JP6053868B2 - Actinic ray-sensitive or radiation-sensitive resin composition, and resist film, pattern forming method, and electronic device manufacturing method using the same - Google Patents

Description

  The present invention relates to a pattern forming method, an actinic ray-sensitive or radiation-sensitive resin composition, and a resist film. More specifically, the present invention relates to a pattern forming method and actinic ray sensitivity suitable for use in semiconductor manufacturing processes such as ICs, circuit boards such as liquid crystal and thermal heads, and other photofabrication lithography processes. Or it relates to a radiation sensitive resin composition and a resist film. In particular, the present invention relates to an ArF exposure apparatus, an ArF immersion projection exposure apparatus, and an EUV exposure apparatus that use far ultraviolet light having a wavelength of 300 nm or less as a light source. Or it relates to a radiation sensitive resin composition and a resist film.

  Since the resist for KrF excimer laser (248 nm), an image forming method called chemical amplification has been used as an image forming method for a resist in order to compensate for sensitivity reduction due to light absorption. An example of a positive-type chemical amplification image forming method will be described. When exposed, the acid generator in the exposed area decomposes to generate an acid, and the acid generated in the exposure bake (PEB) is a reaction catalyst. Is used to change an alkali-insoluble group to an alkali-soluble group, and an exposed portion is removed by alkali development. A positive-type image forming method using this chemical amplification mechanism is currently mainstream. For example, it is also known to form a contact hole using this method (see Patent Documents 1 and 2). .

  However, in the positive image forming method, isolated lines and dot patterns can be formed satisfactorily. However, when an isolated space or a fine hole pattern is formed, the shape of the pattern tends to deteriorate.

  In recent years, there has been a demand for further miniaturization of patterns. Recently, not only the currently mainstream positive type, but also a resist film obtained using a negative chemically amplified resist composition is solved using an organic developer. A technique for imaging is also known (for example, Patent Document 3).

International Publication No. 08/149701 JP 2004-361629 A JP 2011-123469 A

However, in recent years, the need for miniaturization of contact holes has increased rapidly, and in response to this, a hole pattern having an extremely fine hole diameter (for example, 60 nm or less) is to be formed in a resist film. In the conventional method, it is difficult to obtain a pattern having an excellent shape.
In particular, in the formation of a hole pattern having an ultrafine hole diameter, the influence of the hole diameter on the development time is large (that is, the increase / decrease amount of the hole diameter associated with the development time cannot be ignored), and the hole diameter is set to a desired size. It was difficult.

  The present invention has been made in view of the above problems, and its object is to provide a hole pattern having an ultrafine pore diameter (for example, 60 nm or less) and excellent in roundness, and having good development time dependency. (That is, an actinic ray-sensitive or radiation-sensitive resin composition that can be formed with a low performance of the development time with respect to the pore diameter), and a resist film, a pattern formation method, and an electron using the same It is in providing the manufacturing method of a device, and an electronic device.

上記一般式（Ｉ）中、Ｒ_０は、水素原子又はメチル基を表す。
Ｒ_１、Ｒ_２及びＲ_３は、各々独立に、直鎖状又は分岐状のアルキル基を表す。

上記一般式中、
Ｘｆは、各々独立に、フッ素原子、又は、少なくとも１つのフッ素原子で置換されたアルキル基を表す。
Ｒ_１及びＲ_２は、各々独立に、水素原子、フッ素原子、又は、アルキル基を表す。
Ｌは、各々独立に、２価の連結基を表す。
Ｃｙは、環状の有機基を表す。
Ｒｆは、フッ素原子を含んだ基である。
ｘは、１〜２０の整数を表す。
ｙは、０〜１０の整数を表す。
ｚは、０〜１０の整数を表す。
＜２＞
（Ｐ）下記一般式（Ｉ）で表される繰り返し単位（ａ）を有し、芳香族基を有する繰り返し単位の比率が５モル％以下で、かつフッ素原子及び珪素原子を有さない樹脂、
（Ｂ）活性光線又は放射線の照射により、下記一般式（ＩＩ）又は（ＩＩＩ）で表される有機酸を発生する化合物、１価のパーフルオロアルカンスルホン酸を発生する化合物、及びフッ素置換イミド酸を発生する化合物の少なくともいずれか１種の化合物、並びに、
（Ｃ）活性光線又は放射線の照射により塩基性が低下する、塩基性化合物又はアンモニウム塩化合物を含有する感活性光線性又は感放射線性樹脂組成物であって、
前記化合物（Ｂ）と前記化合物（Ｃ）とは異なる化合物であり、
前記化合物（Ｃ）の前記化合物（Ｂ）に対するモル比率［Ｃ］／［Ｂ］が０．４０以上であり、
前記樹脂（Ｐ）が、ヒドロキシアダマンチル基又はジヒドロキシアダマンチル基を有する繰り返し単位を更に有する樹脂である、感活性光線性又は感放射線性樹脂組成物。

上記一般式（Ｉ）中、Ｒ _０ は、水素原子又はメチル基を表す。
Ｒ _１ 、Ｒ _２ 及びＲ _３ は、各々独立に、直鎖状又は分岐状のアルキル基を表す。

上記一般式中、
Ｘｆは、各々独立に、フッ素原子、又は、少なくとも１つのフッ素原子で置換されたアルキル基を表す。
Ｒ _１ 及びＲ _２ は、各々独立に、水素原子、フッ素原子、又は、アルキル基を表す。
Ｌは、各々独立に、２価の連結基を表す。
Ｃｙは、環状の有機基を表す。
Ｒｆは、フッ素原子を含んだ基である。
ｘは、１〜２０の整数を表す。
ｙは、０〜１０の整数を表す。
ｚは、０〜１０の整数を表す。
＜３＞
（Ｐ）下記一般式（Ｉ）で表される繰り返し単位（ａ）を有し、芳香族基を有する繰り返し単位の比率が５モル％以下で、かつフッ素原子及び珪素原子を有さない樹脂、
（Ｂ）活性光線又は放射線の照射により、下記一般式（ＩＩ）又は（ＩＩＩ）で表される有機酸を発生する化合物、１価のパーフルオロアルカンスルホン酸を発生する化合物、及びフッ素置換イミド酸を発生する化合物の少なくともいずれか１種の化合物、並びに、
（Ｃ）活性光線又は放射線の照射により塩基性が低下する、塩基性化合物又はアンモニウム塩化合物を含有する感活性光線性又は感放射線性樹脂組成物であって、
前記化合物（Ｂ）と前記化合物（Ｃ）とは異なる化合物であり、
前記化合物（Ｃ）の前記化合物（Ｂ）に対するモル比率［Ｃ］／［Ｂ］が０．４０以上であり、
前記樹脂（Ｐ）が、スルトン構造を有する繰り返し単位を含む樹脂である、感活性光線性又は感放射線性樹脂組成物。

上記一般式（Ｉ）中、Ｒ _０ は、水素原子又はメチル基を表す。
Ｒ _１ 、Ｒ _２ 及びＲ _３ は、各々独立に、直鎖状又は分岐状のアルキル基を表す。

上記一般式中、
Ｘｆは、各々独立に、フッ素原子、又は、少なくとも１つのフッ素原子で置換されたアルキル基を表す。
Ｒ _１ 及びＲ _２ は、各々独立に、水素原子、フッ素原子、又は、アルキル基を表す。
Ｌは、各々独立に、２価の連結基を表す。
Ｃｙは、環状の有機基を表す。
Ｒｆは、フッ素原子を含んだ基である。
ｘは、１〜２０の整数を表す。
ｙは、０〜１０の整数を表す。
ｚは、０〜１０の整数を表す。
＜４＞
前記感活性光線性又は感放射線性樹脂組成物の全固形分に対する前記化合物（Ｃ）の含有量が１．０質量％以上である、＜１＞〜＜３＞のいずれか１項に記載の感活性光線性又は感放射線性樹脂組成物。
＜５＞
前記感活性光線性又は感放射線性樹脂組成物の全固形分に対する前記化合物（Ｃ）の含有量が４．０質量％以上である、＜４＞に記載の感活性光線性又は感放射線性樹脂組成物。
＜６＞
前記モル比率［Ｃ］／［Ｂ］が０．４０〜１．４０である、＜１＞〜＜５＞のいずれか１項に記載の感活性光線性又は感放射線性樹脂組成物。
＜７＞
前記化合物（Ｃ）が、塩基性窒素原子を有するとともに、活性光線又は放射線の照射により有機酸を発生する化合物である、＜２＞又は＜３＞に記載の感活性光線性又は感放射線性樹脂組成物。
＜８＞
活性光線又は放射線の照射により前記化合物（Ｃ）が発生する前記有機酸が、下記一般式（Ｃ１）又は（Ｃ２）で表される有機酸である、＜１＞又は＜７＞に記載の感活性光線性又は感放射線性樹脂組成物。

上記一般式中、
Ｘｆは、各々独立に、フッ素原子、又は、少なくとも１つのフッ素原子で置換されたアルキル基を表す。
Ｒ_１及びＲ_２は、各々独立に、水素原子、フッ素原子、又は、アルキル基を表す。
Ｌは、各々独立に、２価の連結基を表す。
Ｂａは、前記塩基性窒素原子を含む官能基を表す。
Ｒｆは、フッ素原子を含んだ基である。
ｘは、１〜２０の整数を表す。
ｙは、０〜１０の整数を表す。
ｚは、０〜１０の整数を表す。
＜９＞
前記化合物（Ｃ）がオニウム塩化合物である、＜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＞
前記繰り返し単位（ａ）の前記樹脂（Ｐ）の全繰り返し単位に対する含有量が、４５モル％以上である、＜１＞〜＜９＞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。
＜１１＞
前記Ｒ_１、Ｒ_２及びＲ_３についての直鎖状又は分岐状のアルキル基が炭素数１〜４のアルキル基である、＜１＞〜＜１０＞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。
＜１２＞
前記感活性光線性又は感放射線性樹脂組成物が、フッ素原子及び珪素原子の少なくともいずれかを有する疎水性樹脂を更に含有する、＜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＞
前記樹脂（Ｐ）が、ヒドロキシアダマンチル基又はジヒドロキシアダマンチル基を有する繰り返し単位を更に有する樹脂である、＜１＞又は＜３＞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により形成されるレジスト膜。
＜１５＞
＜１４＞に記載のレジスト膜を露光する工程、及び
有機溶剤を含む現像液を用いて現像してネガ型のパターンを形成する工程
を含む、パターン形成方法。
＜１６＞
前記有機溶剤を含む現像液における有機溶剤の含有量が、前記現像液の全量に対して、９０質量％以上１００質量％以下である、＜１５＞に記載のパターン形成方法。
＜１７＞
前記現像液が、ケトン系溶剤、エステル系溶剤、アルコール系溶剤、アミド系溶剤及びエーテル系溶剤からなる群より選択される少なくとも１種類の有機溶剤を含有する現像液である、＜１５＞又は＜１６＞に記載のパターン形成方法。
＜１８＞
更に、有機溶剤を含有するリンス液を用いて洗浄する工程を含む、＜１５＞〜＜１７＞のいずれか１項に記載のパターン形成方法。
＜１９＞
前記レジスト膜を露光する工程における露光が液浸露光である、＜１５＞〜＜１８＞のいずれか１項に記載のパターン形成方法。
＜２０＞
＜１５＞〜＜１９＞のいずれか１項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＞〜＜２０＞に係る発明であるが、以下、それ以外の事項（例えば、下記〔１〕〜〔２２〕）についても記載している。 The present invention has the following configuration, whereby the above object of the present invention is achieved.
<1>
(P) a resin having the repeating unit (a) represented by the following general formula (I), the ratio of the repeating unit having an aromatic group being 5 mol% or less, and having no fluorine atom and silicon atom;
(B) a compound that generates an organic acid represented by the following general formula (II) or (III) upon irradiation with actinic rays or radiation, a compound that generates a monovalent perfluoroalkanesulfonic acid, and a fluorine-substituted imide acid At least any one of the compounds that generate
(C) an actinic ray-sensitive or radiation-sensitive resin composition containing a basic compound or an ammonium salt compound, the basicity of which decreases when irradiated with actinic rays or radiation,
The compound (B) and the compound (C) are different compounds,
Ri der wherein the molar ratio of compound (B) [C] / [ B] is 0.40 or more of the compound (C),
The actinic ray-sensitive or radiation-sensitive resin composition, wherein the compound (C) has a basic nitrogen atom and generates an organic acid upon irradiation with actinic rays or radiation .

In the general formula (I), R ₀ represents a hydrogen atom or a methyl group.
R ₁ , R ₂ and R ₃ each independently represents a linear or branched alkyl group.

In the above general formula,
Xf each independently represents a fluorine atom or an alkyl group substituted with at least one fluorine atom.
R ₁ and R ₂ each independently represents a hydrogen atom, a fluorine atom, or an alkyl group.
L each independently represents a divalent linking group.
Cy represents a cyclic organic group.
Rf is a group containing a fluorine atom.
x represents an integer of 1 to 20.
y represents an integer of 0 to 10.
z represents an integer of 0 to 10.
<2>
(P) a resin having the repeating unit (a) represented by the following general formula (I), the ratio of the repeating unit having an aromatic group being 5 mol% or less, and having no fluorine atom and silicon atom;
(B) a compound that generates an organic acid represented by the following general formula (II) or (III) upon irradiation with actinic rays or radiation, a compound that generates a monovalent perfluoroalkanesulfonic acid, and a fluorine-substituted imide acid At least any one of the compounds that generate
(C) an actinic ray-sensitive or radiation-sensitive resin composition containing a basic compound or an ammonium salt compound, the basicity of which decreases when irradiated with actinic rays or radiation,
The compound (B) and the compound (C) are different compounds,
The molar ratio [C] / [B] of the compound (C) to the compound (B) is 0.40 or more,
The actinic ray-sensitive or radiation-sensitive resin composition, wherein the resin (P) further has a repeating unit having a hydroxyadamantyl group or a dihydroxyadamantyl group.

In the general formula (I), R ₀ represents a hydrogen atom or a methyl group.
R ₁ , R ₂ and R ₃ each independently represents a linear or branched alkyl group.

In the above general formula,
Xf each independently represents a fluorine atom or an alkyl group substituted with at least one fluorine atom.
R ₁ and R ₂ each independently represents a hydrogen atom, a fluorine atom, or an alkyl group.
L each independently represents a divalent linking group.
Cy represents a cyclic organic group.
Rf is a group containing a fluorine atom.
x represents an integer of 1 to 20.
y represents an integer of 0 to 10.
z represents an integer of 0 to 10.
<3>
(P) a resin having the repeating unit (a) represented by the following general formula (I), the ratio of the repeating unit having an aromatic group being 5 mol% or less, and having no fluorine atom and silicon atom;
(B) a compound that generates an organic acid represented by the following general formula (II) or (III) upon irradiation with actinic rays or radiation, a compound that generates a monovalent perfluoroalkanesulfonic acid, and a fluorine-substituted imide acid At least any one of the compounds that generate
(C) an actinic ray-sensitive or radiation-sensitive resin composition containing a basic compound or an ammonium salt compound, the basicity of which decreases when irradiated with actinic rays or radiation,
The compound (B) and the compound (C) are different compounds,
The molar ratio [C] / [B] of the compound (C) to the compound (B) is 0.40 or more,
The actinic ray-sensitive or radiation-sensitive resin composition, wherein the resin (P) is a resin containing a repeating unit having a sultone structure.

In the general formula (I), R ₀ represents a hydrogen atom or a methyl group.
R ₁ , R ₂ and R ₃ each independently represents a linear or branched alkyl group.

In the above general formula,
Xf each independently represents a fluorine atom or an alkyl group substituted with at least one fluorine atom.
R ₁ and R ₂ each independently represents a hydrogen atom, a fluorine atom, or an alkyl group.
L each independently represents a divalent linking group.
Cy represents a cyclic organic group.
Rf is a group containing a fluorine atom.
x represents an integer of 1 to 20.
y represents an integer of 0 to 10.
z represents an integer of 0 to 10.
< 4 >
<1> to <3>, wherein the content of the compound (C) with respect to the total solid content of the actinic ray-sensitive or radiation-sensitive resin composition is 1.0% by mass or more. An actinic ray-sensitive or radiation-sensitive resin composition.
< 5 >
The actinic ray-sensitive or radiation-sensitive resin according to < 4 >, wherein the content of the compound (C) with respect to the total solid content of the actinic ray-sensitive or radiation-sensitive resin composition is 4.0% by mass or more. Composition.
< 6 >
The actinic ray-sensitive or radiation-sensitive resin composition according to any one of <1> to < 5 >, wherein the molar ratio [C] / [B] is 0.40 to 1.40.
< 7 >
The actinic ray-sensitive or radiation-sensitive resin according to <2> or <3> , wherein the compound (C) has a basic nitrogen atom and generates an organic acid upon irradiation with actinic rays or radiation. Composition.
< 8 >
The organic acid which the said compound (C) generate | occur | produces by irradiation of actinic light or a radiation is an organic acid represented by the following general formula (C1) or (C2), The feeling as described in <1> or <7> . Actinic ray-sensitive or radiation-sensitive resin composition.

In the above general formula,
Xf each independently represents a fluorine atom or an alkyl group substituted with at least one fluorine atom.
R ₁ and R ₂ each independently represents a hydrogen atom, a fluorine atom, or an alkyl group.
L each independently represents a divalent linking group.
Ba represents a functional group containing the basic nitrogen atom.
Rf is a group containing a fluorine atom.
x represents an integer of 1 to 20.
y represents an integer of 0 to 10.
z represents an integer of 0 to 10.
< 9 >
The actinic ray-sensitive or radiation-sensitive resin composition according to any one of <1> to < 8 >, wherein the compound (C) is an onium salt compound.
< 10 >
The actinic ray-sensitive or radiation-sensitive content according to any one of <1> to < 9 >, wherein the content of the repeating unit (a) with respect to all repeating units of the resin (P) is 45 mol% or more. Resin composition.
< 11 >
The actinic ray according to any one of <1> to < 10 >, wherein the linear or branched alkyl group for R ₁ , R _2, and R ₃ is an alkyl group having 1 to 4 carbon atoms. Or radiation sensitive resin composition.
< 12 >
The actinic ray-sensitive or radiation-sensitive resin composition according to any one of <1> to < 11 >, further containing a hydrophobic resin having at least one of a fluorine atom and a silicon atom. A light-sensitive or radiation-sensitive resin composition.
< 13 >
The actinic ray-sensitive or radiation-sensitive resin composition according to <1> or <3> , wherein the resin (P) is a resin further having a repeating unit having a hydroxyadamantyl group or a dihydroxyadamantyl group.
< 14 >
<1>-< 13 > The resist film formed with the actinic-ray-sensitive or radiation-sensitive resin composition of any one of < 13 >.
< 15 >
< 14 > The pattern formation method including the process of exposing using the resist film as described in < 14 >, and developing using the developing solution containing an organic solvent, and forming a negative pattern.
< 16 >
The pattern formation method as described in < 15 > whose content of the organic solvent in the developing solution containing the said organic solvent is 90 to 100 mass% with respect to the whole quantity of the said developing solution.
< 17 >
< 15 > or < 15 >, wherein the developer is a developer containing at least one organic solvent selected from the group consisting of ketone solvents, ester solvents, alcohol solvents, amide solvents, and ether solvents. 16 > The pattern forming method according to the above.
< 18 >
Furthermore, the pattern formation method of any one of < 15 >-< 17 > including the process wash | cleaned using the rinse liquid containing an organic solvent.
< 19 >
The pattern formation method according to any one of < 15 > to < 18 >, wherein the exposure in the step of exposing the resist film is immersion exposure.
< 20 >
< 15 >-< 19 > The manufacturing method of an electronic device containing the pattern formation method of any one of < 19 >.
Although this invention is invention concerning said <1>-< 20 >, hereafter, other matters (for example, following [1]-[22]) are also described.

