JP2011148967A - Resin, resist composition and pattern forming method - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To form a pattern having more satisfactory shape and focus margin. <P>SOLUTION: A resin is provided comprising a structural unit derived from a compound represented by formula (I), wherein R<SP>1</SP>represents a hydrogen atom, a halogen atom or a 1-6C alkyl group that optionally has a halogen atom; X<SP>1</SP>represents a 2-36C heterocycle, one or more hydrogen atoms contained in the heterocycle may be replaced by a halogen atom, a hydroxy group, a 1-24C hydrocarbon group, a 1-12C alkoxy group, a 2-4C acyl group or a 2-4C acyloxy group, and one or more -CH<SB>2</SB>- contained in the heterocycle may be replaced by -CO- or -O-. <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

  The present invention relates to a resin, a resist composition, and a pattern forming method.

A resist composition used for fine processing of a semiconductor using a lithography technique contains a resin.
For example, Patent Document 1 describes a resin having the following structural unit and a resist composition containing the resin.

JP 2006-276851 A

  In a resist composition containing a conventional resin, the pattern shape and focus margin obtained from the resist composition may not always be satisfactory.

［式（Ｉ）中、
Ｒ^１は、水素原子、ハロゲン原子又はハロゲン原子を有してもよい炭素数１〜６のアルキル基を表す。
Ｘ^１は、炭素数２〜３６の複素環を表し、該複素環に含まれる水素原子は、ハロゲン原子、水酸基、炭素数１〜２４の炭化水素基、炭素数１〜１２のアルコキシ基、炭素数２〜４のアシル基又は炭素数２〜４のアシルオキシ基で置換されていてもよく、該複素環に含まれる−ＣＨ_２−は、−ＣＯ−又は−Ｏ−で置き換わっていてもよい。］ The present invention includes the following inventions [1] to [8].
[1] A resin having a structural unit derived from the compound represented by the formula (I).

[In the formula (I),
R ¹ represents a hydrogen atom, a halogen atom or an alkyl group having 1 to 6 carbon atoms which may have a halogen atom.
X ¹ represents a heterocyclic ring having 2 to 36 carbon atoms, and the hydrogen atom contained in the heterocyclic ring is a halogen atom, a hydroxyl group, a hydrocarbon group having 1 to 24 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, carbon The acyl group having 2 to 4 carbon atoms or the acyloxy group having 2 to 4 carbon atoms may be substituted, and —CH ₂ — contained in the heterocyclic ring may be replaced with —CO— or —O—. ]

［式（III）中、
Ｒ^２は、水素原子、ハロゲン原子又はハロゲン原子を有してもよい炭素数１〜６のアルキル基を表す。
Ｒ^３〜Ｒ^８は、それぞれ独立に、水素原子又は炭素数１〜２４の炭化水素基を表すか、Ｒ^３〜Ｒ^８の中から選ばれる少なくとも２つが互いに結合して炭素数３〜３０の環を形成し、該炭化水素基及び該環に含まれる水素原子は、ハロゲン原子、水酸基、炭素数１〜１２のアルキル基、炭素数１〜１２のアルコキシ基、炭素数２〜４のアシル基又は炭素数２〜４のアシルオキシ基で置換されていてもよく、該炭化水素基及び該環に含まれる−ＣＨ_２−は、−ＣＯ−又は−Ｏ−で置き換わっていてもよい。
ｔ１は、０〜３の整数を表す。］ [2] The resin according to [1], wherein the compound represented by the formula (I) is a compound represented by the formula (III).

[In the formula (III),
R ² represents a hydrogen atom, a halogen atom or an alkyl group having 1 to 6 carbon atoms which may have a halogen atom.
R ^{3 to} R ⁸ each independently represents a hydrogen atom or a hydrocarbon group having 1 to 24 carbon atoms, or at least two selected from R ^{3 to} R ⁸ are bonded to each other to form 3 to 30 carbon atoms. Forming a ring, the hydrocarbon group and the hydrogen atom contained in the ring are a halogen atom, a hydroxyl group, an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, and an acyl group having 2 to 4 carbon atoms. Alternatively, it may be substituted with an acyloxy group having 2 to 4 carbon atoms, and —CH ₂ — contained in the hydrocarbon group and the ring may be replaced with —CO— or —O—.
t1 represents an integer of 0 to 3. ]

［式（ＩＶ）中、
Ｒ^９は、水素原子、ハロゲン原子又はハロゲン原子を有してもよい炭素数１〜６のアルキル基を表す。
Ｒ^１０〜Ｒ^１９は、それぞれ独立に、水素原子又は炭素数１〜１２の炭化水素基を表すか、Ｒ^１０〜Ｒ^１９の中から選ばれる少なくとも２つが互いに結合して炭素数３〜２４の環を形成し、該炭化水素基及び該環に含まれる水素原子は、ハロゲン原子、水酸基、炭素数１〜１２のアルキル基、炭素数１〜１２のアルコキシ基、炭素数２〜４のアシル基又は炭素数２〜４のアシルオキシ基で置換されていてもよく、該炭化水素基及び該環に含まれる−ＣＨ_２−は、−ＣＯ−又は−Ｏ−で置き換わっていてもよい。
ｔ２及びｔ３は、それぞれ独立に、０〜３の整数を表す。］ [3] The resin according to [1] or [2], wherein the compound represented by the formula (I) is a compound represented by the formula (IV).

[In the formula (IV),
R ⁹ represents a hydrogen atom, a halogen atom or an alkyl group having 1 to 6 carbon atoms which may have a halogen atom.
R ^{10 to} R ¹⁹ each independently represent a hydrogen atom or a hydrocarbon group having 1 to 12 carbon atoms, or at least two selected from R ^{10 to} R ¹⁹ are bonded to each other to form 3 to 24 carbon atoms. Forming a ring, the hydrocarbon group and the hydrogen atom contained in the ring are a halogen atom, a hydroxyl group, an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, and an acyl group having 2 to 4 carbon atoms. Alternatively, it may be substituted with an acyloxy group having 2 to 4 carbon atoms, and —CH ₂ — contained in the hydrocarbon group and the ring may be replaced with —CO— or —O—.
t2 and t3 each independently represents an integer of 0 to 3. ]

［式（ＶＩ）中、
Ｒ^２２は、水素原子、ハロゲン原子又はハロゲン原子を有してもよい炭素数１〜６のアルキル基を表す。
Ｒ^２３〜Ｒ^３８は、それぞれ独立に、水素原子又は炭素数１〜１２の炭化水素基を表すか、Ｒ^２３〜Ｒ^３８の中から選ばれる少なくとも２つが互いに結合して炭素数３〜１８の環を形成し、該炭化水素基及び該環に含まれる水素原子は、ハロゲン原子、水酸基、炭素数１〜１２のアルキル基、炭素数１〜１２のアルコキシ基、炭素数２〜４のアシル基又は炭素数２〜４のアシルオキシ基で置換されていてもよく、該炭化水素基及び該環に含まれる−ＣＨ_２−は、−ＣＯ−又は−Ｏ−で置き換わっていてもよい。
ｔ５、ｔ６及びｔ７は、それぞれ独立に、０〜３の整数を表す。］
〔５〕式（Ｉ）で表される化合物が、式（Ｖ）で表される化合物である〔１〕記載の樹脂。

［式（Ｖ）中、
Ｒ^２０は、水素原子、ハロゲン原子又はハロゲン原子を有してもよい炭素数１〜６のアルキル基を表す。
Ｒ^２１は、ハロゲン原子、水酸基、炭素数１〜１２のアルキル基、炭素数１〜１２のアルコキシ基、炭素数２〜４のアシル基又は炭素数２〜４のアシルオキシ基を表す。
t４は、０〜８の整数を表す。］
〔６〕式（Ｉ）で表される化合物が、式（ＶＩＩ）で表される化合物である〔１〕記載の樹脂。

［式（ＶＩＩ）中、
Ｒ^３９は、水素原子、ハロゲン原子又はハロゲン原子を有してもよい炭素数１〜６のアルキル基を表す。
Ｒ^４０は、ハロゲン原子、水酸基、炭素数１〜１２のアルキル基、炭素数１〜１２のアルコキシ基、炭素数２〜４のアシル基又は炭素数２〜４のアシルオキシ基を表す。
ｔ８は、０〜１４の整数を表す。］ [4] The resin according to any one of [1] to [3], wherein the compound represented by the formula (I) is a compound represented by the formula (VI).

[In the formula (VI)
R ²² represents a hydrogen atom, a halogen atom or an alkyl group having 1 to 6 carbon atoms which may have a halogen atom.
R ^{23 to} R ³⁸ each independently represent a hydrogen atom or a hydrocarbon group having 1 to 12 carbon atoms, or at least two selected from R ^{23 to} R ³⁸ are bonded to each other to form 3 to 18 carbon atoms. Forming a ring, the hydrocarbon group and the hydrogen atom contained in the ring are a halogen atom, a hydroxyl group, an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, and an acyl group having 2 to 4 carbon atoms. Alternatively, it may be substituted with an acyloxy group having 2 to 4 carbon atoms, and —CH ₂ — contained in the hydrocarbon group and the ring may be replaced with —CO— or —O—.
t5, t6 and t7 each independently represents an integer of 0 to 3. ]
[5] The resin according to [1], wherein the compound represented by the formula (I) is a compound represented by the formula (V).

[In the formula (V),
R ²⁰ represents a hydrogen atom, a halogen atom or an alkyl group having 1 to 6 carbon atoms which may have a halogen atom.
R ²¹ represents a halogen atom, a hydroxyl group, an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, an acyl group having 2 to 4 carbon atoms, or an acyloxy group having 2 to 4 carbon atoms.
t4 represents an integer of 0 to 8. ]
[6] The resin according to [1], wherein the compound represented by the formula (I) is a compound represented by the formula (VII).

[In the formula (VII),
R ³⁹ represents a hydrogen atom, a halogen atom or an alkyl group having 1 to 6 carbon atoms which may have a halogen atom.
R ⁴⁰ represents a halogen atom, a hydroxyl group, an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, an acyl group having 2 to 4 carbon atoms, or an acyloxy group having 2 to 4 carbon atoms.
t8 represents an integer of 0 to 14. ]

  [7] The resin according to any one of [1] to [6], which has an acid labile group and is insoluble or hardly soluble in an alkaline aqueous solution, and the resin that has reacted with an acid can be dissolved in an alkaline aqueous solution .

[8] A resist composition containing the resin according to any one of [1] to [7] and an acid generator.
[9] The resist composition according to [8], which contains a basic compound.

[10] (1) A step of applying the resist composition according to [8] or [9] on a substrate,
(2) a step of removing the solvent from the composition after coating to form a composition layer;
(3) a step of exposing the composition layer using an exposure machine;
(4) A step of heating the composition layer after exposure,
(5) A pattern forming method including a step of developing the heated composition layer using a developing device.

  According to the resin of the present invention, a pattern having an excellent shape and a focus margin can be formed using a resist composition containing the resin.

In this specification, unless otherwise specified, examples of each substituent are applied to any chemical structural formula having the same substituent while appropriately selecting the number of carbon atoms. Those which can be linear, branched or cyclic include any of them, and they may be mixed.
Each substituent can be a monovalent or divalent or higher substituent depending on the binding site. When stereoisomers exist, all stereoisomers are included.
Further, "(meth) acrylic monomer" means at least one monomer having a structure of "CH ₂ = CH-CO-" or _{"CH 2 = C (CH 3)} -CO- ". Similarly, “(meth) acrylate” and “(meth) acrylic acid” mean “at least one of acrylate and methacrylate” and “at least one of acrylic acid and methacrylic acid”, respectively.

