JP5070802B2 - Salt for acid generator of chemically amplified resist composition - Google Patents

Description

  The present invention relates to a salt used as an acid generator contained in a chemically amplified resist composition used in a chemically amplified resist composition used for semiconductor microfabrication.

A chemically amplified resist composition used for fine processing of a semiconductor using a lithography technique contains an acid generator composed of a compound that generates an acid upon exposure.
In microfabrication of semiconductors, it is desirable to form a pattern with a good pattern shape at a high resolution. As a chemically amplified resist composition, a pattern having a good pattern shape can be formed, and a high resolution is exhibited. Things are sought.

  Recently, a chemically amplified resist composition comprising triphenylsulfonium 1-adamantanemethoxycarbonyldifluoromethanesulfonate (salt) and p-tolyldiphenylsulfonium perfluorooctanesulfonate (salt) as an acid generator has been proposed. However, there has been a demand for a salt that can form a pattern having an even better pattern shape and serves as an acid generator that provides a chemically amplified resist composition exhibiting high resolution (see, for example, Patent Document 1).

Japanese Patent Laid-Open No. 2004-4561

  An object of the present invention is to provide a salt as an acid generator that can form a pattern having a good pattern shape and provides a chemically amplified resist composition exhibiting high resolution.

  Therefore, as a result of intensive studies on the salt used as the acid generator contained in the chemically amplified resist composition in order to solve the above problems, the present inventors have found that a specific salt having a cyclic residue is present. The inventors have found that a pattern having a good pattern shape can be formed and can be an acid generator that provides a chemically amplified resist composition exhibiting high resolution, and the present invention has been completed.

（式（Ｉ）中、Ｑ¹、Ｑ²は互いに独立にフッ素原子又は炭素数１〜６のペルフルオロアルキル基を表し、環Ｘは単環式または２環式の炭素数３〜３０の炭化水素基を表す。ｎは１〜１２の整数を表し、Ａ⁺は有機対イオンを表す。式中の環Ｘは炭素数１〜６のアルキル基、炭素数２〜６のアルケニル基、炭素数２〜６のアルコキシ基又は炭素数１〜４のペルフルオロアルキル基の一つ以上を置換基として含んでいてもよい。） That is, the present invention provides a salt represented by the formula (I).

(In formula (I), Q < ¹ >, Q < ² > represents a fluorine atom or a C1-C6 perfluoroalkyl group mutually independently, and the ring X is a monocyclic or bicyclic C3-C30 hydrocarbon. N represents an integer of 1 to 12 and A ⁺ represents an organic counter ion, wherein ring X is an alkyl group having 1 to 6 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, and 2 carbon atoms. One or more of a -6 alkoxy group or a C1-C4 perfluoroalkyl group may be included as a substituent.)

  Moreover, this invention provides the acid generator which uses the salt shown by Formula (I) as an active ingredient.

（式（ＶＩ）中、Ｑ¹、Ｑ²は互いに独立にフッ素原子又は炭素数１〜６のペルフルオロアルキル基を表し、環Ｘは単環式または２環式の炭素数３〜３０の炭化水素基を表す。ｎは１〜１２の整数を表し、式中の環Ｘは炭素数１〜６のアルキル基、炭素数２〜６のアルケニル基、炭素数２〜６のアルコキシ基又は炭素数１〜４のペルフルオロアルキル基の一つ以上を置換基として含んでいてもよい。Ｍは、Ｌｉ、Ｎａ、Ｋ又はＡｇを表す。） The present invention also provides an ester form represented by the formula (VI), which is a synthetic intermediate of the salt represented by the formula (I).

(In Formula (VI), Q < ¹ >, Q < ² > represents a fluorine atom or a C1-C6 perfluoroalkyl group mutually independently, and the ring X is a monocyclic or bicyclic C3-C30 hydrocarbon. N represents an integer of 1 to 12, and ring X in the formula is an alkyl group having 1 to 6 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, an alkoxy group having 2 to 6 carbon atoms, or 1 carbon atom. One or more of ˜4 perfluoroalkyl groups may be contained as a substituent, and M represents Li, Na, K or Ag.)

（式（ＶII）中、環Ｘは単環式または２環式の炭素数３〜３０の炭化水素基を表す。ｎは１〜１２の整数を表し、式中の環Ｘは炭素数１〜６のアルキル基、炭素数２〜６のアルケニル基、炭素数２〜６のアルコキシ基又は炭素数１〜４のペルフルオロアルキル基の一つ以上を置換基として含んでいてもよい。）
式（ＶIII）で示されるカルボン酸とをエステル化反応させることを特徴とするエステル体（ＶＩ）の製造方法を提供する。

（式（ＶIII）中、Ｑ¹、Ｑ²は互いに独立にフッ素原子又は炭素数１〜６のペルフルオロアルキル基を表し、Ｍは、前記と同じ意味を表す。） The present invention also provides an alcohol represented by the formula (VII):

(In formula (VII), ring X represents a monocyclic or bicyclic hydrocarbon group having 3 to 30 carbon atoms. N represents an integer of 1 to 12, and ring X in the formula represents 1 to 1 carbon atoms. 6 or more alkyl groups having 2 to 6 carbon atoms, alkoxy groups having 2 to 6 carbon atoms, or perfluoroalkyl groups having 1 to 4 carbon atoms may be included as a substituent.
Provided is a method for producing an ester (VI), which comprises an esterification reaction with a carboxylic acid represented by the formula (VIII).

(In formula (VIII), Q ¹ and Q ² each independently represent a fluorine atom or a C 1-6 perfluoroalkyl group, and M represents the same meaning as described above.)

（式中、Ａ⁺は、有機対イオンを表し、ＺはＦ、Ｃｌ、Ｂｒ、Ｉ、ＢＦ₄、ＡｓＦ₆、ＳｂＦ₆、ＰＦ₆、又はＣｌＯ₄を表す。） Moreover, this invention provides the manufacturing method of the salt shown by the formula (I) characterized by making the ester body shown by a formula (VI), and the compound shown by a formula (IX) react.

(In the formula, A ⁺ represents an organic counter ion, and Z represents F, Cl, Br, I, BF ₄ , AsF ₆ , SbF ₆ , PF ₆ , or ClO _4. )

  The present invention also provides a resin composition comprising an acid generator containing a salt represented by formula (I) as an active ingredient and a resin, the resin having an acid-labile group, and an alkaline aqueous solution. Provided is a resin composition characterized in that it is an insoluble or hardly soluble resin, and the resin that has reacted with an acid is a resin that can be dissolved in an alkaline aqueous solution.

  Furthermore, the present invention provides a chemically amplified resist composition comprising the resin composition and a basic organic compound.

  By using the salt of the present invention as an acid generator, a pattern having a good pattern shape can be produced, and a chemically amplified resist composition showing high resolution can be produced. Very useful.

（式（Ｉ）中、Ｑ¹、Ｑ²は互いに独立にフッ素原子又は炭素数１〜６のペルフルオロアルキル基を表し、環Ｘは単環式または２環式の炭素数３〜３０の炭化水素基を表す。ｎは１〜１２の整数を表し、Ａ⁺は有機対イオンを表す。式中の環Ｘは炭素数１〜６のアルキル基、炭素数２〜６のアルケニル基、炭素数２〜６のアルコキシ基又は炭素数１〜４のペルフルオロアルキル基の一つ以上を置換基として含んでいてもよい。）
ここで、環Ｘの炭素数は３〜１２の範囲が好ましく、ｎは１〜４の範囲が好ましい。 The salt of the present invention is represented by the formula (I).

(In formula (I), Q < ¹ >, Q < ² > represents a fluorine atom or a C1-C6 perfluoroalkyl group mutually independently, and the ring X is a monocyclic or bicyclic C3-C30 hydrocarbon. N represents an integer of 1 to 12 and A ⁺ represents an organic counter ion, wherein ring X is an alkyl group having 1 to 6 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, and 2 carbon atoms. One or more of a -6 alkoxy group or a C1-C4 perfluoroalkyl group may be included as a substituent.)
Here, the carbon number of the ring X is preferably in the range of 3 to 12, and n is preferably in the range of 1 to 4.

（式（IIIａ）〜（IIIｆ）中、ｆは１〜１０の整数を表し、Ｘ¹はアルキレン基、酸素原子、硫黄原子を表す。式中の環は炭素数１〜６のアルキル基、炭素数２〜６のアルコキシ又は炭素数１〜４のペルフルオロアルキル基の一つ以上を置換基として含んでいてもよい。）
式（IIIａ）、（IIIｃ）のｆとしては１〜６の整数が好ましい。 Such a ring X is preferably a monovalent residue of a compound represented by the formula (IIIa), (IIIb), (IIIc), (IIId), (IIIe) or the formula (IIIf).