上記一般式（Ｉ）中、Ｒ_０は、水素原子又はメチル基を表す。
Ｒ_１、Ｒ_２及びＲ_３は、各々独立に、直鎖状又は分岐状のアルキル基を表す。
〔２〕 前記感活性光線性又は感放射線性樹脂組成物の全固形分に対する前記化合物（Ｃ）の含有量が１．０質量％以上である、上記〔１〕に記載の感活性光線性又は感放射線性樹脂組成物。
〔３〕 前記感活性光線性又は感放射線性樹脂組成物の全固形分に対する前記化合物（Ｃ）の含有量が４．０質量％以上である、上記〔２〕に記載の感活性光線性又は感放射線性樹脂組成物。
〔４〕 前記モル比率［Ｃ］／［Ｂ］が０．４０〜１．４０である、上記〔１〕〜〔３〕のいずれか１項に記載の感活性光線性又は感放射線性樹脂組成物。
〔５〕 前記化合物（Ｃ）が、塩基性窒素原子を有するとともに、活性光線又は放射線の照射により有機酸を発生する化合物であり、かつ、前記化合物（Ｂ）と前記化合物（Ｃ）とは異なる化合物である、上記〔１〕〜〔４〕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。
〔６〕 活性光線又は放射線の照射により前記化合物（Ｃ）が発生する前記有機酸が、下記一般式（Ｃ１）又は（Ｃ２）で表される有機酸である、上記〔５〕に記載の感活性光線性又は感放射線性樹脂組成物。

上記一般式中、
Ｘｆは、各々独立に、フッ素原子、又は、少なくとも１つのフッ素原子で置換されたアルキル基を表す。
Ｒ_１及びＲ_２は、各々独立に、水素原子、フッ素原子、又は、アルキル基を表す。
Ｌは、各々独立に、２価の連結基を表す。
Ｂａは、前記塩基性窒素原子を含む官能基を表す。
Ｒｆは、フッ素原子を含んだ基である。
ｘは、１〜２０の整数を表す。
ｙは、０〜１０の整数を表す。
ｚは、０〜１０の整数を表す。
〔７〕 前記化合物（Ｃ）がオニウム塩化合物である、上記〔１〕〜〔６〕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。
〔８〕 前記繰り返し単位（ａ）の前記樹脂（Ｐ）の全繰り返し単位に対する含有量が、４５モル％以上である、上記〔１〕〜〔７〕のいずれか１項に記載の感活性光線性又は感放射線性樹脂組成物。
〔９〕 前記Ｒ_１、Ｒ_２及びＲ_３についての直鎖状又は分岐状のアルキル基が炭素数１〜４のアルキル基である、上記〔１〕〜〔８〕のいずれか１項に記載の感活性光線性又は感放射線性樹脂組成物。
〔１０〕 前記感活性光線性又は感放射線性樹脂組成物が、フッ素原子及び珪素原子の少なくともいずれかを有する疎水性樹脂を更に含有する、上記〔１〕〜〔９〕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。
〔１１〕 前記樹脂（Ｐ）が、ラクトン構造又はスルトン構造を有する繰り返し単位を更に有する、上記〔１〕〜〔１０〕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。
〔１２〕 前記樹脂（Ｐ）が、ヒドロキシアダマンチル基又はジヒドロキシアダマンチル基を有する繰り返し単位を更に有する樹脂である、上記〔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〕 上記〔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により形成されるレジスト膜。
〔１４〕 上記〔１３〕に記載のレジスト膜を露光する工程、及び
有機溶剤を含む現像液を用いて現像してネガ型のパターンを形成する工程
を含む、パターン形成方法。
〔１５〕 前記有機溶剤を含む現像液における有機溶剤の含有量が、前記現像液の全量に対して、９０質量％以上１００質量％以下である、上記〔１４〕に記載のパターン形成方法。
〔１６〕 前記現像液が、ケトン系溶剤、エステル系溶剤、アルコール系溶剤、アミド系溶剤及びエーテル系溶剤からなる群より選択される少なくとも１種類の有機溶剤を含有する現像液である、上記〔１４〕又は〔１５〕に記載のパターン形成方法。
〔１７〕 更に、有機溶剤を含有するリンス液を用いて洗浄する工程を含む、上記〔１４〕〜〔１６〕のいずれか１項に記載のパターン形成方法。
〔１８〕 前記レジスト膜を露光する工程における露光が液浸露光である、上記〔１４〕〜〔１７〕のいずれか１項に記載のパターン形成方法。
〔１９〕 上記〔１４〕〜〔１８〕のいずれか１項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。
〔２０〕 上記〔１９〕に記載の電子デバイスの製造方法により製造された電子デバイス。 [1] (P) a resin having a repeating unit (a) represented by the following general formula (I):
(B) a compound that generates an organic acid upon irradiation with actinic rays or radiation, and
(C) an actinic ray-sensitive or radiation-sensitive resin composition containing a basic compound or an ammonium salt compound, the basicity of which decreases when irradiated with actinic rays or radiation,
The actinic ray-sensitive or radiation-sensitive resin composition, wherein the molar ratio [C] / [B] of the compound (C) to the compound (B) is 0.40 or more.

In the general formula (I), R ₀ represents a hydrogen atom or a methyl group.
R ₁ , R ₂ and R ₃ each independently represents a linear or branched alkyl group.
[2] The actinic ray-sensitive or actinic ray-sensitive composition according to [1] above, wherein the content of the compound (C) relative to the total solid content of the actinic ray-sensitive or radiation-sensitive resin composition is 1.0% by mass or more. Radiation sensitive resin composition.
[3] The actinic ray-sensitive or actinic ray-sensitive composition according to [2] above, wherein the content of the compound (C) is 4.0% by mass or more based on the total solid content of the actinic ray-sensitive or radiation-sensitive resin composition. Radiation sensitive resin composition.
[4] The actinic ray-sensitive or radiation-sensitive resin composition according to any one of [1] to [3], wherein the molar ratio [C] / [B] is 0.40 to 1.40. object.
[5] The compound (C) has a basic nitrogen atom and generates an organic acid upon irradiation with actinic rays or radiation, and the compound (B) is different from the compound (C). The actinic ray-sensitive or radiation-sensitive resin composition according to any one of the above [1] to [4], which is a compound.
[6] The sensation according to [5] above, wherein the organic acid generated from the compound (C) upon irradiation with actinic rays or radiation is an organic acid represented by the following general formula (C1) or (C2): Actinic ray-sensitive or radiation-sensitive resin composition.

In the above general formula,
Xf each independently represents a fluorine atom or an alkyl group substituted with at least one fluorine atom.
R ₁ and R ₂ each independently represents a hydrogen atom, a fluorine atom, or an alkyl group.
L each independently represents a divalent linking group.
Ba represents a functional group containing the basic nitrogen atom.
Rf is a group containing a fluorine atom.
x represents an integer of 1 to 20.
y represents an integer of 0 to 10.
z represents an integer of 0 to 10.
[7] The actinic ray-sensitive or radiation-sensitive resin composition according to any one of [1] to [6], wherein the compound (C) is an onium salt compound.
[8] The actinic ray according to any one of [1] to [7], wherein the content of the repeating unit (a) with respect to all repeating units of the resin (P) is 45 mol% or more. Or radiation sensitive resin composition.
[9] The linear or branched alkyl group for R ₁ , R ₂ and R ₃ is any one of [1] to [8] above, wherein the alkyl group has 1 to 4 carbon atoms. An actinic ray-sensitive or radiation-sensitive resin composition.
[10] The above [1] to [9], wherein the actinic ray-sensitive or radiation-sensitive resin composition further contains a hydrophobic resin having at least one of a fluorine atom and a silicon atom. The actinic ray-sensitive or radiation-sensitive resin composition described.
[11] The actinic ray-sensitive or radiation-sensitive resin composition according to any one of [1] to [10], wherein the resin (P) further includes a repeating unit having a lactone structure or a sultone structure. .
[12] The actinic ray-sensitive or sensation according to any one of [1] to [11] above, wherein the resin (P) further includes a repeating unit having a hydroxyadamantyl group or a dihydroxyadamantyl group. Radiation resin composition.
[13] A resist film formed from the actinic ray-sensitive or radiation-sensitive resin composition according to any one of [1] to [12].
[14] A pattern forming method including a step of exposing the resist film according to [13], and a step of developing using a developer containing an organic solvent to form a negative pattern.
[15] The pattern forming method according to [14], wherein the content of the organic solvent in the developer containing the organic solvent is 90% by mass or more and 100% by mass or less with respect to the total amount of the developer.
[16] The developer described above, wherein the developer is a developer containing at least one organic solvent selected from the group consisting of ketone solvents, ester solvents, alcohol solvents, amide solvents, and ether solvents. 14] or [15] The pattern forming method.
[17] The pattern forming method according to any one of [14] to [16], further including a step of washing with a rinse liquid containing an organic solvent.
[18] The pattern forming method according to any one of [14] to [17], wherein the exposure in the step of exposing the resist film is immersion exposure.
[19] A method for manufacturing an electronic device, comprising the pattern forming method according to any one of [14] to [18].
[20] An electronic device manufactured by the method for manufacturing an electronic device according to [19].

The present invention preferably further has the following configuration.
[21]
The actinic ray-sensitive or radiation-sensitive resin composition according to any one of [1] to [12], which is a chemically amplified resist composition for organic solvent development.
[22]
The actinic ray-sensitive or radiation-sensitive resin composition according to any one of [1] to [12] and [21], which is for immersion exposure.

  According to the present invention, an actinic ray sensitivity or a hole pattern having an ultrafine pore diameter (for example, 60 nm or less) and excellent roundness can be formed with good development time dependency. A radiation-sensitive resin composition, and a resist film, a pattern formation method, an electronic device manufacturing method, and an electronic device using the same can be provided.

Hereinafter, embodiments of the present invention will be described in detail.
In the description of the group (atomic group) in this specification, the notation which does not describe substitution and non-substitution includes the thing which has a substituent with the thing which does not have a substituent. For example, the “alkyl group” includes not only an alkyl group having no substituent (unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group).
In the present specification, “active light” or “radiation” means, for example, the emission line spectrum of a mercury lamp, far ultraviolet rays represented by excimer laser, extreme ultraviolet rays (EUV light), X-rays, electron beams (EB), etc. To do. In the present invention, light means actinic rays or radiation.
In addition, “exposure” in the present specification is not limited to exposure to far ultraviolet rays, extreme ultraviolet rays, X-rays, EUV light and the like represented by mercury lamps and excimer lasers, but also electron beams, ion beams, and the like, unless otherwise specified. The exposure with the particle beam is also included in the exposure.

The actinic ray-sensitive or radiation-sensitive resin composition of the present invention comprises (P) a resin having a repeating unit (a) represented by the following general formula (I), (B) an organic acid upon irradiation with actinic rays or radiation. And (C) an actinic ray-sensitive or radiation-sensitive resin composition containing a basic compound or an ammonium salt compound, the basicity of which decreases when irradiated with actinic rays or radiation, The molar ratio [C] / [B] of (C) to the compound (B) is 0.40 or more.
According to the actinic ray-sensitive or radiation-sensitive resin composition, even when a hole pattern having an ultrafine pore diameter (for example, 60 nm or less) is formed in a resist film formed from the composition, An excellent hole pattern can be formed with good development time dependency. The reason is not clear, but is estimated as follows.

First, in a method of forming a negative pattern by developing using a developer containing an organic solvent (hereinafter also referred to as an organic developer), the resist film is applied to a region other than a region where a hole pattern is formed. Exposure is made.
In the exposed portion of the resist film, an acid generated from the compound (B) (hereinafter also referred to as an acid generator) and an ester of the repeating unit (a) represented by the general formula (I) in the resin (P) When the site reacts and the repeating unit (a) generates a carboxyl group, the polarity of the resin (P) increases and the solubility in an organic developer decreases.
As a result, the resist film is subsequently developed using an organic developer to remove the unexposed areas and form a hole pattern.

  In the unexposed area, the compound (C) exhibits a function of capturing acid due to the basicity of the compound (C), whereas in the exposed area, the acid is reduced due to the decrease in basicity. It is a compound that reduces the function it supplements. Therefore, when the acid generated from the acid generator in the exposed area diffuses into the unexposed area, the compound (C) captures such an acid and reacts the acid and the resin (P) in the unexposed area. It has a function to suppress.

By the way, in order to improve the roundness of the hole pattern and the development time dependency, it is considered effective to increase the contrast of the latent image in the exposed area and the unexposed area. As a means for achieving this, by increasing the content of the compound (C) with respect to the acid generator, the acid diffused from the exposed area to the unexposed area can be more reliably captured at the unexposed area. Conceivable.
However, in the exposed area, the compound (C) typically has a lower basicity by capturing an acid. Therefore, when the content of the compound (C) with respect to the acid generator is increased, exposure is performed. The effective acid in the part tends to decrease. And since this becomes the direction which reduces the efficiency of the said reaction of the acid and resin (P) in an exposure part, a concern of a sensitivity fall arises.

  Actually, in the case of developing a general ArF exposure resist composition containing a resin whose polarity is increased by the action of an acid such as resin (P) with an alkali developer (in this case, in positive development) In order to obtain a sufficient dissolution rate in the exposed area, the resin is used because the dissolution rate of the resist film before the exposure step in the alkaline developer is extremely slow (in other words, it is very difficult to dissolve in the alkaline developer). It is necessary to carry out the reaction between the acid and the acid with high efficiency. Therefore, in such an image forming method by alkali development, when the content of the compound (C) with respect to the acid generator is increased, the content of the acid generator (effective acid) with respect to the resin is reduced as described above. It is difficult to form an image in a practical sensitivity region.

However, when the present inventors develop a resist film containing the resin (P) with an organic developer (negative development), surprisingly, the acid generator (compound) of the compound (C) Even when the molar ratio [C] / [B] to (B)) is 0.40 or more, the pattern can be resolved with an exposure amount that is not problematic in practice, and the compound (C) is abundant with respect to the acid generator. The present inventors have found that the presence of the latent image contrast can be expected to improve.
As described above, in the case of development with an organic developer, the reason why the pattern can be resolved with an exposure amount that has no practical problem is that the removal of the unexposed portion with the organic developer is mainly an organic resin. Originally, the mechanism based on the interaction between the high-affinity substances, ie, the component film and the organic developer, is used. Even if the efficiency of the reaction with P) is low, it is presumed that the unexposed portion was sufficiently dissolved in the organic developer.

Furthermore, the resin (P) in the actinic ray-sensitive or radiation-sensitive resin composition of the present invention has the repeating unit (a) represented by the general formula (I), and the action of acid in the exposed area. The structure desorbed from the repeating unit (a) by, for example, is a structure that is not so bulky as compared with the chemical structure in which R ₁ and R ₂ in general formula (I) are combined to form a ring. The volume of the exposed area (for example, volume shrinkage) is small and contributes to uniform dissolution in the organic developer in the unexposed area (in other words, uniform removal of the unexposed area with the organic developer). It is thought that. The synergistic effect of this action and the improvement in the latent image contrast described above makes it possible to obtain a more precise pattern, and as a result, a hole pattern with excellent roundness has a good development time dependency. It is guessed that it can be formed.

  By the way, as described above, when a fine hole pattern is formed by a positive image forming method, the shape of the pattern is likely to deteriorate, and an ultrafine hole pattern (for example, a hole diameter of 60 nm or less) is formed. That is virtually impossible. This is because, when a hole pattern is formed by a positive image forming method, an area where the hole pattern is to be formed becomes an exposure part. Because it is almost impossible.

  Therefore, the actinic ray-sensitive or radiation-sensitive resin composition according to the present invention has a negative development (exposure) particularly when a hole pattern having an ultrafine hole diameter (for example, 60 nm or less) is formed in a resist film. Then, the solubility in the developer is reduced, and the exposed portion remains as a pattern, and the unexposed portion is removed. That is, the actinic ray-sensitive or radiation-sensitive resin composition according to the present invention is an actinic ray-sensitive or radiation-sensitive resin composition for organic solvent development used in development using a developer containing an organic solvent. be able to. Here, the term “for organic solvent development” means an application that is used in a step of developing using a developer containing at least an organic solvent.

In general, a negative type image forming method using a developer containing an organic solvent has a lower dissolution contrast with respect to a developer in an unexposed portion and an exposed portion than a positive type image forming method using an alkali developer. . For this reason, in order to form a hole pattern having an ultrafine hole diameter, it is necessary to adopt a negative type image forming method, but the deterioration of roundness and development time dependency are required. The increase is likely to manifest. Further, as the hole diameter of the hole pattern to be obtained becomes finer, the above problem becomes more obvious.
Therefore, the present invention solves the problem that is easily manifested in the negative type image forming method and in the case of forming a hole pattern having an ultrafine hole diameter, and is true even though it has an ultrafine hole diameter. The technical significance is significant in that a hole pattern having excellent circularity can be formed with good development time dependency.

  The actinic ray-sensitive or radiation-sensitive resin composition of the present invention is typically a resist composition, particularly a negative resist composition (that is, a resist composition for developing an organic solvent). It is preferable because a high effect can be obtained. The composition according to the present invention is typically a chemically amplified resist composition.

  [1] (P) Resin having a repeating unit (a) represented by the following general formula (I)

In the general formula (I), R ₀ represents a hydrogen atom or a methyl group.
R ₁ , R ₂ and R ₃ each independently represents a linear or branched alkyl group.
The linear or branched alkyl group for R ₁ , R ₂ and R ₃ is preferably an alkyl group having 1 to 4 carbon atoms, such as a methyl group, an ethyl group, an n-propyl group, an isopropyl group, Examples include n-butyl group, isobutyl group, and tert-butyl group.
R ₁ is preferably a methyl group, an ethyl group, an n-propyl group, or an n-butyl group, more preferably a methyl group or an ethyl group, and particularly preferably a methyl group.
R ₂ is preferably a methyl group, an ethyl group, an n-propyl group, an isopropyl group, or an n-butyl group, more preferably a methyl group or an ethyl group, and particularly preferably a methyl group.
R ₃ is preferably a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group or a tert-butyl group, more preferably a methyl group, an ethyl group, an isopropyl group or an isobutyl group. A group, an ethyl group and an isopropyl group are particularly preferred.

The repeating unit (a) represented by the general formula (I) is a repeating unit having a group (hereinafter also referred to as “acid-decomposable group”) that decomposes by the action of an acid to generate a polar group (carboxyl group). is there.
The resin having the repeating unit (a) represented by the general formula (I) (hereinafter, also referred to as “resin (P)”) used in the actinic ray-sensitive or radiation-sensitive resin composition according to the present invention is as follows. , A resin having an acid-decomposable group (hereinafter also referred to as “acid-decomposable resin”), a resin whose polarity is increased by the action of an acid and its solubility in a developer containing an organic solvent is reduced.
The resin (P) is also a resin whose polarity is increased by the action of an acid and its solubility in an alkaline developer is increased.
In the resin (P) in the present invention, the content of the repeating unit (a) represented by the general formula (I) (the total when there are a plurality of types) is not particularly limited, but the effect of the present invention can be further improved. From the viewpoint of surely achieving, it is preferably 45 mol% or more with respect to all repeating units in the resin (P), and more preferably 50 mol% or more, particularly from the viewpoint of improving dissolution contrast, 55 It is particularly preferred that it is at least mol%. Moreover, as an upper limit, it is preferable that it is 90 mol% or less from a viewpoint of forming a favorable pattern, It is more preferable that it is 80 mol% or less, It is still more preferable that it is 70 mol% or less.
Hereinafter, although the specific example of the repeating unit (a) represented by the said general formula (I) is illustrated, this invention is not limited to these.

In the present invention, the resin (P) may have a repeating unit (b) having an acid-decomposable group different from the repeating unit (a).
The acid-decomposable group different from the repeating unit (a) preferably has a structure in which a polar group is protected with a group capable of decomposing and leaving by the action of an acid.
The polar group is not particularly limited as long as it is a group that is hardly soluble or insoluble in a developer containing an organic solvent. .38 mass% tetramethylammonium hydroxide aqueous group), or alcoholic hydroxyl groups.
The alcoholic hydroxyl group is a hydroxyl group bonded to a hydrocarbon group, and means a hydroxyl group other than a hydroxyl group directly bonded on an aromatic ring (phenolic hydroxyl group). An aliphatic alcohol substituted with an attractive group (for example, a fluorinated alcohol group (such as hexafluoroisopropanol group)) is excluded. The alcoholic hydroxyl group is preferably a hydroxyl group having a pKa of 12 or more and 20 or less.

A preferable group as the acid-decomposable group is a group in which the hydrogen atom of these groups is substituted with a group capable of leaving with an acid.
As the acid eliminable group, there can be, for _{example, -C (R 36) (R} 37) (R 38), - C (R 36) (R 37) (OR 39), - C (R 01) (R 02 ) (OR ₃₉ ) and the like.
In said general formula, R < ₃₆ > -R < ₃₉ > represents an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, or an alkenyl group each independently. R ₃₆ and R ₃₇ may be bonded to each other to form a ring.
R ₀₁ and R ₀₂ each independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group or an alkenyl group.
The alkyl group of R _{36 to} R ₃₉ , R ₀₁ and R ₀₂ is preferably an alkyl group having 1 to 8 carbon atoms, such as methyl group, ethyl group, propyl group, n-butyl group, sec-butyl group, hexyl. Group, octyl group and the like.
The cycloalkyl group of R _{36 to} R ₃₉ , R ₀₁ and R ₀₂ may be monocyclic or polycyclic. The monocyclic type is preferably a cycloalkyl group having 3 to 8 carbon atoms, and examples thereof include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, and a cyclooctyl group. As the polycyclic type, a cycloalkyl group having 6 to 20 carbon atoms is preferable. For example, an adamantyl group, norbornyl group, isobornyl group, camphanyl group, dicyclopentyl group, α-pinel group, tricyclodecanyl group, tetracyclododecyl group. Group, androstanyl group and the like. Note that at least one carbon atom in the cycloalkyl group may be substituted with a heteroatom such as an oxygen atom.
The aryl group of R _{36 to} R ₃₉ , R ₀₁ and R ₀₂ is preferably an aryl group having 6 to 10 carbon atoms, and examples thereof include a phenyl group, a naphthyl group, and an anthryl group.
The aralkyl group of R _{36 to} R ₃₉ , R ₀₁ and R ₀₂ is preferably an aralkyl group having 7 to 12 carbon atoms, and examples thereof include a benzyl group, a phenethyl group, and a naphthylmethyl group.
The alkenyl group of R _{36 to} R ₃₉ , R ₀₁ and R ₀₂ is preferably an alkenyl group having 2 to 8 carbon atoms, and examples thereof include a vinyl group, an allyl group, a butenyl group, and a cyclohexenyl group.
The ring formed by combining R ₃₆ and R ₃₇ is preferably a cycloalkyl group (monocyclic or polycyclic). The cycloalkyl group is preferably a monocyclic cycloalkyl group such as a cyclopentyl group or a cyclohexyl group, or a polycyclic cycloalkyl group such as a norbornyl group, a tetracyclodecanyl group, a tetracyclododecanyl group or an adamantyl group. A monocyclic cycloalkyl group having 5 to 6 carbon atoms is more preferable, and a monocyclic cycloalkyl group having 5 carbon atoms is particularly preferable.

  The repeating unit (b) having an acid-decomposable group different from the repeating unit (a) that can be contained in the resin (P) is preferably a repeating unit represented by the following general formula (AI).