［式（Ｉ）中、
Ｒ^１は、水素原子、ハロゲン原子又はハロゲン原子を有してもよい炭素数１〜６のアルキル基を表す。
Ｘ^１は、炭素数２〜３６の複素環を表し、該複素環に含まれる水素原子は、ハロゲン原子、水酸基、炭素数１〜２４の炭化水素基、炭素数１〜１２のアルコキシ基、炭素数２〜４のアシル基又は炭素数２〜４のアシルオキシ基で置換されていてもよく、該複素環に含まれる−ＣＨ_２−は、−ＣＯ−又は−Ｏ−で置き換わっていてもよい。］ The resin of the present invention has a structural unit derived from the compound represented by the formula (I).
<Compound represented by formula (I)>

[In the formula (I),
R ¹ represents a hydrogen atom, a halogen atom or an alkyl group having 1 to 6 carbon atoms which may have a halogen atom.
X ¹ represents a heterocyclic ring having 2 to 36 carbon atoms, and the hydrogen atom contained in the heterocyclic ring is a halogen atom, a hydroxyl group, a hydrocarbon group having 1 to 24 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, carbon The acyl group having 2 to 4 carbon atoms or the acyloxy group having 2 to 4 carbon atoms may be substituted, and —CH ₂ — contained in the heterocyclic ring may be replaced with —CO— or —O—. ]

The structural unit derived from the compound represented by the formula (I) is the following structural unit.

Examples of the halogen atom include fluorine, chlorine, bromine and iodine atoms.
Examples of the alkyl group include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, tert-butyl group, isobutyl group, n-pentyl group, isopentyl group, tert-pentyl group, Neopentyl group, 1-methylbutyl group, 2-methylbutyl group, n-hexyl group, 1-methylpentyl group, heptyl group, 2-ethylhexyl group, 1,2-dimethylpropyl group, 1-ethylpropyl group, octyl group, nonyl Group, decyl group, undecyl group, dodecyl group and the like.
Examples of the alkyl group that may have a halogen atom include a perfluoromethyl group, a perfluoroethyl group, a perfluoropropyl group, a perfluoroisopropyl group, a perfluorobutyl group, a perfluorosec-butyl group, a perfluorotert-butyl group, and a perfluoropentyl group. And perfluorohexyl group.

Any heterocyclic ring may be used as long as it contains —CO— and a nitrogen atom, and it may be an aromatic heterocyclic ring or may not have aromaticity. Moreover, any of monocyclic and polycyclic may be sufficient.
Specific examples of the following groups include the following.

As a hydrocarbon group, any of an aliphatic hydrocarbon group, a saturated cyclic hydrocarbon group, and an aromatic hydrocarbon group may be sufficient.
For example, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, tert-butyl group, n-pentyl group, n-hexyl group, heptyl group, 2-ethylhexyl group, octyl An aliphatic hydrocarbon group such as a group, nonyl group, decyl group, undecyl group, dodecyl group;
Monocyclic and polycyclic such as cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclooctyl group, cyclononyl group, cyclodecyl group, norbornyl group, 1-adamantyl group, 2-adamantyl group, isobornyl group A saturated cyclic hydrocarbon group of the formula;
Phenyl group, naphthyl group, anthranyl group, p-methylphenyl group, p-tert-butylphenyl group, p-adamantylphenyl group, tolyl group, xylyl group, cumenyl group, mesityl group, biphenyl group, anthryl group, phenanthryl group, And aromatic hydrocarbon groups such as 2,6-diethylphenyl group and 2-methyl-6-ethylphenyl. Moreover, the combination of these groups may be sufficient.
As a hydrocarbon group, a C1-C12 alkyl group is preferable.

As an alkoxy group, a methoxy group, an ethoxy group, an n-propoxy group, an isopropoxy group, an n-butoxy group, a sec-butoxy group, a tert-butoxy group, an n-pentoxy group, an n-hexoxy group, a heptoxy group, an octoxy group , 2-ethylhexoxy group, nonyloxy group, decyloxy group, undecyloxy group, dodecyloxy group and the like.
Examples of the acyl group include an acetyl group, a propionyl group, and a butyryl group.
Examples of the acyloxy group include an acetyloxy group, a propionyloxy group, a butyryloxy group, and an isobutyryloxy group.

In the formula (I), R ¹ is preferably a hydrogen atom or a methyl group.
X ¹ is preferably a 4-6 membered heterocyclic ring containing a nitrogen atom or a heterocyclic ring containing such a 4-6 membered ring. -CO- is preferably arranged at a position adjacent to the nitrogen atom.

［式（III）中、
Ｒ^２は、水素原子、ハロゲン原子又はハロゲン原子を有してもよい炭素数１〜６のアルキル基を表す。
Ｒ^３〜Ｒ^８は、それぞれ独立に、水素原子又は炭素数１〜２４の炭化水素基を表すか、Ｒ^３〜Ｒ^８の中から選ばれる少なくとも２つが互いに結合して炭素数３〜３０の環を形成し、該炭化水素基及び該環に含まれる水素原子は、ハロゲン原子、水酸基、炭素数１〜１２のアルキル基、炭素数１〜１２のアルコキシ基、炭素数２〜４のアシル基又は炭素数２〜４のアシルオキシ基で置換されていてもよく、該炭化水素基及び該環に含まれる−ＣＨ_２−は、−ＣＯ−又は−Ｏ−で置き換わっていてもよい。
ｔ１は、０〜３の整数を表す。］ The compound represented by the formula (I) is preferably a compound represented by the formula (III).

[In the formula (III),
R ² represents a hydrogen atom, a halogen atom or an alkyl group having 1 to 6 carbon atoms which may have a halogen atom.
R ^{3 to} R ⁸ each independently represents a hydrogen atom or a hydrocarbon group having 1 to 24 carbon atoms, or at least two selected from R ^{3 to} R ⁸ are bonded to each other to form 3 to 30 carbon atoms. Forming a ring, the hydrocarbon group and the hydrogen atom contained in the ring are a halogen atom, a hydroxyl group, an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, and an acyl group having 2 to 4 carbon atoms. Alternatively, it may be substituted with an acyloxy group having 2 to 4 carbon atoms, and —CH ₂ — contained in the hydrocarbon group and the ring may be replaced with —CO— or —O—.
t1 represents an integer of 0 to 3. ]

［式（ＩＶ）中、
Ｒ^９は、水素原子、ハロゲン原子又はハロゲン原子を有してもよい炭素数１〜６のアルキル基を表す。
Ｒ^１０〜Ｒ^１９は、それぞれ独立に、水素原子又は炭素数１〜１２の炭化水素基を表すか、Ｒ^１０〜Ｒ^１９の中から選ばれる少なくとも２つが互いに結合して炭素数３〜２４の環を形成し、該炭化水素基及び該環に含まれる水素原子は、ハロゲン原子、水酸基、炭素数１〜１２のアルキル基、炭素数１〜１２のアルコキシ基、炭素数２〜４のアシル基又は炭素数２〜４のアシルオキシ基で置換されていてもよく、該炭化水素基及び該環に含まれる−ＣＨ_２−は、−ＣＯ−又は−Ｏ−で置き換わっていてもよい。
ｔ２及びｔ３は、それぞれ独立に、０〜３の整数を表す。］ The compound represented by formula (I) is preferably a compound represented by formula (IV).

[In the formula (IV),
R ⁹ represents a hydrogen atom, a halogen atom or an alkyl group having 1 to 6 carbon atoms which may have a halogen atom.
R ^{10 to} R ¹⁹ each independently represent a hydrogen atom or a hydrocarbon group having 1 to 12 carbon atoms, or at least two selected from R ^{10 to} R ¹⁹ are bonded to each other to form 3 to 24 carbon atoms. Forming a ring, the hydrocarbon group and the hydrogen atom contained in the ring are a halogen atom, a hydroxyl group, an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, and an acyl group having 2 to 4 carbon atoms. Alternatively, it may be substituted with an acyloxy group having 2 to 4 carbon atoms, and —CH ₂ — contained in the hydrocarbon group and the ring may be replaced with —CO— or —O—.
t2 and t3 each independently represents an integer of 0 to 3. ]

［式（ＶＩ）中、
Ｒ^２２は、水素原子、ハロゲン原子又はハロゲン原子を有してもよい炭素数１〜６のアルキル基を表す。
Ｒ^２３〜Ｒ^３８は、それぞれ独立に、水素原子又は炭素数１〜１２の炭化水素基を表すか、Ｒ^２３〜Ｒ^３８の中から選ばれる少なくとも２つが互いに結合して炭素数３〜１８の環を形成し、該炭化水素基及び該環に含まれる水素原子は、ハロゲン原子、水酸基、炭素数１〜１２のアルキル基、炭素数１〜１２のアルコキシ基、炭素数２〜４のアシル基又は炭素数２〜４のアシルオキシ基で置換されていてもよく、該炭化水素基及び該環に含まれる−ＣＨ_２−は、−ＣＯ−又は−Ｏ−で置き換わっていてもよい。
ｔ５、ｔ６及びｔ７は、それぞれ独立に、０〜３の整数を表す。］ The compound represented by the formula (I) is preferably a compound represented by the formula (VI).

[In the formula (VI)
R ²² represents a hydrogen atom, a halogen atom or an alkyl group having 1 to 6 carbon atoms which may have a halogen atom.
R ^{23 to} R ³⁸ each independently represent a hydrogen atom or a hydrocarbon group having 1 to 12 carbon atoms, or at least two selected from R ^{23 to} R ³⁸ are bonded to each other to form 3 to 18 carbon atoms. Forming a ring, the hydrocarbon group and the hydrogen atom contained in the ring are a halogen atom, a hydroxyl group, an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, and an acyl group having 2 to 4 carbon atoms. Alternatively, it may be substituted with an acyloxy group having 2 to 4 carbon atoms, and —CH ₂ — contained in the hydrocarbon group and the ring may be replaced with —CO— or —O—.
t5, t6 and t7 each independently represents an integer of 0 to 3. ]

［式（Ｖ）中、
Ｒ^２０は、水素原子、ハロゲン原子又はハロゲン原子を有してもよい炭素数１〜６のアルキル基を表す。
Ｒ^２１は、ハロゲン原子、水酸基、炭素数１〜１２のアルキル基、炭素数１〜１２のアルコキシ基、炭素数２〜４のアシル基又は炭素数２〜４のアシルオキシ基を表す。
t４は、０〜８の整数を表す。］ The compound represented by the formula (I) is preferably a compound represented by the formula (V).

[In the formula (V),
R ²⁰ represents a hydrogen atom, a halogen atom or an alkyl group having 1 to 6 carbon atoms which may have a halogen atom.
R ²¹ represents a halogen atom, a hydroxyl group, an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, an acyl group having 2 to 4 carbon atoms, or an acyloxy group having 2 to 4 carbon atoms.
t4 represents an integer of 0 to 8. ]

［式（ＶＩＩ）中、
Ｒ^３９は、水素原子、ハロゲン原子又はハロゲン原子を有してもよい炭素数１〜６のアルキル基を表す。
Ｒ^４０は、ハロゲン原子、水酸基、炭素数１〜１２のアルキル基、炭素数１〜１２のアルコキシ基、炭素数２〜４のアシル基又は炭素数２〜４のアシルオキシ基を表す。
ｔ８は、０〜１４の整数を表す。］ The compound represented by the formula (I) is preferably a compound represented by the formula (VII).

[In the formula (VII),
R ³⁹ represents a hydrogen atom, a halogen atom or an alkyl group having 1 to 6 carbon atoms which may have a halogen atom.
R ⁴⁰ represents a halogen atom, a hydroxyl group, an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, an acyl group having 2 to 4 carbon atoms, or an acyloxy group having 2 to 4 carbon atoms.
t8 represents an integer of 0 to 14. ]

Examples of the ring formed by combining two of R ^{3 to} R ⁸ , R ^{10 to} R ^19, or R ^{23 to} R ³⁸ include those exemplified as the heterocyclic ring described above.

t1 is preferably 0 or 1, and more preferably 0.
t2 is preferably 0 or 1, more preferably 0.
t3 is preferably 1 or 2, and more preferably 1.
t4 is preferably 0 or 1, and more preferably 0.
t5 is preferably 0 or 1, more preferably 0.
t6 is preferably 0 or 1, and more preferably 1.
t7 is preferably 0 or 1, and more preferably 0.
t8 is preferably 0 or 1, and more preferably 0.

Examples of the compound represented by the formula (I) include the following compounds.