(In formulas (IIIa) to (IIIf), f represents an integer of 1 to 10, X ¹ represents an alkylene group, an oxygen atom, or a sulfur atom. The ring in the formula is an alkyl group having 1 to 6 carbon atoms, carbon (One or more of C2-C6 alkoxy or C1-C4 perfluoroalkyl groups may be included as a substituent.)
As f in the formulas (IIIa) and (IIIc), an integer of 1 to 6 is preferable.

Q ¹ and Q ² are preferably each independently a fluorine atom or —CF ₃ , and more preferably a fluorine atom.

Specific examples of the anion moiety of the salt represented by the formula (I) include the following anions.

In the salt represented by the formula (I), A ⁺ represents an organic counter ion, specifically, any one of the following formula (IIf), formula (IIb), formula (IIc) or formula (IId) And at least one cation selected from the group consisting of cations represented by the formula:

（式（IIｆ）中、Ｐ²⁵〜Ｐ²⁷は、互いに独立に、直鎖状又は分岐状の炭素数１〜３０のアルキル基又は炭素数３〜３０の環式炭化水素基を表す。Ｐ²⁵〜Ｐ²⁷がアルキル基である場合には、水酸基、炭素数１〜１２のアルコキシ基又は炭素数３〜１２の環式炭化水素基の一つ以上を置換基として含んでいてもよく、Ｐ²⁵〜Ｐ²⁷が環式炭化水素基である場合には、水酸基、炭素数１〜１２のアルキル基又は炭素数１〜１２のアルコキシ基の一つ以上を置換基として含んでいてもよい。該アルキル基及び該アルコキシ基は、直鎖でも分岐していてもよい。）
該アルキル基の具体例としては、メチル基、エチル基、ｎ−プロピル基、イソプロピル基、ｎ−ブチル基、sec−ブチル基、tert−ブチル基、ペンチル基、ヘキシル基、オクチル基、２−エチルヘキシル基などが挙げられ、アルコキシ基の例としては、メトキシ基、エトキシ基、プロポキシ基、ブトキシ基、ヘキシルオキシ基、オクチルオキシ基、２−エチルヘキシルオキシ基などが挙げられる。
該環式炭化水素基の具体例としては、シクロペンチル基、シクロヘキシル基、アダマンチル基、ビシクロヘキシル基、フェニル基、ナフチル基、フルオレニル、ビフェニル基などが挙げられる。 Here, the formula (IIf) is the following formula.

(In Formula (IIf), P ^{25 to} P ²⁷ each independently represent a linear or branched alkyl group having 1 to 30 carbon atoms or a cyclic hydrocarbon group having 3 to 30 carbon atoms. P ²⁵ If to P ²⁷ is an alkyl group, a hydroxyl group may comprise as one or more substituents of the cyclic hydrocarbon group having 3 to 12 alkoxy group or a carbon number of 1 to 12 carbon atoms, P ²⁵ If to P ²⁷ is a cyclic hydrocarbon group, a hydroxyl group, it may be included as one or more of the substituents for the alkyl group or alkoxy group having 1 to 12 carbon atoms having 1 to 12 carbon atoms. the alkyl The group and the alkoxy group may be linear or branched.)
Specific examples of the alkyl group include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, tert-butyl group, pentyl group, hexyl group, octyl group, 2-ethylhexyl. Examples of the alkoxy group include methoxy group, ethoxy group, propoxy group, butoxy group, hexyloxy group, octyloxy group, 2-ethylhexyloxy group and the like.
Specific examples of the cyclic hydrocarbon group include a cyclopentyl group, a cyclohexyl group, an adamantyl group, a bicyclohexyl group, a phenyl group, a naphthyl group, a fluorenyl group, and a biphenyl group.

式（IIｂ）中、Ｐ⁴、Ｐ⁵は、互いに独立に、水素原子、水酸基、炭素数１〜１２のアルキル基又は炭素数１〜１２のアルコキシ基を表す。該アルキル基及び該アルコキシ基は、式（IIｆ）のアルキル基及びアルコキシ基と同じ意味を表す。 Formula (IIb) is the following formula.

In formula (IIb), P ⁴ and P ⁵ each independently represent a hydrogen atom, a hydroxyl group, an alkyl group having 1 to 12 carbon atoms, or an alkoxy group having 1 to 12 carbon atoms. The alkyl group and the alkoxy group have the same meaning as the alkyl group and alkoxy group of the formula (IIf).

式（IIｃ）中、Ｐ⁶、Ｐ⁷は、互いに独立に、炭素数１〜１２のアルキル基又は炭素数３〜１２のシクロアルキル基を表し、該アルキル基は、直鎖でも分岐していてもよい。該アルキル基の具体例としては、メチル基、エチル基、ｎ−プロピル基、イソプロピル基、ｎ−ブチル基、sec−ブチル基、tert−ブチル基、ペンチル基、ヘキシル基、オクチル基、２−エチルヘキシル基などが挙げられる。該シクロアルキル基としては、シクロプロピル基、シクロブチル基、シクロペンチル基、シクロヘキシル基、シクロヘプチル基、シクロデシル基などが挙げられる。また、Ｐ⁶とＰ⁷とが結合して、アルキレン基などの炭素数３〜１２の２価の炭化水素基であってもよい。Ｐ⁸は水素原子を表し、Ｐ⁹は炭素数１〜１２のアルキル基、炭素数３〜１２のシクロアルキル基、またはフェニル基、ベンジル基などの置換されていてもよい芳香環基を表すか、Ｐ⁸とＰ⁹とが結合して、アルキレン基などの炭素数３〜１２の２価の炭化水素基を表す。Ｐ⁹がアルキル基の場合、該アルキル基の具体例としては、メチル基、エチル基、ｎ−プロピル基、イソプロピル基、ｎ−ブチル基、sec−ブチル基、tert−ブチル基、ペンチル基、ヘキシル基、オクチル基、２−エチルヘキシル基などが挙げられる。Ｐ⁹がシクロアルキル基の場合、該シクロアルキル基としては、シクロプロピル基、シクロブチル基、シクロペンチル基、シクロヘキシル基、シクロヘプチル基、シクロデシル基などが挙げられる。ここで、式（IIｃ）における２価の炭化水素基に含まれる炭素原子は、いずれも、カルボニル基、酸素原子、硫黄原子に置換されていてもよい。 Formula (IIc) is the following formula.

In formula (IIc), P ⁶ and P ⁷ each independently represent an alkyl group having 1 to 12 carbon atoms or a cycloalkyl group having 3 to 12 carbon atoms, and the alkyl group is branched even in a straight chain. Also good. Specific examples of the alkyl group include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, tert-butyl group, pentyl group, hexyl group, octyl group, 2-ethylhexyl. Group and the like. Examples of the cycloalkyl group include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, and a cyclodecyl group. Further, by bonding P ⁶ and P ^7, it may be a divalent hydrocarbon group having 3 to 12 carbon atoms such as an alkylene group. P ⁸ represents a hydrogen atom, and P ⁹ represents an optionally substituted aromatic ring group such as an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group having 3 to 12 carbon atoms, or a phenyl group or a benzyl group. , P ⁸ and P ⁹ are bonded to each other to represent a C 3-12 divalent hydrocarbon group such as an alkylene group. When P ⁹ is an alkyl group, specific examples of the alkyl group include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, a tert-butyl group, a pentyl group, and a hexyl group. Group, octyl group, 2-ethylhexyl group and the like. When P ⁹ is a cycloalkyl group, examples of the cycloalkyl group include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, and a cyclodecyl group. Here, any carbon atom contained in the divalent hydrocarbon group in formula (IIc) may be substituted with a carbonyl group, an oxygen atom, or a sulfur atom.

式（IIｄ）中、Ｐ¹⁰〜Ｐ²¹は、互いに独立に、水素原子、水酸基、炭素数１〜１２のアルキル基又は炭素数１〜１２のアルコキシ基を表す。該アルキル基及び該アルコキシ基は、式（IIｆ）のアルキル基及びアルコキシ基と同じ意味を表す。Ｂは、硫黄原子又は酸素原子を表す。ｍは、０又は１を表す。 Formula (IId) is a following formula.

