JP2002116546A - Chemical amplification type positive type resist composition and sulfonium salt - Google Patents

Abstract

(57) [Summary] A chemically amplified positive resist composition having excellent resist performance such as sensitivity and resolution, and giving particularly improved line edge roughness. Kind Code: A1 A chemical compound containing a resin and an acid generator, which has a polymerized unit having an acid-labile group and is itself insoluble or hardly soluble in alkali, but is soluble in alkali by the action of an acid. An amplification-type positive resist composition, wherein the acid generator is a sulfonium salt represented by the following formula (I): And a sulfonium salt represented by the following formula (I ') At least one sulfonium salt selected from: as well as And at least one onium salt selected from the group consisting of:

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a chemically amplified positive resist composition used for fine processing of semiconductors.

[0002]

2. Description of the Related Art A lithography process using a resist composition is usually employed for fine processing of a semiconductor.
In lithography, the shorter the exposure wavelength, the higher the resolution in principle, as expressed by the Rayleigh diffraction limit equation. Exposure light sources for lithography used in the production of semiconductors are g-line at 436 nm, i-line at 365 nm, KrF excimer laser at 248 nm, and ArF excimer laser at 193 nm. As an exposure light source, an F ₂ excimer laser having a wavelength of 157 nm is considered promising, and thereafter, soft X-rays (EUV) having a wavelength of 13 nm or less have been proposed as light sources.

Light sources with wavelengths shorter than g-line and i-line, such as excimer lasers, have low illuminance, so that it is necessary to increase the sensitivity of the resist. A so-called chemically amplified resist containing a resin having a group that can be cleaved is used.

However, in the conventionally known chemically amplified resist composition, the line edge roughness, that is, the smoothness of the pattern side wall is reduced due to the generation of standing waves and the like.
There is a problem that the uniformity of the line width is deteriorated.

[0005]

An object of the present invention is to provide a chemically amplified positive resist composition containing a resin component and an acid generator and suitable for excimer laser lithography such as ArF or KrF. It is an object of the present invention to provide a positive resist composition which has various resist performances such as high resolution and resolution, and gives particularly improved line edge roughness.

The present inventors have already reported that at least one onium salt selected from a triphenylsulfonium salt and a diphenyliodonium salt as an acid generator is added to a cyclohexylmethyl (2-oxosulfonium) perfluoroalkyl sulfonate or the like. -By using peroxoalkylsulfonate salt of oxosulfonium, the resolution is improved, and the profile on a basic substrate or a low-reflectance substrate is also improved (Japanese Patent Application No. 2000-060057). . As a result of further examination, 2
The present inventors have found that line edge roughness can be improved by using a specific sulfonium salt in place of a perfluoroalkyl sulfonate salt of -oxosulfonium, and completed the present invention.

[0007]

That is, the present invention provides:
The sulfonium salt represented by the following formula (I) and the following formula (I ′)
Sulfonium salt represented by (Wherein, Q ¹ and Q ² independently represent an alkyl group having 1 to 6 carbon atoms or a cycloalkyl group having 3 to 10 carbon atoms. Q ³ represents a hydrogen atom, and Q ⁴ represents a carbon atom. Represents an alkyl group of numbers 1 to 6, a cycloalkyl group of 3 to 10 carbon atoms,
Or Q ³ and Q ⁴ together with an adjacent CHC (O) group
-Represents an oxocycloalkyl group. Q ⁵ SO ₃ ^- represents an organic sulfonate ions. However, when Q ⁵ represents a perfluoroalkyl group having 1 to 8 carbon atoms, Q ¹ has ¹ carbon atom.
Q ² represents an alkyl group having 1 to 6 carbon atoms or a cycloalkyl group having 3 to 10 carbon atoms;
Except when ³ and Q ⁴ together with the adjacent CHC (O) group represent a 2-oxocyclohexyl group. )

[0008] (In the formula, Q represents an alicyclic hydrocarbon group having 3 to 7 carbon atoms which completes a ring together with the described S ⁺ . The alicyclic hydrocarbon group may have a ketone group, Further, at least one —CH ₂ — of the alicyclic hydrocarbon group may be substituted with an oxygen atom or a sulfur atom, Q ³ represents a hydrogen atom, and Q ⁴ represents an alkyl having 1 to 6 carbon atoms. Group, carbon number 3 ~
10 represents a cycloalkyl group, or Q ³ and Q ⁴ together with an adjacent CHC (O) group represent a 2-oxocycloalkyl group. Q ⁵ SO ₃ ^- represents an organic sulfonate ions. At least one sulfonium salt selected from the group consisting of a triphenylsulfonium salt represented by the following formula (IIa) and a diphenyliodonium salt represented by the following formula (IIb) (Wherein, P ^{1 to} P ³ independently represent hydrogen, a hydroxyl group, an alkyl group having 1 to 6 carbon atoms or an alkoxy group having 1 to 6 carbon atoms, and P ⁶ SO ₃ ⁻ represents an organic sulfonate ion. Represents.) (In the formula, P ⁴ and P ⁵ independently represent hydrogen, a hydroxyl group, an alkyl group having 1 to 6 carbon atoms or an alkoxy group having 1 to 6 carbon atoms, and P ⁷ SO ₃ ⁻ represents an organic sulfonate ion. And an acid generator containing at least one onium salt selected from the group consisting of an onium salt and a polymerized unit having an acid-labile group, which itself is insoluble or hardly soluble in alkali, It is intended to provide a practically excellent chemically amplified positive resist composition containing a resin which becomes soluble in alkali by the action of (1).

Further, the present invention provides a compound of the formula (Ia) (Wherein, Q ⁶ is perfluoroalkyl group having 1 to 8 carbon atoms, an alkyl group having 1 to 8 carbon atoms, .Q ⁶ which represents an aromatic group or a camphor group having 6 to 12 carbon atoms, 1 to 4 carbon atoms When it represents a perfluoroalkyl group having from 8 to 8, Q ¹ and Q ² each independently represent an alkyl group having 1 to 6 carbon atoms and 3 to 1 carbon atoms.
Represents a cycloalkyl group of 0. Q ³ represents a hydrogen atom, and Q ⁴ represents an alkyl group having 1 to 6 carbon atoms and a cycloalkyl group having 3 to 10 carbon atoms. Q ⁶ is an alkyl group having 1 to 8 carbon atoms,
When representing an aromatic group having 6 to 12 carbon atoms or a camphor group, Q ¹ and Q ² independently represent an alkyl group having 1 to 6 carbon atoms or a cycloalkyl group having 3 to 10 carbon atoms. Q ³
Represents a hydrogen atom, Q ⁴ represents an alkyl group having 1 to 6 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, or Q ³ and Q ⁴
Represents a 2-oxocycloalkyl group together with an adjacent CHC (O) group. ) Is provided.

Further, the present invention provides a compound of the formula (I'a) (In the formula, Q represents an alicyclic hydrocarbon group having 3 to 7 carbon atoms that completes a ring together with the described S ⁺ . The alicyclic hydrocarbon group may have a ketone group, Further, at least one —CH ₂ — of the alicyclic hydrocarbon group may be substituted with an oxygen atom or a sulfur atom, Q ³ represents a hydrogen atom, and Q ⁴ represents an alkyl having 1 to 6 carbon atoms. Group, having 3 to 1 carbon atoms
0 represents a cycloalkyl group, or Q ³ and Q ⁴ together with an adjacent CHC (O) group represent a 2-oxocycloalkyl group. Q ⁵ SO ₃ ^- represents an organic sulfonate ions. ) Is provided. here,
The camphor group refers to the following groups.

[0011]

BEST MODE FOR CARRYING OUT THE INVENTION An acid generator used in a chemically amplified resist composition is obtained by applying radiation such as light or an electron beam to the substance itself or a resist composition containing the substance. The substance is decomposed to generate an acid. In the composition according to the present invention, as the acid generator, at least one sulfonium salt selected from the sulfonium salt represented by the formula (I) and the sulfonium salt represented by the formula (I ′), and the acid generator represented by the formula (IIa) )
And a triphenylsulfonium salt represented by the formula (II)
and at least one onium salt selected from the diphenyliodonium salts shown in b).

In the formula (I), Q ¹ and Q ² can be each independently an alkyl group having 1 to 6 carbon atoms or a cycloalkyl group having 3 to 10 carbon atoms. May be linear or branched. Specific examples of the alkyl group and the cycloalkyl group include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a tert-butyl group, a pentyl group, a hexyl group, and a cyclohexyl group. In the formula (I), Q ³ represents a hydrogen atom, Q ⁴ represents a linear or branched alkyl group having 1 to 6 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms,
Or Q ³ and Q ⁴ together with an adjacent CHC (O) group
—Oxocycloalkyl group can be represented. Specific alkyl group for Q ^4, and examples of the cycloalkyl group, a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, tert- butyl group, a pentyl group, a hexyl group, and cyclohexyl group. When Q ³ and Q ⁴ can be taken together with an adjacent CHC (O) group to represent a 2-oxocycloalkyl group, examples of such a 2-oxocycloalkyl group include a 2-oxocyclohexyl group, Examples include a 2-oxocyclopentyl group and a camphor group.