The compound represented by the formula (I) can be produced by a method known in the art, and examples thereof include the following production methods.
A compound represented by the formula (I) can be obtained by reacting a compound represented by the formula (Ia) and a compound represented by the formula (Ib) in a solvent under a catalyst. it can. Here, as a catalyst, N-methylpyrrolidine is preferable. As the solvent, dimethylformamide is preferable.

［式中、Ｘ^１、及びＲ^１は、上記と同じ意味を表す。
Ｘは、ハロゲン原子又は（メタ）クリロイルオキシ基を表す。］

[Wherein, X ¹ and R ¹ represent the same meaning as described above.
X represents a halogen atom or a (meth) acryloyloxy group. ]

  As a halogen atom, a chlorine atom, a bromine atom, and an iodine atom are mentioned, and a chlorine atom is preferable.

Examples of the compound represented by the formula (Ia) include the following compounds. These compounds can use what is marketed.

式（Ｉ−ｂ）で表される化合物としては、メタクリル酸クロライド及びメタクリル酸無水物等が挙げられる。 The compound represented by the formula (I-a-1) can be obtained by a reaction between cyclopentene and chlorosulfonyl isocyanate (see JP-T-2007-514775).

Examples of the compound represented by the formula (Ib) include methacrylic acid chloride and methacrylic anhydride.

  In the resin, the structural unit derived from the compound represented by the formula (I) is, for example, 1 to 100%, preferably 5 to 95%, more preferably in terms of mass in the total unit of the resin. 10 to 80%.

  The resin of the present invention preferably contains a structural unit derived from a monomer having an acid labile group in addition to the structural unit derived from the compound represented by the formula (I). That is, any of a polymer / oligomer mixture or a copolymer containing these structural units may be used. Such a resin is a resin that is insoluble or hardly soluble in an alkaline aqueous solution, and can be dissolved in an alkaline aqueous solution by the action of an acid.

  The term “acid-labile group” means a group that cleaves a leaving group upon contact with an acid to form a hydrophilic group (for example, a hydroxy group or a carboxy group). Examples of the acid labile group include an alkoxycarbonyl group represented by the formula (1) in which —O— is bonded to a tertiary carbon atom. Hereinafter, the group represented by the formula (1) may be referred to as “acid-labile group (1)”.

式（１）中、Ｒ^a1〜Ｒ^a3は、それぞれ独立に、炭素数１〜８の脂肪族炭化水素基又は炭素数３〜２０の飽和環状炭化水素基を表すか、あるいはＲ^a1及びＲ^a2は互いに結合して炭素数３〜２０の環を形成する。＊は結合手を表す（以下同じ）。

In formula (1), R ^{a1 to} R ^a3 each independently represent an aliphatic hydrocarbon group having 1 to 8 carbon atoms or a saturated cyclic hydrocarbon group having 3 to 20 carbon atoms, or R ^a1 and R ^a2 Combine with each other to form a ring having 3 to 20 carbon atoms. * Represents a bond (same below).

式（１）では、飽和環状炭化水素基の炭素数は、好ましくは炭素数１〜１６である。 The saturated cyclic hydrocarbon group may be monocyclic or polycyclic, and examples of the monocyclic saturated cyclic hydrocarbon group include a cyclopentyl group, a cyclohexyl group, a methylcyclohexyl group, and dimethylcyclohexyl. Cycloalkyl groups such as a group, a cycloheptyl group, and a cyclooctyl group. Examples of the polycyclic saturated hydrocarbon group include decahydronaphthyl group, adamantyl group, norbornyl group, methylnorbornyl group, and the following groups.

In the formula (1), the saturated cyclic hydrocarbon group preferably has 1 to 16 carbon atoms.

When R ^a1 and R ^a2 are bonded to each other to form a ring, examples of the —C (R ^a1 ) (R ^a2 ) (R ^a3 ) group include the following groups. The number of carbon atoms in the ring is preferably 3 to 12 carbon atoms.

When an acid labile group is exemplified as the -COOR R ester (-COO-C (CH ₃ ) ₃ is referred to as tert-butyl ester), examples of the acid labile group include:
alkyl esters represented by tert-butyl ester;
Methoxymethyl ester, ethoxymethyl ester, 1-ethoxyethyl ester, 1-isobutoxyethyl ester, 1-isopropoxyethyl ester, 1-ethoxypropyl ester, 1- (2-methoxyethoxy) ethyl ester, 1- (2- Acetoxyethoxy) ethyl ester, 1- [2- (1-adamantyloxy) ethoxy] ethyl ester, 1- [2- (1-adamantanecarbonyloxy) ethoxy] ethyl ester, tetrahydro-2-furyl ester and tetrahydro-2- Acetal-type esters such as pyranyl esters; and saturated carbonization such as isobornyl esters and 1-alkyl cycloalkyl esters, 2-alkyl-2-adamantyl esters, 1- (1-adamantyl) -1-alkylalkyl esters Examples include hydrogen ring type esters.

A resin containing a structural unit derived from a monomer having an acid labile group can be produced by addition polymerization of a monomer having an acid labile group and an olefinic double bond.
The acid-labile group is a bulky group such as a 2-alkyl-2-adamantyl group or 1- (1-adamantyl) -1-alkylalkyl group, and the resulting resist tends to have excellent resolution. This is preferable.

  Examples of the monomer containing an acid labile group include 2-alkyl-2-adamantyl (meth) acrylate, 1- (1-adamantyl) -1-alkylalkyl (meth) acrylate, and 5-norbornene-2. -2-alkyl-2-adamantyl carboxylate, 1- (1-adamantyl) -1-alkylalkyl 5-norbornene-2-carboxylate, 2-alkyl-2-adamantyl α-chloroacrylate, α-chloroacrylic acid 1- (1-adamantyl) -1-alkylalkyl, 5-tertbornene-2-carboxylic acid-tert-butyl, 5-norbornene-2-carboxylic acid 1-cyclohexyl-1-methylethyl, 5-norbornene-2-carboxylic acid 1-methylcyclohexyl acid, 2-methyl-2-adamantyl 5-norbornene-2-carboxylate, 2-norbornene-2-carboxylic acid 2-ethyl-2-adamantyl, 5-norbornene-2-carboxylic acid 1- (4-methylcyclohexyl) -1-methylethyl, 5-norbornene-2-carboxylic acid 1- (4 -Hydroxycyclohexyl) -1-methylethyl, 5-norbornene-2-carboxylic acid 1-methyl-1- (4-oxocyclohexyl) ethyl, 5-norbornene-2-carboxylic acid 1- (1-adamantyl) -1- Examples include methyl ethyl.

  In particular, when 2-alkyl-2-adamantyl (meth) acrylate or 2-alkyl-2-adamantyl α-chloroacrylate is used as a monomer, the resolution of the resulting resist tends to be excellent, which is preferable.

  Specifically, as 2-alkyl-2-adamantyl (meth) acrylate, for example, 2-methyl-2-adamantyl acrylate, 2-methyl-2-adamantyl methacrylate, 2-ethyl-2-acrylate Examples include adamantyl, 2-ethyl-2-adamantyl methacrylate, 2-n-butyl-2-adamantyl acrylate, and the like. Examples of the α-chloro-2-alkyl-2-adamantyl α-chloroacrylate include 2-methyl-2-adamantyl α-chloroacrylate, 2-ethyl-2-adamantyl α-chloroacrylate, and the like.

  Among them, when 2-ethyl-2-adamantyl (meth) acrylate or 2-isopropyl-2-adamantyl (meth) acrylate is used, the sensitivity of the resulting resist is excellent and the heat resistance tends to be excellent, which is preferable.

  The content of the structural unit derived from the monomer having an acid labile group in the resin is usually 10 to 95 mol%, preferably 15 to 90 mol%, more preferably 20 in all units of the resin. -85 mol%.

  For example, 2-alkyl-2-adamantyl (meth) acrylate can be usually produced by a reaction of 2-alkyl-2-adamantanol or a metal salt thereof with acrylic acid halide or methacrylic acid halide.

As a structural unit derived from a monomer having an acid labile group,
2-alkyl-2-adamantyl methacrylate,
2-alkyl-2-adamantyl acrylate,
1- (1-adamantyl) -1-alkylalkyl methacrylate,
When a structural unit derived from 1- (1-adamantyl) -1-alkylalkyl acrylate is included and the structural unit is 15 mol% or more of all structural units constituting the resin, the resin has an alicyclic group. Therefore, it has a strong structure and is advantageous in terms of dry etching resistance of the resist to be provided.

  As the monomer having an acid labile group, monomers having the same olefinic double bond and different acid labile groups may be used in combination, or the acid labile group may be the same and the olefin Monomers having different ionic double bonds may be used in combination, or monomers having different combinations of acid-labile groups and olefinic double bonds may be used in combination.

In addition to the structural unit derived from the compound represented by the formula (I) and the structural unit derived from the monomer having an acid-labile group, the resin of the present invention further includes a structure derived from an acid-stable monomer. Units may be included. Here, the acid-stable monomer means a monomer having no acid-labile group.
In particular,
Structural units derived from free carboxylic acids such as acrylic acid and methacrylic acid,
Structural units derived from aliphatic unsaturated dicarboxylic anhydrides, such as maleic anhydride and itaconic anhydride,
A structural unit derived from 2-norbornene,
A structural unit derived from (meth) acrylonitrile,
The hydrogen atom of —COOH of (meth) acrylic acid is —CH (R ^a4 ) (R ^a5 ), —CH ₂ (R ^a6 ) (R ^a4 and R ^a6 represent the same meaning as R ^a1, and R ^a5 represents Represents the same meaning as R ^a2 ) or a structural unit derived from (meth) acrylic acid esters substituted with 1-adamantyl,
a structural unit derived from a styrenic monomer such as p- or m-hydroxystyrene,
Examples include structural units derived from (meth) acryloyloxy-γ-butyrolactone in which the lactone ring may be substituted with an alkyl group.
In addition, the hydrogen atom contained in 1-adamantyl may be substituted with a hydroxyl group or the like.

  As the acid-stable monomer, it is preferable to use an acid-stable monomer having a hydroxyadamantyl group and an acid-stable monomer having a lactone ring because the resolution and adhesion of the resulting resist tend to be excellent. Any of these may be used alone or in combination of two or more.

  Examples of the acid stable monomer having a hydroxyadamantyl group include a monomer represented by the formula (a2-1).

式（ａ２−１）中、
Ｌ^a3は、−Ｏ−又は^＊−Ｏ−（ＣＨ₂）_k2−ＣＯ−Ｏ−を表し、
ｋ２は１〜７の整数を表す。＊は−ＣＯ−との結合手を表す。
Ｒ^a14は、水素原子又はメチル基を表す。
Ｒ^a15及びＲ^a16は、それぞれ独立に、水素原子、メチル基又はヒドロキシ基を表す。
ｏ１は、０〜１０の整数を表す。

In formula (a2-1),
L ^a3 represents —O— or ^* —O— (CH ₂ ) _k2 —CO—O—,
k2 represents an integer of 1 to 7. * Represents a bond with -CO-.
R ^a14 represents a hydrogen atom or a methyl group.
R ^a15 and R ^a16 each independently represent a hydrogen atom, a methyl group or a hydroxy group.
o1 represents an integer of 0 to 10.

In the formula (a2-1), L ^a3 is preferably, -O -, - O- (CH 2) f1 -CO-O- and is (wherein f1 is an integer from 1 to 4), more preferably Is —O—.
R ^a14 is preferably a methyl group.
R ^a15 is preferably a hydrogen atom.
R ^a16 is preferably a hydrogen atom or a hydroxy group.
o1 is preferably an integer of 0 to 3, more preferably 0 or 1.

As an acid stable monomer (a2-1) which has a hydroxyadamantyl group, the following are mentioned, for example.

  Among them, 3-hydroxy-1-adamantyl (meth) acrylate, 3,5-dihydroxy-1-adamantyl (meth) acrylate, and 1- (3,5-dihydroxy-1-adamantyloxycarbonyl) methyl (meth) acrylate are Preferably, 3-hydroxy-1-adamantyl (meth) acrylate and 3,5-dihydroxy-1-adamantyl (meth) acrylate are more preferable, 3-hydroxy-1-adamantyl methacrylate and 3,5-dihydroxy-1-adamantyl methacrylate Is more preferable.