In formula (IId), P ^{10 to} P ²¹ each independently represent a hydrogen atom, a hydroxyl group, an alkyl group having 1 to 12 carbon atoms, or an alkoxy group having 1 to 12 carbon atoms. The alkyl group and the alkoxy group have the same meaning as the alkyl group and alkoxy group of the formula (IIf). B represents a sulfur atom or an oxygen atom. m represents 0 or 1.

Specific examples of the cation A ^{+ represented by} the formula (IIf) include cations represented by the following formula.

Specific examples of the cation A ^{+ represented by} the formula (IIb) include the following cations.

Specific examples of the cation A ^{+ represented by} the formula (IIc) include cations represented by the following formula.

Specific examples of the cation A ^{+ represented by} the formula (IId) include cations represented by the following formula.

式（IIｇ）〜（IIｉ）中、Ｐ²⁸〜Ｐ³⁰は互いに独立に、直鎖状又は分岐状の炭素数１〜２０のアルキル基を表すか又はフェニル基以外の炭素数３〜３０の環式炭化水素基を表す。Ｐ²⁸〜Ｐ³⁰がアルキル基である場合には、水酸基、炭素数１〜１２のアルコキシ基又は炭素数３〜１２の環式炭化水素基の一つ以上を置換基として含んでいてもよく、Ｐ²⁸〜Ｐ³⁰が環式炭化水素基の場合には、水酸基、炭素数１〜１２のアルキル基又は炭素数１〜１２のアルコキシ基の一つ以上を置換基として含んでいてもよい。式中のＰ³¹〜Ｐ³⁶は、水酸基、炭素数１〜１２のアルキル基、炭素数１〜１２のアルコキシ基又は炭素数３〜１２の環式炭化水素基を表し、ｌ、ｋ、ｊ、ｉ、ｈおよびｇは、互いに独立に０〜５の整数を表す。 The cation represented by the formula (IIf) is a cation represented by any one of the formula (IIg), the formula (IIh) or the formula (IIi), and A ⁺ represents the formula (IIg), the formula (IIh), the formula (II) The case where it is at least one cation selected from the group consisting of cations represented by any of IIi), formula (IIb), formula (IIc) or formula (IId) is preferred.

In formulas (IIg) to (IIi), P ^{28 to} P ³⁰ each independently represent a linear or branched alkyl group having 1 to 20 carbon atoms, or a ring having 3 to 30 carbon atoms other than a phenyl group. Represents a hydrocarbon group. When P ^{28 to} P ³⁰ are alkyl groups, they may contain one or more of a hydroxyl group, an alkoxy group having 1 to 12 carbon atoms, or a cyclic hydrocarbon group having 3 to 12 carbon atoms as a substituent, If P ²⁸ to P ³⁰ is a cyclic hydrocarbon group, a hydroxyl group, it may be included as one or more of the substituents for the alkyl group or alkoxy group having 1 to 12 carbon atoms having 1 to 12 carbon atoms. P ^{31 to} P ³⁶ in the formula represent a hydroxyl group, an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms or a cyclic hydrocarbon group having 3 to 12 carbon atoms, and l, k, j, i, h and g each independently represent an integer of 0 to 5.

式（IIａ）中、Ｐ¹〜Ｐ³は互いに独立に、水素原子、水酸基、炭素数１〜１２のアルキル基又は炭素数１〜１２のアルコキシ基を表し、該アルキル基及び該アルコキシ基は、直鎖でも分岐していてもよい。 Further, the cation represented by the formula (IIf) is a cation represented by the formula (IIa), and A ⁺ is any one of the formula (IIa), the formula (IIb), the formula (IIc), or the formula (IId). The cation is preferably at least one cation selected from the group consisting of the cations shown, and among the cations shown by the formula (IIa), the cation shown by the formula (IIe) is more preferable because of easy production.

In formula (IIa), P ^{1 to} P ³ each independently represent a hydrogen atom, a hydroxyl group, an alkyl group having 1 to 12 carbon atoms, or an alkoxy group having 1 to 12 carbon atoms, and the alkyl group and the alkoxy group are It may be linear or branched.

  Specific examples of the alkyl group include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, tert-butyl group, pentyl group, hexyl group, octyl group, 2-ethylhexyl. Examples of the alkoxy group include methoxy group, ethoxy group, propoxy group, butoxy group, hexyloxy group, octyloxy group, 2-ethylhexyloxy group and the like.

式（IIｅ）中、Ｐ²²〜Ｐ²⁴は、互いに独立に、水素原子、炭素数１〜４のアルキル基を表し、該アルキル基は、直鎖でも分岐していてもよい。

In formula (IIe), P ^{22 to} P ²⁴ each independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and the alkyl group may be linear or branched.

（式中、Ｐ²²〜Ｐ²⁴は互いに独立に、水素原子、炭素数１〜４のアルキル基を表す。） Among the salts represented by the formula (I) of the present invention, among them, the salt represented by the formula (IV) or (V) is an acid generator that provides a chemically amplified resist composition having excellent resolution and pattern shape. Even more preferable.

(Wherein, the P ²² to P ²⁴ are independently of each other, represent a hydrogen atom, an alkyl group having 1 to 4 carbon atoms.)

（式中、Ｑ¹、Ｑ²は互いに独立にフッ素原子又は炭素数１〜６のペルフルオロアルキル基を表し、環Ｘは単環式または２環式の炭素数３〜３０の炭化水素基を表す。ｎは１〜１２の整数を表し、式中の環Ｘは炭素数１〜６のアルキル基、炭素数２〜６のアルケニル基、炭素数２〜６のアルコキシ基又は炭素数１〜４のペルフルオロアルキル基の一つ以上を置換基として含んでいてもよい。Ｍは、Ｌｉ、Ｎａ、Ｋ又はＡｇを表す。）
式（ＩＸ）で示されるオニウム塩とを、

（式中、Ａ⁺は、有機対イオンを表し、ＺはＦ、Ｃｌ、Ｂｒ、Ｉ、ＢＦ₄、ＡｓＦ₆、ＳｂＦ₆、ＰＦ₆、又はＣｌＯ₄を表す。）
例えば、アセトニトリル、水、メタノール、クロロホルム、塩化メチレン等の不活性溶媒中にて、０℃〜１５０℃程度の温度範囲、好ましくは０℃〜１００℃程度の温度範囲にて攪拌して反応させて、式（Ｉ）で示される塩を得る方法などが挙げられる。 Examples of the production method of the formula (I) include an ester form represented by the formula (VI) and

(In the formula, Q ¹ and Q ² each independently represent a fluorine atom or a C 1-6 perfluoroalkyl group, and ring X represents a monocyclic or bicyclic hydrocarbon group having 3 to 30 carbon atoms. N represents an integer of 1 to 12, and the ring X in the formula is an alkyl group having 1 to 6 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, an alkoxy group having 2 to 6 carbon atoms, or an alkyl group having 1 to 4 carbon atoms. One or more perfluoroalkyl groups may be contained as a substituent, and M represents Li, Na, K, or Ag.)
An onium salt represented by the formula (IX):

(In the formula, A ⁺ represents an organic counter ion, and Z represents F, Cl, Br, I, BF ₄ , AsF ₆ , SbF ₆ , PF ₆ , or ClO _4. )
For example, in an inert solvent such as acetonitrile, water, methanol, chloroform, and methylene chloride, the reaction is performed with stirring in a temperature range of about 0 ° C. to 150 ° C., preferably in a temperature range of about 0 ° C. to 100 ° C. And a method for obtaining a salt represented by the formula (I).

Here, Q ¹ and Q ² are preferably each independently a fluorine atom or —CF ₃ , and more preferably a fluorine atom.
Also, examples and preferred ranges of X in the formula (VI) are the same as described above, and examples and preferred ranges of A ⁺ in the formula (IX) are also the same as described above. n is preferably an integer of 1 to 6, and more preferably an integer of 1 to 4.

  The amount of the onium salt of the formula (IX) is usually about 0.5 to 2 mol with respect to 1 mol of the ester compound represented by the formula (VI). The salt (I) may be taken out by recrystallization or may be purified by washing with water.