[0013] Further, in the equation _{^{(I), Q 5 SO 3}} - represents an organic sulfonate ions. Here, Q ⁵ may be an organic group having about 1 to 12 carbon atoms, for example, 1 to 8 carbon atoms.
, An alkyl group having 1 to 8 carbon atoms, an aromatic group having 6 to 12 carbon atoms, and a camphor group. Specific examples corresponding to the perfluoroalkyl group include a trifluoromethyl group, a perfluorobutyl group, a perfluorooctyl group, and the like.
Examples of the alkyl group of No. 8 to 8 include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a pentyl group, a hexyl group, a cyclohexyl group, and an octyl group. As the aromatic group, a phenyl group, a tolyl group , A xylyl group, a medityl group, a naphthyl group and the like.

Next, in the formula (I '), Q represents an alicyclic hydrocarbon group having 5 to 7 carbon atoms which completes a ring together with the described S ⁺ . The alicyclic hydrocarbon group may have a ketone group, and at least one —CH ₂ — of the alicyclic hydrocarbon group may be substituted with an oxygen atom or a sulfur atom. Examples of the alicyclic hydrocarbon having 5 to 7 carbon atoms that completes a ring together with the described sulfur atom include tetrahydrothiophene, thioxane, dithiane, tetrahydrothiophen-3-one, and tetrahydrothiopyran-4-one. Among these, a sulfonium salt having an alicyclic hydrocarbon group represented by the formula (I ′) is preferable in terms of thermal stability. When the sulfonium salt is used, the baking temperature
(PEB temperature) can be increased, and line edge roughness is improved.

In the formula (I ′), Q ³ represents a hydrogen atom, Q ⁴ represents an alkyl group having 1 to 6 carbon atoms, and ^{3 to} 1 carbon atoms.
0 represents a cycloalkyl group, or Q ³ and Q ⁴ together with an adjacent CHC (O) group represent a 2-oxocycloalkyl group. Q ⁵ SO ₃ ^- represents an organic sulfonate ions. Specific alkyl group for Q ^4, and examples of the cycloalkyl group, a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, tert- butyl group, a pentyl group, a hexyl group, and cyclohexyl group.
When Q ³ and Q ⁴ can be taken together with an adjacent CHC (O) group to represent a 2-oxocycloalkyl group, examples of such a 2-oxocycloalkyl group include 2-oxocycloalkyl group.
Examples thereof include an oxocyclohexyl group, a 2-oxocyclopentyl group, and a camphor group.

The sulfonium salts represented by the formulas (I) and (Ia) can be produced according to a known method. For example, JV Crivello et al., J. Polymer Scie
nce., Polymer Chemistry Edition, Vol. 17, 2877-2892
(1979), and can be produced according to the following reaction scheme.

[0017]

In the formula, Q ¹ , Q ² , Q ³ , Q ⁴ and Q ⁵ are as defined above, X represents a halogen such as bromine or iodine, and M represents an alkali such as sodium or potassium. Represents metal, silver or hydrogen.

That is, a β-halogenoketone corresponding to (A2) is allowed to act on a sulfide compound corresponding to the above formula (A1) to form a sulfonium halide corresponding to the above formula (B), and further to a formula Q ⁵ SO _By reacting a sulfonic acid metal salt or sulfonic acid corresponding to ₃ M,
The sulfonium salt represented by the formula (I) can be obtained. These reactions are carried out in a suitable solvent, for example, a solvent such as acetone, acetonitrile, nitromethane and the like. The sulfide compound of the formula (A1) is preferably used in an amount of from 0.7 to 0 relative to the β-halogenoketone corresponding to the formula (A2).
1.5 molar ratio, more preferably 0.8 to 1.1
Use the molar ratio. Further, the sulfonic acid metal salt or sulfonic acid corresponding to the formula Q ⁵ SO ₃ M is 0.7 to 1.1 with respect to the sulfide compound of the formula (A1) used for forming the sulfonium halide of the formula (B). A 2 mole ratio, preferably 0.8 to 1.0 mole ratio may be used. After completion of the reaction, the produced metal halide salt and the like are removed by filtration or the like, and then subjected to post-treatment such as concentration or recrystallization, whereby the compound represented by formula (I)
Can be obtained.

The sulfonium salts represented by formulas (I ') and (I'a) can be produced according to known methods. For example, DN Kevill et al., J. Am. Chem. So
c., Vol. 108, 1579-1585 (1986).

Formulas (I), (I '), (Ia) and (I')
Specific examples of the sulfonium salt represented by a) include:
The following compounds can be mentioned.

Dimethyl (2-oxopropyl) sulfonium trifluoromethanesulfonate, dimethyl (2
-Oxobutyl) sulfonium trifluoromethanesulfonate, dimethyl (2-oxopentyl) sulfonium trifluoromethanesulfonate, dimethyl (2
-Oxohexyl) sulfonium trifluoromethanesulfonate, dimethyl (2-oxoheptyl) sulfonium trifluoromethanesulfonate, dimethyl (2-oxooctyl) sulfonium trifluoromethanesulfonate, dimethyl (3-methyl-2-oxobutyl) sulfonium trifluoromethanesulfonate Nato, 3,3-dimethyl-2-oxobutyl dimethylsulfonium trifluoromethanesulfonate, 2-cyclohexyl-2-oxoethyl dimethylsulfonium trifluoromethanesulfonate, 2-cyclopentyl-2-oxoethyl dimethylsulfonium trifluoromethanesulfonate,

Diethyl (2-oxopropyl) sulfonium trifluoromethanesulfonate, diethyl (2
-Oxobutyl) sulfonium trifluoromethanesulfonate, diethyl (2-oxopentyl) sulfonium trifluoromethanesulfonate, diethyl (2
-Oxohexyl) sulfonium trifluoromethanesulfonate, diethyl (2-oxoheptyl) sulfonium trifluoromethanesulfonate, diethyl (2-oxooctyl) sulfonium trifluoromethanesulfonate, diethyl (3-methyl-2-oxobutyl) sulfonium trifluoromethanesulfonate Nato, 3,3-dimethyl-2-oxobutyl diethylsulfonium trifluoromethanesulfonate, 2-cyclohexyl-2-oxoethyl diethylsulfonium trifluoromethanesulfonate, 2-cyclopentyl-2-oxoethyl diethylsulfonium trifluoromethanesulfonate,

Dibutyl (2-oxopropyl) sulfonium trifluoromethanesulfonate, dibutyl (2
-Oxobutyl) sulfonium trifluoromethanesulfonate, dibutyl (2-oxopentyl) sulfonium trifluoromethanesulfonate, dibutyl (2
-Oxohexyl) sulfonium trifluoromethanesulfonate, dibutyl (2-oxoheptyl) sulfonium trifluoromethanesulfonate, dibutyl (2-oxooctyl) sulfonium trifluoromethanesulfonate, dibutyl (3-methyl-2-oxobutyl) sulfonium trifluoromethanesulfonate Nato, dibutyl (3,3-dimethyl 2-oxobutyl) sulfonium trifluoromethanesulfonate, dibutyl (2-cyclohexyl-2-oxoethyl) sulfonium trifluoromethanesulfonate, dibutyl (2-cyclopentyl-2-oxoethyl) sulfonium trifluoromethanesulfonate , Diisopropyl (2-oxopropyl) sulfonium trifluoromethanesulfonate, diisopropyl 2-oxobutyl) sulfonium trifluoromethanesulfonate,
Diisopropyl (2-oxopentyl) sulfonium
Trifluoromethanesulfonate, diisopropyl (2
-Oxohexyl) sulfonium trifluoromethanesulfonate, diisopropyl (2-oxoheptyl)
Sulfonium trifluoromethanesulfonate, diisopropyl (2-oxooctyl) sulfonium trifluoromethanesulfonate, diisopropyl (3-methyl-2-oxobutyl) sulfonium trifluoromethanesulfonate,