  Monomers such as 3-hydroxy-1-adamantyl (meth) acrylate and 3,5-dihydroxy-1-adamantyl (meth) acrylate are commercially available. For example, the corresponding hydroxyadamantane is (meth) acrylic acid or its It can also be produced by reacting with a halide.

  The content of the structural unit derived from the monomer represented by the formula (a2-1) in the resin is usually 3 to 40 mol%, preferably 5 to 35 mol%, more preferably in all units of the resin. Is 5 to 30 mol%.

  Examples of the acid-stable monomer having a lactone ring include monomers represented by formula (a3-1), formula (a3-2), or formula (a3-3).

式（ａ３−１）〜式（ａ３−３）中、
Ｌ^a4〜Ｌ^a6は、それぞれ独立に、−Ｏ−又は^＊−Ｏ−（ＣＨ₂）_k3−ＣＯ−Ｏ−を表す。
ｋ３は１〜７の整数を表す。＊は−ＣＯ−との結合手を表す。
Ｒ^a18〜Ｒ^a20は、それぞれ独立に、水素原子又はメチル基を表す。
Ｒ^a21は、炭素数１〜４の脂肪族炭化水素基を表す。
ｐ１は０〜５の整数を表す。
Ｒ^a22及びＲ^a23は、それぞれ独立に、カルボキシ基、シアノ基又は炭素数１〜４の脂肪族炭化水素基を表す。
ｑ１及びｒ１は、それぞれ独立に０〜３の整数を表す。ｐ１、ｑ１又はｒ１が２以上のとき、それぞれ、複数のＲ^a21、Ｒ^a22又はＲ^a23は、互いに同一でも異なってもよい。

In formula (a3-1) to formula (a3-3),
L ^{a4 to} L ^a6 each independently represent —O— or ^* —O— (CH ₂ ) _k3 —CO—O—.
k3 represents an integer of 1 to 7. * Represents a bond with -CO-.
R ^{a18 to} R ^a20 each independently represents a hydrogen atom or a methyl group.
R ^a21 represents an aliphatic hydrocarbon group having 1 to 4 carbon atoms.
p1 represents an integer of 0 to 5.
R ^a22 and R ^a23 each independently represent a carboxy group, a cyano group, or an aliphatic hydrocarbon group having 1 to 4 carbon atoms.
q1 and r1 each independently represents an integer of 0 to 3. When p1, q1 or r1 is 2 or more, a plurality of R ^a21 , R ^a22 or R ^a23 may be the same as or different from each other.

In the formula (a3-1) to the formula (a3-3), examples of L ^{a4 to} L ^a6 include those described for L ^a3 .
L ^{a4 to} L ^a6 are each independently preferably —O— or ^* —O— (CH ₂ ) _d1 —CO—O— (the d1 is an integer of 1 to 4), more preferably. Is —O—.
R ^{a18 to} R ^a21 are preferably methyl groups.
R ^a22 and R ^a23 are each independently preferably a carboxy group, a cyano group or a methyl group.
p1 to r1 are each independently preferably 0 to 2, more preferably 0 or 1.

  Examples of the acid stable monomer (a3-1) having a γ-butyrolactone ring include the following.

As the acid stable monomer (a3-1) having a γ-butyrolactone ring, an acid labile monomer can also be exemplified. For example, the following are mentioned.

Examples of the acid stable monomer (a3-2) having a condensed ring of γ-butyrolactone ring and norbornane ring include the following.

As the acid stable monomer (a3-2) having a condensed ring of γ-butyrolactone ring and norbornane ring, an acid labile monomer can be exemplified. For example, the following are mentioned.

Examples of the acid stable monomer (a3-3) having a condensed ring of γ-butyrolactone ring and cyclohexane ring include the following.

An acid labile monomer can also be exemplified as the monomer (a3-3) having a condensed ring of γ-butyrolactone ring and cyclohexane ring. For example, the following are mentioned.

Among acid-stable monomers (a3) having a lactone ring, (meth) acrylic acid (5-oxo-4-oxatricyclo [4.2.1.0 ^3,7 ] nonan-2-yl, (meth) acrylic Acid tetrahydro-2-oxo-3-furyl, 2- (5-oxo-4-oxatricyclo [4.2.1.0 ^3,7 ] nonan-2-yloxy) -2-oxoethyl (meth) acrylate Are preferred, and those in the form of methacrylate are more preferred.

  The monomer that gives the structural unit represented by the formula (a3-1) is obtained by reacting (meth) acrylic acid with α- or β-bromo-γ-butyrolactone in which the lactone ring may be substituted with an alkyl group, or The lactone ring can be produced by reacting (meth) acrylic acid halide with α- or β-hydroxy-γ-butyrolactone which may be substituted with an alkyl group.

  Content of the structural unit derived from the monomer represented by Formula (a3-1), Formula (a3-2), or Formula (a3-3) in the resin is usually 5 to 50 mol% in all units of the resin. Yes, preferably 10 to 45 mol%, more preferably 15 to 40 mol%.

As an acid stable monomer other than the above,
styrenic monomers such as p- or m-hydroxystyrene,
An alicyclic compound having an olefinic double bond in the molecule, such as norbornene,
Examples thereof include aliphatic unsaturated dicarboxylic anhydrides such as maleic anhydride, itaconic anhydride and the like.

  When a structural unit derived from a styrene monomer such as p- or m-hydroxystyrene is used as the structural unit of the resin, a sufficient transmittance can be obtained even when KrF excimer laser exposure or EUV exposure is used. Such a copolymer resin can be obtained by radical polymerization of the corresponding (meth) acrylic acid ester monomer, acetoxystyrene and styrene, and then deacetylation with an acid.

スチレン系モノマーとしては、４−ヒドロキシスチレン又は４−ヒドロキシ−α−メチルスチレンが特に好ましい。 As a monomer which gives the structural unit derived from a styrene-type monomer, the following compounds are mentioned, for example.

As the styrene monomer, 4-hydroxystyrene or 4-hydroxy-α-methylstyrene is particularly preferable.

  Moreover, since the resin containing a structural unit derived from 2-norbornene has an alicyclic skeleton directly in the main chain, it has a sturdy structure and exhibits excellent dry etching resistance. The structural unit derived from 2-norbornene can be introduced into the main chain by radical polymerization using, in addition to the corresponding 2-norbornene, an aliphatic unsaturated dicarboxylic anhydride such as maleic anhydride or itaconic anhydride. . Therefore, the one formed by opening the double bond of the norbornene structure can be represented by the formula (c), and the one formed by opening the double bond of maleic anhydride and itaconic anhydride is respectively It can represent with Formula (d) and Formula (e).

Here, R ^{5 ′} and R ^{6 ′} in formula (c) are each independently a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, a carboxyl group, a cyano group, or —COOU (U is an alcohol residue) Or R ^{5 ′} and R ^{6 ′} are bonded to each other to represent a carboxylic anhydride residue represented by —C (═O) OC (═O) —.
When R ^{5 ′} and R ^{6 ′} are a group —COOU, the carboxyl group is an ester group, and examples of the alcohol residue corresponding to U include an optionally substituted carbon number of 1 to 8 alkyl group, 2-oxooxolan-3- or -4-yl group and the like can be mentioned. Here, in the alkyl group, a hydroxyl group, an alicyclic hydrocarbon residue, or the like may be bonded as a substituent.
Specific examples when R ^{5 ′} and R ^{6 ′} are an alkyl group include a methyl group, an ethyl group, and a propyl group. Specific examples of the alkyl group to which a hydroxyl group is bonded include a hydroxymethyl group, 2- Examples thereof include a hydroxyethyl group.

As described above, specific examples of the norbornene structure represented by the formula (c), which is a monomer that gives a stable structural unit to an acid, include the following compounds.
2-norbornene,
2-hydroxy-5-norbornene,
5-norbornene-2-carboxylic acid,
Methyl 5-norbornene-2-carboxylate,
2-hydroxy-1-ethyl 5-norbornene-2-carboxylate,
5-norbornene-2-methanol,
5-norbornene-2,3-dicarboxylic anhydride.

In the formula (c), U of —COOU of R ^{5 ′} and R ^{6 ′} is an acid labile group such as an alicyclic ester in which the carbon atom adjacent to —O— is a quaternary carbon atom. If present, it is a structural unit having an acid labile group even though it has a norbornene structure. Examples of the monomer containing a norbornene structure and an acid labile group include, for example, 5-norbornene-2-carboxylic acid-t-butyl, 5-norbornene-2-carboxylic acid 1-cyclohexyl-1-methylethyl, and 5-norbornene. 2-carboxylate 1-methylcyclohexyl, 5-norbornene-2-carboxylic acid 2-methyl-2-adamantyl, 5-norbornene-2-carboxylic acid 2-ethyl-2-adamantyl, 5-norbornene-2-carboxylic acid 1- (4-methylcyclohexyl) -1-methylethyl, 5-norbornene-2-carboxylic acid 1- (4-hydroxycyclohexyl) -1-methylethyl, 5-norbornene-2-carboxylic acid 1-methyl-1- (4-Oxocyclohexyl) ethyl, 5-norbornene-2-carboxylic acid 1- (1-adama) Chill) -1-methylethyl and the like.

  Furthermore, you may contain the structural unit containing the fluorine atom represented by Formula (b1) as an acid stable group.

［式（ｂ１）中、
Ｒ^１ｂは、水素原子、メチル基又はトリフルオロメチル基を表す。
ＡＲは、炭素数１〜３０の炭化水素基を表し、該炭化水素基に含まれる水素原子の少なくとも１個以上がフッ素原子で置換されている。該炭化水素基に含まれる−ＣＨ_２−は、−Ｏ−、−Ｓ−又は−Ｎ（Ｒ^ｃ）−で置き換わっていてもよく、該炭化水素基に含まれる水素原子は、水酸基又は炭素数１〜６の脂肪族炭化水素基で置換されていてもよい。
Ｒ^ｃは、水素原子又は炭素数１〜６の脂肪族炭化水素基を表す。］

[In the formula (b1),
R ^1b represents a hydrogen atom, a methyl group or a trifluoromethyl group.
AR represents a hydrocarbon group having 1 to 30 carbon atoms, and at least one hydrogen atom contained in the hydrocarbon group is substituted with a fluorine atom. —CH ₂ — contained in the hydrocarbon group may be replaced by —O—, —S— or —N (R ^c ) —, and the hydrogen atom contained in the hydrocarbon group is a hydroxyl group or a carbon number. It may be substituted with 1 to 6 aliphatic hydrocarbon groups.
R ^c represents a hydrogen atom or an aliphatic hydrocarbon group having 1 to 6 carbon atoms. ]

Specific examples of the monomer that gives the structural unit represented by the formula (b1) include the following monomers.

  The weight average molecular weight of the resin is preferably 2,500 or more and 100,000 or less, more preferably 2,700 or more and 50,000 or less, and still more preferably 3,000 or more and 40,000 or less.

  The resist composition of the present invention contains a resin and an acid generator. The resist composition of the present invention preferably further contains a basic compound.

<Acid generator (hereinafter sometimes referred to as "acid generator (B)")>
The acid generator (B) is classified into a nonionic type and an ionic type. Nonionic acid generators include organic halides, sulfonate esters (for example, 2-nitrobenzyl ester, aromatic sulfonate, oxime sulfonate, N-sulfonyloxyimide, N-sulfonyloxyimide, sulfonyloxyketone, DNQ 4- Sulfonate), sulfones (for example, disulfone, ketosulfone, sulfonyldiazomethane) and the like. The ionic acid generator is typically an onium salt containing an onium cation (for example, diazonium salt, phosphonium salt, sulfonium salt, iodonium salt). Examples of the anion of the onium salt include a sulfonate anion, a sulfonylimide anion, and a sulfonylmethide anion.

