content (mass %) of each component other than the solvent means the content ratio with respect to the total solid content. Further, in Table 2 below, the content ratio (mass %) of the used solvent to the total solvent is listed.

From the results in Table 3, it can be seen that the pattern obtained by the pattern forming method of the present invention has excellent resolution and roughness performance, and has suppressed development defects.

[Extreme ultraviolet (EUV) exposure and development]
(4) Preparation of resist pattern The wafer coated with the resist film obtained in (3) above was exposed to an EUV exposure device (Exitech Micro Exposure Tool, NA (numerical aperture) 0.3, Quadrupole, Outer Sigma 0.3. 68, inner sigma 0.36) and an exposure mask (line/space=1/1), pattern exposure was performed. After exposure, it was heated on a hot plate at 100° C. for 90 seconds, immersed in a 2.38% by mass tetramethylammonium hydroxide (TMAH) aqueous solution for 60 seconds, and then rinsed with water for 30 seconds. Thereafter, the wafer was rotated at a rotation speed of 4000 rpm for 30 seconds, and then baked at 95° C. for 60 seconds to dry it.

[evaluation]
(5) Evaluation of resist pattern The obtained pattern was evaluated for resolution, roughness performance, and development defects using the following methods. The results are shown in Table 4 below.

The irradiation energy used to resolve a 1:1 line-and-space pattern with a line width of 50 nm was defined as the sensitivity (Eop).

<L/S resolution>
The critical resolving power (minimum line width at which lines and spaces (line:space=1:1) are separated and resolved) at the exposure amount showing the above sensitivity (Eop) was defined as the resolving power (nm).

<Isolated space pattern (IS) resolution>
The critical resolution (minimum space width at which lines and spaces can be separated and resolved) of an isolated space (line:space=100:1) at the above sensitivity (Eop) was determined. This value was defined as "isolated space pattern resolution (nm)". The smaller this value is, the better the performance is.

<Roughness performance (LWR)>
A 20 nm (1:1) line-and-space pattern resolved at the optimum exposure dose for resolving a line pattern with an average line width of 30 nm was examined using a length-measuring scanning electron microscope (SEM Co., Ltd.). When observing from above the pattern using Hitachi S-9380II)), the line width was observed at arbitrary points, and the measurement variation was evaluated in 3σ (nm). The smaller the value, the better the performance.

<Development defects>
A 1:1 line and space pattern with a line width of 50 nm formed at the above sensitivity (Eop) was measured using a defect inspection device KLA2360 (trade name) manufactured by KLA-Tencor Co., Ltd., and the pixel size of the defect inspection device was set to 0. 16 μm and the threshold value is set to 20, detect the defects (number/cm ² ) extracted from the difference caused by superimposing the comparison image and pixel by pixel, and calculate the number of defects per unit area (number/cm ^{2 )} . ) was calculated. Thereafter, by conducting a defect review, development defects were classified and extracted from all the defects, and the number of development defects per unit area (pieces/cm ² ) was calculated. AA for values less than 0.25, A for 0.25 or more and less than 0.5, B for 0.5 or more and less than 1.0, C for 1.0 or more and less than 5.0. Those with a score of 5.0 or higher were rated D. The smaller the value, the better the performance.

From the results in Table 4, it can be seen that the pattern obtained by the pattern forming method of the present invention has excellent resolution and roughness performance, and has suppressed development defects.

According to the present invention, in the formation of ultra-fine patterns (in particular, line width or space width of 30 nm or less), actinic ray sensitivity can improve roughness performance, improve resolution, and reduce development defects at a high level. Alternatively, a radiation-sensitive resin composition can be provided. According to the present invention, there is provided an actinic ray-sensitive or radiation-sensitive film, a pattern forming method, a photomask, a method for manufacturing an electronic device, and a compound using the above-mentioned actinic ray-sensitive or radiation-sensitive resin composition. I can do it.

Although the invention has been described in detail and with reference to specific embodiments, it will be apparent to those skilled in the art that various changes and modifications can be made without departing from the spirit and scope of the invention.
This application is based on a Japanese patent application (Japanese Patent Application No. 2020-65184) filed on March 31, 2020, the contents of which are incorporated herein as a reference.

Claims (17)

An actinic ray-sensitive or radiation-sensitive resin composition containing the following (A) and (B).
(A) A resin whose polarity increases due to the action of an acid. (B) A compound that generates an acid upon irradiation with actinic rays or radiation and is represented by the following general formula (1).