3,3-dimethyl-2-oxobutyl diisopropyl sulfonium trifluoromethanesulfonate, 2-cyclohexyl-2-oxoethyl diisopropylsulfonium trifluoromethanesulfonate, 2-cyclopentyl-2-oxoethyl diisopropylsulfonium trifluoromethanesulfonate, tert-butyl Methyl (2-oxopropyl) sulfonium trifluoromethanesulfonate,
tert-butyl methyl (2-oxobutyl) sulfonium trifluoromethanesulfonate, tert-butyl
Butyl methyl (2-oxopentyl) sulfonium
Trifluoromethanesulfonate, tert-butyl
Methyl (2-oxohexyl) sulfonium trifluoromethanesulfonate, tert-butylmethyl (2-oxoheptyl) sulfonium trifluoromethanesulfonate, tert-butylmethyl (2-oxooctyl) sulfonium trifluoromethanesulfonate, tert-butylmethyl ( 3-methyl-2
-Oxobutyl) sulfonium trifluoromethanesulfonate, tert-butyl (3,3-dimethyl2
-Oxobutyl) methyl sulfonium trifluoromethanesulfonate, tert-butyl (2-cyclohexyl-2-oxoethyl) methylsulfonium trifluoromethanesulfonate, tert-butyl (2-cyclopentyl-2-oxoethyl) methylsulfonium trifluoromethanesulfonate,

Cyclohexylmethyl (2-oxopropyl) sulfonium trifluoromethanesulfonate, cyclohexylmethyl (2-oxobutyl) sulfonium trifluoromethanesulfonate, cyclohexylmethyl (2-oxopentyl) sulfonium
Trifluoromethanesulfonate, cyclohexylmethyl (2-oxohexyl) sulfonium trifluoromethanesulfonate, cyclohexylmethyl (2-
Oxoheptyl) sulfonium trifluoromethanesulfonate, cyclohexylmethyl (2-oxooctyl) sulfonium trifluoromethanesulfonate, cyclohexylmethyl (3-methyl-2-oxobutyl) sulfonium trifluoromethanesulfonate, cyclohexyl (3,3-dimethyl2-oxobutyl) ) Methyl sulfonium trifluoromethanesulfonate, cyclohexyl (2-cyclohexyl-
2-oxoethyl) methylsulfonium trifluoromethanesulfonate, cyclohexyl (2-cyclopentyl-2-oxoethyl) methylsulfonium
Trifluoromethanesulfonate,

2-oxopropyl thiacyclopentanium trifluoromethanesulfonate, 2-oxobutyl thiacyclopentanium trifluoromethanesulfonate, 2-oxopentyl thiacyclopentanium trifluoromethanesulfonate, 2-oxohexyl thiacyclopentanium trifluoro Methanesulfonate, 2-oxoheptyl thiacyclopentanium trifluoromethanesulfonate, 2-oxooctylthiacyclopentanium trifluoromethanesulfonate, 3-methyl-2-oxobutylthiacyclopentanium trifluoromethanesulfonate, 3,3- Dimethyl-2-oxobutyl thiacyclopentanium trifluoromethanesulfonate,

2-cyclohexyl-2-oxoethyl
Thiacyclopentanium trifluoromethanesulfonate, 2-cyclopentyl-2-oxoethyl thiacyclopentanium trifluoromethanesulfonate,
2-oxopropyl thiacyclohexanium trifluoromethanesulfonate, 2-oxobutyl thiacyclohexanium trifluoromethanesulfonate,
2-oxopentyl thiacyclohexanium trifluoromethanesulfonate, 2-oxohexyl thiacyclohexanium trifluoromethanesulfonate, 2-oxoheptyl thiacyclohexanium trifluoromethanesulfonate, 2-oxooctyl
Thiacyclohexanium trifluoromethanesulfonate, 3-methyl-2-oxobutyl thiacyclohexanium trifluoromethanesulfonate, 3,3-
Dimethyl-2-oxobutyl thiacyclohexanium trifluoromethanesulfonate,

2-cyclohexyl-2-oxoethyl
Thiacyclohexanium trifluoromethanesulfonate, 2-cyclopentyl-2-oxoethyl thiacyclohexanium trifluoromethanesulfonate,
2-oxopropyl (1,4-thioxanium) trifluoromethanesulfonate, 2-oxobutyl
(1,4-thioxanium) trifluoromethanesulfonate, 2-oxopentyl (1,4-thioxanium) trifluoromethanesulfonate, 2-oxohexyl (1,4-thioxanium) trifluoromethanesulfonate, 2-oxoheptyl (1 , 4-
Thioxanium) trifluoromethanesulfonate,
2-oxooctyl (1,4-thioxanium) trifluoromethanesulfonate, 3-methyl-2-oxobutyl (1,4-thioxanium) trifluoromethanesulfonate, 3,3-dimethyl-2-oxobutyl (1,4-thioxanium) ) Trifluoromethanesulfonate,

2-cyclohexyl-2-oxoethyl
(1,4-thioxanium) trifluoromethanesulfonate, 2-cyclopentyl-2-oxoethyl
(1,4-thioxanium) trifluoromethanesulfonate, 2-oxopropyl (4-oxothiacyclohexanium) trifluoromethanesulfonate,
2-oxobutyl (4-oxothiacyclohexanium) trifluoromethanesulfonate, 2-oxopentyl (4-oxothiacyclohexanium) trifluoromethanesulfonate, 2-oxohexyl
(4-oxothiacyclohexanium) trifluoromethanesulfonate, 2-oxoheptyl (4-oxothiacyclohexanium) trifluoromethanesulfonate, 2-oxooctyl (4-oxothiacyclohexanium) trifluoromethanesulfonate,
3-methyl-2-oxobutyl (4-oxothiacyclohexanium) trifluoromethanesulfonate,
3,3-dimethyl-2-oxobutyl (4-oxothiacyclohexanium) trifluoromethanesulfonate,

2-cyclohexyl-2-oxoethyl
(4-oxothiacyclohexanium) trifluoromethanesulfonate, 2-cyclopentyl-2-oxoethyl (4-oxothiacyclohexanium) trifluoromethanesulfonate, 2-oxopropyl
(1,4-dithianium) trifluoromethanesulfonate, 2-oxobutyl (1,4-dithianium)
Trifluoromethanesulfonate, 2-oxopentyl (1,4-dithianium) trifluoromethanesulfonate, 2-oxohexyl (1,4-dithianium) trifluoromethanesulfonate, 2-oxoheptyl (1,4-dithianium) trifluoromethane Sulfonate, 2-oxooctyl (1,4-dithianium) trifluoromethanesulfonate, 3-
Methyl-2-oxobutyl (1,4-dithianium)
Trifluoromethanesulfonate, 3,3-dimethyl-2-oxobutyl (1,4-dithianium) trifluoromethanesulfonate,

2-cyclohexyl-2-oxoethyl
(1,4-dithianium) trifluoromethanesulfonate, 2-cyclopentyl-2-oxoethyl
(1,4-dithianium) trifluoromethanesulfonate, 2-oxocyclohexyl thiacyclopentanium trifluoromethanesulfonate, dimethyl (2-oxopropyl) sulfonium perfluorobutanesulfonate, dimethyl (2-oxobutyl) sulfonium perfluorobutanesulfo Nato, dimethyl (2-oxopentyl) sulfonium perfluorobutanesulfonate, dimethyl (2-oxohexyl) sulfonium perfluorobutanesulfonate, dimethyl (2-oxoheptyl) sulfonium perfluorobutanesulfonate, dimethyl (2-oxooctyl) )
Sulfonium perfluorobutanesulfonate, dimethyl (3-methyl-2-oxobutyl) sulfonium
Perfluorobutane sulfonate, 3,3-dimethyl-
2-oxobutyl dimethylsulfonium perfluorobutanesulfonate,

2-cyclohexyl-2-oxoethyl
Dimethylsulfonium perfluorobutanesulfonate, 2-cyclopentyl-2-oxoethyl dimethylsulfonium perfluorobutanesulfonate, diethyl (2-oxopropyl) sulfonium perfluorobutanesulfonate, diethyl (2-oxobutyl)
Sulfonium perfluorobutanesulfonate, diethyl (2-oxopentyl) sulfonium perfluorobutanesulfonate, diethyl (2-oxohexyl) sulfonium perfluorobutanesulfonate,
Diethyl (2-oxoheptyl) sulfonium perfluorobutanesulfonate, diethyl (2-oxooctyl) sulfonium perfluorobutanesulfonate, diethyl (3-methyl-2-oxobutyl) sulfonium perfluorobutanesulfonate, 3,3-dimethyl -2-oxobutyl diethylsulfonium perfluorobutanesulfonate,

2-cyclohexyl-2-oxoethyl
Diethylsulfonium perfluorobutanesulfonate, 2-cyclopentyl-2-oxoethyl diethylsulfonium perfluorobutanesulfonate, dibutyl (2-oxopropyl) sulfonium perfluorobutanesulfonate, dibutyl (2-oxobutyl)
Sulfonium perfluorobutanesulfonate, dibutyl (2-oxopentyl) sulfonium perfluorobutanesulfonate, dibutyl (2-oxohexyl) sulfonium perfluorobutanesulfonate,
Dibutyl (2-oxoheptyl) sulfonium perfluorobutanesulfonate, dibutyl (2-oxooctyl) sulfonium perfluorobutanesulfonate, dibutyl (3-methyl-2-oxobutyl) sulfonium perfluorobutanesulfonate, dibutyl (3,3 -Dimethyl 2-oxobutyl) sulfonium
Perfluorobutanesulfonate, dibutyl (2-cyclohexyl-2-oxoethyl) sulfonium perfluorobutanesulfonate, dibutyl (2-cyclopentyl-2-oxoethyl) sulfonium perfluorobutanesulfonate,