  Examples of the acid generator (B) include not only an acid generator (particularly a photoacid generator) used in the resist field, but also a photoinitiator for photocationic polymerization, a photodecolorant for dyes, or a photochromic agent. Known compounds that generate an acid by radiation (light) and mixtures thereof can also be used as appropriate. For example, JP-A 63-26653, JP-A 55-164824, JP-A 62-69263, JP-A 63-146038, JP-A 63-163452, JP-A 62-153853, Acid can be obtained by radiation described in Japanese Utility Model Laid-Open No. 63-146029, U.S. Pat. No. 3,779,778, U.S. Pat. The resulting compound can be used.

  The acid generator (B) is preferably a fluorine-containing acid generator, more preferably a sulfonate represented by the formula (B1).

In formula (B1), Q ¹ and Q ² each independently represent a fluorine atom or a C 1-6 perfluoroalkyl group.
Examples of the perfluoroalkyl group include a perfluoromethyl group, a perfluoroethyl group, a perfluoropropyl group, a perfluoroisopropyl group, a perfluorobutyl group, a perfluorosec-butyl group, a perfluorotert-butyl group, a perfluoropentyl group, and a perfluorohexyl group. .
Q ¹ and Q ² are each independently preferably a perfluoromethyl group or a fluorine atom, more preferably a fluorine atom.

In formula (B1), Y represents an aliphatic hydrocarbon group having 1 to 36 carbon atoms or a saturated cyclic hydrocarbon group having 3 to 36 carbon atoms. Y may be a saturated cyclic hydrocarbon group in which —CH ₂ — is replaced by —O— or —CO—.
Y is, for example, a cyclic ether group (a group in which —CH ₂ — is replaced by —O—), a saturated cyclic hydrocarbon group having an oxo group (a group in which —CH ₂ — is replaced by —CO—), a sultone ring Group (two adjacent —CH ₂ — are each replaced by —O— or —SO ₂ —) or a lactone ring group (two adjacent —CH ₂ — are each —O— or A group substituted by —CO—.

As an aliphatic hydrocarbon group of Y, a C1-C6 alkyl group is mentioned, for example.
Examples of the saturated cyclic hydrocarbon group for Y include groups represented by formulas (Y1) to (Y26).

  The saturated cyclic hydrocarbon group is preferably a group represented by any of the formulas (Y1) to (Y19), and more preferably the formula (Y11), the formula (Y14), the formula (Y15), or the formula (Y19 ), More preferably a group represented by formula (Y11) or formula (Y14).

Y may have a substituent. Examples of the substituent for Y include a halogen atom (excluding a fluorine atom), a hydroxy group, an oxo group, an aliphatic hydrocarbon group having 1 to 12 carbon atoms, and an aliphatic hydrocarbon having 1 to 12 carbon atoms containing a hydroxy group. Group, C3-C16 saturated cyclic hydrocarbon group, C1-C12 alkoxy group, C6-C18 aromatic hydrocarbon group, C7-C21 aralkyl group, C2-C4 An acyl group, a glycidyloxy group or — (CH ₂ ) _j2 —O—CO—R ^b1 group (wherein R ^b1 is an aliphatic hydrocarbon group having 1 to 16 carbon atoms, saturated cyclic carbonization having 3 to 16 carbon atoms) Represents a hydrogen group or an aromatic hydrocarbon group having 6 to 18 carbon atoms, j2 represents an integer of 0 to 4).
Examples of the hydroxy group-containing aliphatic hydrocarbon group include a hydroxymethyl group.
Examples of the aralkyl group include benzyl group, phenethyl group, phenylpropyl group, trityl group, naphthylmethyl group, naphthylethyl group, and the like.
The plurality of substituents may be the same as or different from each other.
The aliphatic hydrocarbon group, saturated cyclic hydrocarbon group, aromatic hydrocarbon group, aralkyl group, and the like, which are substituents for Y, may further have a substituent. Substituents here are, for example, C ₁ -C ₆ alkyl group, a halogen atom, hydroxy group, etc. oxo group.

Examples of Y having an aliphatic hydrocarbon group include the following.

Examples of Y having a hydroxy group or a hydroxy group-containing aliphatic hydrocarbon group include the following.

Examples of Y having an aromatic hydrocarbon group include the following.

Examples of Y having a — (CH ₂ ) _j2 —O—CO—R ^b1 group include the following.

  Y is preferably an adamantyl group optionally having a substituent (for example, an oxo group), more preferably an adamantyl group or an oxoadamantyl group.

In formula (B1), L ^b1 represents a divalent saturated hydrocarbon group having 1 to 17 carbon atoms which may have a single bond or a substituent.
As a divalent saturated hydrocarbon group, a linear alkanediyl group such as a methylene group, an ethylene group, a propane-1,3-diyl group, a butane-1,4-diyl group, a pentane-1,5-diyl group, Hexane-1,6-diyl group, heptane-1,7-diyl group, octane-1,8-diyl group, nonane-1,9-diyl group, decane-1,10-diyl group, undecane-1,11 -Diyl group, dodecane-1,12-diyl group, tridecane-1,13-diyl group, tetradecane-1,14-diyl group, pentadecane-1,15-diyl group, hexadecane-1,16-diyl group, heptadecane A -1,17-diyl group is mentioned.
L ^b1 may be a branched alkanediyl group.
Examples of the branched alkanediyl group include an alkyl group having 1 to 4 carbon atoms (for example, a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a sec-butyl group) to the linear alkanediyl group. , Tert-butyl group and the like).
Examples of the cyclic divalent saturated hydrocarbon group include a cycloalkanediyl group (for example, cyclohexanediyl group) and a divalent bridged cyclic hydrocarbon group (for example, an adamantanediyl group).
L ^b1 may be a combination of two or more of these groups.

Examples of the substituent for the divalent saturated hydrocarbon group represented by L ^b1 include a halogen atom, a hydroxy group, a carboxy group, an aromatic hydrocarbon group having 6 to 18 carbon atoms, an aralkyl group having 7 to 21 carbon atoms, and 2 carbon atoms. ˜4 acyl groups or glycidyloxy groups.

Examples of the group in which —CH ₂ — contained in the saturated hydrocarbon group of L ^b1 is replaced by —O— or —CO— include, for example, formula (b1-1) to formula (b1-6), preferably Formula (b1-1)-Formula (b1-4) are mentioned, More preferably, Formula (b1-1) or Formula (b1-2) is mentioned. The formula (b1-1) to the formula (b1-6) are described in accordance with the formula (B1) on the left and right sides, combined with C (Q ¹ ) (Q ² )-on the left side, and -Y on the right side. Combine with. The same applies to specific examples of the following formulas (b1-1) to (b1-6).

Here, L ^d represents a single bond or a saturated hydrocarbon group having 1 to 15 carbon atoms.
^Le represents a single bond or a saturated hydrocarbon group having 1 to 12 carbon atoms.
L ^f represents a saturated hydrocarbon group having 1 to 13 carbon atoms. However, the upper limit number of carbon atoms of ^{L e} and ^{L f} is 13 or less.
L ^g represents a saturated hydrocarbon group having 1 to 15 carbon atoms.
L ^h and ^{L i} independently represent a saturated hydrocarbon group having 1 to 15 carbon atoms. However, the upper limit of the carbon number of L ^h + L ⁱ is 16 or less.
L ^j represents a saturated hydrocarbon group having 1 to 14 carbon atoms.

Here, L ^b2 represents a single bond or a saturated hydrocarbon group having 1 to 15 carbon atoms.
L ^b3 represents a single bond or a saturated hydrocarbon group having 1 to 12 carbon atoms, and L ^b4 represents an alkanediyl group having 1 to 13 carbon atoms.
L ^b5 represents a saturated hydrocarbon group having 1 to 15 carbon atoms.
L ^b6 and L ^b7 each independently represent a saturated hydrocarbon group having 1 to 15 carbon atoms.
L ^b8 represents a saturated hydrocarbon group having 1 to 14 carbon atoms.
L ^b9 and L ^b10 each independently represent a saturated hydrocarbon group having 1 to 11 carbon atoms.
The saturated hydrocarbon group here is preferably a linear or branched alkylene group, but may be a mixture of linear, branched or cyclic saturated hydrocarbon groups.
Among these, a divalent group represented by the formula (b1-1) is preferable, and a divalent group represented by the formula (b1-1) in which L ^b2 is a single bond or —CH ₂ — is more preferable.

Examples of the divalent group represented by the formula (b1-1) include the following.

Examples of the divalent group represented by the formula (b1-2) include the following.

Examples of the divalent group represented by the formula (b1-3) include the following.

Examples of the divalent group represented by the formula (b1-4) include the following.

Examples of the divalent group represented by the formula (b1-5) include the following.

Examples of the divalent group represented by the formula (b1-6) include the following.

The sulfonate anion preferably has a divalent group represented by the formula (b1-1), more preferably one represented by the formula (b1-1-1) to the formula (b1-1-9). .

In formula (b1-1-1) to formula (b1-1-9), Q ¹ , Q ² and L ^b2 are the same as described above. R ^b2 and R ^b3 each independently represent an aliphatic hydrocarbon group having 1 to 4 carbon atoms (preferably a methyl group).

Next, specific sulfonate anions are exemplified. First, Y having a sulfonate anion or aliphatic hydrocarbon group containing unsubstituted Y and a divalent group represented by formula (b1-1) and a divalent represented by formula (b1-1) Examples of the sulfonate anion containing a group include the following.

Examples of the sulfonate anion containing Y having — (CH ₂ ) _j2 —O—CO—R ^b1 group and the divalent group represented by the formula (b1-1) include the following.

Examples of the sulfonate anion containing Y having a hydroxy group or a hydroxy group-containing aliphatic hydrocarbon group and the divalent group represented by the formula (b1-1) include the following.

Examples of the sulfonate anion containing Y having an aromatic hydrocarbon group or aralkyl group and the divalent group represented by the formula (b1-1) include the following.

Examples of the sulfonate anion containing Y which is a cyclic ether and the divalent group represented by the formula (b1-1) include the following.

Examples of the sulfonate anion containing Y which is a lactone ring and the divalent group represented by the formula (b1-1) include the following.

Examples of the sulfonate anion containing Y having an oxo group and the divalent group represented by the formula (b1-1) include the following.

Y having a sulfonate anion or an aliphatic hydrocarbon group containing unsubstituted Y and a divalent group represented by formula (b1-2), and a divalent group represented by formula (b1-2) Examples of the sulfonate anion containing include the following.

Examples of the sulfonate anion containing Y having a — (CH ₂ ) _j2 —O—CO—R ^b1 group and the divalent group represented by the formula (b1-2) include the following.

Examples of the sulfonate anion containing Y having a hydroxy group or a hydroxy group-containing aliphatic hydrocarbon group and the divalent group represented by the formula (b1-2) include the following.

Examples of the sulfonate anion containing Y which is a cyclic ether and the divalent group represented by the formula (b1-2) include the following.

Examples of the sulfonate anion containing Y which is a lactone ring and the divalent group represented by the formula (b1-2) include the following.

Examples of the sulfonate anion containing Y having an oxo group and the divalent group represented by the formula (b1-2) include the following.

Examples of the sulfonate anion containing Y having an aromatic hydrocarbon group and the divalent group represented by the formula (b1-2) include the following.

Y having a sulfonate anion or an aliphatic hydrocarbon group containing unsubstituted Y and a divalent group represented by the formula (b1-3), and a divalent group represented by the formula (b1-3) Examples of the sulfonate anion containing include the following.

Examples of the sulfonate anion containing Y having an alkoxy group and the divalent group represented by the formula (b1-3) include the following.

Examples of the sulfonate anion containing Y having a hydroxy group or a hydroxy group-containing aliphatic hydrocarbon group and the divalent group represented by the formula (b1-3) include the following.

Examples of the sulfonate anion containing Y having an oxo group and the divalent group represented by the formula (b1-3) include the following.

Examples of the sulfonate anion containing Y having an aliphatic hydrocarbon group and the divalent group represented by the formula (b1-4) include the following.

Examples of the sulfonate anion containing Y having an alkoxy group and the divalent group represented by the formula (b1-4) include the following.

Examples of the sulfonate anion containing Y having a hydroxy group or a hydroxy group-containing aliphatic hydrocarbon group and the divalent group represented by the formula (b1-4) include the following.