In general formula (AI),
Xa ₁ represents a hydrogen atom, a methyl group which may have a substituent, or a group represented by —CH ₂ —R ₉ . R ₉ represents a hydroxyl group or a monovalent organic group, and examples of the monovalent organic group include an alkyl group having 5 or less carbon atoms and an acyl group having 5 or less carbon atoms, preferably 3 or less carbon atoms. An alkyl group, more preferably a methyl group. Xa ₁ preferably represents a hydrogen atom, a methyl group, a trifluoromethyl group or a hydroxymethyl group.
T represents a single bond or a divalent linking group.
Rx _{1 to} Rx ₃ each independently represents an alkyl group (straight or branched) or a cycloalkyl group (monocyclic or polycyclic).
Two of Rx _{1 to} Rx ₃ may combine to form a cycloalkyl group (monocyclic or polycyclic).
However, when T represents a single bond, not all of Rx _{1 to} Rx ₃ represent an alkyl group.

Examples of the divalent linking group for T include an alkylene group, —COO—Rt— group, —O—Rt— group, and a phenylene group. In the formula, Rt represents an alkylene group or a cycloalkylene group.
T is preferably a single bond or a —COO—Rt— group. Rt is preferably an alkylene group having 1 to 5 carbon atoms, more preferably a —CH ₂ — group, — (CH ₂ ) ₂ — group, or — (CH ₂ ) ₃ — group.
Examples of the alkyl group rx ₁ to Rx _3, methyl, ethyl, n- propyl group, an isopropyl group, n- butyl group, an isobutyl group, those having 1 to 4 carbon atoms such as t- butyl group.
Examples of the cycloalkyl group represented by Rx _{1 to} Rx ₃ include monocyclic cycloalkyl groups such as cyclopentyl group and cyclohexyl group, polycyclic cycloalkyl groups such as norbornyl group, tetracyclodecanyl group, tetracyclododecanyl group, and adamantyl group. Groups are preferred.
Examples of the cycloalkyl group formed by combining two of Rx _{1 to} Rx ₃ include a monocyclic cycloalkyl group such as a cyclopentyl group and a cyclohexyl group, a norbornyl group, a tetracyclodecanyl group, a tetracyclododecanyl group, an adamantyl group A polycyclic cycloalkyl group such as a group is preferred. A monocyclic cycloalkyl group having 5 to 6 carbon atoms is particularly preferable.
An embodiment in which Rx ₁ is a methyl group or an ethyl group, and Rx ₂ and Rx ₃ are bonded to form the above-described cycloalkyl group is preferable.
Each of the above groups may have a substituent, and examples of the substituent include an alkyl group (1 to 4 carbon atoms), a cycloalkyl group (3 to 8 carbon atoms), a halogen atom, an alkoxy group (carbon). Number 1-4), a carboxyl group, an alkoxycarbonyl group (carbon number 2-6) etc. are mentioned, and carbon number 8 or less is preferable. Among these, from the viewpoint of further improving the dissolution contrast with respect to a developer containing an organic solvent before and after acid decomposition, a substituent having no hetero atom such as an oxygen atom, a nitrogen atom, or a sulfur atom is more preferable ( For example, it is more preferable that it is not an alkyl group substituted with a hydroxyl group, etc.), a group consisting of only a hydrogen atom and a carbon atom is more preferable, and a linear or branched alkyl group or a cycloalkyl group is particularly preferable. preferable.

Although the preferable specific example of the repeating unit (b) which has an acid-decomposable group different from the said repeating unit (a) is shown below, this invention is not limited to this.
In specific examples, Rx and Xa ₁ represent a hydrogen atom, CH ₃ , CF ₃ , or CH ₂ OH. Rxa and Rxb each represents an alkyl group having 1 to 4 carbon atoms. Z represents a substituent, and when a plurality of Zs are present, the plurality of Zs may be the same as or different from each other. p represents 0 or a positive integer. Specific examples and preferred examples of Z are the same as the specific examples and preferred examples of the substituent that each group such as Rx _{1 to} Rx ₃ may have.

  The resin (P) may contain a repeating unit represented by the following general formula (VI) as the repeating unit (b), and is particularly preferable when exposed with KrF, electron beam or EUV.

In the general formula (VI), R ₆₁ , R ₆₂ and R ₆₃ each independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, a cyano group or an alkoxycarbonyl group. R ₆₂ may be bonded to Ar ₆ to form a ring (preferably a 5-membered or 6-membered ring), in which case R ₆₂ represents an alkylene group.
X ₆ represents a single bond, —COO—, —CONR ₆₄ — (R ₆₄ represents a hydrogen atom or an alkyl group). L ₆ represents a single bond or an alkylene group. Ar ₆ represents a divalent aromatic ring group. Y, when there are a plurality, each independently represents a hydrogen atom or a group capable of leaving by the action of an acid. However, at least one of Y represents a group capable of leaving by the action of an acid. n represents an integer of 1 to 4.

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

In general formulas (1) and (2),
R ₁ and R ₃ each independently represent a hydrogen atom, a methyl group which may have a substituent, or a group represented by —CH ₂ —R ₉ . R ₉ represents a hydroxyl group or a monovalent organic group.
R ₂ represents an alkyl group or a cycloalkyl group.
R ₄ , R ₅ and R ₆ each independently represents an alkyl group or a cycloalkyl group, and at least one of R ₄ , R ₅ and R ₆ represents a cycloalkyl group. R is an alicyclic ring together with a carbon atom. Represents an atomic group necessary to form a structure.

R ₁ and R ₃ preferably represent a hydrogen atom, a methyl group, a trifluoromethyl group or a hydroxymethyl group. Specific examples and preferred examples of the monovalent organic group in R ₉ are the same as those described for R ₉ in formula (AI).

The alkyl group in R ₂ may be linear or branched, and may have a substituent.
The cycloalkyl group in R ₂ may be monocyclic or polycyclic and may have a substituent.
R ₂ is preferably an alkyl group, more preferably one having 1 to 10 carbon atoms, still more preferably 1 to 5, and examples thereof include a methyl group and an ethyl group.

  R represents an atomic group necessary for forming an alicyclic structure together with a carbon atom. The alicyclic structure formed by R together with the carbon atom is preferably a monocyclic alicyclic structure, and the carbon number thereof is preferably 3 to 7, more preferably 5 or 6.

The alkyl group in R ₄ , R ₅ , and R ₆ may be linear or branched and may have a substituent. As the alkyl group, those having 1 to 4 carbon atoms such as methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group and t-butyl group are preferable.
The cycloalkyl group in R ₄ , R ₅ and R ₆ may be monocyclic or polycyclic and may have a substituent. The cycloalkyl group is preferably a monocyclic cycloalkyl group such as a cyclopentyl group or a cyclohexyl group, or a polycyclic cycloalkyl group such as a norbornyl group, a tetracyclodecanyl group, a tetracyclododecanyl group or an adamantyl group.

Moreover, as a repeating unit (b), the aspect of the repeating unit which produces an alcoholic hydroxyl group as represented below may be sufficient as an aspect different from the repeating unit illustrated above.
In the following specific examples, Xa ₁ represents a hydrogen atom, CH ₃ , CF ₃ , or CH ₂ OH.

The resin (P) may or may not contain the repeating unit (b) having an acid-decomposable group different from the repeating unit (a), but the resin (P) contains the repeating unit (b). In this case, the content of the repeating unit (b) is preferably 1 to 40 mol%, more preferably 1 to 35 mol%, still more preferably 1 to 30 mol%, based on all repeating units in the resin (P).
In the present invention, the molecular weight of a leaving product generated by the decomposition of the acid-decomposable group in the repeating unit (a) or (b) (when a plurality of types of leaving products are generated, the weighted average of the molecular weights by mole fraction) The value (hereinafter also referred to as molar average value) is preferably 140 or less. Thereby, particularly when a negative image is formed, since the exposed portion remains as a pattern, it is possible to prevent a decrease in the film thickness of the pattern portion by reducing the molecular weight of the desorbed material.
In the present invention, the “leaving product generated by the decomposition of an acid-decomposable group” refers to a product that is decomposed and eliminated by the action of an acid corresponding to a group that is decomposed and eliminated by the action of an acid. For example, when R _{1 to} R ₃ in the general formula (I) of the repeating unit (a) are all methyl groups and form a t-butyl group, an alkene formed by decomposition of the t-butyl moiety ( H ₂ C═C (CH ₃ ) ₂ ).

The resin (P) preferably has a repeating unit having a polar group. By having the repeating unit having a polar group, the dissolution rate of the resin (composition) in the developer containing the organic solvent can be easily controlled within an appropriate range.
Although it does not specifically limit as a repeating unit which has a polar group, Specifically, the repeating unit (c) which has a lactone structure or a sultone structure, the repeating unit (d) which has an acid group, a hydroxyl group, or a cyano group as mentioned later And repeating unit (e) having

  The repeating unit (c) having a lactone structure or a sultone structure is more preferably a repeating unit represented by the following general formula (AII).

In general formula (AII),
Rb ₀ represents a hydrogen atom, a halogen atom or an alkyl group (preferably having 1 to 4 carbon atoms) which may have a substituent.
Preferable substituents that the alkyl group of Rb ₀ may have include a hydroxyl group and a halogen atom. Examples of the halogen atom for Rb ₀ include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. Rb ₀ is preferably a hydrogen atom, a methyl group, a hydroxymethyl group or a trifluoromethyl group, and particularly preferably a hydrogen atom or a methyl group.

Ab represents a single bond, an alkylene group, a divalent linking group having a monocyclic or polycyclic cycloalkyl structure, an ether bond, an ester bond, a carbonyl group, or a divalent linking group obtained by combining these. Ab is preferably a single bond or a divalent linking group represented by —Ab ₁ —CO ₂ —.
Ab ₁ is a linear or branched alkylene group, a monocyclic or polycyclic cycloalkylene group, preferably a methylene group, an ethylene group, a cyclohexylene group, an adamantylene group, or a norbornylene group.
V represents a group having a lactone structure or a sultone structure.

  As the group having a lactone structure or a sultone structure, any group having a lactone structure or a sultone structure can be used, but preferably a 5- to 7-membered ring lactone structure, and a 5- to 7-membered ring lactone structure. Those in which other ring structures are condensed to form a bicyclo structure or a spiro structure are preferred. A repeating unit having a lactone structure represented by any one of the following general formulas (LC1-1) to (LC1-17) or a sultone structure represented by any one of the general formulas (SL1-1) to (SL1-3) It is more preferable to have. A lactone structure or a sultone structure may be directly bonded to the main chain. Preferred lactone structures are (LC1-1), (LC1-4), (LC1-5), (LC1-6), (LC1-8), (LC1-13), and (LC1-14).

The lactone structure or sultone structure portion may or may not have a substituent (Rb ₂ ). Preferred substituents (Rb ₂ ) include an alkyl group having 1 to 8 carbon atoms, a monovalent cycloalkyl group having 4 to 7 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, and an alkoxycarbonyl group having 2 to 8 carbon atoms. , Carboxyl group, halogen atom, hydroxyl group, cyano group, acid-decomposable group and the like. More preferably, they are a C1-C4 alkyl group, a cyano group, and an acid-decomposable group. n ₂ represents an integer of 0-4. When n ₂ is 2 or more, a plurality of substituents (Rb ₂ ) may be the same or different, and a plurality of substituents (Rb ₂ ) may be bonded to form a ring. .

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

When the resin (P) contains the repeating unit (c), the content of the repeating unit (c) in the resin (P) is preferably in the range of 0.5 to 80 mol% with respect to all the repeating units, More preferably, it is the range of 1-65 mol%, More preferably, it is the range of 3-50 mol%. One type of repeating unit (c) may be used, or two or more types may be used in combination. By using a specific lactone structure, the roundness of the hole pattern and the development time dependency are improved.
Although the specific example of the repeating unit (c) in resin (P) is shown below, this invention is not limited to this.

  In the following specific examples, R represents a hydrogen atom, an alkyl group which may have a substituent, or a halogen atom, preferably a hydrogen atom, a methyl group, a hydroxymethyl group or an acetoxymethyl group.

As the acid group in the repeating unit (d) having an acid group, a carboxyl group, a sulfonic acid group, a sulfonamide group, a sulfonylimide group, a bissulfonylimide group, an aliphatic alcohol in which the α-position is substituted with an electron-attracting group And a hydroxyl group (for example, hexafluoroisopropanol group) is mentioned, and it is more preferable to have a repeating unit having a carboxyl group.
When the resin (P) contains a repeating unit having an acid group, the resolution for use in contact holes is increased. The repeating unit having an acid group includes a repeating unit in which an acid group is directly bonded to the main chain of the resin, such as a repeating unit of acrylic acid or methacrylic acid, or an acid group in the main chain of the resin through a linking group. Either a repeating unit that is bonded, or a polymerization initiator or chain transfer agent having an acid group, is introduced at the end of the polymer chain during polymerization, and the linking group is a monocyclic or polycyclic cyclic hydrocarbon structure. You may have. Particularly preferred are repeating units of acrylic acid or methacrylic acid.

  The repeating unit (d) having an acid group is preferably a repeating unit (d1) represented by the following general formula (II).

In the general formula (II),
X ₁ represents a polymer unit structure constituting the polymer main chain independently of each other.
Ra ₁ represents an (n + 1) -valent alicyclic hydrocarbon group.
L ₁₁ and L ₂₁ each independently represents a single bond or a divalent linking group.
n represents an integer of 1 or more.
Y ₁ represents an acid group.

In the general formula (II), examples of the acid group of Y ₁ include a carboxyl group, a sulfonic acid group, and an alcoholic hydroxyl group (for example, hexafluoroisopropanol group) in which the α-position is substituted with an electron withdrawing group. A carboxyl group is preferred.

The (n + 1) -valent alicyclic hydrocarbon group Ra ₁ may be a monocyclic hydrocarbon ring group such as a cyclopentane ring group or a cyclohexane ring group, but may be a polycyclic hydrocarbon group. Preferably, it is a polycyclic hydrocarbon group having 7 or more carbon atoms (preferably 7 to 30 carbon atoms).
Examples of the monocyclic hydrocarbon ring group for the alicyclic hydrocarbon group Ra ₁ include groups obtained by removing (n + 1) arbitrary hydrogen atoms from a monocyclic hydrocarbon ring.
The polycyclic hydrocarbon group for the alicyclic hydrocarbon group Ra ₁ includes a ring-assembled hydrocarbon ring group and a bridged cyclic hydrocarbon ring group, each of (n + 1) arbitrary groups from the ring-assembled hydrocarbon ring. And a group formed by removing (n + 1) arbitrary hydrogen atoms from a bridged cyclic hydrocarbon ring.
Examples of the ring assembly hydrocarbon ring group include a bicyclohexane ring group and a perhydronaphthalene ring group. Examples of the bridged cyclic hydrocarbon ring group include a pinane ring group, a bornane ring group, a norpinane ring group, a norbornane ring group, a bicyclooctane ring group (bicyclo [2.2.2] octane ring group, bicyclo [3.2. 1) octane ring group, etc.), bicyclic hydrocarbon ring groups such as bicyclononane ring group, homobredan ring group, adamantane ring group, tricyclo [5.2.1.0 ^2,6 ] decane ring group, tricyclo [4 .3.1.1 ^2,5 ] tricyclic hydrocarbon ring group such as undecane ring group, tetracyclo [4.4.0.1 ^2,5 . And a tetracyclic hydrocarbon ring group such as a 1 ^7,10 ] dodecane ring group and a perhydro-1,4-methano-5,8-methanonaphthalene ring group. The bridged cyclic hydrocarbon ring group includes a condensed cyclic hydrocarbon ring group such as a perhydronaphthalene (decalin) ring group, a perhydroanthracene ring group, a perhydrophenanthrene ring group, a perhydroacenaphthene ring group, A condensed ring group in which a plurality of 5- to 8-membered cycloalkane ring groups such as a perhydrofluorene ring group, a perhydroindene ring group, and a perhydrophenalene ring group are condensed is also included.
Preferred examples of the bridged cyclic hydrocarbon ring group include a norbornane ring group, an adamantane ring group, a bicyclooctane ring group, and a tricyclo [5.2.1.0 ^2,6 ] decane ring group. More preferable examples of the bridged cyclic hydrocarbon ring group include a norbonane ring group and an adamantane ring group.

The alicyclic hydrocarbon group Ra ₁ may have a substituent. Examples of the substituent that Ra ₁ may have include substituents such as an alkyl group and a cycloalkyl group.
The alkyl group or cycloalkyl group as a substituent that Ra ₁ may have may further have a substituent, and as such a substituent, a halogen atom (preferably a fluorine atom) is included. Can be mentioned.

In the alicyclic hydrocarbon group Ra ₁ , the carbon constituting the alicyclic ring (carbon contributing to ring formation) may be a carbonyl carbon. In addition, as described above, the polycycle may have a hetero atom such as an oxygen atom or a sulfur atom as a ring member. However, Ra ₁ does not contain an ester bond as an atomic group constituting an alicyclic ring.

Examples of the linking group represented by L ₁₁ and L ₂₁ include —COO—, —OCO—, —CONH—, —NHCO—, —CO—, —O—, —S—, —SO—, —SO ₂ —. , An alkylene group (preferably having 1 to 6 carbon atoms), a cycloalkylene group (preferably having 3 to 10 carbon atoms), an alkenylene group (preferably having 2 to 6 carbon atoms), or a linking group in which a plurality of these groups are combined. And a linking group having a total carbon number of 12 or less is preferred. In the alkylene group, the cycloalkylene group, the alkenylene group, and the combined linking group, the alkylene group, the cycloalkylene group, and the alkenylene group may have a substituent, and the substituent may be an alkyl group (preferably May include 1 to 4 carbon atoms.
L ₁₁ represents a single bond, an alkylene group, -COO-, -OCO-, -CONH-, -NHCO-, -alkylene group -COO-, -alkylene group -OCO-, -alkylene group -CONH-, -alkylene group -NHCO -, - CO -, - O -, - SO 2 -, - -O- alkylene group, more preferably a single bond, an alkylene group, - an alkylene group -COO-, or, - -O- alkylene group is more preferable .
L ₂₁ is a single bond, an alkylene group, -COO-, -OCO-, -CONH-, -NHCO-, -COO-alkylene group-, -OCO-alkylene group-, -CONH-alkylene group-, -NHCO- alkylene group -, - CO -, - O -, - _SO 2 -, - O-alkylene group -, - O-cycloalkylene group - is preferably a single bond, an alkylene group, -COO- alkylene group -, - O- An alkylene group- or -O-cycloalkylene group- is more preferable.

In the above description method, the leftmost bond “−” means connecting to X ₁ on the main chain side in L ₁₁ , and connecting to Ra ₁ in L ₂₁ . It means that it is connected to Ra ₁ in L _{11 and} Y ₁ in L ₂₁ .

L ₁₁ may be bonded to the same atom constituting the alicyclic ring in Ra ₁ .
n is preferably an integer of 1 to 3, more preferably 1 or 2, and still more preferably 1.

The polymer unit structure constituting the polymer main chain for X ₁ is preferably a repeating unit derived from a polymerizable monomer. The polymerization unit structure X ₁ constituting the polymer main chain, for example, a polymerizable monomer (meth) polymerized unit structure represented by the following general formula derived from the acrylate (a), the following formula derived from styrene monomer Examples thereof include a polymerization unit structure represented by (b) and a polymerization unit structure represented by the following general formula (c) derived from a vinyl monomer.

In the above general formula,
* Represents a bonding position with L ₁₁ in the general formula (II).
X ₀ represents a hydrogen atom, an alkyl group, a cyano group or a halogen atom.
The alkyl group for X ₀ may have a substituent, and examples of the substituent include a hydroxyl group and a halogen atom (preferably a fluorine atom).
The alkyl group for X ₀ is preferably an alkyl group having 1 to 4 carbon atoms, and examples thereof include a methyl group, an ethyl group, a propyl group, a hydroxymethyl group, and a trifluoromethyl group, and a methyl group is preferable.
X ₀ is preferably a hydrogen atom or a methyl group.
In the present invention, X ₁ in the general formula (II) is preferably a polymer unit structure derived from (meth) acrylate. When X ₁ is a polymer unit structure derived from (meth) acrylate, the repeating unit (d1) represented by the general formula (II) can be represented by the following general formula (II ′).

In the general formula (II ′),
X ₀ has the same meaning as _{X 0} in formula (a).
_{Ra 1, L 11, L 21} , n and _{Y 1} have the same meanings as _{Ra 1, L 11, L 21} , n and _{Y 1} in the general formula (II).

Specific examples of the repeating unit (d) having an acid 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 . Xa represents a hydrogen atom, CH ₃ , CF ₃ , or CH ₂ OH.

The repeating unit (d) having an acid group is an acid group having an aromatic ring group when exposed to KrF excimer laser light, an electron beam, X-rays, or a high-energy beam (eg EUV) having a wavelength of 50 nm or less. Is preferred.
One type of repeating unit having an acid group may be used, or two or more types may be used in combination.
The resin (P) may or may not contain the repeating unit (d) having an acid group, but when the resin (P) contains the repeating unit (d), the repeating unit (d) having an acid group. The content of is preferably from 1 to 50 mol%, more preferably from 3 to 50 mol%, still more preferably from 3 to 45 mol%, more preferably from 5 to 45 mol%, based on all repeating units in the resin (P). It is particularly preferred that

The resin (P) is a repeating unit other than the repeating units described above, and may further have a repeating unit (e) having a hydroxyl group or a cyano group. As a result, substrate adhesion and developer compatibility can be improved. The repeating unit having a hydroxyl group or a cyano group is preferably a repeating unit having an alicyclic hydrocarbon structure substituted with a hydroxyl group or a cyano group, and preferably has no acid-decomposable group. In the alicyclic hydrocarbon structure substituted with a hydroxyl group or a cyano group, the alicyclic hydrocarbon structure is preferably an adamantyl group, a diamantyl group or a norbornane group, more preferably an adamantyl group. Further, it is preferably substituted with a hydroxyl group, and more preferably contains a repeating unit having an adamantyl group substituted with at least one hydroxyl group.
In particular, the resin (P) most preferably contains a repeating unit having a hydroxyadamantyl group or a dihydroxyadamantyl group from the viewpoint of suppressing diffusion of the generated acid. As the alicyclic hydrocarbon structure substituted with a hydroxyl group or a cyano group, partial structures represented by the following general formulas (VIIa) to (VIId) are preferable, and partial structures represented by the following general formula (VIIa) are more preferable. .