Diisopropyl (2-oxopropyl) sulfonium perfluorobutanesulfonate, diisopropyl (2-oxobutyl) sulfonium perfluorobutanesulfonate, diisopropyl (2-oxopentyl) sulfonium perfluorobutanesulfonate, diisopropyl (2-oxohexyl) ) Sulfonium perfluorobutanesulfonate, diisopropyl (2-oxoheptyl) sulfonium perfluorobutanesulfonate, diisopropyl (2-oxooctyl) sulfonium perfluorobutanesulfonate, diisopropyl (3-methyl-2-oxobutyl)
Sulfonium perfluorobutane sulfonate, 3,
3-dimethyl-2-oxobutyl diisopropyl sulfonium perfluorobutanesulfonate, 2-cyclohexyl-2-oxoethyl diisopropylsulfonium perfluorobutanesulfonate, 2-cyclopentyl-2-oxoethyl diisopropylsulfonium perfluorobutanesulfonate,

Tert-butyl methyl (2-oxopropyl) sulfonium perfluorobutanesulfonate, tert-butylmethyl (2-oxobutyl) sulfonium perfluorobutanesulfonate, ter
t-butylmethyl (2-oxopentyl) sulfonium perfluorobutanesulfonate, tert-butylmethyl (2-oxohexyl) sulfonium perfluorobutanesulfonate, tert-butylmethyl (2-oxoheptyl) sulfonium perfluorobutanesulfonate , Tert-butyl methyl (2-
Oxooctyl) sulfonium perfluorobutanesulfonate, tert-butyl methyl (3-methyl-
2-oxobutyl) sulfonium perfluorobutanesulfonate, tert-butyl (3,3-dimethyl2-oxobutyl) methylsulfonium perfluorobutanesulfonate, tert-butyl (2-cyclohexyl-2-oxoethyl) methylsulfonium perfluorobutanesulfo Nate, tert-butyl (2-cyclopentyl-2-oxoethyl) methylsulfonium perfluorobutanesulfonate,

Cyclohexylmethyl (2-oxopropyl) sulfonium perfluorobutanesulfonate, cyclohexylmethyl (2-oxobutyl) sulfonium perfluorobutanesulfonate, cyclohexylmethyl (2-oxopentyl) sulfonium
Perfluorobutanesulfonate, cyclohexylmethyl (2-oxohexyl) sulfonium perfluorobutanesulfonate, cyclohexylmethyl (2-
Oxoheptyl) sulfonium perfluorobutanesulfonate, cyclohexylmethyl (2-oxooctyl) sulfonium perfluorobutanesulfonate, cyclohexylmethyl (3-methyl-2-oxobutyl) sulfonium perfluorobutanesulfonate, cyclohexyl (3,3-dimethyl 2-oxobutyl) methyl sulfonium perfluorobutanesulfonate, cyclohexyl (2-cyclohexyl-
2-oxoethyl) methylsulfonium perfluorobutanesulfonate, cyclohexyl (2-cyclopentyl-2-oxoethyl) methylsulfonium
Perfluorobutanesulfonate,

2-oxopropyl thiacyclopentanium perfluorobutane sulfonate, 2-oxobutyl thiacyclopentanium perfluorobutane sulfonate, 2-oxopentyl thiacyclopentanium perfluorobutane sulfonate, 2-oxohexyl thiacyclo Pentanium perfluorobutane sulfonate, 2-oxoheptyl thiacyclopentanium perfluorobutane sulfonate, 2-oxooctyl thiacyclopentanium perfluorobutane sulfonate, 3-methyl-2-oxobutyl thiacyclopentanium perfluorobutane Sulfonate, 3,3-dimethyl-2-oxobutyl thiacyclopentanium perfluorobutanesulfonate, 2-
Cyclohexyl-2-oxoethyl thiacyclopentanium perfluorobutanesulfonate, 2-cyclopentyl-2-oxoethyl thiacyclopentanium perfluorobutanesulfonate,

2-oxopropyl thiacyclohexanium perfluorobutanesulfonate, 2-oxobutylthiacyclohexanium perfluorobutanesulfonate, 2-oxopentylthiacyclohexanium perfluorobutanesulfonate, 2-oxohexyl thiacyclohexyl Sanium perfluorobutane sulfonate, 2-oxoheptyl thiacyclohexanium perfluorobutane sulfonate, 2-oxooctyl thiacyclohexanium perfluorobutane sulfonate, 3-methyl-2-oxobutyl thiacyclohexanium perfluorobutane Sulfonate, 3,3-dimethyl-2-oxobutyl thiacyclohexanium perfluorobutanesulfonate, 2-
Cyclohexyl-2-oxoethyl thiacyclohexanium perfluorobutanesulfonate, 2-cyclopentyl-2-oxoethyl thiacyclohexanium perfluorobutanesulfonate,

2-oxopropyl (1,4-thioxanium) perfluorobutanesulfonate, 2-oxobutyl (1,4-thioxanium) perfluorobutanesulfonate, 2-oxopentyl (1,4-
Thioxanium) perfluorobutanesulfonate,
2-oxohexyl (1,4-thioxanium) perfluorobutanesulfonate, 2-oxoheptyl
(1,4-thioxanium) perfluorobutanesulfonate, 2-oxooctyl (1,4-thioxanium) perfluorobutanesulfonate, 3-methyl-2-oxobutyl (1,4-thioxanium) perfluorobutanesulfonate, 3,3-dimethyl-2
-Oxobutyl (1,4-thioxanium) perfluorobutanesulfonate,

2-cyclohexyl-2-oxoethyl
(1,4-thioxanium) perfluorobutanesulfonate, 2-cyclopentyl-2-oxoethyl
(1,4-thioxanium) perfluorobutanesulfonate, 2-oxopropyl (4-oxothiacyclohexanium) perfluorobutanesulfonate,
2-oxobutyl (4-oxothiacyclohexanium) perfluorobutanesulfonate, 2-oxopentyl (4-oxothiacyclohexanium) perfluorobutanesulfonate, 2-oxohexyl
(4-oxothiacyclohexanium) perfluorobutanesulfonate, 2-oxoheptyl (4-oxothiacyclohexanium) perfluorobutanesulfonate, 2-oxooctyl (4-oxothiacyclohexanium) perfluorobutane Sulfonate,
3-methyl-2-oxobutyl (4-oxothiacyclohexanium) perfluorobutanesulfonate,
3,3-dimethyl-2-oxobutyl (4-oxothiacyclohexanium) perfluorobutanesulfonate,

2-cyclohexyl-2-oxoethyl
(4-oxothiacyclohexanium) perfluorobutanesulfonate, 2-cyclopentyl-2-oxoethyl (4-oxothiacyclohexanium) perfluorobutanesulfonate, 2-oxopropyl
(1,4-dithianium) perfluorobutanesulfonate, 2-oxobutyl (1,4-dithianium)
Perfluorobutanesulfonate, 2-oxopentyl (1,4-dithianium) Perfluorobutanesulfonate, 2-oxohexyl (1,4-dithianium) Perfluorobutanesulfonate, 2-oxoheptyl (1,4-dithianium) ) Perfluorobutanesulfonate, 2-oxooctyl (1,4-dithianium) perfluorobutanesulfonate, 3-
Methyl-2-oxobutyl (1,4-dithianium)
Perfluorobutanesulfonate, 3,3-dimethyl-2-oxobutyl (1,4-dithianium) perfluorobutanesulfonate,

2-cyclohexyl-2-oxoethyl
(1,4-dithianium) perfluorobutanesulfonate, 2-cyclopentyl-2-oxoethyl
(1,4-dithianium) perfluorobutanesulfonate, 2-oxocyclohexyl thiacyclopentanium perfluorobutanesulfonate, dimethyl (2-oxopropyl) sulfonium perfluorooctanesulfonate, dimethyl (2-oxobutyl) sulfonium perfluoro Octanesulfonate, dimethyl (2-oxopentyl) sulfonium perfluorooctanesulfonate, dimethyl (2-oxohexyl) sulfonium perfluorooctanesulfonate, dimethyl (2-oxoheptyl) sulfonium perfluorooctanesulfonate, dimethyl (2- Oxooctyl) sulfonium perfluorooctanesulfonate, dimethyl (3-methyl-2-oxobutyl)
Sulfonium perfluorooctanesulfonate,
3,3-dimethyl-2-oxobutyl dimethylsulfonium perfluorooctanesulfonate,