（式（ＶII）中、環Ｘは単環式または２環式の炭素数３〜３０の炭化水素基を表す。ｎは１〜１２の整数を表し、式中の環Ｘは炭素数１〜６のアルキル基、炭素数２〜６のアルケニル基、炭素数２〜６のアルコキシ基又は炭素数１〜４のペルフルオロアルキル基の一つ以上を置換基として含んでいてもよい。）
で示されるアルコールと、式（ＶIII）

（式（ＶIII）中、Ｑ¹、Ｑ²は互いに独立にフッ素原子又は炭素数１〜６のペルフルオロアルキル基を表し、Ｍは、前記と同じ意味を表す。）
で示されるカルボン酸とをエステル化反応させて、式（ＶＩ）で示されるエステル体を得る方法などが挙げられる。
ここで、Ｑ¹、Ｑ²としてはそれぞれ独立にフッ素原子または−ＣＦ₃である場合が好ましく、フッ素原子である場合がさらに好ましい。 As a manufacturing method of ester body shown by Formula (VI) used for manufacture of Formula (I), for example, first, Formula (VII)

(In formula (VII), ring X represents a monocyclic or bicyclic hydrocarbon group having 3 to 30 carbon atoms. N represents an integer of 1 to 12, and ring X in the formula represents 1 to 1 carbon atoms. 6 or more alkyl groups having 2 to 6 carbon atoms, alkoxy groups having 2 to 6 carbon atoms, or perfluoroalkyl groups having 1 to 4 carbon atoms may be included as a substituent.
An alcohol represented by formula (VIII)

(In formula (VIII), Q ¹ and Q ² each independently represent a fluorine atom or a C 1-6 perfluoroalkyl group, and M represents the same meaning as described above.)
And a method of obtaining an ester form represented by the formula (VI) by esterifying the carboxylic acid represented by formula (VI).
Here, Q ¹ and Q ² are preferably each independently a fluorine atom or —CF ₃ , and more preferably a fluorine atom.

  The esterification reaction is usually carried out in an aprotic solvent such as dichloroethane, toluene, ethylbenzene, monochlorobenzene, acetonitrile, N, N-dimethylformamide, etc. in a temperature range of about 20 ° C. to 200 ° C., preferably 50 ° C. What is necessary is just to stir in the temperature range of about -150 degreeC. In the esterification reaction, an organic acid such as p-toluenesulfonic acid and / or an inorganic acid such as sulfuric acid is usually added as an acid catalyst. Alternatively, 1,1′-carbonyldiimidazole, N, N′-dicyclohexylcarbodiimide or the like may be added as a dehydrating agent.

The esterification reaction using an acid catalyst is preferably carried out while dehydrating using a Dean Stark apparatus or the like because the reaction time tends to be shortened.
The amount of the carboxylic acid represented by the formula (VIII) in the esterification reaction is about 0.2 to 3 mol, preferably about 0.5 to 2 mol, per 1 mol of the alcohol represented by the formula (VII). It is. The acid catalyst in the esterification reaction may be a catalytic amount or an amount corresponding to a solvent with respect to 1 mol of the alcohol represented by the formula (VII), and is usually about 0.001 mol to 5 mol. The dehydrating agent in the esterification reaction is about 0.2 to 5 mol, preferably about 0.5 to 3 mol, per 1 mol of the alcohol represented by the formula (VII).

  The salt represented by the formula (I) is used as an acid generator, and the acid generated by exposure is cleaved by catalytically acting on a group in the resin which is unstable to the acid, and the resin. Becomes soluble in an alkaline aqueous solution. Such a resin composition is suitable as a chemically amplified positive resist composition.

  The resin composition of the present invention is a resin composition containing a salt represented by the formula (I) and a resin, and the resin has an acid-labile group and is insoluble or hardly soluble in an alkaline aqueous solution. This resin is a resin that can be dissolved in an alkaline aqueous solution.

Examples of the acid labile group include a group having an alkyl ester in which the α position of the ether bond is a quaternary carbon atom, a group having a carboxylic acid ester such as an alicyclic ester, and the α position of the ether bond in a quaternary carbon atom. And a group having a lactone ring.
Here, the quaternary carbon atom means a carbon atom bonded to a substituent other than a hydrogen atom and not bonded to hydrogen, and an acid labile group is a carbon at the α-position of an ether bond. It is preferred that the atom is a quaternary carbon atom bonded to three carbon atoms.

To illustrate a group having a carboxylic acid ester which is one of the acid labile group as R ester of -COOR, (-. The COO-C (CH ₃₎ referred in ₃ form a tert- butyl ester), tert An alkyl ester in which the α-position of the ether bond represented by butyl ester is a quaternary carbon atom; 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, tetrahi Acetal type esters such as dro-2-furyl ester and tetrahydro-2-pyranyl ester; isobornyl ester and 1-alkyl cycloalkyl ester, 2-alkyl-2-adamantyl ester, 1- (1-adamantyl) -1- An alicyclic ester in which the α-position of the ether bond is a quaternary carbon atom, such as an alkylalkyl ester.

  Examples of the group having a carboxylic acid ester include a group having a (meth) acrylic acid ester, a norbornene carboxylic acid ester, a tricyclodecene carboxylic acid ester, and a tetracyclodecene carboxylic acid ester.

The resin of the resin composition of the present invention can be produced by addition polymerization of a monomer having an acid labile group and an olefinic double bond.
Such monomers include bulky groups such as alicyclic structures such as 2-alkyl-2-adamantyl groups and 1- (1-adamantyl) -1-alkylalkyl groups as acid labile groups. Monomers are preferred because the resolution of the resulting resist tends to be excellent.
Specific examples of the monomer containing a bulky 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 and the like.

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

  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 thereof include adamantyl, 2-ethyl-2-adamantyl methacrylate, 2-n-butyl-2-adamantyl acrylate, and the like. Examples of α-chloroacrylic acid 2-alkyl-2-adamantyl include α-chloroacrylic acid. Examples include 2-methyl-2-adamantyl and 2-ethyl-2-adamantyl α-chloroacrylate.

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

  (Meth) acrylic acid 2-alkyl-2-adamantyl 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.

The resin used in the present invention may contain a structural unit derived from an acid-stable monomer in addition to a structural unit derived from a monomer having an acid-labile group. Here, the structure derived from an acid-stable monomer means a structure that is not cleaved by the salt (I) of the present invention.
Specifically, a structural unit derived from a monomer having a free carboxylic acid group such as acrylic acid or methacrylic acid, or a structural unit derived from an aliphatic unsaturated dicarboxylic anhydride such as maleic anhydride or itaconic anhydride , Structural units derived from 2-norbornene, structural units derived from (meth) acrylonitrile, (meth) acrylic acid wherein the α-position of the ether bond is a secondary or tertiary carbon atom alkyl ester or 1-adamantyl ester Structural units derived from esters, structural units derived from styrenic monomers such as p- or m-hydroxystyrene, and structures derived from (meth) acryloyloxy-γ-butyrolactone in which the lactone ring may be substituted with an alkyl group Examples include units. The 1-adamantyl ester is a quaternary carbon atom at the α-position of the ether bond, but is a group that is stable to acids, and a hydroxyl group or the like may be bonded to the 1-adamantyl ester.

  Specific acid-stable monomers include 3-hydroxy-1-adamantyl (meth) acrylate, (meth) acrylic acid 3, 5-dihydroxy-1-adamantyl, α- (meth) acryloyloxy-γ-butyrolactone, β- (meth) acryloyloxy-γ-butyrolactone, formulas (a) and (b), hydroxystyrene, norbornene (c) and other alicyclic compounds having an olefinic double bond in the molecule, maleic anhydride (d) Examples thereof include aliphatic unsaturated dicarboxylic acid anhydrides, itaconic anhydride (e) and the like.

  Among these, in particular, a structural unit derived from a styrenic monomer such as p- or m-hydroxystyrene, a structural unit derived from 3-hydroxy-1-adamantyl (meth) acrylate, and (meth) acrylic acid 3, 5 A resist obtained from a resin comprising a structural unit derived from dihydroxy-1-adamantyl, a structure derived from a monomer represented by formula (a), and a structural unit derived from a monomer represented by formula (b) This is preferable because the adhesion and the resolution of the resist tend to be improved.

（式中、Ｒ¹及びＲ²は、互いに独立に、水素原子又はメチル基を表し、Ｒ³及びＲ⁴は、互いに独立に水素原子、メチル基、トリフルオロメチル基又はハロゲン原子を表し、ｐ及びｑは、互いに独立に１〜３の整数を表す。ｐが２または３のときには、Ｒ³は互いに異なる基であってもよく、ｑが２または３のときには、Ｒ⁴は互いに異なる基であってもよい。）

(In the formula, R ¹ and R ² each independently represent a hydrogen atom or a methyl group; R ³ and R ⁴ each independently represent a hydrogen atom, a methyl group, a trifluoromethyl group, or a halogen atom; And q each independently represents an integer of 1 to 3. When p is 2 or 3, R ³ may be a different group, and when q is 2 or 3, R ⁴ is a different group. May be.)