In general formula (1), R ₁ to R ₅ each independently represent a hydrogen atom or a substituent. At least one of R ₁ to R ₅ represents a group represented by the following general formula (R-1). (M ⁺ ) _n represents a cation moiety. n represents an integer of 2 or more.

In the general formula (R-1), A represents a single bond or a (m+1)-valent linking group.
Y each independently represents a group represented by any one of the following formulas (A1) to (A6).
m represents an integer of 1 or more.
When m represents an integer of 2 or more, the plurality of Y's may be the same or different.
* represents a bond to the benzene ring.

In formulas (A1) to (A6), * represents a bond to A.
In formula (A2), R ₆ represents a substituent having a carbon atom. The sulfur atom in _SO2 of formula (A2) bonds with the carbon atom in _R6 . Further, R ₆ may be combined with A or L to form a ring.
L represents a single bond, a carbonyl bond, an alkylene group, or a divalent aromatic group.
In formula (A3), R ₇ represents a substituent having a carbon atom. N ⁻ in formula (A3) is bonded to the carbon atom in R ₇ . Furthermore, R ₇ may combine with A to form a ring.
In formula (A4), R ₈ represents a substituent having a carbon atom. The carbon atom in the carbonyl bond of formula (A4) bonds with the carbon atom in R ₈ . Moreover, R ₈ may combine with A to form a ring.
In formula (A5), R ₉ and R _9' each independently represent a hydrogen atom or a substituent. R ₉ and R _9' may be combined with each other to form a ring. The actinic ray-sensitive or radiation-sensitive resin composition according to claim 1, wherein the compound (B) is a compound represented by the following general formula (2).

In general formula (2), R ₁ to R ₅ each independently represent a hydrogen atom or a substituent. At least one of R ₁ to R ₅ represents a group represented by the general formula (R-1).
R ₁₀₁ to R ₁₀₃ each independently represent a hydrogen atom or a substituent. Two of R ₁₀₁ to R ₁₀₃ may be bonded to each other to form a ring.
n represents an integer of 2 or more. A plurality of R ₁₀₁ s, a plurality of R _{102 s} , and a plurality of R ₁₀₃ may be the same or different. The actinic ray-sensitive or radiation-sensitive resin composition according to claim 2, wherein the compound represented by the general formula (2) is a compound represented by the following general formula (3).

In general formula (3), Q ₁ and Q ₂ each independently represent a substituent.
R ₃ to R ₅ each independently represent a hydrogen atom or a substituent. At least one of R ₃ to R ₅ represents a group represented by the general formula (R-1).
R ₁₀₁ to R ₁₀₃ each independently represent a hydrogen atom or a substituent. Two of R ₁₀₁ to R ₁₀₃ may be bonded to each other to form a ring.
n represents an integer of 2 or more. A plurality of R ₁₀₁ s, a plurality of R _{102 s} , and a plurality of R ₁₀₃ may be the same or different. The actinic ray-sensitive or radiation-sensitive resin according to claim 3, wherein in the general formula (3), Q ₁ and Q ₂ are each independently an aliphatic hydrocarbon ring group, an aryl group, or a heteroaryl group. Composition. The actinic ray-sensitive or radiation-sensitive resin composition according to claim 3 or 4, wherein in the general formula (3), Q ₁ and Q ₂ are each an aryl group. Actinic ray-sensitive or radiation-sensitive according to any one of claims 3 to 5, wherein Q ₁ and Q ₂ in the general formula (3) are each a group represented by the following general formula (Ar). resin composition.

In the general formula (Ar), R ₁₀ to R ₁₄ each independently represent a hydrogen atom or a substituent. At least one of R ₁₀ to R ₁₄ is a group containing a polar group, a group containing a group whose polarity increases when decomposed by the action of an acid, or a group which decomposes by the action of an alkaline developer and has solubility in the alkaline developer. It is a group containing a group in which .
* represents a bond to the benzene ring in general formula (3). Actinic ray-sensitive or radiation-sensitive according to any one of claims 3 to 5, wherein Q ₁ and Q ₂ in the general formula (3) are each a group represented by the following general formula (Ar1). resin composition.

In the general formula (Ar1), R ₁₅ to R ₁₉ each independently represent a hydrogen atom or a substituent. At least one of R ₁₅ to R ₁₉ represents the following substituent X.
* represents a bond to the benzene ring in general formula (3).
Substituent X: hydroxy group, carboxyl group, group having a carbonyl bond, alkoxy group, acyloxy group, alkoxycarbonyloxy group, aryloxycarbonyloxy group, aryloxycarbonyl group, alkoxycarbonyl group, aryloxyalkyloxy group, alkoxyalkyl Oxy group, carbamoyl group, or imide group The actinic ray-sensitive or radiation-sensitive resin composition according to any one of claims 1 to 7, wherein the compound (B) is a compound represented by the following general formula (4).