2-cyclohexyl-2-oxoethyl
Dimethylsulfonium perfluorooctanesulfonate, 2-cyclopentyl-2-oxoethyl dimethylsulfonium perfluorooctanesulfonate,
Diethyl (2-oxopropyl) sulfonium perfluorooctanesulfonate, diethyl (2-oxobutyl) sulfonium perfluorooctanesulfonate, diethyl (2-oxopentyl) sulfonium perfluorooctanesulfonate, diethyl (2-oxohexyl) sulfonium par Fluorooctanesulfonate, diethyl (2-oxoheptyl) sulfonium Perfluorooctanesulfonate, diethyl (2
-Oxooctyl) sulfonium perfluorooctanesulfonate, diethyl (3-methyl-2-oxobutyl) sulfonium perfluorooctanesulfonate, 3,3-dimethyl-2-oxobutyl diethylsulfonium perfluorooctanesulfonate,

2-cyclohexyl-2-oxoethyl
Diethylsulfonium perfluorooctanesulfonate, 2-cyclopentyl-2-oxoethyl diethylsulfonium perfluorooctanesulfonate,
Dibutyl (2-oxopropyl) sulfonium perfluorooctanesulfonate, dibutyl (2-oxobutyl) sulfonium perfluorooctanesulfonate, dibutyl (2-oxopentyl) sulfonium perfluorooctanesulfonate, dibutyl (2-oxohexyl) sulfonium par Fluorooctanesulfonate, dibutyl (2-oxoheptyl) sulfonium Perfluorooctanesulfonate, dibutyl (2
-Oxooctyl) sulfonium perfluorooctanesulfonate, dibutyl (3-methyl-2-oxobutyl) sulfonium perfluorooctanesulfonate, dibutyl (3,3-dimethyl2-oxobutyl) sulfonium perfluorooctanesulfonate, dibutyl (2- Cyclohexyl-2-oxoethyl) sulfonium perfluorooctanesulfonate, dibutyl (2-cyclopentyl-2-oxoethyl) sulfonium perfluorooctanesulfonate,

Diisopropyl (2-oxopropyl) sulfonium perfluorooctanesulfonate, diisopropyl (2-oxobutyl) sulfonium perfluorooctanesulfonate, diisopropyl (2-oxopentyl) sulfonium perfluorooctanesulfonate, diisopropyl (2-oxohexyl) ) Sulfonium perfluorooctanesulfonate, diisopropyl (2-oxoheptyl) sulfonium perfluorooctanesulfonate, diisopropyl (2-
Oxooctyl) sulfonium perfluorooctanesulfonate, diisopropyl (3-methyl-2-oxobutyl) sulfonium perfluorooctanesulfonate, 3,3-dimethyl2-oxobutyldiisopropylsulfonium perfluorooctanesulfonate,

2-cyclohexyl-2-oxoethyl
Diisopropylsulfonium perfluorooctanesulfonate, 2-cyclopentyl-2-oxoethyl
Diisopropylsulfonium perfluorooctanesulfonate, tert-butylmethyl (2-oxopropyl) sulfonium perfluorooctanesulfonate, tert-butylmethyl (2-oxobutyl)
Sulfonium perfluorooctanesulfonate, t
tert-butyl methyl (2-oxopentyl) sulfonium perfluorooctanesulfonate, tert
-Butylmethyl (2-oxohexyl) sulfonium perfluorooctanesulfonate, tert-butylmethyl (2-oxoheptyl) sulfonium perfluorooctanesulfonate, tert-butylmethyl (2-oxooctyl) sulfonium perfluorooctanesulfonate, tert-butyl methyl (3-methyl-2-oxobutyl) sulfonium perfluorooctanesulfonate, tert-butyl
(3,3-dimethyl 2-oxobutyl) methyl sulfonium perfluorooctanesulfonate, ter
t-butyl (2-cyclohexyl-2-oxoethyl) methylsulfonium perfluorooctanesulfonate, tert-butyl (2-cyclopentyl-
2-oxoethyl) methylsulfonium perfluorooctanesulfonate,

Cyclohexylmethyl (2-oxopropyl) sulfonium perfluorooctanesulfonate, cyclohexylmethyl (2-oxobutyl) sulfonium perfluorooctanesulfonate, cyclohexylmethyl (2-oxopentyl) sulfonium perfluorooctanesulfonate, cyclohexylmethyl ( 2-oxohexyl) sulfonium perfluorooctanesulfonate, cyclohexylmethyl (2-oxoheptyl) sulfonium perfluorooctanesulfonate, cyclohexylmethyl (2-oxooctyl) sulfonium perfluorooctanesulfonate, cyclohexylmethyl (3-methyl-2
-Oxobutyl) sulfonium perfluorooctanesulfonate, cyclohexyl (3,3-dimethyl2
-Oxobutyl) methyl sulfonium perfluorooctanesulfonate, cyclohexyl (2-cyclohexyl-2-oxoethyl) methylsulfonium perfluorooctanesulfonate, cyclohexyl (2-cyclopentyl-2-oxoethyl) methylsulfonium perfluorooctanesulfonate, 2
-Oxopropyl thiacyclopentanium perfluorooctanesulfonate,

2-oxobutyl thiacyclopentanium perfluorooctanesulfonate, 2-oxopentylthiacyclopentanium perfluorooctanesulfonate, 2-oxohexyl thiacyclopentanium perfluorooctanesulfonate, 2-oxoheptylthiacyclo Pentanium perfluorooctanesulfonate, 2-oxooctyl thiacyclopentanium perfluorooctanesulfonate,
3-methyl-2-oxobutyl thiacyclopentanium perfluorooctanesulfonate, 3,3-dimethyl-2-oxobutylthiacyclopentanium perfluorooctanesulfonate,

2-cyclohexyl-2-oxoethyl
Thiacyclopentanium perfluorooctanesulfonate, 2-cyclopentyl-2-oxoethyl thiacyclopentanium perfluorooctanesulfonate, 2-oxopropyl thiacyclohexanium perfluorooctanesulfonate, 2-oxobutyl
Thiacyclohexanium perfluorooctane sulfonate, 2-oxopentyl Thiacyclohexanium perfluorooctane sulfonate, 2-oxohexyl thiacyclohexanium perfluorooctane sulfonate, 2-oxoheptyl thiacyclohexanium perfluorooctane sulfonate Nato, 2-oxooctyl thiacyclohexanium perfluorooctanesulfonate, 3-methyl-2-oxobutyl
Thiacyclohexanium perfluorooctanesulfonate, 3,3-dimethyl-2-oxobutyl thiacyclohexanium perfluorooctanesulfonate,

2-cyclohexyl-2-oxoethyl
Thiacyclohexanium perfluorooctanesulfonate, 2-cyclopentyl-2-oxoethyl thiacyclohexanium perfluorooctanesulfonate, 2-oxopropyl (1,4-thioxanium)
Perfluorooctanesulfonate, 2-oxobutyl (1,4-thioxanium) perfluorooctanesulfonate, 2-oxopentyl (1,4-thioxanium) perfluorooctanesulfonate, 2
-Oxohexyl (1,4-thioxanium) perfluorooctanesulfonate, 2-oxoheptyl
(1,4-thioxanium) perfluorooctanesulfonate, 2-oxooctyl (1,4-thioxanium) perfluorooctanesulfonate, 3-methyl-2-oxobutyl (1,4-thioxanium)
Perfluorooctane sulfonate, 3,3-dimethyl-2-oxobutyl (1,4-thioxanium)
Perfluorooctanesulfonate,

2-cyclohexyl-2-oxoethyl
(1,4-thioxanium) perfluorooctanesulfonate, 2-cyclopentyl-2-oxoethyl
(1,4-thioxanium) perfluorooctanesulfonate, 2-oxopropyl (4-oxothiacyclohexanium) perfluorooctanesulfonate, 2-oxobutyl (4-oxothiacyclohexanium) perfluorooctanesulfonate, 2-oxopentyl (4-oxothiacyclohexanium)
Perfluorooctane sulfonate, 2-oxohexyl (4-oxothiacyclohexanium) Perfluorooctane sulfonate, 2-oxoheptyl
(4-oxothiacyclohexanium) perfluorooctanesulfonate, 2-oxooctyl (4-oxothiacyclohexanium) perfluorooctanesulfonate, 3-methyl-2-oxobutyl (4-
Oxothiacyclohexanium) perfluorooctanesulfonate, 3,3-dimethyl-2-oxobutyl (4-oxothiacyclohexanium) perfluorooctanesulfonate,