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

  In addition, a monomer such as (meth) acryloyloxy-γ-butyrolactone is obtained by reacting α- or β-bromo-γ-butyrolactone, in which the lactone ring may be substituted with an alkyl group, with acrylic acid or methacrylic acid, or lactone It can be produced by reacting an α- or β-hydroxy-γ-butyrolactone whose ring may be substituted with an alkyl group with an acrylic acid halide or a methacrylic acid halide.

  Specific examples of the monomer that gives the structural unit represented by formula (a) or formula (b) include (meth) acrylic acid esters of alicyclic lactones having a hydroxyl group such as the following, and mixtures thereof. It is done. These esters can be produced, for example, by reacting an alicyclic lactone having a corresponding hydroxyl group with (meth) acrylic acids (for example, JP-A No. 2000-26446).

  Here, as (meth) acryloyloxy-γ-butyrolactone, for example, α-acryloyloxy-γ-butyrolactone, α-methacryloyloxy-γ-butyrolactone, α-acryloyloxy-β, β-dimethyl-γ-butyrolactone, α- Methacryloyloxy-β, β-dimethyl-γ-butyrolactone, α-acryloyloxy-α-methyl-γ-butyrolactone, α-methacryloyloxy-α-methyl-γ-butyrolactone, β-acryloyloxy-γ-butyrolactone, β- Examples include methacryloyloxy-γ-butyrolactone, β-methacryloyloxy-α-methyl-γ-butyrolactone, and the like.

  In the case of KrF excimer laser exposure, sufficient transmittance can be obtained even if a structural unit derived from a styrene monomer such as p- or m-hydroxystyrene is used as the structural unit of the resin. Such a copolymer resin can be obtained by radically polymerizing the corresponding (meth) acrylic acid ester monomer, acetoxystyrene, and styrene and then deacetylating with an acid.

  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 the 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 acid anhydride residue represented by —C (═O) OC (═O) —.
When R ⁵ and / or R ⁶ is a group —COOU, carboxyl is an ester, and the alcohol residue corresponding to U has, for example, about 1 to 8 carbon atoms that may be substituted. And an alkyl group, a 2-oxooxolan-3- or -4-yl group. Here, in the alkyl group, a hydroxyl group, an alicyclic hydrocarbon residue, or the like may be bonded as a substituent.
Specific examples of R ⁵ and / or R ⁶ being an alkyl group include a methyl group, an ethyl group, a propyl group, and the like. Specific examples of an alkyl having a hydroxyl group bonded thereto include a hydroxymethyl group, 2-hydroxy An ethyl group etc. are mentioned.

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 addition, if U of —COOU of R ⁵ and / or R ⁶ in formula (c) is an acid-labile group such as an alicyclic ester in which the α position of the ether bond is a quaternary carbon atom, Although it has a norbornene structure, it is a structural unit having an acid labile group. 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.

  The resin used in the resin composition of the present invention varies depending on the type of radiation used for patterning exposure and the type of acid labile group, but is usually derived from a monomer having an acid labile group in the resin. The content of the structural unit is adjusted to a range of 10 to 80 mol%.

  And as a structural unit derived from a monomer having an acid labile group, in particular, 2-alkyl-2-adamantyl (meth) acrylate and 1- (1-adamantyl) -1-alkylalkyl (meth) acrylate When the derived structural unit is included, if the structural unit is 15 mol% or more of the total structural units constituting the resin, the resin has a rugged structure because of the alicyclic group, and the resist has a dry etching resistance. Is advantageous.

  In addition, when using an alicyclic compound having an olefinic double bond in the molecule and an aliphatic unsaturated dicarboxylic acid anhydride as monomers, these tend to be difficult to undergo addition polymerization. These are preferably used in excess.

  Further, as the monomer used, monomers having the same olefinic double bond but different acid labile groups may be used in combination, or monomers having the same acid labile group but different olefinic double bonds may be used. You may use together, and you may use together the monomer from which the combination of an acid labile group and an olefinic double bond differs.

  The chemically amplified resist composition of the present invention preferably contains a basic compound, more preferably a basic nitrogen-containing organic compound, particularly preferably an amine or ammonium salt. By adding a basic compound as a quencher, it is possible to improve the performance degradation due to the deactivation of the acid accompanying the holding after exposure. Specific examples of the basic compound used for the quencher include those represented by the following formulas.

In the formula, R ¹¹ and R ¹² each independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, or an aryl group. The alkyl group preferably has about 1 to 6 carbon atoms, the cycloalkyl group preferably has about 5 to 10 carbon atoms, and the aryl group preferably has about 6 to 10 carbon atoms. Of carbon atoms. Further, at least one hydrogen atom on the alkyl group, cycloalkyl group or aryl group may be independently substituted with a hydroxyl group, an amino group, or an alkoxy group having 1 to 6 carbon atoms. Good. At least one hydrogen atom on the amino group may be independently substituted with an alkyl group having 1 to 4 carbon atoms.

R ¹³ , R ¹⁴ and R ¹⁵ each independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group or an alkoxy group. The alkyl group preferably has about 1 to 6 carbon atoms, the cycloalkyl group preferably has about 5 to 10 carbon atoms, and the aryl group preferably has 6 to 10 carbon atoms. The alkoxy group preferably has 1 to 6 carbon atoms.
Further, at least one hydrogen atom on the alkyl group, cycloalkyl group, aryl group, or alkoxy group is independently a hydroxyl group, an amino group, or an alkoxy group having about 1 to 6 carbon atoms. May be substituted. At least one of the hydrogen atoms on the amino group may be substituted with an alkyl group having 1 to 4 carbon atoms.

R ¹⁶ represents an alkyl group or a cycloalkyl group. The alkyl group preferably has about 1 to 6 carbon atoms, and the cycloalkyl group preferably has about 5 to 10 carbon atoms. Furthermore, at least one hydrogen atom on the alkyl group or cycloalkyl group may be independently substituted with a hydroxyl group, an amino group, or an alkoxy group having 1 to 6 carbon atoms. At least one of the hydrogen atoms on the amino group may be substituted with an alkyl group having 1 to 4 carbon atoms.

R ¹⁷ , R ¹⁸ , R ¹⁹ and R ²⁰ each independently represents an alkyl group, a cycloalkyl group or an aryl group. The alkyl group preferably has about 1 to 6 carbon atoms, the cycloalkyl group preferably has about 5 to 10 carbon atoms, and the aryl group preferably has 6 to 10 carbon atoms. Has about carbon atoms. Furthermore, at least one hydrogen atom on the alkyl group, cycloalkyl group or aryl group may be independently substituted with a hydroxyl group, an amino group, or an alkoxy group having 1 to 6 carbon atoms. . At least one of the hydrogen atoms on the amino group may be substituted with an alkyl group having 1 to 4 carbon atoms.

W represents an alkylene group, a carbonyl group, an imino group, a sulfide group or a disulfide group. The alkylene group preferably has about 2 to 6 carbon atoms.
Further, in R ^{11 to} R ²⁰ , any of those that can take both a linear structure and a branched structure may be used.