Examples of the sulfonate anion containing Y having an oxo group and the divalent group represented by the formula (b1-4) include the following.

Among the above-mentioned ones, the following sulfonate anions having a divalent group represented by the formula (b1-1) are preferable.

  Examples of the cation of the acid generator (B) include onium cations such as sulfonium cations, iodonium cations, ammonium cations, benzothiazolium cations, and phosphonium cations. Among these, a sulfonium cation and an iodonium cation are preferable, and an arylsulfonium cation is more preferable.

式（ｂ２−１）中、Ｒ^b4〜Ｒ^b6は、それぞれ独立に、炭素数１〜３０の脂肪族炭化水素基、炭素数３〜３６の飽和環状炭化水素基又は炭素数６〜１８の芳香族炭化水素基を表す。前記脂肪族炭化水素基は、ヒドロキシ基、炭素数１〜１２のアルコキシ基又は炭素数６〜１８の芳香族炭化水素基で置換されていてもよく、前記飽和環状炭化水素基は、ハロゲン原子、炭素数２〜４のアシル基又はグリシジルオキシ基で置換されていてもよく、前記芳香族炭化水素基は、ハロゲン原子、ヒドロキシ基、炭素数１〜３６の脂肪族炭化水素基、炭素数３〜３６の飽和環状炭化水素基又は炭素数１〜１２のアルコキシ基で置換されていてもよい。 Z ⁺ in formula (B1) is preferably represented by any of formula (b2-1) to formula (b2-4).

In formula (b2-1), R ^{b4 to} R ^b6 each independently represent an aliphatic hydrocarbon group having 1 to 30 carbon atoms, a saturated cyclic hydrocarbon group having 3 to 36 carbon atoms, or an aromatic having 6 to 18 carbon atoms. Represents a group hydrocarbon group. The aliphatic hydrocarbon group may be substituted with a hydroxy group, an alkoxy group having 1 to 12 carbon atoms or an aromatic hydrocarbon group having 6 to 18 carbon atoms, and the saturated cyclic hydrocarbon group includes a halogen atom, The aromatic hydrocarbon group which may be substituted with an acyl group having 2 to 4 carbon atoms or a glycidyloxy group is a halogen atom, a hydroxy group, an aliphatic hydrocarbon group having 1 to 36 carbon atoms, or 3 to 3 carbon atoms. It may be substituted with 36 saturated cyclic hydrocarbon groups or C1-C12 alkoxy groups.

In formula (b2-2), R ^b7 and R ^b8 each independently represent a hydroxy group, an aliphatic hydrocarbon group having 1 to 12 carbon atoms, or an alkoxy group having 1 to 12 carbon atoms,
m2 and n2 each independently represent an integer of 0 to 5.

In formula (b2-3), R ^b9 and R ^b10 each independently represent an aliphatic hydrocarbon group having 1 to 36 carbon atoms or a saturated cyclic hydrocarbon group having 3 to 36 carbon atoms.
R ^b11 represents a hydrogen atom, an aliphatic hydrocarbon group having 1 to 36 carbon atoms, a saturated cyclic hydrocarbon group having 3 to 36 carbon atoms, or an aromatic hydrocarbon group having 6 to 18 carbon atoms.
R ^b12 represents an aliphatic hydrocarbon group having 1 to 12 carbon atoms, a saturated cyclic hydrocarbon group having 3 to 18 carbon atoms, or an aromatic hydrocarbon group having 6 to 18 carbon atoms. The aromatic hydrocarbon group is substituted with an aliphatic hydrocarbon group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, a saturated cyclic hydrocarbon group having 3 to 18 carbon atoms, or an alkylcarbonyloxy group. Also good.
R ^b9 and R ^b10 and R ^b11 and R ^b12 may be independently bonded to each other to form a 3- to 12-membered ring (preferably a 3- to 7-membered ring). —CH ₂ — may be replaced by —O—, —S—, or —CO—.
The aliphatic hydrocarbon group of R ^{b9 to} R ^b11 preferably has 1 to 12 carbon atoms, and the saturated cyclic hydrocarbon group preferably has 3 to 36 carbon atoms, more preferably 4 to 12 carbon atoms.

In formula (b2-4), R ^{b13 to} R ^b18 each independently represent a hydroxy group, an aliphatic hydrocarbon group having 1 to 12 carbon atoms, or an alkoxy group having 1 to 12 carbon atoms.
L ^b11 represents -S- or -O-.
o2, p2, s2, and t2 each independently represents an integer of 0 to 5,
q2 and r2 each independently represents an integer of 0 to 4,
u2 represents 0 or 1. When any of o2 to t2 is 2, any of the plurality of R ^{b13 to} R ^b18 may be the same as or different from each other.

In formula (b2-1) to formula (b2-4),
Preferred aliphatic hydrocarbon groups are methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, pentyl, hexyl, octyl, and 2-ethylhexyl. It is a group.
Preferred saturated cyclic hydrocarbon groups are cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclodecyl group, 2-alkyl-2-adamantyl group, 1- (1-adamantyl) -1-alkyl group, And an isobornyl group. Preferred aromatic hydrocarbon groups are phenyl group, 4-methylphenyl group, 4-ethylphenyl group, 4-tert-butylphenyl group, 4-cyclohexylphenyl group, 4-methoxyphenyl group, biphenylyl group, naphthyl group. It is.
Examples of the aliphatic hydrocarbon group (aralkyl group) whose substituent is an aromatic hydrocarbon group include a benzyl group.
Examples of the ring formed by R ^b9 and R ^b10 include a thiolane-1-ium ring (tetrahydrothiophenium ring), a thian-1-ium ring, and a 1,4-oxathian-4-ium ring.
^Examples of the ring formed by R ^b11 and R ^b12 include an oxocycloheptane ring, an oxocyclohexane ring, an oxonorbornane ring, and an oxoadamantane ring.

  Among the cations (b2-1) to (b2-4), the cation (b2-1) is preferable, the cation represented by the formula (b2-1-1) is more preferable, and the triphenylsulfonium cation (formula (b2) In (1-1), v2 = w2 = x2 = 0) is more preferable.

In formula (b2-1-1), R ^{b19 to} R ^b21 each independently represent a halogen atom, a hydroxy group, an aliphatic hydrocarbon group having 1 to 36 carbon atoms, or a saturated cyclic hydrocarbon group having 3 to 36 carbon atoms. Or represents a C1-C12 alkoxy group.
The aliphatic hydrocarbon group may be substituted with a hydroxy group, an alkoxy group having 1 to 12 carbon atoms or an aromatic hydrocarbon group having 6 to 18 carbon atoms, and the saturated cyclic hydrocarbon group includes a halogen atom, It may be substituted with an acyl group having 2 to 4 carbon atoms or a glycidyloxy group.
v2 to x2 each independently represents an integer of 0 to 5 (preferably 0 or 1). When any one of v2 to x2 is 2 or more, any one of the plurality of R ^{b19 to} R ^b21 may be the same as or different from each other.

The aliphatic hydrocarbon group preferably has 1 to 12 carbon atoms.
The saturated cyclic hydrocarbon group preferably has 4 to 36 carbon atoms.
R ^{b19 to} R ^b21 in formula (b2-1-1) are preferably each independently a halogen atom (more preferably a fluorine atom), a hydroxy group, an alkyl group having 1 to 12 carbon atoms, or a carbon number of 1 Represents an alkoxy group of ˜12, and v2 to x2 each independently represent an integer of 0 to 5 (preferably 0 or 1).

Specific examples of the cation (b2-1-1) include the following.

Specific examples of the cation (b2-2) include the following.

Specific examples of the cation (b2-3) include the following.

Specific examples of the cation (b2-4) include the following.

  The acid generator (B1) is a combination of the above-described sulfonate anion and organic cation. The above-mentioned anion and cation can be arbitrarily combined, but any one of anion (b1-1-1) to anion (b1-1-9) and a cation (b2-1-1), and an anion ( A combination of any one of b1-1-3) to (b1-1-5) and a cation (b2-3) is preferable.

  Preferred acid generators (B1) are those represented by formulas (B1-1) to (B1-17), and among these, acid generators (B1-1) and (B1) containing a triphenylsulfonium cation. -2), (B1-6), (B1-11), (B1-12), (B1-13), (B1-14) and (B1-18) are more preferred.

  The content of the acid generator (B) is preferably 1 part by mass or more (more preferably 3 parts by mass or more), preferably 30 parts by mass or less (more preferably 25 parts by mass) with respect to 100 parts by mass of the resin (A). Part or less).

<Basic compound (hereinafter sometimes referred to as “basic compound (C)”)>
The resist composition of the present invention contains a basic compound (C). The content of the basic compound (C) is preferably about 0.01 to 1% by mass based on the solid content of the resist composition.

  The basic compound (C) is preferably a basic nitrogen-containing organic compound (for example, an amine). The amine may be an aliphatic amine or an aromatic amine. As the aliphatic amine, any of primary amine, secondary amine and tertiary amine can be used. The aromatic amine may be any of an amino group bonded to an aromatic ring such as aniline and a heteroaromatic amine such as pyridine. Preferable basic compound (C) includes an aromatic amine represented by the formula (C2), particularly an aniline represented by the formula (C2-1).

In the formula (C2), Ar ^c1 represents an aromatic hydrocarbon group. R ^c5 and R ^c6 each independently represents a hydrogen atom, an aliphatic hydrocarbon group (preferably an alkyl group or a cycloalkyl group), a saturated cyclic hydrocarbon group or an aromatic hydrocarbon group. The hydrogen atom of the aliphatic hydrocarbon group, the saturated cyclic hydrocarbon group or the aromatic hydrocarbon group may be substituted with a hydroxy group, an amino group, or an alkoxy group having 1 to 6 carbon atoms, and the amino The group may be substituted with an alkyl group having 1 to 4 carbon atoms.
The aliphatic hydrocarbon group preferably has about 1 to 6 carbon atoms, the saturated cyclic hydrocarbon group preferably has about 5 to 10 carbon atoms, and the aromatic hydrocarbon group preferably has about carbon atoms. It is about 6-10.

In formula (C2-1), R ^c5 and R ^c6 are the same as described above. R ^c7 represents an aliphatic hydrocarbon group (preferably an alkyl group or a cycloalkyl group), an alkoxy group, a saturated cyclic hydrocarbon group, or an aromatic hydrocarbon group. The hydrogen atom of the aliphatic hydrocarbon group, alkoxy group, saturated cyclic hydrocarbon group, and aromatic hydrocarbon group may have the substituent described in formula (C2). m3 represents an integer of 0 to 3. When m3 is 2 or more, the plurality of R ^c7 may be the same as or different from each other.
Aliphatic hydrocarbon group R ^c7, preferable number of carbon atoms of the saturated cyclic hydrocarbon group and the aromatic hydrocarbon group are the same as those of the formula (C2), an alkoxy group of R ^c7 is independently in, preferably 1 carbon atoms It is about 6.

  Examples of the aromatic amine (C2) include 1-naphthylamine and 2-naphthylamine. Examples of aniline (C2-1) include aniline, diisopropylaniline, 2-, 3- or 4-methylaniline, 4-nitroaniline, N-methylaniline, N, N-dimethylaniline, diphenylamine and the like. Of these, diisopropylaniline (particularly 2,6-diisopropylaniline) is preferable.

式（Ｃ３）中のＲ^c8は、式（Ｃ２）のＲ^c7で説明したいずれかの基を表す。
式（Ｃ３）〜式（Ｃ８）中の窒素原子と結合するＲ^c9、Ｒ^c10、Ｒ^c11〜Ｒ^c14、Ｒ^c16〜Ｒ^c19及びＲ^c22は、それぞれ独立に、式（Ｃ２）のＲ^c5及びＲ^c6で説明したいずれかの基を表す。
式（Ｃ７）〜式（Ｃ１１）中の芳香族炭素と結合するＲ^c20、Ｒ^c21、Ｒ^c23〜Ｒ^c28は、それぞれ独立に、式（Ｃ２−１）のＲ^c7で説明したいずれかの基を表す。
式（Ｃ７）、式（Ｃ９）〜式（Ｃ１１）中のｏ３〜ｕ３は、それぞれ独立に０〜３の整数を表す。ｏ３〜ｕ３のいずれかが２以上であるとき、それぞれ、複数のＲ^c20〜Ｒ^c28のいずれかは互いに同一でも異なってもよい。 Moreover, as a basic compound (C), the compound represented by Formula (C3)-Formula (C11) is mentioned.