2-cyclohexyl-2-oxoethyl
(4-oxothiacyclohexanium) perfluorooctanesulfonate, 2-cyclopentyl-2-oxoethyl (4-oxothiacyclohexanium) perfluorooctanesulfonate, 2-oxopropyl (1,4-dithianium) perfluoro Octanesulfonate, 2-oxobutyl (1,4-dithianium) perfluorooctanesulfonate, 2-oxopentyl (1,4-dithianium) perfluorooctanesulfonate, 2-oxohexyl (1,4-dithionium)
Dithianium) perfluorooctanesulfonate,
2-oxoheptyl (1,4-dithianium) perfluorooctanesulfonate, 2-oxooctyl
(1,4-dithianium) perfluorooctanesulfonate, 3-methyl-2-oxobutyl (1,4-
Dithianium) perfluorooctanesulfonate,
3,3-dimethyl-2-oxobutyl (1,4-dithianium) perfluorooctanesulfonate,

2-cyclohexyl-2-oxoethyl
(1,4-dithianium) perfluorooctanesulfonate, 2-cyclopentyl-2-oxoethyl
(1,4-dithianium) perfluorooctanesulfonate, 2-oxocyclohexyl thiacyclopentanium perfluorooctanesulfonate, dimethyl (2-oxopropyl) sulfonium butanesulfonate, dimethyl (2-oxobutyl) sulfonium
Butanesulfonate, dimethyl (2-oxopentyl)
Sulfonium butanesulfonate, dimethyl (2-oxohexyl) sulfonium butanesulfonate, dimethyl (2-oxoheptyl) sulfonium butanesulfonate, dimethyl (2-oxooctyl) sulfonium butanesulfonate, dimethyl (3-methyl-2)
-Oxobutyl) sulfonium butanesulfonate,
3,3-dimethyl-2-oxobutyl dimethylsulfonium butanesulfonate,

2-cyclohexyl-2-oxoethyl
Dimethylsulfonium butanesulfonate, 2-cyclopentyl-2-oxoethyl dimethylsulfonium butanesulfonate, diethyl (2-oxopropyl) sulfonium butanesulfonate, diethyl (2
-Oxobutyl) sulfonium butanesulfonate,
Diethyl (2-oxopentyl) sulfonium butanesulfonate, diethyl (2-oxohexyl) sulfonium butanesulfonate, diethyl (2-oxoheptyl) sulfonium butanesulfonate, diethyl (2-oxooctyl) sulfonium butanesulfonate, diethyl ( 3-methyl-2-oxobutyl) sulfonium butanesulfonate, 3,3-dimethyl-2
Oxobutyl diethylsulfonium butanesulfonate,

2-cyclohexyl-2-oxoethyl
Diethylsulfonium butanesulfonate, 2-cyclopentyl-2-oxoethyl diethylsulfonium butanesulfonate, dibutyl (2-oxopropyl) sulfonium butanesulfonate, dibutyl (2
-Oxobutyl) sulfonium butanesulfonate,
Dibutyl (2-oxopentyl) sulfonium butanesulfonate, dibutyl (2-oxohexyl) sulfonium butanesulfonate, dibutyl (2-oxoheptyl) sulfonium butanesulfonate, dibutyl (2-oxooctyl) sulfonium butanesulfonate, dibutyl ( 3-methyl-2-oxobutyl) sulfonium butanesulfonate, dibutyl (3,3-dimethyl2-oxobutyl) sulfonium butanesulfonate, dibutyl (2-cyclohexyl-2-oxoethyl) sulfonium butanesulfonate, dibutyl (2-cyclopentyl- 2-oxoethyl) sulfonium butanesulfonate, diisopropyl (2-oxopropyl) sulfonium butanesulfonate, diisopropyl (2-oxobutyl) sulfonate Honiumu butane sulfonate, diisopropyl (2- oxopentyl)
Sulfonium butanesulfonate, diisopropyl (2-oxohexyl) sulfonium butanesulfonate, diisopropyl (2-oxoheptyl) sulfonium butanesulfonate, diisopropyl (2-oxooctyl) sulfonium butanesulfonate, diisopropyl (3-methyl-2-oxobutyl) ) Sulfonium butanesulfonate, 3,3-dimethyl 2-oxobutyl diisopropyl sulfonium butanesulfonate,

2-cyclohexyl-2-oxoethyl
Diisopropylsulfonium butanesulfonate, 2
-Cyclopentyl-2-oxoethyl diisopropylsulfonium butanesulfonate, tert-butyl methyl (2-oxopropyl) sulfonium butanesulfonate, tert-butylmethyl (2-oxobutyl) sulfonium butanesulfonate, tert
-Butylmethyl (2-oxopentyl) sulfonium butanesulfonate, tert-butylmethyl (2
-Oxohexyl) sulfonium butanesulfonate, tert-butyl methyl (2-oxoheptyl)
Sulfonium butanesulfonate, tert-butyl methyl (2-oxooctyl) sulfonium butanesulfonate, tert-butyl methyl (3-methyl-2-oxobutyl) sulfonium butanesulfonate, tert-butyl (3,3-dimethyl2-oxobutyl) ) Methyl sulfonium butanesulfonate, tert-butyl (2-cyclohexyl-2-oxoethyl) methylsulfonium butanesulfonate, tert-butyl (2-cyclopentyl-2-oxoethyl) methylsulfonium butanesulfonate,

Cyclohexylmethyl (2-oxopropyl) sulfonium butanesulfonate, cyclohexylmethyl (2-oxobutyl) sulfonium butanesulfonate, cyclohexylmethyl (2-oxopentyl) sulfonium butanesulfonate, cyclohexylmethyl (2-oxohexyl) sulfonium Butanesulfonate, cyclohexylmethyl (2-
Oxoheptyl) sulfonium butanesulfonate,
Cyclohexylmethyl (2-oxooctyl) sulfonium butanesulfonate, cyclohexylmethyl (3-methyl-2-oxobutyl) sulfoniumbutanesulfonate, cyclohexyl (3,3-dimethyl2-oxobutyl) methylsulfoniumbutanesulfonate, cyclohexyl (2- Cyclohexyl-
2-oxoethyl) methylsulfonium butanesulfonate, cyclohexyl (2-cyclopentyl-2)
-Oxoethyl) methylsulfonium butanesulfonate, 2-oxopropyl thiacyclopentanium butanesulfonate, 2-oxobutyl thiacyclopentanium butanesulfonate, 2-oxopentyl thiacyclopentanium butanesulfonate, 2
-Oxohexyl thiacyclopentanium butanesulfonate, 2-oxoheptyl thiacyclopentanium butanesulfonate, 2-oxooctylthiacyclopentanium butanesulfonate, 3-methyl-2-oxobutylthiacyclopentanium butanesulfonate, 3,3-dimethyl-2-oxobutyl
Thiacyclopentanium butanesulfonate,

2-cyclohexyl-2-oxoethyl
Thiacyclopentanium butanesulfonate, 2-cyclopentyl-2-oxoethyl thiacyclopentanium butanesulfonate, 2-oxopropyl thiacyclohexanium butanesulfonate, 2-oxobutyl thiacyclohexanium butanesulfonate, 2-oxopentyl Thiacyclohexanium butanesulfonate, 2-oxohexyl thiacyclohexanium butanesulfonate, 2-oxoheptyl thiacyclohexanium butanesulfonate, 2-oxohexyl
Oxooctyl thiacyclohexanium butanesulfonate, 3-methyl-2-oxobutyl thiacyclohexanium butanesulfonate, 3,3-dimethyl-2-oxobutyl thiacyclohexanium butanesulfonate,

2-cyclohexyl-2-oxoethyl
Thiacyclohexanium butanesulfonate, 2-cyclopentyl-2-oxoethyl thiacyclohexanium butanesulfonate, 2-oxopropyl
(1,4-thioxanium) butanesulfonate, 2
-Oxobutyl (1,4-thioxanium) butanesulfonate, 2-oxopentyl (1,4-thioxanium) butanesulfonate, 2-oxohexyl (1,4-thioxanium) butanesulfonate,
2-oxoheptyl (1,4-thioxanium) butanesulfonate, 2-oxooctyl (1,4-thioxanium) butanesulfonate, 3-methyl-2
-Oxobutyl (1,4-thioxanium) butanesulfonate, 3,3-dimethyl-2-oxobutyl
(1,4-thioxanium) butanesulfonate,

2-cyclohexyl-2-oxoethyl
(1,4-thioxanium) butanesulfonate, 2
-Cyclopentyl-2-oxoethyl (1,4-thioxanium) butanesulfonate, 2-oxopropyl (4-oxothiacyclohexanium) butanesulfonate, 2-oxobutyl (4-oxothiacyclohexanium) butanesulfonate, 2-oxopentyl (4-oxothiacyclohexanium) butanesulfonate, 2-oxohexyl (4-oxothiacyclohexanium) butanesulfonate, 2-oxoheptyl (4-oxothiacyclohexanium)
Butanesulfonate, 2-oxooctyl (4-oxothiacyclohexanium) butanesulfonate,
3-methyl-2-oxobutyl (4-oxothiacyclohexanium) butanesulfonate, 3,3-dimethyl-2-oxobutyl (4-oxothiacyclohexanium) butanesulfonate,