  Specific examples of such compounds include hexylamine, heptylamine, octylamine, nonylamine, decylamine, aniline, 2-, 3- or 4-methylaniline, 4-nitroaniline, 1- or 2-naphthylamine, and ethylenediamine. Tetramethylenediamine, hexamethylenediamine, 4,4'-diamino-1,2-diphenylethane, 4,4'-diamino-3,3'-dimethyldiphenylmethane, 4,4'-diamino-3,3'- Diethyldiphenylmethane, dibutylamine, dipentylamine, dihexylamine, diheptylamine, dioctylamine, dinonylamine, didecylamine, N-methylaniline, piperidine, diphenylamine, triethylamine, trimethylamine, tripropylamine, tributylamine , Tripentylamine, trihexylamine, triheptylamine, trioctylamine, trinonylamine, tridecylamine, methyldibutylamine, methyldipentylamine, methyldihexylamine, methyldicyclohexylamine, methyldiheptylamine, methyldioctylamine Methyldinonylamine, methyldidecylamine, ethyldibutylamine, ethyldipentylamine, ethyldihexylamine, ethyldiheptylamine, ethyldioctylamine, ethyldinonylamine, ethyldidecylamine, dicyclohexylmethylamine, tris [2- (2-methoxyethoxy) ethyl] amine, triisopropanolamine, N, N-dimethylaniline, 2,6-isopropylaniline, imidazole, pyridine, -Methylpyridine, 4-methylimidazole, bipyridine, 2,2'-dipyridylamine, di-2-pyridyl ketone, 1,2-di (2-pyridyl) ethane, 1,2-di (4-pyridyl) ethane, 1,3-di (4-pyridyl) propane, 1,2-bis (2-pyridyl) ethylene, 1,2-bis (4-pyridyl) ethylene, 1,2-bis (4-pyridyloxy) ethane, 4 , 4'-dipyridyl sulfide, 4,4'-dipyridyl disulfide, 1,2-bis (4-pyridyl) ethylene, 2,2'-dipicolylamine, 3,3'-dipicolylamine, tetramethylammonium hydroxide Tetraisopropylammonium hydroxide, tetrabutylammonium hydroxide, tetra-n-hexylammonium hydroxide, tetra-n- Examples include octylammonium hydroxide, phenyltrimethylammonium hydroxide, 3-trifluoromethylphenyltrimethylammonium hydroxide, (2-hydroxyethyl) trimethylammonium hydroxide (common name: choline), and the like.

  Furthermore, a hindered amine compound having a piperidine skeleton as disclosed in JP-A-11-52575 can be used as a quencher.

The composition of the present invention preferably contains the resin in the range of about 80 to 99.9% by weight and the acid generator in the range of about 0.1 to 20% by weight based on the total solid content.
Further, when a basic compound that is a quencher is used as the chemically amplified resist composition, it is preferably contained in a range of about 0.01 to 1% by weight based on the total solid content of the resist composition.
The resist composition can further contain small amounts of various additives such as sensitizers, dissolution inhibitors, other resins, surfactants, stabilizers, and dyes as necessary.

  The resist composition of the present invention is usually used as a resist solution composition in a state in which each of the above components is dissolved in a solvent, and is usually used in industrial processes such as spin coating on a substrate such as a silicon wafer. Applied according to The solvent used here may be any solvent that dissolves each component, has an appropriate drying rate, and gives a uniform and smooth coating film after the solvent evaporates, and is usually used industrially in this field. Solvents can be used.

  For example, 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, esters such as ethyl lactate, butyl acetate, amyl acetate and ethyl pyruvate And ketones such as acetone, methyl isobutyl ketone, 2-heptanone and cyclohexanone, and cyclic esters such as γ-butyrolactone. These solvents can be used alone or in combination of two or more.

  The resist film coated and dried on the substrate is subjected to an exposure process for patterning, followed by a heat treatment for promoting a deprotecting group reaction, and then developed with an alkali developer. The alkaline developer used here may be various alkaline aqueous solutions used in this field, but in general, an aqueous solution of tetramethylammonium hydroxide or (2-hydroxyethyl) trimethylammonium hydroxide (common name: choline). Is often used.

EXAMPLES Next, although an Example is given and this invention is demonstrated further more concretely, this invention is not limited at all by these Examples.
In Examples and Comparative Examples, “%” and “part” representing content or use amount are based on weight unless otherwise specified. Further, the weight average molecular weight is a value obtained by gel permeation chromatography (HLC-8120GPC type manufactured by Tosoh Corporation, column is TSKgel Multipore HXL-M3, solvent is tetrahydrofuran) using polystyrene as a standard product.
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).

Acid generator synthesis example 1: Synthesis of triphenylsulfonium (1-cyclohexylmethoxycarbonyl) difluoromethanesulfonate (acid generator B1) (1) 100 parts of difluoro (fluorosulfonyl) acetic acid methyl ester, 250 parts of ion-exchanged water, In an ice bath, 230 parts of a 30% aqueous sodium hydroxide solution was added dropwise. The mixture was refluxed at 100 ° C. for 2.5 hours, cooled, and neutralized with 88 parts of concentrated hydrochloric acid. The obtained solution was concentrated to obtain 158.4 parts of sodium difluorosulfoacetate (containing inorganic salt, purity: 65.1%).
(2) Difluorosulfoacetate sodium salt 50.0 parts (purity 65.1%), cyclohexylmethanol 18.76 parts, dichloroethane 377 parts were added, p-toluenesulfonic acid 31.26 parts was added, and the mixture was heated to reflux for 6 hours. . Then, after concentrating and distilling off dichloroethane, 200 parts of n-heptane was added, filtered after repulping. 200 parts of acetonitrile was added to the residue, stirred, filtered, and concentrated to obtain 39.03 parts of difluorosulfoacetic acid-1-cyclohexylmethyl ester sodium salt.

¹ H-NMR (dimethyl sulfoxide-d ₆ , internal standard substance tetramethylsilane): δ (ppm) 0.90-1.27 (m, 5H); 1.58-1.71 (m, 6H); 4 .02 (d, 2H)

(3) 39.03 parts of difluorosulfoacetic acid-1-cyclohexylmethyl ester sodium salt obtained in (2) above was charged and dissolved in 195.2 parts of ion-exchanged water. To this solution, 39.64 parts of triphenylsulfonium chloride and 196.4 parts of ion-exchanged water were added, and 500 parts of acetonitrile was added. After stirring for 15 hours, the mixture was concentrated and extracted twice with 250 parts of chloroform. The organic layers were combined and washed with ion exchange water, and the resulting organic layer was concentrated. By repulping the concentrated solution with 200 parts of tert-butyl methyl ether, 40.16 parts of triphenylsulfonium (1-cyclohexylmethoxycarbonyl) difluoromethanesulfonate difluoromethanesulfonate (B1) was obtained as a white solid.

¹ H-NMR (dimethyl sulfoxide-d ₆ , internal standard substance tetramethylsilane): δ (ppm) 0.88-1.28 (m, 5H); 1.56-1.71 (m, 6H); 4 .01 (d, 2H); 7.75-7.90 (m, 15H)
MS (ESI (+) Spectrum): M + 263.1 (C ₁₈ H ₁₅ S ⁺ = 263.09)
MS (ESI (−) Spectrum): M− 271.1 (C ₉ H ₁₃ F ₂ O ₅ S ⁻ = 271.05)

Synthesis Example of Acid Generator 2: Synthesis of 1- (2-oxo-2-phenylethyl) tetrahydrothiophenium (1-cyclohexylmethoxycarbonyl) difluoromethanesulfonate (acid generator B2) (1) 2-bromoacetophenone 150 Part was dissolved in 375 parts of acetone, and 66.5 parts of tetrahydrothiophene was added dropwise. After stirring at room temperature for 24 hours, the obtained white precipitate was filtered, washed and dried to obtain 207.9 parts of 1- (2-oxo-2-phenylethyl) tetrahydrothiophenium bromide as white crystals. .

¹ H-NMR (dimethyl sulfoxide-d ₆ , internal standard substance tetramethylsilane): δ (ppm) 2.13-2.36 (m, 4H); 3.50-3.67 (m, 4H); 5 .41 (s, 2H); 7.63 (t, 2H); 7.78 (t, 1H); 8.02 (d, 2H)

(2) Acid generator B1 acid generator synthesis example (acid generator synthesis example 1) (2) of (2) difluorosulfoacetic acid-1-cyclohexylmethyl ester sodium salt 6.00 parts was charged, acetonitrile 60. Dissolved in 0 parts. To this solution, 5.86 parts of 1- (2-oxo-2-phenylethyl) tetrahydrothiophenium bromide obtained in (1) above and 58.6 parts of ion-exchanged water were added. After stirring for 15 hours, the mixture was concentrated and extracted once with 100 parts of chloroform and once with 50 parts. The organic layers were combined and washed with ion exchange water, and the resulting organic layer was concentrated. The concentrated solution was added with 30 parts of tert-butyl methyl ether, stirred, filtered, and dried under reduced pressure to give 1- (2-oxo-2-phenylethyl) tetrahydrothiophenium (1-cyclohexylmethoxycarbonyl) difluoromethanesulfone as white crystals. 5.6 parts of Nart (B2) were obtained.