R ^c8 in formula (C3) represents any of the groups described for R ^c7 in formula (C2).
R ^c9 , R ^c10 , R ^{c11 to} R ^c14 , R ^{c16 to} R ^c19 and R ^c22 bonded to the nitrogen atom in formula (C3) to formula (C8) are each independently R ^{c5 in} formula (C2) and It represents one of the groups described for R ^c6 .
R ^c20 , R ^c21 and R ^{c23 to} R ^c28 bonded to the aromatic carbon in formula (C7) to formula (C11) are each independently any group described for R ^c7 in formula (C2-1) Represents.
O3 to u3 in Formula (C7) and Formula (C9) to Formula (C11) each independently represents an integer of 0 to 3. When any of o3 to u3 is 2 or more, any of the plurality of R ^{c20 to} R ^c28 may be the same as or different from each other.

R ^c15 in formula (C6) represents an aliphatic hydrocarbon group, a saturated cyclic hydrocarbon group, or an alkanoyl group, and n3 represents an integer of 0 to 8. When n3 is 2 or more, the plurality of R ^c15 may be the same as or different from each other.
The aliphatic hydrocarbon group for R ^c15 preferably has about 1 to 6 carbon atoms, the saturated cyclic hydrocarbon group for R ^c15 preferably has about 3 to 6 carbon atoms, and the alkanoyl group for R ^c15 is preferably Is about 2 to 6 carbon atoms.

L ^c1 and L ^{c2 in} formula (C7) and formula (C10) are each independently a divalent aliphatic hydrocarbon group (preferably an alkylene group), —CO—, —C (═NH) —, —C (= ^NRc3 )-, -S-, -SS-, or a combination thereof.
The divalent aliphatic hydrocarbon group preferably has about 1 to 6 carbon atoms. R ^c3 represents an alkyl group having 1 to 4 carbon atoms.

  Examples of the compound (C3) include hexylamine, heptylamine, octylamine, nonylamine, decylamine, dibutylamine, dipentylamine, dihexylamine, diheptylamine, dioctylamine, dinonylamine, didecylamine, triethylamine, trimethylamine, tripropylamine, Tributylamine, tripentylamine, trihexylamine, triheptylamine, trioctylamine, trinonylamine, tridecylamine, methyldibutylamine, methyldipentylamine, methyldihexylamine, methyldicyclohexylamine, methyldiheptylamine, methyldioctyl Amine, methyl dinonyl amine, methyl didecyl amine, ethyl dibutyl amine, ethyl dipentyl amine, ethyl di Silamine, ethyldiheptylamine, ethyldioctylamine, ethyldinonylamine, ethyldidecylamine, dicyclohexylmethylamine, tris [2- (2-methoxyethoxy) ethyl] amine, triisopropanolamine ethylenediamine, tetramethylenediamine, hexamethylene Examples include diamine, 4,4′-diamino-1,2-diphenylethane, 4,4′-diamino-3,3′-dimethyldiphenylmethane, 4,4′-diamino-3,3′-diethyldiphenylmethane, and the like.

Examples of the compound (C4) include piperazine.
Examples of the compound (C5) include morpholine.
Examples of the compound (C6) include piperidine and hindered amine compounds having a piperidine skeleton described in JP-A No. 11-52575.
Examples of the compound (C7) include 2,2′-methylenebisaniline.
Examples of the compound (C8) include imidazole and 4-methylimidazole.
Examples of the compound (C9) include pyridine and 4-methylpyridine.
Examples of the compound (C10) include 1,2-di (2-pyridyl) ethane, 1,2-di (4-pyridyl) ethane, 1,2-di (2-pyridyl) ethene, and 1,2-di. (4-pyridyl) ethene, 1,3-di (4-pyridyl) propane, 1,2-di (4-pyridyloxy) ethane, di (2-pyridyl) ketone, 4,4′-dipyridyl sulfide, 4, 4'-dipyridyl disulfide, 2,2'-dipyridylamine, 2,2'-dipicolylamine and the like can be mentioned.
Examples of the compound (C11) include bipyridine.

<Solvent (sometimes referred to as "solvent (E)")
The resist composition of the present invention may contain the solvent (E) in an amount of 90% by mass or more in the composition. The resist composition of the present invention containing the solvent (E) is suitable for producing a thin film resist. The content of the solvent (E) is 90% by mass or more (preferably 92% by mass or more, more preferably 94% by mass or more) and 99.9% by mass or less (preferably 99% by mass or less) in the composition. The content of the solvent (E) can be measured by a known analysis means such as liquid chromatography or gas chromatography.

  Examples of the solvent (E) include glycol ether esters such as ethyl cellosolve acetate, methyl cellosolve acetate and propylene glycol monomethyl ether acetate; glycol ethers such as propylene glycol monomethyl ether; ethyl lactate, butyl acetate, amyl acetate and And esters such as ethyl pyruvate; ketones such as acetone, methyl isobutyl ketone, 2-heptanone and cyclohexanone; cyclic esters such as γ-butyrolactone; A solvent (E) may be used individually by 1 type, and may use 2 or more types together.

<Other components (hereinafter sometimes referred to as “other components (F)”)>
The resist composition of this invention may contain the other component (F) as needed. Component (F) is not particularly limited, and additives known in the resist field, such as sensitizers, dissolution inhibitors, surfactants, stabilizers, dyes, and the like can be used.

<Method for producing resist pattern>
The method for producing a resist pattern of the present invention comprises:
(1) The process of apply | coating the resist composition of this invention mentioned above on a board | substrate,
(2) a step of removing the solvent from the composition after coating to form a composition layer;
(3) a step of exposing the composition layer using an exposure machine;
(4) A step of heating the composition layer after exposure,
(5) The process which develops the composition layer after a heating using a image development apparatus is included.

Application of the resist composition onto the substrate can be performed by a commonly used apparatus such as a spin coater.
The removal of the solvent is performed, for example, by evaporating the solvent using a heating device such as a hot plate or by using a decompression device to form a composition layer from which the solvent has been removed. As for the temperature in this case, about 50-200 degreeC is illustrated, for example. The pressure is exemplified by about 1 to 1.0 × 10 ⁵ Pa.

The obtained composition layer is exposed using an exposure machine. At this time, exposure is usually performed through a mask corresponding to a required pattern. The exposure light source emits ultraviolet laser light such as KrF excimer laser (wavelength 248 nm), ArF excimer laser (wavelength 193 nm), F ₂ laser (wavelength 157 nm), solid-state laser light source (YAG or semiconductor laser, etc.) Various types of laser beam can be used, such as those that convert the wavelength of the laser beam from) to radiate a harmonic laser beam in the far ultraviolet region or the vacuum ultraviolet region.

The composition layer after the exposure is subjected to heat treatment for promoting the deprotection group reaction. As heating temperature, it is about 50-200 degreeC normally, Preferably it is about 70-150 degreeC.
The heated composition layer is usually developed using an alkali developer using a developing device.
The alkaline developer used here may be various alkaline aqueous solutions used in this field. Examples thereof include an aqueous solution of tetramethylammonium hydroxide and (2-hydroxyethyl) trimethylammonium hydroxide (commonly called choline).
After development, it is preferable to rinse with ultrapure water to remove water remaining on the substrate and the pattern.

<Application>
The resin of the present invention and the composition using the same are useful for resist compositions, in particular, chemically amplified photoresist compositions, microfabrication of semiconductors, production of circuit boards such as liquid crystals and thermal heads, and other It can be suitably used for a wide range of applications such as a photofabrication process. In particular, it can be used as a chemically amplified photoresist composition suitable for excimer laser lithography such as ArF and KrF, ArF immersion exposure lithography, and EUV exposure lithography. In addition to immersion exposure, it can also be used for dry exposure. Furthermore, it can be used for double imaging and is industrially useful.

EXAMPLES Hereinafter, although an Example demonstrates this invention in detail, this invention is not limited to these.
In Examples and Comparative Examples, “%” and “part” representing content and use amount are based on mass unless otherwise specified.
The weight average molecular weight is a value determined by gel permeation chromatography using polystyrene as a standard product.
Column: 3 TSKgel Multipore HXL-M + guard column (manufactured by Tosoh Corporation)
Eluent: Tetrahydrofuran Flow rate: 1.0 mL / min
Detector: RI detector Column temperature: 40 ° C
Injection volume: 100 μl
Molecular weight standard: Standard polystyrene (manufactured by Tosoh Corporation)

  The structure of the compound was confirmed by NMR (GX-270 type or EX-270 type manufactured by JEOL Ltd.) and mass spectrometry (LC: Agilent 1100 type, MASS: Agilent LC / MSD type or LC / MSD TOF type).

Example 1: Synthesis of Resin A1 Monomer E, monomer F, monomer B, monomer G, monomer C, and monomer D were charged in a molar ratio of 28: 14: 6: 5: 16: 31, and 1.5 wt. Double dioxane was added to make a solution. 1 mol% and 3 mol% of azobisisobutyronitrile and azobis (2,4-dimethylvaleronitrile) were added as initiators to the total monomer amount, respectively, and heated at 73 ° C. for about 5 hours. Thereafter, the reaction solution was purified by pouring it into a mixed solvent of a large amount of methanol and water three times to obtain a copolymer having a weight average molecular weight of 7.6 × 10 ^{3 in} a yield of 81%. . This copolymer has a structural unit derived from a monomer of the following formula, and this is designated as resin A1.

Example 2: Synthesis of Resin A2 Monomer E, monomer F, monomer B, monomer G, and monomer D were charged in a molar ratio of 28: 14: 10: 10: 38, and 1.5 weight times dioxane of the total monomer amount was added. Solution. 1 mol% and 3 mol% of azobisisobutyronitrile and azobis (2,4-dimethylvaleronitrile) as initiators were added to the total monomer amount, respectively, and heated at 75 ° C. for about 5 hours. Thereafter, the reaction solution was purified by pouring it into a mixed solvent of a large amount of methanol and water three times to obtain a copolymer having a weight average molecular weight of 7.2 × 10 ^{3 in} a yield of 76%. . This copolymer has a structural unit derived from a monomer of the following formula, and this is designated as resin A2.

Example 3: Synthesis of Resin A3 Monomer A, Monomer F, Monomer B, Monomer G, and Monomer D were charged at a molar ratio of 25: 18: 3: 9: 45, and 1.5 times the total amount of dioxane was added. Solution. 1 mol% and 3 mol% of azobisisobutyronitrile and azobis (2,4-dimethylvaleronitrile) as initiators were added to the total monomer amount, respectively, and heated at 75 ° C. for about 5 hours. Thereafter, the reaction solution was purified by pouring it into a mixed solvent of a large amount of methanol and water three times to obtain a copolymer having a weight average molecular weight of 7.6 × 10 ^{3 in} a yield of 70%. . This copolymer has a structural unit derived from a monomer of the following formula, and this is designated as resin A3.

Example 4: Synthesis of Resin A4 Monomer A, Monomer I, Monomer B, Monomer G, and Monomer D were charged at a molar ratio of 25: 14: 10: 8: 43, and 1.5 weight times dioxane of the total monomer amount was added. Solution. 1 mol% and 3 mol% of azobisisobutyronitrile and azobis (2,4-dimethylvaleronitrile) as initiators were added to the total monomer amount, respectively, and heated at 70 ° C. for about 5 hours. Thereafter, the reaction solution was purified by pouring it into a mixed solvent of a large amount of methanol and water three times to obtain a copolymer having a weight average molecular weight of 8.6 × 10 ³ at a yield of 85%. . This copolymer has a structural unit derived from a monomer of the following formula, and this is designated as resin A4.