2-cyclohexyl-2-oxoethyl
(4-oxothiacyclohexanium) butanesulfonate, 2-cyclopentyl-2-oxoethyl (4
-Oxothiacyclohexanium) butanesulfonate, 2-oxopropyl (1,4-dithianium)
Butanesulfonate, 2-oxobutyl (1,4-dithianium) butanesulfonate, 2-oxopentyl (1,4-dithianium) butanesulfonate,
2-oxohexyl (1,4-dithianium) butanesulfonate, 2-oxoheptyl (1,4-dithianium) butanesulfonate, 2-oxooctyl (1,4-dithianium) butanesulfonate, 3
-Methyl-2-oxobutyl (1,4-dithianium) butanesulfonate, 3,3-dimethyl-2-oxobutyl (1,4-dithianium) butanesulfonate,

2-cyclohexyl-2-oxoethyl
(1,4-dithianium) butanesulfonate, 2-
Cyclopentyl-2-oxoethyl (1,4-dithianium) butanesulfonate, 2-oxocyclohexyl thiacyclopentanium butanesulfonate,
Dimethyl (2-oxopropyl) sulfonium p-toluenesulfonate, dimethyl (2-oxobutyl) sulfonium p-toluenesulfonate, dimethyl (2
-Oxopentyl) sulfonium p-toluenesulfonate, dimethyl (2-oxohexyl) sulfonium p-toluenesulfonate, dimethyl (2-oxoheptyl) sulfonium p-toluenesulfonate, dimethyl (2-oxooctyl) sulfonium p-toluene Sulfonate, dimethyl (3-methyl-2-oxobutyl) sulfonium p-toluenesulfonate,
3,3-dimethyl-2-oxobutyl dimethylsulfonium p-toluenesulfonate,

2-cyclohexyl-2-oxoethyl
Dimethylsulfonium p-toluenesulfonate, 2
-Cyclopentyl-2-oxoethyl dimethylsulfonium p-toluenesulfonate, diethyl (2-oxopropyl) sulfonium p-toluenesulfonate, diethyl (2-oxobutyl) sulfonium p-
Toluenesulfonate, diethyl (2-oxopentyl) sulfonium p-toluenesulfonate, diethyl (2-oxohexyl) sulfonium p-toluenesulfonate, diethyl (2-oxoheptyl) sulfonium p-toluenesulfonate, diethyl (2- Oxooctyl) sulfonium p-toluenesulfonate, diethyl (3-methyl-2-oxobutyl) sulfonium p-toluenesulfonate, 3,3-dimethyl-2-oxobutyl diethylsulfonium p-toluenesulfonate,

2-cyclohexyl-2-oxoethyl
Diethylsulfonium p-toluenesulfonate, 2
-Cyclopentyl-2-oxoethyl diethylsulfonium p-toluenesulfonate, dibutyl (2-oxopropyl) sulfonium p-toluenesulfonate, dibutyl (2-oxobutyl) sulfonium p-
Toluenesulfonate, dibutyl (2-oxopentyl) sulfonium p-toluenesulfonate, dibutyl (2-oxohexyl) sulfonium p-toluenesulfonate, dibutyl (2-oxoheptyl) sulfonium p-toluenesulfonate, dibutyl (2- Oxooctyl) sulfonium p-toluenesulfonate, dibutyl (3-methyl-2-oxobutyl) sulfonium p-toluenesulfonate, dibutyl (3.3
-Dimethyl 2-oxobutyl) sulfonium p-toluenesulfonate, dibutyl (2-cyclohexyl-2)
-Oxoethyl) sulfonium p-toluenesulfonate, dibutyl (2-cyclopentyl-2-oxoethyl) sulfonium p-toluenesulfonate, diisopropyl (2-oxopropyl) sulfonium p
-Toluenesulfonate, diisopropyl (2-oxobutyl) sulfonium p-toluenesulfonate, diisopropyl (2-oxopentyl) sulfonium p
-Toluenesulfonate, diisopropyl (2-oxohexyl) sulfonium p-toluenesulfonate,
Diisopropyl (2-oxoheptyl) sulfonium
p-toluenesulfonate, diisopropyl (2-oxooctyl) sulfonium p-toluenesulfonate, diisopropyl (3-methyl-2-oxobutyl)
Sulfonium p-toluenesulfonate, 3,3-dimethyl 2-oxobutyl diisopropyl sulfonium p-toluenesulfonate,

2-cyclohexyl-2-oxoethyl
Diisopropylsulfonium p-toluenesulfonate, 2-cyclopentyl-2-oxoethyl diisopropylsulfonium p-toluenesulfonate, te
rt-butyl methyl (2-oxopropyl) sulfonium p-toluenesulfonate, tert-butyl
Methyl (2-oxobutyl) sulfonium p-toluenesulfonate, tert-butylmethyl (2-oxopentyl) sulfonium p-toluenesulfonate, tert-butylmethyl (2-oxohexyl)
Sulfonium p-toluenesulfonate, tert-
Butyl methyl (2-oxoheptyl) sulfonium
p-toluenesulfonate, tert-butylmethyl (2-oxooctyl) sulfonium p-toluenesulfonate, tert-butylmethyl (3-methyl-
2-oxobutyl) sulfonium p-toluenesulfonate, tert-butyl (3,3-dimethyl2-oxobutyl) methyl sulfonium p-toluenesulfonate, tert-butyl (2-cyclohexyl-2-oxoethyl) methylsulfonium p-toluenesulfo Nate, tert-butyl (2-cyclopentyl-2-oxoethyl) methylsulfonium p
-Toluenesulfonate,

Cyclohexylmethyl (2-oxopropyl) sulfonium p-toluenesulfonate, cyclohexylmethyl (2-oxobutyl) sulfonium p-toluenesulfonate, cyclohexylmethyl (2-oxopentyl) sulfonium p-toluenesulfonate, cyclohexylmethyl ( 2-oxohexyl) sulfonium p-toluenesulfonate, cyclohexylmethyl (2-oxoheptyl) sulfonium p-toluenesulfonate, cyclohexylmethyl (2-oxooctyl) sulfonium p-toluenesulfonate, cyclohexylmethyl (3-methyl-
2-oxobutyl) sulfonium p-toluenesulfonate, cyclohexyl (3,3-dimethyl2-oxobutyl) methyl sulfonium p-toluenesulfonate, cyclohexyl (2-cyclohexyl-2)
-Oxoethyl) methylsulfonium p-toluenesulfonate, cyclohexyl (2-cyclopentyl-2-oxoethyl) methylsulfonium p-toluenesulfonate,

2-oxopropyl thiacyclopentanium p-toluenesulfonate, 2-oxobutyl
Thiacyclopentanium p-toluenesulfonate,
2-oxopentyl thiacyclopentanium p-toluenesulfonate, 2-oxohexyl thiacyclopentanium p-toluenesulfonate, 2-oxoheptyl thiacyclopentanium p-toluenesulfonate, 2-oxooctyl thiacyclopentanium p-toluenesulfonate, 3-methyl-2-oxobutylthiacyclopentanium p-toluenesulfonate, 3,3-dimethyl-2-oxobutylthiacyclopentanium p-toluenesulfonate, 2-
Cyclohexyl-2-oxoethyl thiacyclopentanium p-toluenesulfonate, 2-cyclopentyl-2-oxoethyl thiacyclopentanium p-
Toluenesulfonate, 2-oxopropyl thiacyclohexanium p-toluenesulfonate, 2-oxobutylthiacyclohexanium p-toluenesulfonate, 2-oxopentyl thiacyclohexanium p-toluenesulfonate, 2-oxohexyl
Thiacyclohexanium p-toluenesulfonate,
2-oxoheptyl thiacyclohexanium p-toluenesulfonate, 2-oxooctyl thiacyclohexanium p-toluenesulfonate, 3-methyl-2-oxobutyl thiacyclohexanium p-toluenesulfonate, 3,3-dimethyl -2-oxobutyl thiacyclohexanium p-toluenesulfonate,

2-cyclohexyl-2-oxoethyl
Thiacyclohexanium p-toluenesulfonate,
2-cyclopentyl-2-oxoethyl thiacyclohexanium p-toluenesulfonate, 2-oxopropyl (1,4-thioxanium) p-toluenesulfonate, 2-oxobutyl (1,4-thioxanium) p-toluenesulfonate, 2-oxopentyl (1,4-thioxanium) p-toluenesulfonate, 2-oxohexyl (1,4-thioxanium) p-toluenesulfonate, 2-oxoheptyl (1,4-thioxanium) p-toluenesulfonate , 2-oxooctyl (1,4-thioxanium) p-toluenesulfonate, 3-methyl-2-oxobutyl (1,4-thioxanium) p-toluenesulfonate, 3,3-dimethyl-2-oxobutyl (1, 4-Thioxanium) p-toluenes Luhonart,