¹ H-NMR (dimethylsulfoxide-d ₆ , internal standard substance tetramethylsilane): δ (ppm) 0.88-1.28 (m, 5H); 1.56-1.70 (m, 6H); 2 .13-2.33 (m, 4H); 3.46-3.64 (m, 4H); 4.02 (s, 2H); 5.31 (s, 2H); 7.63 (t, 2H) ); 7.78 (t, 1H); 8.00 (d, 2H)
MS (ESI (+) Spectrum): M + 207.0 (C ₁₂ H ₁₅ OS ⁺ = 207.08)
MS (ESI (−) Spectrum): M− 271.0 (C ₉ H ₁₃ F ₂ O ₅ S ⁻ = 271.05)

Acid generator synthesis example 3: Synthesis of triphenylsulfonium (2-norbornanemethoxycarbonyl) difluoromethanesulfonate (acid generator B3) (1) 8.1 parts of difluorosulfoacetate sodium salt (purity 61.9%), 2 -Norbornane methanol (3.2 parts) and dichloroethane (200 parts) were added, p-toluenesulfonic acid (p-TsOH) (4.8 parts) was added, and the mixture was heated to reflux for 7 hours. Then, after concentrating and distilling off dichloroethane, 100 parts of tert-butyl methyl ether was added, and after repulping, filtration was performed. 154 parts of difluorosulfoacetic acid-2-norbornane methyl ester sodium salt was obtained by adding 100 parts of ethyl acetate to the residue, stirring and then filtering and concentrating.

¹ H-NMR (dimethylsulfoxide-d ₆ , internal standard substance tetramethylsilane): δ (ppm) 0.65-0.72 (m, 1H); 1.03-1.78 (m, 7H); 2 14-2.24 (m, 3H); 3.87-4.27 (m, 2H)

(2) 5.4 parts of difluorosulfoacetic acid-2-norbornane methyl ester sodium salt obtained in (1) above was charged and dissolved in 54.3 parts of ion-exchanged water. To this solution, 5.3 parts of triphenylsulfonium chloride and 55 parts of methanol were added, stirred for 24 hours, concentrated, and extracted twice with 54 parts of chloroform. The organic layers were combined and washed with ion exchange water, and the resulting organic layer was concentrated. The concentrated solution was repulped with 54 parts of tert-butyl methyl ether to obtain 8.4 parts of triphenylsulfonium (2-norbornanemethoxycarbonyl) difluoromethanesulfonate (B3) as a white solid.

¹ H-NMR (dimethyl sulfoxide-d ₆ , internal standard substance tetramethylsilane): δ (ppm) 0.64-0.72 (m, 1H); 1.03-1.80 (m, 7H); 2 .13-2.22 (m, 3H); 3.86-4.26 (m, 2H); 7.75-7.91 (m, 15H)
MS (ESI (+) Spectrum): M + 263.2 (C ₁₈ H ₁₅ S ⁺ = 263.09)
MS (ESI (−) Spectrum): M-283.0 (C ₁₀ H ₁₃ F ₂ O ₅ S ⁻ = 283.05)

Resin Synthesis Example 1: Synthesis of Resin A1 2-ethyl-2-adamantyl methacrylate, 3-hydroxy-1-adamantyl methacrylate, and α-methacryloyloxy-γ-butyrolactone were mixed with 5: 2.5: 2.5. The methyl isobutyl ketone was added 2 times by weight with respect to the total monomer to prepare a solution. Thereto, 2 mol% of azobisisobutyronitrile as an initiator was added with respect to the total amount of monomers and heated at 80 ° C. for about 8 hours. Thereafter, the operation of pouring the reaction solution into a large amount of heptane and precipitating was performed three times for purification. As a result, a copolymer having a weight average molecular weight of about 9200 was obtained. This copolymer has each unit represented by the following formula, and this is designated as resin A1.

  Next, in addition to the resin (A1) obtained in the above resin synthesis example, a resist composition was prepared and evaluated using the raw materials shown below.

酸発生剤Ｂ３：

酸発生剤Ｃ１：トリフェニルスルホニウム パーフルオロブタンスルホナート
＜クエンチャー＞
クエンチャーＱ１：２，６−ジイソプロピルアニリン
＜溶剤＞
溶剤Ｙ１：
プロピレングリコールモノメチルエーテルアセテート ８０．０部
２−ヘプタノン ２０．０部
γ−ブチロラクトン ３．０部 <Acid generator>
Acid generator B1:

Acid generator B3:

Acid generator C1: triphenylsulfonium perfluorobutanesulfonate <quencher>
Quencher Q1: 2,6-diisopropylaniline <solvent>
Solvent Y1:
Propylene glycol monomethyl ether acetate 80.0 parts 2-heptanone 20.0 parts γ-butyrolactone 3.0 parts

Examples 1-2 and Comparative Example 1
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.

Resin (type and amount are listed in Table 1)
Acid generator (type and amount are listed in Table 1)
Quencher (type and amount are listed in Table 1)
Solvent (type is listed in Table 1)

An organic antireflection film having a thickness of 780 mm is formed by applying “ARC-29A-8”, a composition for organic antireflection film made by Brewer, to a silicon wafer and baking it at 215 ° C. for 60 seconds. Subsequently, the above resist solution was spin-coated thereon so that the film thickness after drying was 0.25 μm. After applying the resist solution, pre-baking was performed on a direct hot plate at a temperature indicated in the column “PB” in Table 1 for 60 seconds. For each wafer on which the resist film was formed in this way, an ArF excimer stepper (“NSR ArF” manufactured by Nikon Corporation, NA = 0.55, 2/3 Annular) was used to change the exposure amount step by step. The space pattern was exposed.
After exposure, post-exposure baking is performed for 60 seconds on the hot plate at the temperature shown in the column of “PEB” in Table 1, and further paddle development is performed for 60 seconds with an aqueous 2.38 wt% tetramethylammonium hydroxide solution. It was.
The bright field pattern after development on the organic antireflection film substrate was observed with a scanning electron microscope, and the results are shown in Table 2. The bright field pattern here is obtained by exposure and development through a reticle in which a chrome layer (light-shielding layer) is formed in a line shape with the glass surface (translucent portion) as a base on the outside, and thus exposure development. After that, the resist layer around the line and space pattern is removed.

  Resolution: Displayed with the minimum dimension of the line and space pattern separated by the exposure amount of effective sensitivity. Here, the effective sensitivity is indicated by an exposure amount at which a 0.13 μm line and space pattern is 1: 1.

[Table 1]
━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━
Example No. Resin Acid generator Quencher Solvent PB / PEB
━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━
Example 1 A1 / 10 part B1 / 0.232 part Q1 / 0.0325 part Y1 130 ° C / 130 ° C
Example 2 A1 / 10 part B3 / 0.237 part Q1 / 0.0325 part Y1 130 ° C / 130 ° C
───────────────────────────────────────
Comparative Example 1 A1 / 10 part C1 / 0.244 part Q1 / 0.0325 part Y1 130 ° C / 130 ° C
━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━

[Table 2]
━━━━━━━━━━━━━━━━━━━━
Example No. Resolution Effective sensitivity
(μm) (mJ / cm ² )
━━━━━━━━━━━━━━━━━━━━
Example 1 0.12 25.0
Example 2 0.12 27.5
────────────────────
Comparative Example 1 0.13 22.5
━━━━━━━━━━━━━━━━━━━━

  Conventionally, the resolution was excellent even at 0.13 μm (Comparative Example 1), but according to Examples 1 and 2, the resolution was further improved to 0.12 μm. Further, the obtained resist had a result showing an excellent pattern shape in which the top side and the bottom side were almost equal.

  The salt of the present invention is suitably used as an acid generator for a chemically amplified positive resist composition that gives excellent resolution and pattern shape, and is particularly suitable for excimer laser lithography such as ArF and KrF and ArF immersion exposure lithography. It can be used as an acid generator for a suitable chemically amplified positive resist composition.

Claims (14)

A salt represented by the formula (I):

(In formula (I), Q ¹ and Q ² represent a fluorine atom, and ring X is a monovalent residue of a compound represented by formula (IIIa), formula (IIIb), formula (IIIc) or formula (IIId )). N represents an integer of 1 to 12, and A ⁺ represents at least one cation selected from the group consisting of cations represented by formula (IIf) or formula (IIc ) .

(In the formulas (IIIa) to (III d ), f represents an integer of 1 to 10 and X ¹ represents an alkylene group . The rings in the formulas (IIIa) to (III d ) are alkyls having 1 to 6 carbon atoms. And one or more of a group, an alkoxy group having 2 to 6 carbon atoms, or a perfluoroalkyl group having 1 to 4 carbon atoms may be included as a substituent.)