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

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

In the general formulas (AIIa) to (AIId),
R ₁ c represents a hydrogen atom, a methyl group, a trifluoromethyl group, or a hydroxymethyl group.
R ₂ c to R ₄ c are in the general formula (VIIa) ~ _(VIIc), same meanings as R 2 c~R ₄ c.
Specific examples of the repeating unit (e) having a hydroxyl group or a cyano group are listed below, but the present invention is not limited thereto.

  The resin (P) may or may not contain a repeating unit having a hydroxyl group or a cyano group. However, when the resin (P) contains a repeating unit (e), a hydroxyl group or a cyano group is added. The content of the repeating unit (e) is preferably 1 to 50 mol%, more preferably 3 to 50 mol%, and further preferably 3 to 45 mol%, based on all repeating units in the resin (P). It is preferably 5 to 45 mol%, particularly preferably.

  The resin (P) in the present invention can further have a repeating unit that has an alicyclic hydrocarbon structure that does not have a polar group (for example, the acid group, hydroxyl group, and cyano group) and does not exhibit acid decomposability. As a result, the elution of low molecular components from the resist film to the immersion liquid during immersion exposure can be reduced, and the solubility of the resin can be appropriately adjusted during development using a developer containing an organic solvent. . Examples of such a repeating unit include a repeating unit represented by the general formula (IV).

In general formula (IV), R ₅ represents a hydrocarbon group having at least one cyclic structure and having no polar group.
Ra represents a hydrogen atom, an alkyl group, or a —CH ₂ —O—Ra ₂ group. In the formula, Ra ₂ represents a hydrogen atom, an alkyl group, or an acyl group. Ra is preferably a hydrogen atom, a methyl group, a hydroxymethyl group or a trifluoromethyl group, particularly preferably a hydrogen atom or a methyl group.

The cyclic structure possessed by R ₅ includes a monocyclic hydrocarbon group and a polycyclic hydrocarbon group. Examples of the monocyclic hydrocarbon group include a cycloalkenyl group having 3 to 12 carbon atoms such as a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group and the like, and a cycloalkyl group having 3 to 12 carbon atoms and a cyclohexenyl group. Groups. Preferable monocyclic hydrocarbon groups are monocyclic hydrocarbon groups having 3 to 7 carbon atoms, and more preferable examples include a cyclopentyl group and a cyclohexyl group.

The polycyclic hydrocarbon group includes a ring assembly hydrocarbon group and a bridged cyclic hydrocarbon group, and examples of the ring assembly hydrocarbon group include a bicyclohexyl group and a perhydronaphthalenyl group. As the bridged cyclic hydrocarbon ring, for example, bicyclic such as pinane, bornane, norpinane, norbornane, bicyclooctane ring (bicyclo [2.2.2] octane ring, bicyclo [3.2.1] octane ring, etc.) Hydrocarbon rings and tricyclic hydrocarbon rings such as homobredan, adamantane, tricyclo [5.2.1.0 ^2,6 ] decane, tricyclo [4.3.1.1 ^2,5 ] undecane ring, tetracyclo [ 4.4.0.1 ^2,5 . 1 ^7,10 ] dodecane, and tetracyclic hydrocarbon rings such as perhydro-1,4-methano-5,8-methanonaphthalene ring. The bridged cyclic hydrocarbon ring includes a condensed cyclic hydrocarbon ring such as perhydronaphthalene (decalin), perhydroanthracene, perhydrophenanthrene, perhydroacenaphthene, perhydrofluorene, perhydroindene, perhydroindene. A condensed ring in which a plurality of 5- to 8-membered cycloalkane rings such as a phenalene ring are condensed is also included.

Preferred examples of the bridged cyclic hydrocarbon ring include a norbornyl group, an adamantyl group, a bicyclooctanyl group, a tricyclo [5,2,1,0 ^2,6 ] decanyl group, and the like. More preferable examples of the bridged cyclic hydrocarbon ring include a norbornyl group and an adamantyl group.

  These alicyclic hydrocarbon groups may have a substituent. Preferred examples of the substituent include a halogen atom, an alkyl group, a hydroxyl group substituted with a hydrogen atom, and an amino group substituted with a hydrogen atom. It is done. Preferred halogen atoms include bromine, chlorine and fluorine atoms, and preferred alkyl groups include methyl, ethyl, butyl and t-butyl groups. The alkyl group described above may further have a substituent, and examples of the substituent that may further include a halogen atom, an alkyl group, a hydroxyl group substituted with a hydrogen atom, and an amino group substituted with a hydrogen atom. The group can be mentioned.

  Examples of the substituent for the hydrogen atom include an alkyl group, a cycloalkyl group, an aralkyl group, a substituted methyl group, a substituted ethyl group, an alkoxycarbonyl group, and an aralkyloxycarbonyl group. Preferred alkyl groups include alkyl groups having 1 to 4 carbon atoms, preferred substituted methyl groups include methoxymethyl, methoxythiomethyl, benzyloxymethyl, t-butoxymethyl, 2-methoxyethoxymethyl groups, and preferred substituted ethyl groups. 1-ethoxyethyl, 1-methyl-1-methoxyethyl, preferred acyl groups include formyl, acetyl, propionyl, butyryl, isobutyryl, valeryl, pivaloyl groups, etc., aliphatic acyl groups having 1 to 6 carbon atoms, alkoxycarbonyl Examples of the group include an alkoxycarbonyl group having 1 to 4 carbon atoms.

The resin (P) has an alicyclic hydrocarbon structure having no polar group and may or may not contain a repeating unit that does not exhibit acid decomposability, but the resin (P) does not contain a polar group. When the repeating unit (f) has a cyclic hydrocarbon structure and does not exhibit acid decomposability, the content of the repeating unit (f) is 1 to 40 mol with respect to all the repeating units in the resin (P). % Is preferable, and more preferably 1 to 20 mol%.
Specific examples of the repeating unit (f) are shown below, but the present invention is not limited thereto. In the formula, Ra represents H, CH ₃ , CH ₂ OH, or CF ₃ .

  The resin (P) used in the composition of the present invention includes, in addition to the above repeating structural units, dry etching resistance, standard developer suitability, substrate adhesion, resist profile, and actinic ray sensitive or radiation sensitive resin composition. It is possible to have various repeating structural units for the purpose of adjusting resolving power, heat resistance, sensitivity, and the like, which are general necessary characteristics.

Examples of such repeating structural units include, but are not limited to, repeating structural units corresponding to the following monomers.
Thereby, performance required for the resin used in the composition of the present invention, in particular,
(1) Solubility in coating solvent,
(2) Film formability (glass transition point),
(3) Alkali developability,
(4) Membrane slip (hydrophobic, alkali-soluble group selection),
(5) Adhesion of unexposed part to substrate,
(6) Fine adjustment such as resistance to dry etching can be performed.

As such monomers, for example, addition polymerization selected from acrylic esters, methacrylic esters, acrylamides, methacrylamides, allyl compounds, vinyl ethers, vinyl esters, styrenes, crotonic esters, and the like. Examples include compounds having one unsaturated bond.
In addition, any addition-polymerizable unsaturated compound that can be copolymerized with monomers corresponding to the above various repeating structural units may be copolymerized.

In the resin (P) used in the composition of the present invention, the content molar ratio of each repeating structural unit is the dry etching resistance of the actinic ray-sensitive or radiation-sensitive resin composition, suitability for standard developer, substrate adhesion, resist The profile is appropriately set to adjust the resolution, heat resistance, sensitivity, and the like, which are general required performances of the resist.
The form of the resin (P) in the present invention may be any of random type, block type, comb type, and star type. The resin (P) can be synthesized, for example, by radical, cation, or anionic polymerization of an unsaturated monomer corresponding to each structure. It is also possible to obtain the desired resin by conducting a polymer reaction after polymerization using an unsaturated monomer corresponding to the precursor of each structure.
When the composition in the present invention is for ArF exposure, the resin (P) used in the composition of the present invention has substantially no aromatic ring from the viewpoint of transparency to ArF light (specifically, The ratio of the repeating unit having an aromatic group in the resin is preferably 5 mol% or less, more preferably 3 mol% or less, ideally 0 mol%, that is, no aromatic group). .
The resin (P) preferably has an alicyclic hydrocarbon structure. The alicyclic hydrocarbon structure may be monocyclic or polycyclic, and the alicyclic hydrocarbon structure may be contained in any location in the resin (P). May be contained in any of the repeating units (excluding the repeating unit (a) represented by the general formula (I)), or may be contained as other repeating units.
Moreover, when the composition of this invention contains resin (E) mentioned later, it is preferable that resin (P) does not contain a fluorine atom and a silicon atom from a compatible viewpoint with resin (E). .
Further, the resin (P) preferably does not have a fluorine atom or a silicon atom, or even if it has a small amount. Specifically, in all the repeating units of the resin (P), the repeating unit having a fluorine atom or a silicon atom is preferably 0 to 20 mol%, more preferably 0 to 10 mol%, 5 mol% is particularly preferable, and ideally does not contain a repeating unit having a fluorine atom or a silicon atom. By carrying out like this, it is preferable from a compatible viewpoint, etc. when ensuring the moderate solubility of resin (P) with respect to the developing solution containing an organic solvent, or the composition of this invention contains the hydrophobic resin mentioned later.

In the resin (P), the main repeating unit is preferably a (meth) acrylate repeating unit. Specifically, in all the repeating units of the resin (P), preferably 50 mol% or more, more preferably 70 mol% or more, still more preferably 90 mol% or more, and particularly preferably all repeating units are (meth) acrylate. It is a system repeating unit.
The resin (P) used in the composition in the present invention is preferably one in which all of the repeating units are composed of (meth) acrylate-based repeating units. In this case, all of the repeating units are methacrylate repeating units, all of the repeating units are acrylate repeating units, or all of the repeating units are methacrylate repeating units and acrylate repeating units. Although it can be used, the acrylate-based repeating unit is preferably 50 mol% or less of the total repeating units. Moreover, the alicyclic hydrocarbon substituted by the (meth) acrylate type repeating unit 20-50 mol% which has an acid-decomposable group, the (meth) acrylate type repeating unit 20-50 mol% which has a lactone group, and a hydroxyl group or a cyano group. A copolymer having 5 to 30 mol% of a (meth) acrylate-based repeating unit having a structure and 0 to 20 mol% of another (meth) acrylate-based repeating unit is also preferred.

  When the composition according to the present invention is irradiated with KrF excimer laser light, electron beam, X-ray, high energy light beam (EUV, etc.) having a wavelength of 50 nm or less, the resin (P) further has a hydroxystyrene-based repeating unit. It is preferable. More preferably, it has a hydroxystyrene-based repeating unit, a hydroxystyrene-based repeating unit protected with an acid-decomposable group, and an acid-decomposable repeating unit such as a (meth) acrylic acid tertiary alkyl ester.

  Examples of the repeating unit having a preferred acid-decomposable group based on hydroxystyrene include, for example, t-butoxycarbonyloxystyrene, 1-alkoxyethoxystyrene, a repeating unit of (meth) acrylic acid tertiary alkyl ester, and the like. More preferred are repeating units of 2-alkyl-2-adamantyl (meth) acrylate and dialkyl (1-adamantyl) methyl (meth) acrylate.

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

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

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

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

The amount of the precipitation or reprecipitation solvent used can be appropriately selected in consideration of efficiency, yield, and the like, but generally 100 to 10000 parts by mass, preferably 200 to 2000 parts by mass with respect to 100 parts by mass of the polymer solution More preferably, it is 300-1000 mass parts.
The temperature for precipitation or reprecipitation can be appropriately selected in consideration of efficiency and operability, but is usually about 0 to 50 ° C., preferably around room temperature (for example, about 20 to 35 ° C.). The precipitation or reprecipitation operation can be performed by a known method such as a batch method or a continuous method using a conventional mixing vessel such as a stirring tank.
The precipitated or re-precipitated polymer is usually subjected to conventional solid-liquid separation such as filtration and centrifugation, and dried before use. Filtration is performed using a solvent-resistant filter medium, preferably under pressure. Drying is performed at a temperature of about 30 to 100 ° C., preferably about 30 to 50 ° C. under normal pressure or reduced pressure (preferably under reduced pressure).
In addition, after depositing and separating the resin once, it may be dissolved again in a solvent, and the resin may be brought into contact with a hardly soluble or insoluble solvent. That is, after completion of the radical polymerization reaction, a solvent in which the polymer is hardly soluble or insoluble is contacted to precipitate a resin (step a), the resin is separated from the solution (step b), and dissolved again in the solvent to obtain a resin solution A. (Step c), and then contact the resin solution A with a solvent in which the resin is hardly soluble or insoluble in a volume amount less than 10 times that of the resin solution A (preferably 5 times or less volume). This may be a method including precipitating a resin solid (step d) and separating the precipitated resin (step e).

In order to prevent the resin from aggregating after the preparation of the composition, for example, as described in JP-A-2009-037108, the synthesized resin is dissolved in a solvent to form a solution. A step of heating at about 30 ° C. to 90 ° C. for about 30 minutes to 4 hours may be added.
The weight average molecular weight of the resin (P) used in the composition of the present invention is preferably 1,000 to 200,000, more preferably 2,000 to 100,000, more preferably in terms of polystyrene by GPC method. More preferably, it is 3,000-70,000, Most preferably, it is 5,000-50,000. By setting the weight average molecular weight to 1,000 to 200,000, deterioration of heat resistance and dry etching resistance can be prevented, and developability is deteriorated, and viscosity is increased, resulting in deterioration of film forming property. Can be prevented.
Further, by strictly controlling the weight average molecular weight, the solubility of the resin (P) in the organic developer can be controlled, and the roundness of the hole pattern and the development time dependency can be improved. As described above, the weight average molecular weight is most preferably 14,000 or more from the viewpoint of the roundness of the hole pattern and the development time dependency. The upper limit of the weight average molecular weight is preferably 50000 or less, more preferably 40,000 or less, and still more preferably 30,000 or less.

The degree of dispersion (molecular weight distribution) is usually in the range of 1.0 to 3.0. Preferably it is 1.0-2.6, More preferably, it is 1.1-2.5, More preferably, it is 1.2-2.4, Especially preferably, it is 1.3-2.2, Most preferably, it is 1.4- Those in the range of 2.0 are used. When the molecular weight distribution satisfies the above range, the resolution and resist shape are excellent, the side wall of the resist pattern is smooth, and the roughness is excellent.
In the actinic ray-sensitive or radiation-sensitive resin composition of the present invention, the content of the resin (P) in the entire composition is preferably 30 to 99% by mass, more preferably 60 to 95% by mass in the total solid content. It is.
In the present invention, the resin (P) may be used alone or in combination.

Furthermore, in the actinic ray-sensitive or radiation-sensitive resin composition of the present invention, the resin (P) and an acid-decomposable resin other than the resin (P) (development including an organic solvent with increased polarity by the action of an acid) (Resin which the solubility with respect to a liquid decreases) may be further included. The acid-decomposable resin other than the resin (P) is an acid-decomposable resin composed of the same repeating unit as the repeating unit that may be contained in the resin (P). The content in is the same as that described for the resin (P).
When an acid-decomposable resin other than the resin (P) is included, the content of the acid-decomposable resin in the composition according to the present invention is the content of the resin (P) and an acid-decomposable resin other than the resin (P). The total amount may be in the above range. The mass ratio between the resin (P) and the acid-decomposable resin other than the resin (P) can be appropriately adjusted within the range in which the effect of the present invention is satisfactorily achieved, but [resin (P) / resin (P) Acid-decomposable resin other than] is preferably in the range of 99.9 / 0.1 to 10/90, and more preferably in the range of 99.9 / 0.1 to 60/40.
The actinic ray-sensitive or radiation-sensitive resin composition in the present invention preferably contains only the resin (P) as the acid-decomposable resin from the viewpoint of the roundness of the hole pattern and the development time dependency.
Specific examples of the resin (P) used in the present invention are listed below, but the present invention is not limited to these.

[2] Compound (B) that generates an organic acid upon irradiation with actinic rays or radiation
The composition in the present invention contains a compound (B) that generates an organic acid upon irradiation with actinic rays or radiation (hereinafter also referred to as “acid generator”). Here, the compound (B) is a compound different from the compound (C) described in detail later (that is, a compound that generates an organic acid upon irradiation with actinic rays or radiation and corresponds to the compound (C)). Is considered herein as compound (C) and not as compound (B)).
As the acid generator, photo-initiator of photocation polymerization, photo-initiator of photo-radical polymerization, photo-decoloring agent of dyes, photo-discoloring agent, irradiation of actinic ray or radiation used for micro resist, etc. The known compounds that generate organic acids and mixtures thereof can be appropriately selected and used.

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

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

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

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

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

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

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

  The aliphatic moiety in the aliphatic sulfonate anion and aliphatic carboxylate anion may be an alkyl group or a cycloalkyl group, preferably an alkyl group having 1 to 30 carbon atoms and a cyclohexane having 3 to 30 carbon atoms. Alkyl groups such as methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, sec-butyl, pentyl, neopentyl, hexyl, heptyl, octyl, nonyl, decyl , Undecyl group, dodecyl group, tridecyl group, tetradecyl group, pentadecyl group, hexadecyl group, heptadecyl group, octadecyl group, nonadecyl group, eicosyl group, cyclopropyl group, cyclopentyl group, cyclohexyl group, adamantyl group, norbornyl group, bornyl group, etc. Can be mentioned.

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

  The alkyl group, cycloalkyl group and aryl group in the aliphatic sulfonate anion and aromatic sulfonate anion may have a substituent. Examples of the substituent of the alkyl group, cycloalkyl group and aryl group in the aliphatic sulfonate anion and aromatic sulfonate anion include, for example, a nitro group, a halogen atom (fluorine atom, chlorine atom, bromine atom, iodine atom), carboxyl group , Hydroxyl group, amino group, cyano group, alkoxy group (preferably having 1 to 15 carbon atoms), cycloalkyl group (preferably having 3 to 15 carbon atoms), aryl group (preferably having 6 to 14 carbon atoms), alkoxycarbonyl group ( Preferably 2 to 7 carbon atoms, acyl group (preferably 2 to 12 carbon atoms), alkoxycarbonyloxy group (preferably 2 to 7 carbon atoms), alkylthio group (preferably 1 to 15 carbon atoms), alkylsulfonyl group (Preferably 1 to 15 carbon atoms), alkyliminosulfonyl group (preferably 1 to 15 carbon atoms), ant Ruoxysulfonyl group (preferably having 6 to 20 carbon atoms), alkylaryloxysulfonyl group (preferably having 7 to 20 carbon atoms), cycloalkylaryloxysulfonyl group (preferably having 10 to 20 carbon atoms), alkyloxyalkyloxy group (Preferably having 5 to 20 carbon atoms), a cycloalkylalkyloxyalkyloxy group (preferably having 8 to 20 carbon atoms), and the like. About the aryl group and ring structure which each group has, an alkyl group (preferably C1-C15) and a cycloalkyl group (preferably C3-C15) can further be mentioned as a substituent.

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

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

  Examples of the sulfonylimide anion include saccharin anion.

  The alkyl group in the bis (alkylsulfonyl) imide anion and tris (alkylsulfonyl) methide anion is preferably an alkyl group having 1 to 5 carbon atoms, for example, methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, isobutyl. Group, sec-butyl group, pentyl group, neopentyl group and the like. Examples of substituents for these alkyl groups include halogen atoms, alkyl groups substituted with halogen atoms, alkoxy groups, alkylthio groups, alkyloxysulfonyl groups, aryloxysulfonyl groups, cycloalkylaryloxysulfonyl groups, and the like. Alkyl groups substituted with fluorine atoms are preferred.

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

The acid generator is preferably a compound that generates an organic acid represented by the following general formula (II) or (III). Since it is a compound that generates an organic acid represented by the following general formula (II) or (III) and has a cyclic organic group, the resolution and roughness performance can be further improved.
The non-nucleophilic anion may be an anion that generates an organic acid represented by the following general formula (II) or (III).

In the above general formula,
Xf each independently represents a fluorine atom or an alkyl group substituted with at least one fluorine atom.
R ₁ and R ₂ each independently represents a hydrogen atom, a fluorine atom, or an alkyl group.
L each independently represents a divalent linking group.
Cy represents a cyclic organic group.
Rf is a group containing a fluorine atom.
x represents an integer of 1 to 20.
y represents an integer of 0 to 10.
z represents an integer of 0 to 10.

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

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

L represents a divalent linking group. Examples of the divalent linking group include —COO—, —OCO—, —CONH—, —NHCO—, —CO—, —O—, —S—, —SO—, —SO ₂ —, and an alkylene group. (Preferably having 1 to 6 carbon atoms), cycloalkylene group (preferably having 3 to 10 carbon atoms), alkenylene group (preferably having 2 to 6 carbon atoms) or a divalent linking group in which a plurality of these are combined. . Among them, -COO -, - OCO -, - CONH -, - NHCO -, - CO -, - O -, - SO 2 -, - COO- alkylene group -, - OCO- alkylene group -, - CONH- alkylene group - or -NHCO- alkylene group - are preferred, -COO -, - OCO -, - CONH -, - SO 2 -, - COO- alkylene group - or -OCO- alkylene group - is more preferable.