In general formula (4), R ₃ and R ₅ each independently represent a hydrogen atom or a substituent.
A represents a single bond or a (m+1)-valent linking group.
Y each independently represents a group represented by any one of the above formulas (A1) to (A6).
m represents an integer of 1 or more.
When m represents an integer of 2 or more, the plurality of Y's may be the same or different.
R ₂₀ to R ₂₄ each independently represent a hydrogen atom or a substituent. At least one of R ₂₀ to R ₂₄ represents the following substituent X.
R ₂₅ to R ₂₉ each independently represent a hydrogen atom or a substituent. At least one of R ₂₅ to R ₂₉ represents the following substituent X.
R ₁₀₁ to R ₁₀₃ each independently represent a hydrogen atom or a substituent. Two of R ₁₀₁ to R ₁₀₃ may be bonded to each other to form a ring.
n represents an integer of 2 or more, and R ₁₀₁ s, R ₁₀₂ s, and R _103s may be the same or different.
Substituent X: hydroxy group, carboxyl group, group having a carbonyl bond, alkoxy group, acyloxy group, alkoxycarbonyloxy group, aryloxycarbonyloxy group, aryloxycarbonyl group, alkoxycarbonyl group, aryloxyalkyloxy group, alkoxyalkyl Oxy group, carbamoyl group, or imide group A claim in which A in the general formula (R-1) and A in the general formula (4) in the compounds represented by the general formulas (1) to (3) are divalent aromatic groups. Actinic ray-sensitive or radiation-sensitive resin composition according to any one of 1 to 8. The actinic ray-sensitive or radiation-sensitive resin composition according to claim 8, wherein the compound represented by the general formula (4) is a compound represented by the following general formula (5).

In general formula (5), R ₃ and R ₅ each independently represent a hydrogen atom or a substituent.
R ₂₀ to R ₂₄ each independently represent a hydrogen atom or a substituent. At least one of R ₂₀ to R ₂₄ represents the following substituent X.
R ₂₅ to R ₂₉ each independently represent a hydrogen atom or a substituent. At least one of R ₂₅ to R ₂₉ represents the following substituent X.
R ₃₀ to R ₃₄ each independently represent a hydrogen atom or a substituent. At least one of R ₃₀ to R ₃₄ represents a group represented by the following general formula (R-2).
R ₁₀₁ to R ₁₀₃ each independently represent a hydrogen atom or a substituent. Two of R ₁₀₁ to R ₁₀₃ may be bonded to each other to form a ring.
n represents an integer of 2 or more, and R ₁₀₁ s, R ₁₀₂ s, and R _103s may be the same or different.
Substituent X: hydroxy group, carboxyl group, group having a carbonyl bond, alkoxy group, acyloxy group, alkoxycarbonyloxy group, aryloxycarbonyloxy group, aryloxycarbonyl group, alkoxycarbonyl group, aryloxyalkyloxy group, alkoxyalkyl Oxy group, carbamoyl group, or imide group

In the general formula (R-2), A' represents a single bond or a (m1+1)-valent linking group.
Y each independently represents a group represented by any one of the above formulas (A1) to (A6).
m1 represents an integer of 1 or more.
When m1 represents an integer of 2 or more, the plurality of Y's may be the same or different.
* represents a bond to the benzene ring in general formula (5). The actinic ray-sensitive or radiation-sensitive resin composition according to claim 10, wherein in the general formula (5), A' is a single bond or a methylene group. The actinic ray-sensitive or radiation-sensitive resin composition according to any one of claims 1 to 11, wherein in the general formulas (1) to (5), n is 2. The actinic ray-sensitive or radiation-sensitive resin composition according to any one of claims 1 to 12, which is used for producing a photomask. An actinic ray-sensitive or radiation-sensitive film formed using the actinic ray-sensitive or radiation-sensitive resin composition according to any one of claims 1 to 13. A resist film forming step of forming a resist film using the actinic ray-sensitive or radiation-sensitive resin composition according to any one of claims 1 to 13, an exposure step of exposing the resist film to light, and a step of exposing the resist film to light. a developing step of developing the resist film using a developer. A photomask produced using the pattern forming method according to claim 15. A method for manufacturing an electronic device, comprising the pattern forming method according to claim 15.