(In Formula (IIf), P ^{25 to} P ²⁷ each independently represent a linear or branched alkyl group having 1 to 30 carbon atoms or a cyclic hydrocarbon group having 3 to 30 carbon atoms. P ²⁵ If to P ²⁷ is an alkyl group, a hydroxyl group may comprise as one or more substituents of the cyclic hydrocarbon group having 3 to 12 alkoxy group or a carbon number of 1 to 12 carbon atoms, P ²⁵ If to P ²⁷ is a cyclic hydrocarbon group, a hydroxyl group, it may be included as one or more of the substituents for the alkyl group or alkoxy group having 1 to 12 carbon atoms having 1 to 12 carbon atoms. the alkyl The group and the alkoxy group may be linear or branched. )

(In the formula (IIc), P ⁶ and P ⁷ each independently represent an alkyl group having 1 to 12 carbon atoms or a cycloalkyl group having 3 to 12 carbon atoms, and the alkyl group is branched even in a straight chain. Or P ⁶ and P ⁷ may be combined to represent a divalent hydrocarbon group having 3 to 12 carbon atoms, P ⁸ represents a hydrogen atom, P ⁹ represents an alkyl group having 1 to 12 carbon atoms, A cycloalkyl group having 3 to 12 carbon atoms or an optionally substituted aromatic ring group is represented, or P ⁸ and P ⁹ are bonded to each other to represent a divalent hydrocarbon group having 3 to 12 carbon atoms. in, the carbon atoms contained in the divalent hydrocarbon group are both carbonyl groups, oxygen atoms, may be substituted by a sulfur atom.)) The salt according to claim 1, wherein the cation represented by the formula (IIf) is a cation represented by any one of the formula (IIg), the formula (IIh) and the formula (IIi).

(In the formula (IIg) ~ (IIi), the P ²⁸ to P ³⁰ are independently a linear or branched number 3-30 carbon other than or a phenyl group represents an alkyl group having 1 to 20 carbon atoms Represents a cyclic hydrocarbon group, and when P ^{28 to} P ³⁰ are alkyl groups, one or more of a hydroxyl group, an alkoxy group having 1 to 12 carbon atoms, or a cyclic hydrocarbon group having 3 to 12 carbon atoms is substituted. In the case where P ^{28 to} P ³⁰ are cyclic hydrocarbon groups, one or more of a hydroxyl group, an alkyl group having 1 to 12 carbon atoms or an alkoxy group having 1 to 12 carbon atoms may be substituted. P ^{31 to} P ³⁶ in the formula represent a hydroxyl group, an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, or a cyclic hydrocarbon group having 3 to 12 carbon atoms. , L, k, j, i, h and g each independently represent an integer of 0 to 5.) The salt according to claim 1 or 2, wherein the cation represented by the formula (IIf) is a cation represented by the formula (IIa).

(In Formula (IIa), P ^{1 to} P ³ each independently represent a hydrogen atom, a hydroxyl group, an alkyl group having 1 to 12 carbon atoms, or an alkoxy group having 1 to 12 carbon atoms, and the alkyl group and the alkoxy group May be linear or branched.) The salt according to any one of claims 1 to 3, wherein A ⁺ is a cation represented by the formula (IIe).

(In formula (IIe), P ^{22 to} P ²⁴ each independently represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and the alkyl group may be linear or branched.)   The salt according to any one of claims 1 to 4, wherein the ring X is a monovalent residue of the compound represented by the formula (IIIa) or the formula (IIIb).   n is an integer of 1-4, The salt in any one of Claims 1-5. The salt according to any one of claims 1 to 6, wherein the salt represented by the formula (I) is a salt represented by the formula (IV) or the formula (V).

(In formula (IV) or formula (V), P ^{22 to} P ²⁴ represent the same meaning as described above).   An acid generator comprising the salt according to any one of claims 1 to 7 as an active ingredient. An ester compound represented by the formula (VI):

(In formula (VI), Q ¹ and Q ² represent a fluorine atom, and ring X is a monovalent residue of a compound represented by formula (IIIa), formula (IIIb), formula (IIIc) or formula (IIId )). the representative .n is an integer of 1 to 12 Table to. M represents Li, Na, and K or Ag.

(In the formulas (IIIa) to (III d ), f represents an integer of 1 to 10 and X ¹ represents an alkylene group . The rings in the formulas (IIIa) to (III d ) are alkyls having 1 to 6 carbon atoms. And one or more of a group, an alkoxy group having 2 to 6 carbon atoms or a perfluoroalkyl group having 1 to 4 carbon atoms may be included as a substituent.)) An alcohol represented by the formula (VII);

(In formula (VII), ring X represents a monovalent residue of a compound represented by formula (IIIa), formula (IIIb), formula (IIIc) or formula (IIId ). N represents an integer of 1 to 12). Table be.

(In the formulas (IIIa) to (III d ), f represents an integer of 1 to 10 and X ¹ represents an alkylene group . The rings in the formulas (IIIa) to (III d ) are alkyls having 1 to 6 carbon atoms. And one or more of a group, an alkoxy group having 2 to 6 carbon atoms or a perfluoroalkyl group having 1 to 4 carbon atoms may be included as a substituent.))
Formula (VIII)

(In formula (VIII), Q ¹ and Q ² represent a fluorine atom, and M represents Li, Na, K, or Ag .)
And a carboxylic acid represented by the formula (VI)

(In formula (VI), Q ¹ , Q ² , rings X, n and M have the same meaning as described above.)
The manufacturing method of the ester body shown by this. A method for producing a salt represented by the formula (I), comprising reacting an ester form represented by the formula (VI) with a compound represented by the formula (IX).

(In formula (VI), Q ¹ and Q ² represent a fluorine atom, and ring X is a monovalent residue of the compound represented by formula (IIIa), formula (IIIb), formula (IIIc) or formula (IIId)). N represents an integer of 1 to 12. M represents Li, Na, K, or Ag.

(In formulas (IIIa) to (IIId), f represents an integer of 1 to 10 and X ¹ represents an alkylene group. The rings in formulas (IIIa) to (IIId) are alkyl groups having 1 to 6 carbon atoms, 1 or more of a C2-C6 alkoxy group or a C1-C4 perfluoroalkyl group may be included as a substituent.))

(In formula (IX), A ⁺ represents at least one cation selected from the group consisting of cations represented by formula (IIf) or formula (IIc ), and Z represents F, Cl, Br, I, BF _4. , AsF ₆ , SbF ₆ , PF ₆ or ClO ₄ .

(In Formula (IIf), P ^{25 to} P ²⁷ each independently represent a linear or branched alkyl group having 1 to 30 carbon atoms or a cyclic hydrocarbon group having 3 to 30 carbon atoms. P ²⁵ If to P ²⁷ is an alkyl group, a hydroxyl group may comprise as one or more substituents of the cyclic hydrocarbon group having 3 to 12 alkoxy group or a carbon number of 1 to 12 carbon atoms, P ²⁵ If to P ²⁷ is a cyclic hydrocarbon group, a hydroxyl group, it may be included as one or more of the substituents for the alkyl group or alkoxy group having 1 to 12 carbon atoms having 1 to 12 carbon atoms. the alkyl The group and the alkoxy group may be linear or branched. )

(In the formula (IIc), P ⁶ and P ⁷ each independently represent an alkyl group having 1 to 12 carbon atoms or a cycloalkyl group having 3 to 12 carbon atoms, and the alkyl group is branched even in a straight chain. Or P ⁶ and P ⁷ may be combined to represent a divalent hydrocarbon group having 3 to 12 carbon atoms, P ⁸ represents a hydrogen atom, P ⁹ represents an alkyl group having 1 to 12 carbon atoms, A cycloalkyl group having 3 to 12 carbon atoms or an optionally substituted aromatic ring group is represented, or P ⁸ and P ⁹ are bonded to each other to represent a divalent hydrocarbon group having 3 to 12 carbon atoms. in, the carbon atoms contained in the divalent hydrocarbon group are both carbonyl groups, oxygen atoms, may be substituted by a sulfur atom.))

(In formula (I), Q ¹ , Q ² , ring X, n and A ⁺ represent the same meaning as described above.)   A resin composition comprising the acid generator according to claim 8 and a resin, wherein the resin has an acid labile group and is a resin that is insoluble or hardly soluble in an aqueous alkali solution, and acts with an acid. The resin composition is a resin that is soluble in an alkaline aqueous solution.   The resin composition according to claim 12, wherein the resin is a resin containing a structural unit derived from a monomer having a bulky group and an acid-labile group.   A chemically amplified resist composition comprising the resin composition according to claim 12 or 13 and a basic compound.