  Cy represents a cyclic organic group. Examples of the cyclic organic group include an alicyclic group, an aryl group, and a heterocyclic group.

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

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

  The heterocyclic group may be monocyclic or polycyclic, but the polycyclic group can further suppress acid diffusion. Moreover, the heterocyclic group may have aromaticity or may not have aromaticity. Examples of the heterocyclic ring having aromaticity include a furan ring, a thiophene ring, a benzofuran ring, a benzothiophene ring, a dibenzofuran ring, a dibenzothiophene ring, and a pyridine ring. Examples of the heterocyclic ring not having aromaticity include a tetrahydropyran ring, a lactone ring, and a decahydroisoquinoline ring. As the heterocyclic ring in the heterocyclic group, a furan ring, a thiophene ring, a pyridine ring, or a decahydroisoquinoline ring is particularly preferable. Examples of the lactone ring include the lactone structure exemplified in the aforementioned resin (P).

  The cyclic organic group may have a substituent. Examples of the substituent include an alkyl group (which may be linear or branched, preferably 1 to 12 carbon atoms), and a cycloalkyl group (monocyclic, polycyclic or spirocyclic). Well, preferably 3 to 20 carbon atoms), aryl group (preferably 6 to 14 carbon atoms), hydroxy group, alkoxy group, ester group, amide group, urethane group, ureido group, thioether group, sulfonamide group, and sulfone An acid ester group is mentioned. The carbon constituting the cyclic organic group (carbon contributing to ring formation) may be a carbonyl carbon.

x is preferably 1 to 8, more preferably 1 to 4, and particularly preferably 1. y is preferably 0 to 4, and more preferably 0. z is preferably 0 to 8, particularly preferably 0 to 4.
Examples of the group containing a fluorine atom represented by Rf include an alkyl group having at least one fluorine atom, a cycloalkyl group having at least one fluorine atom, and an aryl group having at least one fluorine atom. .
These alkyl group, cycloalkyl group and aryl group may be substituted with a fluorine atom, or may be substituted with another substituent containing a fluorine atom. When Rf is a cycloalkyl group having at least one fluorine atom or an aryl group having at least one fluorine atom, other substituents containing a fluorine atom include, for example, alkyl substituted with at least one fluorine atom. Groups.
Further, these alkyl group, cycloalkyl group and aryl group may be further substituted with a substituent not containing a fluorine atom. As this substituent, the thing which does not contain a fluorine atom among what was demonstrated about Cy previously can be mentioned, for example.
Examples of the alkyl group having at least one fluorine atom represented by Rf include those described above as the alkyl group substituted with at least one fluorine atom represented by Xf. Examples of the cycloalkyl group having at least one fluorine atom represented by Rf include a perfluorocyclopentyl group and a perfluorocyclohexyl group. Examples of the aryl group having at least one fluorine atom represented by Rf include a perfluorophenyl group.

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

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

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

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

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

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

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

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

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

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

The organic group not containing an aromatic ring as R _{201 to} R ₂₀₃ generally has 1 to 30 carbon atoms, preferably 1 to 20 carbon atoms.

R _{201 to} R ₂₀₃ are each independently preferably an alkyl group, a cycloalkyl group, an allyl group, or a vinyl group, more preferably a linear or branched 2-oxoalkyl group, 2-oxocycloalkyl group, alkoxy group. A carbonylmethyl group, particularly preferably a linear or branched 2-oxoalkyl group.

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

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

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

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

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

In general formula (ZI-3),
R _{1c to} R _5c are each independently a hydrogen atom, alkyl group, cycloalkyl group, aryl group, alkoxy group, aryloxy group, alkoxycarbonyl group, alkylcarbonyloxy group, cycloalkylcarbonyloxy group, halogen atom, hydroxyl group Represents a nitro group, an alkylthio group or an arylthio group.
R _6c and R _7c each independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, a cyano group or an aryl group.
R _x and R _y each independently represents an alkyl group, a cycloalkyl group, a 2-oxoalkyl group, a 2-oxocycloalkyl group, an alkoxycarbonylalkyl group, an allyl group, or a vinyl group.

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

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

The alkyl group as R _{1c to} R _7c may be either linear or branched, for example, an alkyl group having 1 to 20 carbon atoms, preferably a linear or branched alkyl group having 1 to 12 carbon atoms ( Examples thereof include a methyl group, an ethyl group, a linear or branched propyl group, a linear or branched butyl group, and a linear or branched pentyl group. Examples of the cycloalkyl group include cyclohexane having 3 to 10 carbon atoms. An alkyl group (for example, a cyclopentyl group, a cyclohexyl group) can be mentioned.

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

The alkoxy group as R _{1c to} R _{5c may} be linear, branched or cyclic, for example, an alkoxy group having 1 to 10 carbon atoms, preferably a linear or branched alkoxy group having 1 to 5 carbon atoms. (For example, methoxy group, ethoxy group, linear or branched propoxy group, linear or branched butoxy group, linear or branched pentoxy group), C3-C10 cyclic alkoxy group (for example, cyclopentyloxy group, cyclohexyloxy group) ).

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

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

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

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

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

The ring structure which may be formed by R _5c and R _6c are bonded to each other, bonded R _5c and R _6c are each other a single bond or an alkylene group (methylene group, ethylene group, etc.) by configuring the generally Examples thereof include a carbonyl carbon atom in the formula (I) and a 4-membered ring (particularly preferably a 5- to 6-membered ring) formed together with the carbon atom.

The aryl group as R _6c and R _7c preferably has 5 to 15 carbon atoms, and examples thereof include a phenyl group and a naphthyl group.
As an aspect of R _6c and R _7c , it is preferable that both of them are alkyl groups. In particular, R _6c and R _7c are each preferably a linear or branched alkyl group having 1 to 4 carbon atoms, and particularly preferably both are methyl groups.

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

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

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

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

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

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

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

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

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

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

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

  Examples of the cation of the compound (ZI-2) or (ZI-3) in the present invention include the following specific examples.

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

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

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

Examples of the cycloalkyl group represented by R ₁₃ , R ₁₄ and R ₁₅ include monocyclic or polycyclic cycloalkyl groups (preferably cycloalkyl groups having 3 to 20 carbon atoms), and in particular, cyclopropyl, cyclopentyl, cyclohexyl, Cycloheptyl and cyclooctyl are preferred.

The alkoxy group of R ₁₃ and R ₁₄ is linear or branched and preferably has 1 to 10 carbon atoms, and is preferably a methoxy group, an ethoxy group, an n-propoxy group, an n-butoxy group, or the like.

The alkoxycarbonyl group for R ₁₃ and R ₁₄ is linear or branched and preferably has 2 to 11 carbon atoms, and is preferably a methoxycarbonyl group, an ethoxycarbonyl group, an n-butoxycarbonyl group, or the like.

Examples of the group having a cycloalkyl group of R ₁₃ and R ₁₄ include a monocyclic or polycyclic cycloalkyl group (preferably a cycloalkyl group having 3 to 20 carbon atoms), and examples thereof include a monocyclic or polycyclic cycloalkyl group. Examples thereof include a cycloalkyloxy group and an alkoxy group having a monocyclic or polycyclic cycloalkyl group. These groups may further have a substituent.

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

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

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

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

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

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

  Examples of the alkoxy group include methoxy group, ethoxy group, n-propoxy group, i-propoxy group, n-butoxy group, 2-methylpropoxy group, 1-methylpropoxy group, t-butoxy group, cyclopentyloxy group, Examples thereof include a linear, branched or cyclic alkoxy group having 1 to 20 carbon atoms such as a cyclohexyloxy group.

  Examples of the alkoxyalkyl group include straight chain having 2 to 21 carbon atoms such as methoxymethyl group, ethoxymethyl group, 1-methoxyethyl group, 2-methoxyethyl group, 1-ethoxyethyl group, and 2-ethoxyethyl group. Examples thereof include a chain, branched or cyclic alkoxyalkyl group.

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

  Examples of the alkoxycarbonyloxy group include methoxycarbonyloxy group, ethoxycarbonyloxy group, n-propoxycarbonyloxy group, i-propoxycarbonyloxy group, n-butoxycarbonyloxy group, t-butoxycarbonyloxy group, and cyclopentyloxy. Examples thereof include linear, branched or cyclic alkoxycarbonyloxy groups having 2 to 21 carbon atoms such as carbonyloxy group and cyclohexyloxycarbonyloxy.

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

The substituent that R ₁₃ and R ₁₄ may have is preferably a hydroxyl group, an alkoxy group, an alkoxycarbonyl group, or a halogen atom (particularly a fluorine atom).

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

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

Next, general formulas (ZII) and (ZIII) will be described.
In general formulas (ZII) and (ZIII),
R ₂₀₄ to R ₂₀₇ each independently represents an aryl group, an alkyl group or a cycloalkyl group.
The aryl group for R _{204 to} R ₂₀₇ is preferably a phenyl group or a naphthyl group, and more preferably a phenyl group. The aryl group of R _{204 to} R ₂₀₇ may be an aryl group having a heterocyclic structure having an oxygen atom, a nitrogen atom, a sulfur atom, or the like. Examples of the skeleton of the aryl group having a heterocyclic structure include pyrrole, furan, thiophene, indole, benzofuran, and benzothiophene.
The alkyl group and cycloalkyl group in R _{204 to} R ₂₀₇ are preferably a linear or branched alkyl group having 1 to 10 carbon atoms (for example, methyl group, ethyl group, propyl group, butyl group, pentyl group), carbon Examples thereof include cycloalkyl groups of several 3 to 10 (cyclopentyl group, cyclohexyl group, norbornyl group).
The aryl group, alkyl group, and cycloalkyl group of R _{204 to} R ₂₀₇ may have a substituent. Aryl group, alkyl group of R ₂₀₄ to R _207, the cycloalkyl group substituent which may be possessed by, for example, an alkyl group (for example, 1 to 15 carbon atoms), a cycloalkyl group (for example, 3 to 15 carbon atoms ), An aryl group (for example, having 6 to 15 carbon atoms), an alkoxy group (for example, having 1 to 15 carbon atoms), a halogen atom, a hydroxyl group, and a phenylthio group.
Z ⁻ represents a non-nucleophilic anion, and examples thereof include the same as the non-nucleophilic anion of Z ^{− in} formula (ZI).

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

In general formulas (ZIV) to (ZVI),
Ar ₃ and Ar ₄ each independently represents an aryl group.
R ₂₀₈ , R ₂₀₉ and R ₂₁₀ each independently represents an alkyl group, a cycloalkyl group or an aryl group.
A represents an alkylene group, an alkenylene group or an arylene group.
Specific examples of the aryl group of Ar ₃ , Ar ₄ , R ₂₀₈ , R ₂₀₉ and R ₂₁₀ are the same as the specific examples of the aryl group as R ₂₀₁ , R ₂₀₂ and R ₂₀₃ in the general formula (ZI-1). Things can be mentioned.
Specific examples of the alkyl group and cycloalkyl group represented by R ₂₀₈ , R _209, and R ₂₁₀ include specific examples of the alkyl group and cycloalkyl group represented by R ₂₀₁ , R _202, and R ₂₀₃ in the general formula (ZI-2), respectively. The same thing as an example can be mentioned.
The alkylene group of A is alkylene having 1 to 12 carbon atoms (for example, methylene group, ethylene group, propylene group, isopropylene group, butylene group, isobutylene group, etc.), and the alkenylene group of A is 2 to 2 carbon atoms. 12 alkenylene groups (for example, ethenylene group, propenylene group, butenylene group, etc.), and as the arylene group for A, arylene groups having 6 to 10 carbon atoms (for example, phenylene group, tolylene group, naphthylene group, etc.) Can be mentioned.

Among the acid generators, compounds represented by the general formulas (ZI) to (ZIII) are more preferable.
Further, the acid generator is preferably a compound that generates an acid having one sulfonic acid group or imide group, more preferably a compound that generates monovalent perfluoroalkanesulfonic acid, or a monovalent fluorine atom or fluorine atom. A compound that generates an aromatic sulfonic acid substituted with a group containing fluorinated acid, or a compound that generates an imide acid substituted with a monovalent fluorine atom or a group containing a fluorine atom, and even more preferably, It is a sulfonium salt of a substituted alkanesulfonic acid, a fluorine-substituted benzenesulfonic acid, a fluorine-substituted imide acid or a fluorine-substituted methide acid. The acid generator that can be used is particularly preferably a fluorinated substituted alkane sulfonic acid, a fluorinated substituted benzene sulfonic acid, or a fluorinated substituted imido acid whose pKa of the generated acid is −1 or less, and the sensitivity is improved.

  Among acid generators, particularly preferred examples are given below.

The acid generator can be synthesized by a known method, for example, according to the method described in JP-A No. 2007-161707.
An acid generator can be used individually by 1 type or in combination of 2 or more types.
The content of the compound that generates an organic acid upon irradiation with actinic rays or radiation is preferably 0.1 to 30% by mass based on the total solid content of the actinic ray-sensitive or radiation-sensitive resin composition. More preferably, it is 0.5-25 mass%, More preferably, it is 3-20 mass%, Most preferably, it is 3-15 mass%.
When the acid generator is represented by the general formula (ZI-3) or (ZI-4), the content is preferably 5 to 35% by mass based on the total solid content of the composition. 8-30 mass% is more preferable, 10-30 mass% is still more preferable, and 10-25 mass% is especially preferable. Further, by setting the upper limit of the content to about 20% by mass or less, it can be expected that the generation of acid from the acid generator and the acid decomposition reaction of the resin (P) are in a desirable balance.

[3] Basic compound or ammonium salt compound (C) whose basicity is reduced by irradiation with actinic rays or radiation
The actinic ray-sensitive or radiation-sensitive resin composition in the present invention contains a basic compound or an ammonium salt compound (hereinafter also referred to as “compound (C)”) whose basicity is lowered by irradiation with actinic rays or radiation. To do.

The compound (C) is preferably a compound (C-1) having a basic functional group or an ammonium group and a group that generates an acidic functional group upon irradiation with actinic rays or radiation. That is, the compound (C) is a basic compound having a basic functional group and a group that generates an acidic functional group upon irradiation with actinic light or radiation, or an acidic functional group upon irradiation with an ammonium group and active light or radiation. An ammonium salt compound having a group to be generated is preferable.
Specific examples include compounds in which an anion in which a proton is eliminated from an acidic functional group of a compound having a basic functional group or an ammonium group and an acidic functional group and an onium cation form a salt.
Here, examples of the basic functional group include atomic groups including structures such as crown ethers, primary to tertiary amines, and nitrogen-containing heterocycles (pyridine, imidazole, pyrazine, etc.). Moreover, as a preferable structure of an ammonium group, for example, an atomic group containing a primary to tertiary ammonium, pyridinium, imidazolinium, pyrazinium structure, or the like can be given. In addition, as a basic functional group, the functional group which has a nitrogen atom is preferable, and the structure which has a 1-3 primary amino group, or a nitrogen-containing heterocyclic structure is more preferable. In these structures, it is preferable from the viewpoint of improving basicity that all atoms adjacent to the nitrogen atom contained in the structure are carbon atoms or hydrogen atoms. From the viewpoint of improving basicity, it is preferable that an electron-withdrawing functional group (such as a carbonyl group, a sulfonyl group, a cyano group, or a halogen atom) is not directly connected to the nitrogen atom.
Examples of the acidic functional group include a carboxylic acid group, a sulfonic acid group, a group having a —X—NH—X— (X═CO or SO ₂ ) structure, and the like.
Examples of the onium cation include a sulfonium cation and an iodonium cation. More specifically, (B) what is demonstrated as a cation part of general formula (ZI) (ZII) of an acid generator, etc. are mentioned.
More specifically, the compounds represented by the following general formulas (PA-I) and (PA) are compounds having reduced basicity that are generated by the decomposition of compound (C) or (C-1) upon irradiation with actinic rays or radiation. -II) or a compound represented by (PA-III), and in particular, from the standpoint that both LWR, local pattern dimension uniformity and excellent effect on DOF can be achieved at a high level, A compound represented by (PA-II) or (PA-III) is preferred.
First, the compound represented by general formula (PA-I) is demonstrated.

_{Q-A 1 - (X)} n -B-R (PA-I)

In general formula (PA-I),
A ₁ represents a single bond or a divalent linking group.
Q represents _-SO 3 H, or -CO ₂ H. Q corresponds to an acidic functional group generated by irradiation with actinic rays or radiation.
X represents —SO ₂ — or —CO—.
n represents 0 or 1.
B represents a single bond, an oxygen atom or -N (Rx)-.
Rx represents a hydrogen atom or a monovalent organic group.
R represents a monovalent organic group having a basic functional group or a monovalent organic group having an ammonium group.

The divalent linking group in A ₁ is preferably a divalent linking group having 2 to 12 carbon atoms, and examples thereof include an alkylene group and a phenylene group. More preferably, it is an alkylene group having at least one fluorine atom, and a preferable carbon number is 2 to 6, more preferably 2 to 4. The alkylene chain may have a linking group such as an oxygen atom or a sulfur atom. The alkylene group is particularly preferably an alkylene group in which 30 to 100% of the number of hydrogen atoms are substituted with fluorine atoms, and more preferably, the carbon atom bonded to the Q site has a fluorine atom. Further, a perfluoroalkylene group is preferable, and a perfluoroethylene group, a perfluoropropylene group, and a perfluorobutylene group are more preferable.

The monovalent organic group in Rx preferably has 4 to 30 carbon atoms, and examples thereof include an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, and an alkenyl group.
The alkyl group in Rx may have a substituent, preferably a linear or branched alkyl group having 1 to 20 carbon atoms, and has an oxygen atom, a sulfur atom, or a nitrogen atom in the alkyl chain. May be.
Examples of the alkyl group having a substituent include groups in which a linear or branched alkyl group is substituted with a cycloalkyl group (for example, an adamantylmethyl group, an adamantylethyl group, a cyclohexylethyl group, a camphor residue, etc.). .
The cycloalkyl group in Rx may have a substituent, preferably a cycloalkyl group having 3 to 20 carbon atoms, and may have an oxygen atom in the ring.
The aryl group in Rx may have a substituent, and is preferably an aryl group having 6 to 14 carbon atoms.
The aralkyl group in Rx may have a substituent, and preferably an aralkyl group having 7 to 20 carbon atoms.
The alkenyl group in Rx may have a substituent, and examples thereof include a group having a double bond at an arbitrary position of the alkyl group mentioned as Rx.

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

  Examples of the substituent that each group may have include, for example, a halogen atom, a hydroxyl group, a nitro group, a cyano group, a carboxy group, a carbonyl group, a cycloalkyl group (preferably having 3 to 10 carbon atoms), and an aryl group (preferably Has 6 to 14 carbon atoms, an alkoxy group (preferably 1 to 10 carbon atoms), an acyl group (preferably 2 to 20 carbon atoms), an acyloxy group (preferably 2 to 10 carbon atoms), an alkoxycarbonyl group (preferably C2-C20), an aminoacyl group (preferably C2-C20) etc. are mentioned. As for the cyclic structure in the aryl group, cycloalkyl group and the like, examples of the substituent further include an alkyl group (preferably having a carbon number of 1 to 20). As for the aminoacyl group, examples of the substituent further include 1 or 2 alkyl groups (preferably having 1 to 20 carbon atoms).

When B is -N (Rx)-, R and Rx are preferably bonded to form a ring. By forming the ring structure, the stability is improved, and the storage stability of the composition using the ring structure is improved. The number of carbon atoms forming the ring is preferably 4 to 20, and may be monocyclic or polycyclic, and may contain an oxygen atom, a sulfur atom, or a nitrogen atom in the ring.
Examples of the monocyclic structure include a 4- to 8-membered ring containing a nitrogen atom. Examples of the polycyclic structure include a structure composed of a combination of two or three or more monocyclic structures. The monocyclic structure and polycyclic structure may have a substituent, for example, a halogen atom, a hydroxyl group, a cyano group, a carboxy group, a carbonyl group, a cycloalkyl group (preferably having 3 to 10 carbon atoms), Aryl group (preferably having 6 to 14 carbon atoms), alkoxy group (preferably having 1 to 10 carbon atoms), acyl group (preferably having 2 to 15 carbon atoms), acyloxy group (preferably having 2 to 15 carbon atoms), alkoxycarbonyl A group (preferably having 2 to 15 carbon atoms), an aminoacyl group (preferably having 2 to 20 carbon atoms) and the like are preferable. As for the cyclic structure in the aryl group, cycloalkyl group and the like, examples of the substituent further include an alkyl group (preferably having a carbon number of 1 to 15). As for the aminoacyl group, examples of the substituent include 1 or 2 alkyl groups (preferably having 1 to 15 carbon atoms).

  Among the compounds represented by the general formula (PA-I), a compound in which the Q site is a sulfonic acid can be synthesized by using a general sulfonamidation reaction. For example, a method in which one sulfonyl halide part of a bissulfonyl halide compound is selectively reacted with an amine compound to form a sulfonamide bond, and then the other sulfonyl halide part is hydrolyzed, or a cyclic sulfonic acid anhydride is used. It can be obtained by a method of ring-opening by reacting with an amine compound.

  Next, the compound represented by general formula (PA-II) is demonstrated.

_{Q 1 -X 1 -NH-X 2} -Q 2 (PA-II)

In general formula (PA-II),
Q ₁ and Q ₂ each independently represents a monovalent organic group. However, either Q ₁ or Q ₂ has a basic functional group. Q ₁ and Q ₂ may combine to form a ring, and the formed ring may have a basic functional group.
X ₁ and X ₂ each independently represent —CO— or —SO ₂ —.
Note that —NH— corresponds to an acidic functional group generated by irradiation with actinic rays or radiation.