Example 5: Synthesis of Resin A5 Monomer A, Monomer F, Monomer B, Monomer J, and Monomer D were charged at a molar ratio of 25: 18: 3: 9: 45, and 1.5 weight times dioxane of the total monomer amount was added. Solution. 1 mol% and 3 mol% of azobisisobutyronitrile and azobis (2,4-dimethylvaleronitrile) as initiators were added to the total monomer amount, respectively, and heated at 75 ° C. for about 5 hours. Thereafter, the reaction solution was purified by pouring it into a mixed solvent of a large amount of methanol and water three times to obtain a copolymer having a weight average molecular weight of 8.0 × 10 ^{3 in} a yield of 76%. . This copolymer has a structural unit derived from a monomer of the following formula, and this is designated as resin A5.

Example 6: Synthesis of Resin A6 Monomer A, Monomer I, Monomer B, Monomer J, and Monomer D were charged at a molar ratio of 25: 14: 10: 8: 43, and 1.5 weight times dioxane of the total monomer amount was added. Solution. 1 mol% and 3 mol% of azobisisobutyronitrile and azobis (2,4-dimethylvaleronitrile) as initiators were added to the total monomer amount, respectively, and heated at 70 ° C. for about 5 hours. Thereafter, the reaction solution was purified by pouring it into a mixed solvent of a large amount of methanol and water three times to obtain a copolymer having a weight average molecular weight of 8.7 × 10 ^{3 in} a yield of 84%. . This copolymer has a structural unit derived from a monomer of the following formula, and this is designated as resin A6.

[Synthesis of Resin X1]
Monomer E, monomer F, monomer B, monomer C, and monomer D were charged at a molar ratio of 28: 14: 6: 21: 31, and 1.5 weight times dioxane of the total monomer amount was added to obtain a solution. 1 mol% and 3 mol% of azobisisobutyronitrile and azobis (2,4-dimethylvaleronitrile) as initiators were added to the total monomer amount, respectively, and heated at 75 ° C. for about 5 hours. Thereafter, the reaction solution was purified by pouring it into a mixed solvent of a large amount of methanol and water three times to obtain a copolymer having a weight average molecular weight of 8.5 × 10 ^{3 in} a yield of 74%. . This copolymer has a structural unit derived from a monomer of the following formula, and this is designated as resin X1.

〔樹脂Ｘ３の合成〕
モノマーＬ、モノマーＨ、モノマーＡを、４０：２０：４０で仕込み、全モノマー量の１．５重量倍のジオキサンを加えて溶液とした。そこに開始剤としてアゾビスイソブチロニトリルとアゾビス（２，４−ジメチルバレロニトリル）を全モノマー量に対してそれぞれ１ｍｏｌ％、３ｍｏｌ％添加し、７０℃で約５時間加熱した。その後、反応液を、大量のメタノールと水の混合溶媒に注いで沈殿させる操作を３回行って精製し、重量平均分子量が８．８×１０^３の共重合体を収率８２％で得た。この共重合体は、次式のモノマーに由来する構造単位を有するものであり、これを樹脂Ｘ３とする。

[Synthesis of Resin X2]
Monomer K, monomer L, monomer H, and monomer A were charged at 0.3: 39: 20.7: 40, and 1.5 weight times dioxane of the total monomer amount was added to obtain a solution. As initiators, azobisisobutyronitrile and azobis (2,4-dimethylvaleronitrile) were added in an amount of 0.9 mol% and 2.7 mol% based on the total amount of monomers, respectively, and heated at 70 ° C. for about 5 hours. . Thereafter, the reaction solution was purified by pouring it into a large amount of methanol / water mixed solvent and precipitating three times to obtain a copolymer having a weight average molecular weight of 1.0 × 10 ^{4 in} a yield of 68%. . This copolymer has a structural unit derived from a monomer of the following formula, and this is designated as resin X2.

[Synthesis of Resin X3]
Monomer L, monomer H, and monomer A were charged at 40:20:40, and 1.5 wt. 1 mol% and 3 mol% of azobisisobutyronitrile and azobis (2,4-dimethylvaleronitrile) as initiators were added to the total monomer amount, respectively, and heated at 70 ° C. for about 5 hours. Thereafter, the reaction solution was purified by pouring it into a mixed solvent of a large amount of methanol and water three times to obtain a copolymer having a weight average molecular weight of 8.8 × 10 ^{3 in} a yield of 82%. . This copolymer has a structural unit derived from a monomer of the following formula, and this is designated as resin X3.

Examples and Comparative Examples The following components were mixed and dissolved, and further filtered through a fluororesin filter having a pore size of 0.2 μm to prepare a resist solution.

Ｂ２：

Ｂ３：

Ｂ４：トリフェニルスルホニウム ノナフレート
＜塩基性化合物：クエンチャー＞
Ｃ１：２，６−ジイソプロピルアニリン
＜溶剤＞
プロピレングリコールモノメチルエーテルアセテート ２６５部
２−ヘプタノン ２０．０部
プロピレングリコールモノメチルエーテル ２０．０部
γ−ブチロラクトン ３．５部 <Acid generator>
B1:

B2:

B3:

B4: Triphenylsulfonium nonaflate <Basic compound: Quencher>
C1: 2,6-Diisopropylaniline <Solvent>
Propylene glycol monomethyl ether acetate 265 parts 2-heptanone 20.0 parts Propylene glycol monomethyl ether 20.0 parts γ-butyrolactone 3.5 parts

An organic antireflective coating composition [ARC-29; manufactured by Nissan Chemical Industries, Ltd.] was applied onto a 12-inch silicon wafer and baked at 205 ° C. for 60 seconds to obtain a thickness of 78 nm. An organic antireflection film was formed.
Next, the resist composition was spin-coated on the organic antireflection film so that the film thickness after drying was 85 nm.
The obtained silicon wafer was pre-baked (PB) for 60 seconds on a direct hot plate at the temperature described in the “PB” column of Table 1. The wafer having the resist composition film thus formed was exposed to light using an ArF excimer stepper for immersion exposure [XT: 1900 Gi; manufactured by ASML, NA = 1.35, 3/4 Annular XY deflection]. The line-and-space pattern was subjected to immersion exposure by changing stepwise.
After the exposure, post-exposure baking (PEB) was performed on the hot plate at the temperature described in the “PEB” column of Table 1 for 60 seconds.
Further, paddle development was performed for 60 seconds with an aqueous 2.38 mass% tetramethylammonium hydroxide solution.

In each resist film, the exposure amount at which the 50 nm line and space pattern becomes an exposure amount of 1: 1 was defined as the effective sensitivity.
Shape evaluation: A 50 nm line and space pattern was observed with a scanning electron microscope.
A case where the top shape and the skirt shape were close to a rectangle was good, and a case where the top shape was round or close to a T-shape or a skirt was seen was judged as x.
Focus margin evaluation (DOF): When the focus is moved in the effective sensitivity, the range (47.5-52.5 nm) where the line width is 50 nm ± 5% is used as the line width index, and the DOF is 0.15 μm or more. Was less than 0.15 μm, and x was less than 0.15 μm.
These results are shown in Table 2.

  According to the resin of the present invention, a pattern having an excellent shape and a focus margin can be formed using a resist composition containing the resin.

Claims (10)

A resin having a structural unit derived from the compound represented by formula (I).

[In the formula (I),
R ¹ represents a hydrogen atom, a halogen atom or an alkyl group having 1 to 6 carbon atoms which may have a halogen atom.
X ¹ represents a heterocyclic ring having 2 to 36 carbon atoms, and the hydrogen atom contained in the heterocyclic ring is a halogen atom, a hydroxyl group, a hydrocarbon group having 1 to 24 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, carbon The acyl group having 2 to 4 carbon atoms or the acyloxy group having 2 to 4 carbon atoms may be substituted, and —CH ₂ — contained in the heterocyclic ring may be replaced with —CO— or —O—. ] The resin according to claim 1, wherein the compound represented by the formula (I) is a compound represented by the formula (III).

[In the formula (III),
R ² represents a hydrogen atom, a halogen atom or an alkyl group having 1 to 6 carbon atoms which may have a halogen atom.
R ^{3 to} R ⁸ each independently represents a hydrogen atom or a hydrocarbon group having 1 to 24 carbon atoms, or at least two selected from R ^{3 to} R ⁸ are bonded to each other to form 3 to 30 carbon atoms. Forming a ring, the hydrocarbon group and the hydrogen atom contained in the ring are a halogen atom, a hydroxyl group, an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, and an acyl group having 2 to 4 carbon atoms. Alternatively, it may be substituted with an acyloxy group having 2 to 4 carbon atoms, and —CH ₂ — contained in the hydrocarbon group and the ring may be replaced with —CO— or —O—.
t1 represents an integer of 0 to 3. ] The resin according to claim 1 or 2, wherein the compound represented by the formula (I) is a compound represented by the formula (IV).

[In the formula (IV),
R ⁹ represents a hydrogen atom, a halogen atom or an alkyl group having 1 to 6 carbon atoms which may have a halogen atom.
R ^{10 to} R ¹⁹ each independently represent a hydrogen atom or a hydrocarbon group having 1 to 12 carbon atoms, or at least two selected from R ^{10 to} R ¹⁹ are bonded to each other to form 3 to 24 carbon atoms. Forming a ring, the hydrocarbon group and the hydrogen atom contained in the ring are a halogen atom, a hydroxyl group, an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, and an acyl group having 2 to 4 carbon atoms. Alternatively, it may be substituted with an acyloxy group having 2 to 4 carbon atoms, and —CH ₂ — contained in the hydrocarbon group and the ring may be replaced with —CO— or —O—.
t2 and t3 each independently represents an integer of 0 to 3. ] The resin according to any one of claims 1 to 3, wherein the compound represented by the formula (I) is a compound represented by the formula (VI).

[In the formula (VI)
R ²² represents a hydrogen atom, a halogen atom or an alkyl group having 1 to 6 carbon atoms which may have a halogen atom.
R ^{23 to} R ³⁸ each independently represent a hydrogen atom or a hydrocarbon group having 1 to 12 carbon atoms, or at least two selected from R ^{23 to} R ³⁸ are bonded to each other to form 3 to 18 carbon atoms. Forming a ring, the hydrocarbon group and the hydrogen atom contained in the ring are a halogen atom, a hydroxyl group, an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, and an acyl group having 2 to 4 carbon atoms. Alternatively, it may be substituted with an acyloxy group having 2 to 4 carbon atoms, and —CH ₂ — contained in the hydrocarbon group and the ring may be replaced with —CO— or —O—.
t5, t6 and t7 each independently represents an integer of 0 to 3. ] The resin according to claim 1, wherein the compound represented by the formula (I) is a compound represented by the formula (V).

[In the formula (V),
R ²⁰ represents a hydrogen atom, a halogen atom or an alkyl group having 1 to 6 carbon atoms which may have a halogen atom.
R ²¹ represents a halogen atom, a hydroxyl group, an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, an acyl group having 2 to 4 carbon atoms, or an acyloxy group having 2 to 4 carbon atoms.
t4 represents an integer of 0 to 8. ] The resin according to claim 1, wherein the compound represented by the formula (I) is a compound represented by the formula (VII).

[In the formula (VII),
R ³⁹ represents a hydrogen atom, a halogen atom or an alkyl group having 1 to 6 carbon atoms which may have a halogen atom.
R ⁴⁰ represents a halogen atom, a hydroxyl group, an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, an acyl group having 2 to 4 carbon atoms, or an acyloxy group having 2 to 4 carbon atoms.
t8 represents an integer of 0 to 14. ]   The resin according to any one of claims 1 to 6, which has an acid-labile group and is insoluble or hardly soluble in an aqueous alkali solution, and the resin which has reacted with an acid can be dissolved in an aqueous alkali solution.   A resist composition containing the resin according to claim 1 and an acid generator.   The resist composition according to claim 8 containing a basic compound. (1) The process of apply | coating the resist composition of Claim 8 or 9 on a board | substrate,
(2) a step of removing the solvent from the composition after coating to form a composition layer;
(3) a step of exposing the composition layer using an exposure machine;
(4) A step of heating the composition layer after exposure,
(5) A pattern forming method including a step of developing the heated composition layer using a developing device.