The monovalent organic group as Q ₁ and Q _{2 in} formula (PA-II) preferably has 1 to 40 carbon atoms, and examples thereof include an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, An alkenyl group etc. can be mentioned.
The alkyl group in Q ₁ and Q ₂ may have a substituent, preferably a linear or branched alkyl group having 1 to 30 carbon atoms, and an oxygen atom, sulfur atom, nitrogen atom in the alkyl chain You may have.
The cycloalkyl group in Q ₁ and Q ₂ may have a substituent, preferably a cycloalkyl group having 3 to 20 carbon atoms, and may have an oxygen atom or a nitrogen atom in the ring. Good.
The aryl group in Q ₁ and Q ₂ may have a substituent, and is preferably an aryl group having 6 to 14 carbon atoms.
The aralkyl group in Q ₁ and Q ₂ may have a substituent, and preferably an aralkyl group having 7 to 20 carbon atoms.
The alkenyl group in Q ₁ and Q ₂ may have a substituent, and examples thereof include a group having a double bond at an arbitrary position of the alkyl group.
Examples of the substituent that each group may have include, for example, a halogen atom, a hydroxyl group, a nitro group, a cyano group, a carboxy group, a carbonyl group, a cycloalkyl group (preferably having 3 to 10 carbon atoms), and an aryl group (preferably Has 6 to 14 carbon atoms, an alkoxy group (preferably 1 to 10 carbon atoms), an acyl group (preferably 2 to 20 carbon atoms), an acyloxy group (preferably 2 to 10 carbon atoms), an alkoxycarbonyl group (preferably C2-C20), an aminoacyl group (preferably C2-C10) etc. are mentioned. As for the cyclic structure in the aryl group, cycloalkyl group and the like, examples of the substituent further include an alkyl group (preferably having 1 to 10 carbon atoms). As for the aminoacyl group, examples of the substituent further include an alkyl group (preferably having a carbon number of 1 to 10). Examples of the alkyl group having a substituent include perfluoroalkyl groups such as a perfluoromethyl group, a perfluoroethyl group, a perfluoropropyl group, and a perfluorobutyl group.

Preferable partial structures of the basic functional group possessed by at least one of Q ₁ and Q ₂ include the same partial structures as those described as the basic functional group possessed by R in the general formula (PA-I).

Q ₁ and Q ₂ are combined to form a ring, and the formed ring has a basic functional group. For example, the organic group of Q ₁ and Q ₂ is further an alkylene group, an oxy group, or an imino group. A structure bonded with a group or the like can be given.

In the general formula (PA-II), it is preferable that at least one of X ₁ and X ₂ is —SO ₂ —.

  Next, the compound represented by general formula (PA-III) is demonstrated.

_{Q 1 -X 1 -NH-X 2} -A 2 - (X 3) m -B-Q 3 (PA-III)

In general formula (PA-III),
Q ₁ and Q ₃ each independently represents a monovalent organic group. However, either one of Q ₁ and Q ₃ are a basic functional group. Q ₁ and Q ₃ may combine to form a ring, and the formed ring may have a basic functional group.
X ₁ , X ₂ and X ₃ each independently represent —CO— or —SO ₂ —.
A ₂ represents a divalent linking group.
B represents a single bond, an oxygen atom, or —N (Qx) —.
Qx represents a hydrogen atom or a monovalent organic group.
B is, -N (Qx) - when, _{Q 3} and Qx may combine to form a ring.
m represents 0 or 1.
Note that —NH— corresponds to an acidic functional group generated by irradiation with actinic rays or radiation.

Q ₁ has the same meaning as Q _{1 in} formula (PA-II).
Examples of the organic group of Q ₃ include the same organic groups as Q ₁ and Q ₂ in formula (PA-II).
In addition, Q ₁ and Q ₃ combine to form a ring, and the formed ring has a basic functional group. For example, the organic group of Q ₁ and Q ₃ is further an alkylene group or an oxy group. And a structure bonded with an imino group or the like.

The divalent linking group for A ₂ is preferably a divalent linking group having 1 to 8 carbon atoms, for example, an alkylene group having 1 to 8 carbon atoms, or a phenylene having a fluorine atom. Groups and the like. An alkylene group having a fluorine atom is more preferable, and a preferable carbon number is 2 to 6, more preferably 2 to 4. The alkylene chain may have a linking group such as an oxygen atom or a sulfur atom. The alkylene group is preferably an alkylene group in which 30 to 100% of the number of hydrogen atoms are substituted with fluorine atoms, more preferably a perfluoroalkylene group, and particularly preferably a C 2-4 perfluoroalkylene group.

  The monovalent organic group in Qx is preferably an organic group having 4 to 30 carbon atoms, and examples thereof include an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, and an alkenyl group. As the alkyl group, cycloalkyl group, aryl group, aralkyl group and alkenyl group, the same groups as those described above for Rx in the above formula (PA-I) can be mentioned.

In the general formula (PA-III), X ₁ , X ₂ , and X ₃ are preferably —SO ₂ —.

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

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

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

Compound (C) is decomposed by irradiation with actinic rays or radiation to generate, for example, a compound represented by the general formula (PA-I), (PA-II) or (PA-III).
The compound represented by the general formula (PA-I) has a sulfonic acid group or a carboxylic acid group together with a basic functional group or an ammonium group, so that the basicity is reduced, disappeared, or basic compared to the compound (C). It is a compound that has changed from acidic to acidic.
The compound represented by the general formula (PA-II) or (PA-III) has an organic sulfonylimino group or an organic carbonylimino group together with a basic functional group, so that the basicity is lower than that of the compound (C). , Disappearance, or a compound changed from basic to acidic.

  In particular, the compound (C) is preferably a compound having a basic nitrogen atom and generating an organic acid upon irradiation with an actinic ray or radiation (wherein the compound (C) is the above compound (B) and The organic acid is preferably an organic acid represented by the following general formula (C1) or (C2).

上記一般式中、
Ｘｆは、各々独立に、フッ素原子、又は、少なくとも１つのフッ素原子で置換されたアルキル基を表す。
Ｒ_１及びＲ_２は、各々独立に、水素原子、フッ素原子、又は、アルキル基を表す。
Ｌは、各々独立に、２価の連結基を表す。
Ｂａは、前記塩基性窒素原子を含む官能基を表す。
Ｒｆは、フッ素原子を含んだ基である。
ｘは、１〜２０の整数を表す。
ｙは、０〜１０の整数を表す。
ｚは、０〜１０の整数を表す。

In the above general formula,
Xf each independently represents a fluorine atom or an alkyl group substituted with at least one fluorine atom.
R ₁ and R ₂ each independently represents a hydrogen atom, a fluorine atom, or an alkyl group.
L each independently represents a divalent linking group.
Ba represents a functional group containing the basic nitrogen atom.
Rf is a group containing a fluorine atom.
x represents an integer of 1 to 20.
y represents an integer of 0 to 10.
z represents an integer of 0 to 10.

Specific examples and preferred examples of Xf, R ₁ , R ₂ , L, Rf, x, y and z in the general formulas (C1) and (C2) are the same as those in the general formula (B). Specific examples and preferred examples of Xf, R ₁ , R ₂ , L, Rf, x, y and z in (II) and (III) are the same.
Examples of the functional group containing a basic nitrogen atom as Ba include those described above as examples of the functional group having a nitrogen atom as a basic functional group.

In the present invention, the decrease in basicity upon irradiation with actinic rays or radiation means that the acceptor property to the proton of the compound (C) (acid generated by irradiation with actinic rays or radiation) upon irradiation with actinic rays or radiation. Means lower. The acceptor property decreases when an equilibrium reaction occurs in which a non-covalent complex that is a proton adduct is formed from a compound having a basic functional group and a proton, or the counter cation of a compound having an ammonium group is exchanged for a proton. This means that when an equilibrium reaction occurs, the equilibrium constant at that chemical equilibrium decreases.
Thus, the compound (C) whose basicity is reduced by irradiation with actinic rays or radiation is contained in the resist film, so that the acceptor property of the compound (C) is sufficiently expressed in the unexposed area. In addition, the unintentional reaction between the acid diffused from the exposed portion and the resin and the resin (P) can be suppressed, and the acceptor property of the compound (C) is decreased in the exposed portion, so that the acid and the resin (P) The intended reaction is more reliable.
In addition, basicity can be confirmed by performing pH measurement, and it is also possible to calculate a calculated value with commercially available software.

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

  These compounds are synthesized from a compound represented by the general formula (PA-I) or a lithium, sodium or potassium salt thereof and a hydroxide, bromide or chloride of iodonium or sulfonium. Or a salt exchange method described in JP-A No. 2003-246786. Further, the synthesis method described in JP-A-7-333851 can also be applied.

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

These compounds can be easily synthesized by using a general sulfonic acid esterification reaction or sulfonamidation reaction. For example, one sulfonyl halide part of a bissulfonyl halide compound is selectively reacted with an amine, alcohol, or the like containing a partial structure represented by the general formula (PA-II) or (PA-III), After forming a sulfonate bond, the other sulfonyl halide moiety is hydrolyzed, or the cyclic sulfonic anhydride is opened with an amine or alcohol containing a partial structure represented by the general formula (PA-II) It can be obtained by a method. The amine or alcohol containing a partial structure represented by the general formula (PA-II) or (PA-III) is an amine or alcohol under basicity (R′O ₂ C) ₂ O or (R′SO _2). ) It can be synthesized by reacting with an anhydride such as ₂ O and an acid chloride compound such as R′O ₂ CCl or R′SO ₂ Cl (R ′ is a methyl group, an n-octyl group, a trifluoromethyl group, etc.) . In particular, it can be applied to the synthesis example of JP-A-2006-330098.
The molecular weight of the compound (C) is preferably 500 to 1000.

As described above, the molar ratio [C] / [B] of the compound (C) to the compound (B) is 0.40 or more. As a result, the pattern can be resolved with an exposure amount having no practical problem, and a hole pattern with excellent roundness can be formed with good development time dependency.
The molar ratio [C] / [B] is preferably 0.40 to 1.40, more preferably 0.60 to 1.20, and 0.85 to 1.05. Further preferred.

  The content of the compound (C) with respect to the total solid content of the actinic ray-sensitive or radiation-sensitive resin composition is preferably 1.0% by mass or more, and more preferably 4.0% by mass or more. It is more preferable that it is 8.0 mass% or more, and it is especially preferable that it is 9.5 mass or more. The content of the compound (C) with respect to the total solid content of the actinic ray-sensitive or radiation-sensitive resin composition is preferably 20% by mass or less, and more preferably 15% by mass or less.

[4] Solvent (D)
Examples of the solvent that can be used in preparing the actinic ray-sensitive or radiation-sensitive resin composition in the present invention include alkylene glycol monoalkyl ether carboxylate, alkylene glycol monoalkyl ether, lactate alkyl ester, and alkoxypropion. Organic solvents such as acid alkyl, cyclic lactone (preferably having 4 to 10 carbon atoms), monoketone compound which may have a ring (preferably having 4 to 10 carbon atoms), alkylene carbonate, alkyl alkoxyacetate, alkyl pyruvate, etc. be able to.
Specific examples of these solvents can include those described in US Patent Application Publication No. 2008/0187860 [0441] to [0455].

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

[5] Hydrophobic resin (E)
The actinic ray-sensitive or radiation-sensitive resin composition in the present invention is a hydrophobic resin having at least one of a fluorine atom and a silicon atom (hereinafter referred to as “hydrophobic resin (E)”), particularly when applied to immersion exposure. Or you may contain only "resin (E)." As a result, the hydrophobic resin (E) is unevenly distributed on the surface of the film, and when the immersion medium is water, the static / dynamic contact angle of the resist film surface to water is improved, and the immersion liquid followability is improved. be able to.
The hydrophobic resin (E) is preferably designed to be unevenly distributed at the interface as described above. However, unlike the surfactant, the hydrophobic resin (E) is not necessarily required to have a hydrophilic group in the molecule. There is no need to contribute to uniform mixing.

  The hydrophobic resin (E) typically contains a fluorine atom and / or a silicon atom. The fluorine atom and / or silicon atom in the hydrophobic resin (E) may be contained in the main chain of the resin or may be contained in the side chain.

When the hydrophobic resin (E) contains a fluorine atom, the partial structure having a fluorine atom is a resin having an alkyl group having a fluorine atom, a cycloalkyl group having a fluorine atom, or an aryl group having a fluorine atom. Preferably there is.
The alkyl group having a fluorine atom (preferably having 1 to 10 carbon atoms, more preferably 1 to 4 carbon atoms) is a linear or branched alkyl group in which at least one hydrogen atom is substituted with a fluorine atom, and further a fluorine atom It may have a substituent other than.
The cycloalkyl group having a fluorine atom is a monocyclic or polycyclic cycloalkyl group in which at least one hydrogen atom is substituted with a fluorine atom, and may further have a substituent other than a fluorine atom.
Examples of the aryl group having a fluorine atom include those in which at least one hydrogen atom of an aryl group such as a phenyl group or a naphthyl group is substituted with a fluorine atom, and may further have a substituent other than a fluorine atom. .

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

In general formulas (F2) to (F4),
R _{57 to} R ₆₈ each independently represent a hydrogen atom, a fluorine atom or an alkyl group (straight or branched). However, at least one of R _{57 to} R _61, at least one of R _{62 to} R ₆₄ , and at least one of R _{65 to} R ₆₈ are each independently substituted with a fluorine atom or at least one hydrogen atom. Represents an alkyl group (preferably having 1 to 4 carbon atoms).
R _{57 to} R ₆₁ and R _{65 to} R ₆₇ are preferably all fluorine atoms. R ₆₂ , R ₆₃ and R ₆₈ are preferably an alkyl group (preferably having 1 to 4 carbon atoms) in which at least one hydrogen atom is substituted with a fluorine atom, and preferably a perfluoroalkyl group having 1 to 4 carbon atoms. Further preferred. R ₆₂ and R ₆₃ may be connected to each other to form a ring.

Specific examples of the group represented by the general formula (F2) include a p-fluorophenyl group, a pentafluorophenyl group, and a 3,5-di (trifluoromethyl) phenyl group.
Specific examples of the group represented by the general formula (F3) include trifluoromethyl group, pentafluoropropyl group, pentafluoroethyl group, heptafluorobutyl group, hexafluoroisopropyl group, heptafluoroisopropyl group, hexafluoro (2 -Methyl) isopropyl group, nonafluorobutyl group, octafluoroisobutyl group, nonafluorohexyl group, nonafluoro-t-butyl group, perfluoroisopentyl group, perfluorooctyl group, perfluoro (trimethyl) hexyl group, 2,2 , 3,3-tetrafluorocyclobutyl group, perfluorocyclohexyl group and the like. Hexafluoroisopropyl group, heptafluoroisopropyl group, hexafluoro (2-methyl) isopropyl group, octafluoroisobutyl group, nonafluoro-t-butyl group and perfluoroisopentyl group are preferable, and hexafluoroisopropyl group and heptafluoroisopropyl group are preferable. Further preferred.
Specific examples of the group represented by the general formula (F4) include, for example, —C (CF ₃ ) ₂ OH, —C (C ₂ F ₅ ) ₂ OH, —C (CF ₃ ) (CH ₃ ) OH, -CH _(CF 3) OH and the like, -C _{(CF 3)} 2 OH is preferred.

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

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

In the formula, R ₁₀ and R ₁₁ each independently represent a hydrogen atom, a fluorine atom or an alkyl group. The alkyl group is preferably a linear or branched alkyl group having 1 to 4 carbon atoms, which may have a substituent, and examples of the alkyl group having a substituent include a fluorinated alkyl group. it can.

W _{3 to} W ₆ each independently represents an organic group containing at least one fluorine atom. Specific examples include the atomic groups (F2) to (F4).

  In addition to these, the hydrophobic resin (E) may have a unit as shown below as a repeating unit having a fluorine atom.

In the formula, R _{4 to} R ₇ each independently represents a hydrogen atom, a fluorine atom, or an alkyl group. The alkyl group is preferably a linear or branched alkyl group having 1 to 4 carbon atoms, which may have a substituent, and examples of the alkyl group having a substituent include a fluorinated alkyl group. it can.
However, at least one of R _{4 to} R ₇ represents a fluorine atom. R ₄ and R ₅ or R ₆ and R ₇ may form a ring.
W ₂ represents an organic group containing at least one fluorine atom. Specific examples include the atomic groups (F2) to (F4).
L ₂ represents a single bond or a divalent linking group. Examples of the divalent linking group include a substituted or unsubstituted arylene group, a substituted or unsubstituted alkylene group, a substituted or unsubstituted cycloalkylene group, —O—, —SO ₂ —, —CO—, —N (R )-(Wherein R represents a hydrogen atom or alkyl), —NHSO ₂ — or a divalent linking group in which a plurality of these are combined.
Q represents an alicyclic structure. The alicyclic structure may have a substituent, may be monocyclic, may be polycyclic, and may be bridged in the case of polycyclic. As the monocyclic type, a cycloalkyl group having 3 to 8 carbon atoms is preferable, and examples thereof include a cyclopentyl group, a cyclohexyl group, a cyclobutyl group, and a cyclooctyl group. Examples of the polycyclic type include groups having a bicyclo, tricyclo or tetracyclo structure having 5 or more carbon atoms, and a cycloalkyl group having 6 to 20 carbon atoms is preferable, for example, an adamantyl group, norbornyl group, dicyclopentyl group. , Tricyclodecanyl group, tetocyclododecyl group and the like. A part of carbon atoms in the cycloalkyl group may be substituted with a hetero atom such as an oxygen atom. Particularly preferred examples of Q include a norbornyl group, a tricyclodecanyl group, a tetocyclododecyl group, and the like.

Hereinafter, although the specific example of the repeating unit which has a fluorine atom is shown, this invention is not limited to this.
In specific examples, X ₁ represents a hydrogen atom, —CH ₃ , —F or —CF ₃ . X ₂ represents -F or -CF _3.

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

In general formulas (CS-1) to (CS-3),
R _{12 to} R ₂₆ each independently represent a linear or branched alkyl group (preferably having 1 to 20 carbon atoms) or a cycloalkyl group (preferably having 3 to 20 carbon atoms).
L < ₃ > -L < ₅ > represents a single bond or a bivalent coupling group. Examples of the divalent linking group include an alkylene group, a phenylene group, an ether bond, a thioether bond, a carbonyl group, an ester bond, an amide bond, a urethane bond, and a urea bond, or a combination of two or more ( Preferably, the total carbon number is 12 or less).
n represents an integer of 1 to 5. n is preferably an integer of 2 to 4.

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

Furthermore, the hydrophobic resin (E) may have at least one group selected from the following groups (x) to (z).
(X) Acid group (y) Group having lactone structure or sultone structure, acid anhydride group, or acid imide group (z) Group decomposed by the action of acid

Examples of the acid group (x) include a phenolic hydroxyl group, a carboxylic acid group, a fluorinated alcohol group, a sulfonic acid group, a sulfonamide group, a sulfonylimide group, an (alkylsulfonyl) (alkylcarbonyl) methylene group, and an (alkylsulfonyl) (alkyl Carbonyl) imide group, bis (alkylcarbonyl) methylene group, bis (alkylcarbonyl) imide group, bis (alkylsulfonyl) methylene group, bis (alkylsulfonyl) imide group, tris (alkylcarbonyl) methylene group, tris (alkylsulfonyl) A methylene group etc. are mentioned.
Preferred acid groups include fluorinated alcohol groups (preferably hexafluoroisopropanol), sulfonimide groups, and bis (alkylcarbonyl) methylene groups.

The repeating unit having an acid group (x) includes a repeating unit in which an acid group is directly bonded to the main chain of the resin, such as a repeating unit of acrylic acid or methacrylic acid, or a resin having a linking group. Examples include a repeating unit in which an acid group is bonded to the main chain, and a polymerization initiator or chain transfer agent having an acid group can be introduced at the end of the polymer chain at the time of polymerization. preferable. The repeating unit having an acid group (x) may have at least one of a fluorine atom and a silicon atom.
As for content of the repeating unit which has an acid group (x), 1-50 mol% is preferable with respect to all the repeating units in hydrophobic resin (E), More preferably, it is 3-35 mol%, More preferably, it is 5- 20 mol%.

Specific examples of the repeating unit having an acid group (x) are shown below, but the present invention is not limited thereto. In the formula, Rx represents a hydrogen atom, CH ₃ , CF ₃ , or CH ₂ OH.

As the group having a lactone structure or sultone structure, the acid anhydride group, or the acid imide group (y), a group having a lactone structure or a sultone structure is particularly preferable.
The repeating unit containing these groups is a repeating unit in which this group is directly bonded to the main chain of the resin, such as a repeating unit of acrylic acid ester and methacrylic acid ester. Alternatively, this repeating unit may be a repeating unit in which this group is bonded to the main chain of the resin via a linking group. Or this repeating unit may be introduce | transduced into the terminal of resin using the polymerization initiator or chain transfer agent which has this group at the time of superposition | polymerization.

  Examples of the repeating unit having a group having a lactone structure or a sultone structure include those similar to the repeating unit having a lactone structure or a sultone structure described above in the section of the acid-decomposable resin (P).

  The content of the repeating unit having a group having a lactone structure or a sultone structure, an acid anhydride group, or an acid imide group is preferably 1 to 100 mol% based on all repeating units in the hydrophobic resin, It is more preferably 3 to 98 mol%, and further preferably 5 to 95 mol%.

  In the hydrophobic resin (E), examples of the repeating unit having a group (z) that is decomposed by the action of an acid are the same as the repeating unit having an acid-decomposable group listed for the resin (P). The repeating unit having a group (z) that is decomposed by the action of an acid may have at least one of a fluorine atom and a silicon atom. In the hydrophobic resin (E), the content of the repeating unit having a group (z) that decomposes by the action of an acid is preferably 1 to 80 mol% with respect to all the repeating units in the resin (E). Preferably it is 10-80 mol%, More preferably, it is 20-60 mol%.

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

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

In general formula (III), the alkyl group represented by R _c32 is preferably a linear or branched alkyl group having 3 to 20 carbon atoms.
The cycloalkyl group is preferably a cycloalkyl group having 3 to 20 carbon atoms.
The alkenyl group is preferably an alkenyl group having 3 to 20 carbon atoms.
The cycloalkenyl group is preferably a cycloalkenyl group having 3 to 20 carbon atoms.
The aryl group is preferably an aryl group having 6 to 20 carbon atoms, more preferably a phenyl group or a naphthyl group, and these may have a substituent.
R _c32 is preferably an unsubstituted alkyl group or an alkyl group substituted with a fluorine atom.
The divalent linking group of L _c3 is preferably an alkylene group (preferably having 1 to 5 carbon atoms), an ether bond, a phenylene group, or an ester bond (a group represented by —COO—).
The content of the repeating unit represented by the general formula (III) is preferably 1 to 100 mol%, more preferably 10 to 90 mol%, based on all repeating units in the hydrophobic resin. 30 to 70 mol% is more preferable.

  It is also preferable that the hydrophobic resin (E) further has a repeating unit represented by the following general formula (CII-AB).

In the formula (CII-AB),
R _c11 ′ and R _c12 ′ each independently represents a hydrogen atom, a cyano group, a halogen atom or an alkyl group.
Zc ′ represents an atomic group for forming an alicyclic structure containing two bonded carbon atoms (C—C).
The content of the repeating unit represented by the general formula (CII-AB) is preferably 1 to 100 mol%, and preferably 10 to 90 mol%, based on all repeating units in the hydrophobic resin. More preferably, it is more preferably 30 to 70 mol%.

Specific examples of the repeating unit represented by the general formulas (III) and (CII-AB) are shown below, but the present invention is not limited thereto. In the formula, Ra represents H, CH ₃ , CH ₂ OH, CF ₃ or CN.

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

The weight average molecular weight of the hydrophobic resin (E) in terms of standard polystyrene is preferably 1,000 to 100,000, more preferably 1,000 to 50,000, and still more preferably 2,000 to 15,000. is there.
Moreover, the hydrophobic resin (E) may be used alone or in combination.
The content of the hydrophobic resin (E) in the composition is preferably 0.01 to 10% by mass, more preferably 0.05 to 8% by mass, based on the total solid content in the composition of the present invention. More preferably, the content is 1 to 5% by mass.

  The hydrophobic resin (E), like the resin (P), naturally has few impurities such as metals, and the residual monomer and oligomer components are preferably 0.01 to 5% by mass, more preferably. Is more preferably 0.01 to 3% by mass and 0.05 to 1% by mass. As a result, an actinic ray-sensitive or radiation-sensitive resin composition that does not change over time such as foreign matter in liquid or sensitivity can be obtained. The molecular weight distribution (Mw / Mn, also referred to as dispersity) is preferably in the range of 1 to 5, more preferably 1 to 3, and still more preferably from the viewpoints of resolution, resist shape, resist pattern sidewall, roughness, and the like. It is the range of 1-2.

As the hydrophobic resin (E), various commercially available products can be used, and can be synthesized according to a conventional method (for example, radical polymerization). For example, as a general synthesis method, a monomer polymerization method in which a monomer species and an initiator are dissolved in a solvent and heating is performed, and a solution of the monomer species and the initiator is dropped into the heating solvent over 1 to 10 hours. The dropping polymerization method is added, and the dropping polymerization method is preferable.
The reaction solvent, the polymerization initiator, the reaction conditions (temperature, concentration, etc.) and the purification method after the reaction are the same as those described for the resin (P), but in the synthesis of the hydrophobic resin (E), The reaction concentration is preferably 30 to 50% by mass.

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

[6] Surfactant (F)
The actinic ray-sensitive or radiation-sensitive resin composition in the present invention may or may not further contain a surfactant. When it is contained, fluorine and / or silicon-based surfactant (fluorinated surfactant, It is more preferable to contain any one of a silicon-based surfactant, a surfactant having both a fluorine atom and a silicon atom, or two or more thereof.

When the actinic ray-sensitive or radiation-sensitive resin composition in the present invention contains a surfactant, adhesion and development defects can be obtained with good sensitivity and resolution when using an exposure light source of 250 nm or less, particularly 220 nm or less. A small resist pattern can be provided.
Examples of the fluorine-based and / or silicon-based surfactant include surfactants described in [0276] of US Patent Application Publication No. 2008/0248425. For example, F-top EF301, EF303, (Shin-Akita Kasei Co., Ltd.) )), Florard FC430, 431, 4430 (manufactured by Sumitomo 3M Co., Ltd.), Megafac F171, F173, F176, F189, F113, F110, F177, F120, R08 (manufactured by DIC Corporation), Surflon S-382 SC101, 102, 103, 104, 105, 106, KH-20 (manufactured by Asahi Glass Co., Ltd.), Troisol S-366 (manufactured by Troy Chemical Co., Ltd.), GF-300, GF-150 (Toagosei Chemical Co., Ltd.) ), Surflon S-393 (Seimi Chemical Co., Ltd.), Ftop EF121, EF 22A, EF122B, RF122C, EF125M, EF135M, EF351, EF352, EF801, EF802, EF601 (manufactured by Gemco), PF636, PF656, PF6320, PF6520 (manufactured by OMNOVA), FTX-204G, 230G, 218G 204D, 208D, 212D, 218D, 222D (manufactured by Neos Co., Ltd.) and the like. Polysiloxane polymer KP-341 (manufactured by Shin-Etsu Chemical Co., Ltd.) can also be used as a silicon-based surfactant.

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

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

  These surfactants may be used alone or in several combinations.

When the actinic ray-sensitive or radiation-sensitive resin composition contains a surfactant, the amount of the surfactant used is preferably relative to the total amount of the actinic ray-sensitive or radiation-sensitive resin composition (excluding the solvent). Is 0.0001 to 2 mass%, more preferably 0.0005 to 1 mass%.
On the other hand, the surface unevenness of the hydrophobic resin is increased by setting the addition amount of the surfactant to 10 ppm or less with respect to the total amount of the actinic ray-sensitive or radiation-sensitive resin composition (excluding the solvent). The surface of the resist film can be made more hydrophobic, and the water followability during immersion exposure can be improved.

[7] Other additives (G)
The actinic ray-sensitive or radiation-sensitive resin composition in the present invention contains a basic compound (including a nitrogen-containing organic compound having a group capable of leaving by the action of an acid) different from the compound (C). It may be included to the extent that the effects of the invention can be expressed. Examples of such basic compounds include those described in US Pat. No. 7,998,655, column 70, line 48 and subsequent lines.
Further, the actinic ray-sensitive or radiation-sensitive resin composition in the present invention may or may not contain a carboxylic acid onium salt. Examples of such carboxylic acid onium salts include those described in US Patent Application Publication No. 2008/0187860 [0605] to [0606].

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

When the actinic ray-sensitive or radiation-sensitive resin composition contains a carboxylic acid onium salt, the content thereof is generally 0.1 to 20% by mass, preferably 0, based on the total solid content of the composition. It is 5-10 mass%, More preferably, it is 1-7 mass%.
The actinic ray-sensitive or radiation-sensitive resin composition of the present invention further has solubility in dyes, plasticizers, photosensitizers, light absorbers, alkali-soluble resins, dissolution inhibitors and developers as necessary. A compound to be promoted (for example, a phenol compound having a molecular weight of 1000 or less, an alicyclic compound having a carboxyl group, or an aliphatic compound) and the like can be contained.

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

The actinic ray-sensitive or radiation-sensitive resin composition in the present invention is preferably used at a film thickness of 30 to 250 nm, more preferably at a film thickness of 30 to 200 nm, from the viewpoint of improving resolution. preferable. Such a film thickness can be obtained by setting the solid content concentration in the composition to an appropriate range to give an appropriate viscosity and improving the coating property and film forming property.
The solid content concentration of the actinic ray-sensitive or radiation-sensitive resin composition in the present invention is usually 1.0 to 10% by mass, preferably 2.0 to 5.7% by mass, and more preferably 2.0. It is -5.3 mass%. By setting the solid content concentration within the above range, it is possible to uniformly apply the resist solution on the substrate, and it is possible to form a resist pattern having excellent line width roughness. The reason for this is not clear, but perhaps the solid content concentration is 10% by mass or less, preferably 5.7% by mass or less, which suppresses aggregation of the material in the resist solution, particularly the photoacid generator. As a result, it is considered that a uniform resist film was formed.
The solid content concentration is a weight percentage of the weight of other resist components excluding the solvent with respect to the total weight of the actinic ray-sensitive or radiation-sensitive resin composition.

  In the actinic ray-sensitive or radiation-sensitive resin composition of the present invention, the above components are dissolved in a predetermined organic solvent, preferably the mixed solvent, filtered, and then applied onto a predetermined support (substrate). Use. The pore size of the filter used for filter filtration is preferably 0.1 μm or less, more preferably 0.05 μm or less, and still more preferably 0.03 μm or less made of polytetrafluoroethylene, polyethylene, or nylon. In filter filtration, for example, as in JP-A-2002-62667, circulation filtration may be performed, or filtration may be performed by connecting a plurality of types of filters in series or in parallel. The composition may be filtered multiple times. Furthermore, you may perform a deaeration process etc. with respect to a composition before and behind filter filtration.

[8] Pattern Forming Method The present invention relates to a resist film formed by the actinic ray-sensitive or radiation-sensitive resin composition of the present invention described above. The resist film can be formed by a generally known method. For example, the resist film is preferably formed by applying an actinic ray-sensitive or radiation-sensitive resin composition to a substrate.
The pattern formation method of the present invention (negative pattern formation method)
A step of exposing the resist film, and a step of developing using a developer,
At least.
The exposure in the exposure step may be immersion exposure.
It is preferable that the pattern formation method of this invention has a heating process after an exposure process.
Moreover, the pattern formation method of this invention may further have the process developed using an alkaline developing solution.
The pattern formation method of this invention can have an exposure process in multiple times.
The pattern formation method of this invention can have a heating process in multiple times.

  In the pattern forming method of the present invention, the exposure step and the development step can be performed by generally known methods.

It is also preferable to include a preheating step (PB; Prebake) after the film formation and before the exposure step.
It is also preferable to include a post-exposure heating step (PEB; Post Exposure Bake) after the exposure step and before the development step.
The heating temperature is preferably 70 to 130 ° C., more preferably 80 to 120 ° C. for both PB and PEB.
The heating time is preferably 30 to 300 seconds, more preferably 30 to 180 seconds, and still more preferably 30 to 90 seconds.
Heating can be performed by means provided in a normal exposure / developing machine, and may be performed using a hot plate or the like.
The reaction of the exposed part is promoted by baking, and the sensitivity and pattern profile are improved.

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

Moreover, the immersion exposure method can be applied in the step of performing exposure according to the present invention.
The immersion exposure method is a technology for filling and exposing a projection lens and a sample with a liquid having a high refractive index (hereinafter also referred to as “immersion liquid”) as a technique for increasing the resolving power.
As described above, this “immersion effect” means that λ ₀ is the wavelength of the exposure light in the air, n is the refractive index of the immersion liquid with respect to the air, θ is the convergence angle of the light beam, and NA ₀ = sin θ. When immersed, the resolving power and the depth of focus can be expressed by the following equations. Here, k ₁ and k ₂ are coefficients related to the process.
(Resolving power) = k ₁ · (λ ₀ / n) / NA ₀
(Depth of focus) = ± k ₂ · (λ ₀ / n) / NA ₀ ²
That is, the immersion effect is equivalent to using an exposure wavelength having a wavelength of 1 / n. In other words, in the case of a projection optical system with the same NA, the depth of focus can be increased n times by immersion. This is effective for all pattern shapes, and can be combined with a super-resolution technique such as a phase shift method and a modified illumination method which are currently being studied.

  When performing immersion exposure, (1) after forming the film on the substrate, before the exposure step and / or (2) after exposing the film via the immersion liquid, Prior to the heating step, a step of washing the surface of the membrane with an aqueous chemical may be performed.

  The immersion liquid is preferably a liquid that is transparent to the exposure wavelength and has a refractive index temperature coefficient as small as possible so as to minimize distortion of the optical image projected onto the film. In the case of an ArF excimer laser (wavelength: 193 nm), it is preferable to use water from the viewpoints of availability and ease of handling in addition to the above-described viewpoints.

When water is used, an additive (liquid) that decreases the surface tension of water and increases the surface activity may be added in a small proportion. This additive is preferably one that does not dissolve the resist layer on the wafer and can ignore the influence on the optical coating on the lower surface of the lens element.
As such an additive, for example, an aliphatic alcohol having a refractive index substantially equal to that of water is preferable, and specific examples include methyl alcohol, ethyl alcohol, isopropyl alcohol and the like. By adding an alcohol having a refractive index substantially equal to that of water, even if the alcohol component in water evaporates and the content concentration changes, an advantage that the change in the refractive index of the entire liquid can be made extremely small can be obtained.

  On the other hand, when an opaque substance or impurities whose refractive index is significantly different from that of water are mixed with respect to 193 nm light, the optical image projected on the resist is distorted. Therefore, distilled water is preferable as the water to be used. Further, pure water filtered through an ion exchange filter or the like may be used.

The electrical resistance of water used as the immersion liquid is preferably 18.3 MQcm or more, the TOC (organic substance concentration) is preferably 20 ppb or less, and deaeration treatment is preferably performed.
Moreover, it is possible to improve lithography performance by increasing the refractive index of the immersion liquid. From such a viewpoint, an additive that increases the refractive index may be added to water, or heavy water (D ₂ O) may be used instead of water.

When the film formed using the composition of the present invention is exposed through an immersion medium, the above-described hydrophobic resin (E) can be further added as necessary. By adding the hydrophobic resin (E), the receding contact angle of the surface is improved. The receding contact angle of the film is preferably 60 ° to 90 °, more preferably 70 ° or more.
In the immersion exposure process, the immersion head needs to move on the wafer following the movement of the exposure head to scan the wafer at high speed to form the exposure pattern. In this case, the contact angle of the immersion liquid with respect to the resist film is important, and the resist is required to follow the high-speed scanning of the exposure head without remaining droplets.

In order to prevent the film from directly contacting the immersion liquid between the film formed using the composition of the present invention and the immersion liquid, an immersion liquid hardly soluble film (hereinafter also referred to as “topcoat”). May be provided. Functions necessary for the top coat include suitability for application to the resist upper layer, transparency to radiation, particularly radiation having a wavelength of 193 nm, and poor immersion liquid solubility. It is preferable that the top coat is not mixed with the resist and can be uniformly applied to the upper layer of the resist.
From the viewpoint of transparency at 193 nm, the topcoat is preferably a polymer that does not contain aromatics.
Specific examples include hydrocarbon polymers, acrylic ester polymers, polymethacrylic acid, polyacrylic acid, polyvinyl ether, silicon-containing polymers, and fluorine-containing polymers. The aforementioned hydrophobic resin (E) is also suitable as a top coat. When impurities are eluted from the top coat into the immersion liquid, the optical lens is contaminated. Therefore, it is preferable that the residual monomer component of the polymer contained in the top coat is small.

When peeling the top coat, a developer may be used, or a separate release agent may be used. As the release agent, a solvent having low penetration into the film is preferable. In terms of being able to perform the peeling process simultaneously with the film development process, it is preferable that the peeling process can be performed with an alkaline developer. The top coat is preferably acidic from the viewpoint of peeling with an alkali developer, but may be neutral or alkaline from the viewpoint of non-intermixability with the film.
There is preferably no or small difference in refractive index between the top coat and the immersion liquid. In this case, the resolution can be improved. When the exposure light source is an ArF excimer laser (wavelength: 193 nm), it is preferable to use water as the immersion liquid. Therefore, the top coat for ArF immersion exposure is close to the refractive index of water (1.44). preferable. Moreover, it is preferable that a topcoat is a thin film from a viewpoint of transparency and a refractive index.

  The topcoat is preferably not mixed with the membrane and further not mixed with the immersion liquid. From this point of view, when the immersion liquid is water, the solvent used for the top coat is preferably a water-insoluble medium that is hardly soluble in the solvent used for the composition of the present invention. Further, when the immersion liquid is an organic solvent, the topcoat may be water-soluble or water-insoluble.

In the present invention, the substrate on which the film is formed is not particularly limited, and silicon, SiN, inorganic substrates such as SiO ₂ and SiN, coated inorganic substrates such as SOG, semiconductor manufacturing processes such as IC, liquid crystal, and thermal head For example, a substrate generally used in a circuit board manufacturing process or other photofabrication lithography process can be used. Further, if necessary, an organic antireflection film may be formed between the film and the substrate.

When the pattern forming method of the present invention further includes a step of developing using an alkali developer, examples of the alkali developer include sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, and ammonia. Inorganic alkalis such as water, 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, Alkaline aqueous solutions such as alcohol amines such as ethanolamine, quaternary ammonium salts such as tetramethylammonium hydroxide and tetraethylammonium hydroxide, and cyclic amines such as pyrrole and pihelidine can be used.
Furthermore, an appropriate amount of alcohol or surfactant may be added to the alkaline aqueous solution.
The alkali concentration of the alkali developer is usually from 0.1 to 20% by mass.
The pH of the alkali developer is usually from 10.0 to 15.0.
In particular, an aqueous solution of 2.38% by mass of tetramethylammonium hydroxide is desirable.

As a rinsing solution in the rinsing treatment performed after alkali development, pure water can be used, and an appropriate amount of a surfactant can be added.
In addition, after the developing process or the rinsing process, a process of removing the developing solution or the rinsing liquid adhering to the pattern with a supercritical fluid can be performed.

As the developer in the step of developing using a developer containing an organic solvent by the pattern forming method of the present invention (hereinafter also referred to as an organic developer), a ketone solvent, an ester solvent, an alcohol solvent, Polar solvents such as amide solvents and ether solvents, and hydrocarbon solvents can be used.
Examples of the ketone solvent include 1-octanone, 2-octanone, 1-nonanone, 2-nonanone, acetone, 2-heptanone (methyl amyl ketone), 4-heptanone, 1-hexanone, 2-hexanone, diisobutyl ketone, Examples include cyclohexanone, methylcyclohexanone, phenylacetone, methylethylketone, methylisobutylketone, acetylacetone, acetonylacetone, ionone, diacetylalcohol, acetylcarbinol, acetophenone, methylnaphthylketone, isophorone, and propylene carbonate.
Examples of ester solvents include methyl acetate, butyl acetate, ethyl acetate, isopropyl acetate, pentyl acetate, isopentyl acetate, amyl acetate, propylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, diethylene glycol monoethyl. Examples include 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, and propyl lactate. be able to.
Examples of the alcohol solvent include methyl alcohol, ethyl alcohol, n-propyl alcohol, isopropyl alcohol, n-butyl alcohol, sec-butyl alcohol, tert-butyl alcohol, isobutyl alcohol, n-hexyl alcohol, n-heptyl alcohol, alcohols such as n-octyl alcohol and n-decanol, glycol solvents such as ethylene glycol, diethylene glycol and triethylene glycol, ethylene glycol monomethyl ether, propylene glycol monomethyl ether, ethylene glycol monoethyl ether, propylene glycol monoethyl ether, Diethylene glycol monomethyl ether, triethylene glycol monoethyl ether, methoxymethyl butano It can be mentioned glycol ether solvents such as Le.
Examples of the ether solvent include dioxane, tetrahydrofuran and the like in addition to the glycol ether solvent.
Examples of the amide solvent include N-methyl-2-pyrrolidone, N, N-dimethylacetamide, N, N-dimethylformamide, hexamethylphosphoric triamide, 1,3-dimethyl-2-imidazolidinone and the like. Can be used.
Examples of the hydrocarbon solvent include aromatic hydrocarbon solvents such as toluene and xylene, and aliphatic hydrocarbon solvents such as pentane, hexane, octane and decane.
A plurality of the above solvents may be mixed, or may be used by mixing with a solvent other than those described above or water. However, in order to fully exhibit the effects of the present invention, the water content of the developer as a whole is preferably less than 10% by mass and more preferably substantially free of moisture.
That is, the amount of the organic solvent used in the organic developer is preferably 90% by mass or more and 100% by mass or less, and more preferably 95% by mass or more and 100% by mass or less, with respect to the total amount of the developer.
In particular, the organic developer is preferably a developer containing at least one organic solvent selected from the group consisting of ketone solvents, ester solvents, alcohol solvents, amide solvents and ether solvents. .

The vapor pressure of the organic developer is preferably 5 kPa or less, more preferably 3 kPa or less, and particularly preferably 2 kPa or less at 20 ° C. By setting the vapor pressure of the organic developer to 5 kPa or less, evaporation of the developer on the substrate or in the developing cup is suppressed, and the temperature uniformity in the wafer surface is improved. As a result, the dimensions in the wafer surface are uniform. Sexuality improves.
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, isopentyl acetate, amyl acetate, propylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, diethylene glycol monoethyl Ether acetate, ethyl-3-ethoxypropionate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, formate , Ester solvents such as propyl formate, ethyl lactate, butyl lactate, propyl lactate, n-propyl alcohol, isopropyl alcohol, n-butyl alcohol, sec-butyl alcohol, tert-butyl alcohol, isobutyl alcohol, n-hexyl alcohol, alcohol solvents such as 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, ethylene glycol monoethyl ether, Propylene glycol monoethyl ether, diethylene glycol monomethyl ether, triethylene glycol monoethyl ether, methoxyme Glycol ether solvents such as rubutanol, ether solvents such as tetrahydrofuran, amide solvents such as N-methyl-2-pyrrolidone, N, N-dimethylacetamide, N, N-dimethylformamide, aromatic carbonization such as toluene and xylene Examples thereof include aliphatic hydrocarbon solvents such as hydrogen solvents, octane, and decane.
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, 4-heptanone, 2-hexanone, diisobutyl ketone, cyclohexanone, and methylcyclohexanone. , Ketone solvents such as 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-ethoxypropionate, 3- Ester solvents such as methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, ethyl lactate, butyl lactate and propyl lactate, n-butyl alcohol, alcohol solvents such as ec-butyl alcohol, tert-butyl alcohol, isobutyl alcohol, n-hexyl alcohol, n-heptyl alcohol, n-octyl alcohol and n-decanol; glycol solvents such as ethylene glycol, diethylene glycol and triethylene glycol And glycol ether solvents such as ethylene glycol monomethyl ether, propylene glycol monomethyl ether, ethylene glycol monoethyl ether, propylene glycol monoethyl ether, diethylene glycol monomethyl ether, triethylene glycol monoethyl ether, methoxymethylbutanol, N-methyl-2 Amide solvents of pyrrolidone, N, N-dimethylacetamide, N, N-dimethylformamide, Aromatic hydrocarbon solvents such as cyclohexylene, octane, aliphatic hydrocarbon solvents decane.

An appropriate amount of a surfactant can be added to the organic developer as required.
The surfactant is not particularly limited, and for example, ionic or nonionic fluorine-based and / or silicon-based surfactants can be used. Examples of these fluorine and / or silicon surfactants include, for example, JP-A No. 62-36663, JP-A No. 61-226746, JP-A No. 61-226745, JP-A No. 62-170950, JP 63-34540 A, JP 7-230165 A, JP 8-62834 A, JP 9-54432 A, JP 9-5988 A, US Pat. No. 5,405,720, etc. The surfactants described in US Pat. Nos. 5,360,692, 5,298,881, 5,296,330, 5,346,098, 5,576,143, 5,294,511, and 5,824,451 can be mentioned. Preferably, it is a nonionic surfactant. Although it does not specifically limit as a nonionic surfactant, It is still more preferable to use a fluorochemical surfactant or a silicon-type surfactant.
The amount of the surfactant used is usually 0.001 to 5% by mass, preferably 0.005 to 2% by mass, and more preferably 0.01 to 0.5% by mass with respect to the total amount of the developer.

As a developing method, for example, a method in which a substrate is immersed in a tank filled with a developer for a certain period of time (dip method), a method in which the developer is raised on the surface of the substrate by surface tension and is left stationary for a certain time (paddle) Method), a method of spraying the developer on the substrate surface (spray method), a method of continuously discharging the developer while scanning the developer discharge nozzle on the substrate rotating at a constant speed (dynamic dispensing method) Etc. can be applied.
When the various development methods described above include a step of discharging the developer from the developing nozzle of the developing device toward the resist film, the discharge pressure of the discharged developer (the flow rate per unit area of the discharged developer) is Preferably it is 2 mL / sec / mm ² or less, More preferably, it is 1.5 mL / sec / mm ² or less, More preferably, it is 1 mL / sec / mm ² or less. There is no particular lower limit on the flow rate, but 0.2 mL / sec / mm ² or more is preferable in consideration of throughput.
By setting the discharge pressure of the discharged developer to be in the above range, pattern defects derived from the resist residue after development can be remarkably reduced.
The details of this mechanism are not clear, but perhaps by setting the discharge pressure within the above range, the pressure applied by the developer to the resist film will decrease, and the resist film / resist pattern may be inadvertently cut or collapsed. This is considered to be suppressed.
The developer discharge pressure (mL / sec / mm ² ) is a value at the developing nozzle outlet in the developing device.

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

  Moreover, you may implement the process of stopping image development, after substituting with another solvent after the process developed using the developing solution containing an organic solvent.

  It is preferable to include the process of wash | cleaning using a rinse liquid after the process developed using the developing solution containing an organic solvent.

The rinsing solution used in the rinsing step after the step of developing with a developer containing an organic solvent is not particularly limited as long as the resist pattern is not dissolved, 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 the hydrocarbon solvent, the ketone solvent, the ester solvent, the alcohol solvent, the amide solvent, and the ether solvent are the same as those described in the developer containing an organic solvent.
More preferably, it contains at least one organic solvent selected from the group consisting of ketone solvents, ester solvents, alcohol solvents, and amide solvents after the step of developing using a developer containing an organic solvent. A step of washing with a rinsing liquid is performed, more preferably, a step of washing with a rinsing liquid containing an alcohol solvent or an ester solvent is carried out, and a rinsing liquid containing a monohydric alcohol is particularly preferred. And, most preferably, the step of cleaning with a rinse solution containing a monohydric alcohol having 5 or more carbon atoms is performed.
Here, examples of the monohydric alcohol used in the rinsing step include linear, branched, and cyclic monohydric alcohols, and specifically, 1-butanol, 2-butanol, and 3-methyl-1-butanol. Tert-butyl alcohol, 1-pentanol, 2-pentanol, 1-hexanol, 4-methyl-2-pentanol, 1-heptanol, 1-octanol, 2-hexanol, cyclopentanol, 2-heptanol, 2 -Octanol, 3-hexanol, 3-heptanol, 3-octanol, 4-octanol and the like can be used, and particularly preferable monohydric alcohols having 5 or more carbon atoms include 1-hexanol, 2-hexanol, 4-methyl- Use 2-pentanol, 1-pentanol, 3-methyl-1-butanol, etc. It can be.

  A plurality of these components may be mixed, or may be used by mixing with an organic solvent other than the above.

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

  The vapor pressure of the rinsing solution used after the step of developing with 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 at 20 ° C. 12 kPa or more and 3 kPa or less are the most preferable. By setting the vapor pressure of the rinse liquid to 0.05 kPa or more and 5 kPa or less, the temperature uniformity in the wafer surface is improved, and further, the swelling due to the penetration of the rinse solution is suppressed, and the dimensional uniformity in the wafer surface. Improves.

  An appropriate amount of a surfactant can be added to the rinse solution.

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

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

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

<Synthesis Example (Synthesis of Resin P-6)>
83.1 parts by mass of cyclohexanone was heated to 80 ° C. under a nitrogen stream. While stirring this liquid, 11.1 parts by mass of the monomer represented by the following structural formula A, 24.9 parts by mass of the monomer represented by the following structural formula B, 5.9 masses of the monomer represented by the following structural formula C A mixed solution of 1.15 parts by mass, 154.4 parts by mass of cyclohexanone, dimethyl 2,2′-azobisisobutyrate [V-601, manufactured by Wako Pure Chemical Industries, Ltd.] was added dropwise over 4 hours. After completion of dropping, the mixture was further stirred at 80 ° C. for 2 hours. The reaction solution is allowed to cool, then re-precipitated with a large amount of hexane / ethyl acetate (mass ratio 8: 2), filtered, and the obtained solid is vacuum-dried to obtain 35. Resin (P-6) of the present invention. 8 parts by mass were obtained.

The weight average molecular weight (Mw: converted to polystyrene) obtained from GPC (carrier: tetrahydrofuran (THF)) of the obtained resin was Mw = 14000, and the dispersity was Mw / Mn = 1.65. ^The composition ratio measured by ¹³ C-NMR was 20/70/10.

<Acid-decomposable resin>
Thereafter, resins (P-1) to (P-5) and (P-7) to (P-16) were synthesized in the same manner. The synthesized polymer structure, weight average molecular weight (Mw) and dispersity (Mw / Mn) are described below. Moreover, the composition ratio of each repeating unit of the following polymer structure was shown by molar ratio.

<Acid generator>
The following compounds were used as the acid generator.

<Basic compound (C) or ammonium salt compound whose basicity is reduced by irradiation with actinic rays or radiation>
The following compounds were used as basic compounds or ammonium salt compounds whose basicity is reduced by irradiation with actinic rays or radiation.

<Hydrophobic resin>
As the hydrophobic resin, it was appropriately selected from the resins (HR-1) to (HR-90) listed above.
The hydrophobic resin (HR-79) was synthesized based on the descriptions in US Patent Application Publication No. 2010/0152400, International Publication No. 2010/069705, International Publication No. 2010/067898, and the like.

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

<Solvent>
The following were prepared as solvents.
(Group a)
SL-1: Propylene glycol monomethyl ether acetate (PGMEA)
SL-2: Propylene glycol monomethyl ether propionate SL-3: 2-heptanone (group b)
SL-4: Ethyl lactate SL-5: Propylene glycol monomethyl ether (PGME)
SL-6: Cyclohexanone (group c)
SL-7: γ-butyrolactone SL-8: Propylene carbonate

<Developer>
The following were prepared as developers.
SG-1: Butyl acetate SG-2: Methyl amyl ketone SG-3: Ethyl-3-ethoxypropionate SG-4: Pentyl acetate SG-5: Isopentyl acetate SG-6: Propylene glycol monomethyl ether acetate (PGMEA)
SG-7: Cyclohexanone <Rinse solution>
The following rinse solutions were used.
SR-1: 4-methyl-2-pentanol SR-2: 1-hexanol SR-3: butyl acetate SR-4: methyl amyl ketone SR-5: ethyl-3-ethoxypropionate

<ArF immersion exposure>
(Resist preparation and hole pattern formation)
The components shown in the table below are dissolved in the solvent shown in the table below in a solid content of 3.8% by mass, and each is filtered through a polyethylene filter having a pore size of 0.03 μm, and the actinic ray-sensitive or radiation-sensitive resin composition. (Resist composition) was prepared. An organic antireflection film ARC145A (manufactured by Brewer) is applied on a silicon wafer and baked at 205 ° C. for 60 seconds to form an antireflection film having a film thickness of 46 nm. Further, an organic antireflection film ARC113A (manufactured by Brewer) is formed thereon. ) And baked at 205 ° C. for 60 seconds to form an antireflection film having a thickness of 49 nm. An actinic ray-sensitive or radiation-sensitive resin composition was applied thereon and baked (PB: Prebake) at 100 ° C. for 60 seconds to form a resist film having a thickness of 100 nm.
The obtained wafer was used with an ArF excimer laser immersion scanner (manufactured by ASML; XT1700i, NA1.20, C-Quad, outer sigma 0.900, inner sigma 0.812, XY deflection), and the hole portion was 60 nm. Further, pattern exposure was performed through a square array halftone mask having a pitch between holes of 90 nm. Ultra pure water was used as the immersion liquid. Then, it heated at 105 degreeC for 60 second (PEB: Post Exposure Bake).
Next, the development was carried out by paddle with an organic solvent-based developer described in the following table for 30 seconds, and when the rinse liquid is described in the example table, the rinse liquid was added while rotating the wafer at 1000 rpm. The wafer was supplied onto the wafer for 2 seconds, and then the wafer was rotated at 2000 rpm for 20 seconds to shake off the chemical on the wafer. In the case where there is no description of the rinsing liquid in the example table, the wafer was rotated for 20 seconds at a rotational speed of 2000 rpm after the padding of the organic solvent developer, and the chemical on the wafer was shaken off. In this way, a hole pattern with a hole diameter of 45 nm was obtained.

<Roundness>
The hole patterns in the resist films obtained with the actinic ray-sensitive or radiation-sensitive resin compositions of Examples and Comparative Examples were observed and photographed with a scanning electron microscope (S9380II manufactured by Hitachi, Ltd.), and the images were recorded as Offline CD. The roundness of the hole shape of the hole pattern (Inner Diameter, 3σ) was calculated using Measurement Software (manufactured by Hitachi). A smaller value means higher roundness.

<Development time dependency (Devs, unit: nm / second)>
The hole pattern in the resist film before the rinsing step obtained using the actinic ray-sensitive or radiation-sensitive resin compositions of Examples and Comparative Examples was observed with a scanning electron microscope (S9380II manufactured by Hitachi, Ltd.), and the pore size The ratio of (hole diameter) to half pitch (1/2 of the distance between holes) is 1: 1, and the irradiation energy when resolving a hole pattern with a hole diameter of 45 nm is determined as the optimum exposure amount (Eopt / 30). Except that the development time of 30 seconds was changed to 20 seconds and 40 seconds, respectively, pattern formation was performed in the same manner, and the hole diameter at the optimum exposure amount (Eopt / 30) of each hole pattern obtained was changed to the scanning type. Observation was performed using an electron microscope.
Using the development time as the horizontal axis and the hole diameter of the obtained hole pattern as the vertical axis, plot the hole diameters at development times of 20 seconds, 30 seconds, and 40 seconds, and create an approximate line from these three points by the least square method. The dependence of the pore diameter on development time (Devs) was evaluated by calculating the slope of the approximate line (that is, the pore diameter fluctuation value in the development time unit). The smaller the slope value, the smaller the fluctuation of the hole diameter, the better the development time dependence of the hole diameter, and the larger the development process latitude.

These evaluation results are shown in Table 3 below.
In addition, Example 4 and Example 18 shall be read as Reference Example 4 and Reference Example 18, respectively.

As is apparent from the results shown in Table 3, Comparative Example 1 and Comparative Example 2 in which the acid-decomposable resin does not have the repeating unit represented by the general formula (I) are development time dependency and roundness. Both were inferior.
On the other hand, while using the resin (P) having the repeating unit (a) represented by the general formula (I), the molar ratio [C] / [B] of the compound (C) to the compound (B) is 0. In Examples 1 to 23 which are 40 or more, excellent results were obtained in both development time dependency and roundness.
Further, although the acid-decomposable resin has a repeating unit represented by the above general formula (I), the molar ratio [C] / [B] of the compound (C) to the compound (B) is less than 0.40. 1 and Reference Example 2 did not reach the level of evaluation results of Examples 1 to 23 with respect to development time dependency and roundness.

Claims (20)

(P) a resin having the repeating unit (a) represented by the following general formula (I), the ratio of the repeating unit having an aromatic group being 5 mol% or less, and having no fluorine atom and silicon atom;
(B) a compound that generates an organic acid represented by the following general formula (II) or (III) upon irradiation with actinic rays or radiation, a compound that generates a monovalent perfluoroalkanesulfonic acid, and a fluorine-substituted imide acid At least any one of the compounds that generate
(C) an actinic ray-sensitive or radiation-sensitive resin composition containing a basic compound or an ammonium salt compound, the basicity of which decreases when irradiated with actinic rays or radiation,
The compound (B) and the compound (C) are different compounds,
Ri der wherein the molar ratio of compound (B) [C] / [ B] is 0.40 or more of the compound (C),
The actinic ray-sensitive or radiation-sensitive resin composition, wherein the compound (C) has a basic nitrogen atom and generates an organic acid upon irradiation with actinic rays or radiation .

In the general formula (I), R ₀ represents a hydrogen atom or a methyl group.
R ₁ , R ₂ and R ₃ each independently represents a linear or branched alkyl group.

In the above general formula,
Xf each independently represents a fluorine atom or an alkyl group substituted with at least one fluorine atom.
R ₁ and R ₂ each independently represents a hydrogen atom, a fluorine atom, or an alkyl group.
L each independently represents a divalent linking group.
Cy represents a cyclic organic group.
Rf is a group containing a fluorine atom.
x represents an integer of 1 to 20.
y represents an integer of 0 to 10.
z represents an integer of 0 to 10.   (P) a resin having the repeating unit (a) represented by the following general formula (I), the ratio of the repeating unit having an aromatic group being 5 mol% or less, and having no fluorine atom and silicon atom;
  (B) a compound that generates an organic acid represented by the following general formula (II) or (III) upon irradiation with actinic rays or radiation, a compound that generates a monovalent perfluoroalkanesulfonic acid, and a fluorine-substituted imide acid At least any one of the compounds that generate
  (C) an actinic ray-sensitive or radiation-sensitive resin composition containing a basic compound or an ammonium salt compound, the basicity of which decreases when irradiated with actinic rays or radiation,
  The compound (B) and the compound (C) are different compounds,
  The molar ratio [C] / [B] of the compound (C) to the compound (B) is 0.40 or more,
  The actinic ray-sensitive or radiation-sensitive resin composition, wherein the resin (P) further has a repeating unit having a hydroxyadamantyl group or a dihydroxyadamantyl group.

  In the general formula (I), R ₀ Represents a hydrogen atom or a methyl group.
  R ₁ , R ₂ And R ₃ Each independently represents a linear or branched alkyl group.

  In the above general formula,
  Xf each independently represents a fluorine atom or an alkyl group substituted with at least one fluorine atom.
  R ₁ And R ₂ Each independently represents a hydrogen atom, a fluorine atom, or an alkyl group.
  L each independently represents a divalent linking group.
  Cy represents a cyclic organic group.
  Rf is a group containing a fluorine atom.
  x represents an integer of 1 to 20.
  y represents an integer of 0 to 10.
  z represents an integer of 0 to 10.   (P) a resin having the repeating unit (a) represented by the following general formula (I), the ratio of the repeating unit having an aromatic group being 5 mol% or less, and having no fluorine atom and silicon atom;
  (B) a compound that generates an organic acid represented by the following general formula (II) or (III) upon irradiation with actinic rays or radiation, a compound that generates a monovalent perfluoroalkanesulfonic acid, and a fluorine-substituted imide acid At least any one of the compounds that generate
  (C) an actinic ray-sensitive or radiation-sensitive resin composition containing a basic compound or an ammonium salt compound, the basicity of which decreases when irradiated with actinic rays or radiation,
  The compound (B) and the compound (C) are different compounds,
  The molar ratio [C] / [B] of the compound (C) to the compound (B) is 0.40 or more,
  The actinic ray-sensitive or radiation-sensitive resin composition, wherein the resin (P) is a resin containing a repeating unit having a sultone structure.

  In the general formula (I), R ₀ Represents a hydrogen atom or a methyl group.
  R ₁ , R ₂ And R ₃ Each independently represents a linear or branched alkyl group.

  In the above general formula,
  Xf each independently represents a fluorine atom or an alkyl group substituted with at least one fluorine atom.
  R ₁ And R ₂ Each independently represents a hydrogen atom, a fluorine atom, or an alkyl group.
  L each independently represents a divalent linking group.
  Cy represents a cyclic organic group.
  Rf is a group containing a fluorine atom.
  x represents an integer of 1 to 20.
  y represents an integer of 0 to 10.
  z represents an integer of 0 to 10. The activity sensitivity of any one of Claims 1-3 whose content of the said compound (C) with respect to the total solid of the said actinic-ray-sensitive or radiation-sensitive resin composition is 1.0 mass% or more. A light-sensitive or radiation-sensitive resin composition. The actinic ray-sensitive or radiation-sensitive resin according to claim 4 , wherein the content of the compound (C) with respect to the total solid content of the actinic ray-sensitive or radiation-sensitive resin composition is 4.0% by mass or more. Composition. The actinic ray-sensitive or radiation-sensitive resin composition according to any one of claims 1 to 5 , wherein the molar ratio [C] / [B] is 0.40 to 1.40. The actinic ray-sensitive or radiation-sensitive resin composition according to claim 2 or 3 , wherein the compound (C) has a basic nitrogen atom and generates an organic acid upon irradiation with an actinic ray or radiation. . The actinic ray-sensitive light according to claim 1 or 7 , wherein the organic acid generated from the compound (C) upon irradiation with actinic ray or radiation is an organic acid represented by the following general formula (C1) or (C2). Or radiation sensitive resin composition.

In the above general formula,
Xf each independently represents a fluorine atom or an alkyl group substituted with at least one fluorine atom.
R ₁ and R ₂ each independently represents a hydrogen atom, a fluorine atom, or an alkyl group.
L each independently represents a divalent linking group.
Ba represents a functional group containing the basic nitrogen atom.
Rf is a group containing a fluorine atom.
x represents an integer of 1 to 20.
y represents an integer of 0 to 10.
z represents an integer of 0 to 10. The actinic ray-sensitive or radiation-sensitive resin composition according to any one of claims 1 to 8 , wherein the compound (C) is an onium salt compound. The actinic ray-sensitive or radiation-sensitive resin according to any one of claims 1 to 9 , wherein the content of the repeating unit (a) with respect to all the repeating units of the resin (P) is 45 mol% or more. Composition. The actinic ray sensitive property of any one of Claims 1-10 whose linear or branched alkyl group about said R < ₁ >, R < ₂ > and R < ₃ > is a C1-C4 alkyl group. Radiation sensitive resin composition. The actinic ray-sensitive resin composition according to any one of claims 1 to 11 , wherein the actinic ray-sensitive or radiation-sensitive resin composition further contains a hydrophobic resin having at least one of a fluorine atom and a silicon atom. Or a radiation sensitive resin composition. The actinic ray-sensitive or radiation-sensitive resin composition according to claim 1 or 3 , wherein the resin (P) is a resin further having a repeating unit having a hydroxyadamantyl group or a dihydroxyadamantyl group. Resist film formed from the actinic ray-sensitive or radiation-sensitive resin composition according to any one of claims 1 to 13. A pattern forming method, comprising: exposing the resist film according to claim 14 ; and developing the resist film using a developer containing an organic solvent to form a negative pattern. The pattern formation method of Claim 15 whose content of the organic solvent in the developing solution containing the said organic solvent is 90 to 100 mass% with respect to the whole quantity of the said developing solution. The developer is a developer containing a ketone-based solvent, an ester solvent, an alcohol solvent, at least one organic solvent selected from the group consisting of an amide solvent and an ether-based solvent, according to claim 15 or 16 The pattern forming method according to 1. Further comprising the step of cleaning with a rinse liquid containing an organic solvent, a pattern forming method according to any one of claims 15-17. The exposure in the step of exposing the resist film is immersion exposure, the pattern forming method according to any one of claims 15-18. To any one of claims 15-19 including a pattern forming method according method of manufacturing an electronic device.