2-cyclohexyl-2-oxoethyl
(1,4-thioxanium) p-toluenesulfonate, 2-cyclopentyl-2-oxoethyl (1,4
-Thioxanium) p-toluenesulfonate, 2-
Oxopropyl (4-oxothiacyclohexanium) p-toluenesulfonate, 2-oxobutyl
(4-oxothiacyclohexanium) p-toluenesulfonate, 2-oxopentyl (4-oxothiacyclohexanium) p-toluenesulfonate, 2
-Oxohexyl (4-oxothiacyclohexanium) p-toluenesulfonate, 2-oxoheptyl (4-oxothiacyclohexanium) p-toluenesulfonate, 2-oxooctyl (4-oxothiacyclohexanium) p-toluenesulfonate,
3-methyl-2-oxobutyl (4-oxothiacyclohexanium) p-toluenesulfonate 3,3
-Dimethyl-2-oxobutyl (4-oxothiacyclohexanium) p-toluenesulfonate,

2-cyclohexyl-2-oxoethyl
(4-oxothiacyclohexanium) p-toluenesulfonate, 2-cyclopentyl-2-oxoethyl (4-oxothiacyclohexanium) p-toluenesulfonate, 2-oxopropyl (1,4-dithianium) p- Toluenesulfonate, 2-oxobutyl (1,4-dithianium) p-toluenesulfonate, 2-oxopentyl (1,4-dithianium) p-toluenesulfonate, 2-oxohexyl (1,4-dithianium) p- Toluenesulfonate, 2-oxoheptyl (1,4-dithianium)
p-toluenesulfonate, 2-oxooctyl
(1,4-dithianium) p-toluenesulfonate, 3-methyl-2-oxobutyl (1,4-dithianium) p-toluenesulfonate, 3,3-dimethyl-2-oxobutyl (1,4-dithianium) p
-Toluenesulfonate, 2-cyclohexyl-2-oxoethyl (1,4-dithianium) p-toluenesulfonate, 2-cyclopentyl-2-oxoethyl (1,4-dithianium) p-toluenesulfonate, 2-oxocyclohexylthia Cyclopentanium p-toluenesulfonate,

Dimethyl (2-oxopropyl) sulfonium camphorsulfonate, dimethyl (2-oxobutyl) sulfonium camphorsulfonate, dimethyl (2-oxopentyl) sulfonium camphorsulfonate, dimethyl (2-oxohexyl) sulfonium camphorsulfonate, Dimethyl (2-oxoheptyl) sulfonium camphorsulfonate,
Dimethyl (2-oxooctyl) sulfonium camphorsulfonate, dimethyl (3-methyl-2-oxobutyl) sulfonium camphorsulfonate, 3,
3-dimethyl-2-oxobutyl dimethylsulfonium camphorsulfonate, 2-cyclohexyl-2
-Oxoethyl dimethylsulfonium camphorsulfonate, 2-cyclopentyl-2-oxoethyl
Dimethylsulfonium camphorsulfonate, diethyl (2-oxopropyl) sulfonium camphorsulfonate, diethyl (2-oxobutyl) sulfonium camphorsulfonate, diethyl (2-oxopentyl) sulfonium camphorsulfonate, diethyl (2-oxohexyl) sulfonium camphor Sulfonate, diethyl (2-oxoheptyl) sulfonium camphorsulfonate, diethyl (2-oxooctyl) sulfonium camphorsulfonate, diethyl (3-methyl-2-oxobutyl) sulfonium camphorsulfonate,

3,3-dimethyl-2-oxobutyl diethylsulfonium camphorsulfonate, 2-cyclohexyl-2-oxoethyl diethylsulfonium camphorsulfonate, 2-cyclopentyl-2
-Oxoethyl diethylsulfonium camphorsulfonate, dibutyl (2-oxopropyl) sulfonium camphorsulfonate, dibutyl (2-oxobutyl) sulfonium camphorsulfonate, dibutyl (2-oxopentyl) sulfonium camphorsulfonate, dibutyl (2-oxohexyl) Sulfonium camphorsulfonate, dibutyl (2-oxoheptyl) sulfonium camphorsulfonate,
Dibutyl (2-oxooctyl) sulfonium camphorsulfonate, dibutyl (3-methyl-2-oxobutyl) sulfonium camphorsulfonate, dibutyl (3,3-dimethyl2-oxobutyl) sulfonium camphorsulfonate, dibutyl (2-cyclohexyl-2) -Oxoethyl) sulfonium camphorsulfonate, dibutyl (2-cyclopentyl-2-
Oxoethyl) sulfonium camphorsulfonate,

Diisopropyl (2-oxopropyl) sulfonium camphorsulfonate, diisopropyl (2-oxobutyl) sulfonium camphorsulfonate, diisopropyl (2-oxopentyl) sulfonium camphorsulfonate, diisopropyl (2
-Oxohexyl) sulfonium camphorsulfonate, diisopropyl (2-oxoheptyl) sulfonium camphorsulfonate, diisopropyl (2-
Oxooctyl) sulfonium camphorsulfonate, diisopropyl (3-methyl-2-oxobutyl)
Sulfonium camphorsulfonate, 3,3-dimethyl 2-oxobutyl diisopropyl sulfonium camphorsulfonate, 2-cyclohexyl-2-
Oxoethyl diisopropylsulfonium camphorsulfonate, 2-cyclopentyl-2-oxoethyl diisopropylsulfonium camphorsulfonate,

Tert-butyl methyl (2-oxopropyl) sulfonium camphorsulfonate, te
rt-butyl methyl (2-oxobutyl) sulfonium camphorsulfonate, tert-butyl methyl (2-oxopentyl) sulfonium camphorsulfonate, tert-butyl methyl (2-oxohexyl) sulfonium camphorsulfonate, te
rt-butyl methyl (2-oxoheptyl) sulfonium camphorsulfonate, tert-butyl methyl (2-oxooctyl) sulfonium camphorsulfonate, tert-butyl methyl (3-methyl-2-oxobutyl) sulfonium camphorsulfonate, tert- Butyl (3,3-dimethyl 2-oxobutyl) methyl sulfonium camphorsulfonate, tert-butyl (2-cyclohexyl-
2-oxoethyl) methylsulfonium camphorsulfonate, tert-butyl (2-cyclopentyl-2-oxoethyl) methylsulfonium camphorsulfonate, cyclohexyl methyl (2-oxopropyl) sulfonium camphorsulfonate,

Cyclohexylmethyl (2-oxobutyl) sulfonium camphorsulfonate, cyclohexylmethyl (2-oxopentyl) sulfonium
Camphorsulfonate, cyclohexylmethyl (2
-Oxohexyl) sulfonium camphorsulfonate, cyclohexylmethyl (2-oxoheptyl)
Sulfonium camphorsulfonate, cyclohexylmethyl (2-oxooctyl) sulfonium camphorsulfonate, cyclohexylmethyl (3-methyl-2-oxobutyl) sulfonium camphorsulfonate, cyclohexyl (3,3-dimethyl2-
Oxobutyl) methyl sulfonium camphorsulfonate, cyclohexyl (2-cyclohexyl-
2-oxoethyl) methylsulfonium camphorsulfonate, cyclohexyl (2-cyclopentyl-2-oxoethyl) methylsulfonium camphorsulfonate, 2-oxopropyl thiacyclopentanium camphorsulfonate, 2-oxobutyl thiacyclopentanium camphorsulfonate,
2-oxopentyl thiacyclopentanium camphorsulfonate, 2-oxohexyl thiacyclopentanium camphorsulfonate, 2-oxoheptyl thiacyclopentanium camphorsulfonate, 2-oxooctyl thiacyclopentanium camphorsulfonate, 3- Methyl-2-oxobutyl thiacyclopentanium camphorsulfonate,
3,3-dimethyl-2-oxobutyl thiacyclopentanium camphorsulfonate,

2-cyclohexyl-2-oxoethyl
Thiacyclopentanium camphorsulfonate, 2
-Cyclopentyl-2-oxoethyl thiacyclopentanium camphorsulfonate, 2-oxopropyl thiacyclohexanium camphorsulfonate, 2-oxobutyl thiacyclohexium camphorsulfonate, 2-oxopentyl thiacyclohexanium camphorsulfonate, 2 -Oxohexyl thiacyclohexanium camphorsulfonate, 2-oxoheptyl thiacyclohexanium
Camphorsulfonate, 2-oxooctyl thiacyclohexanium camphorsulfonate, 3-methyl-2-oxobutylthiacyclohexanium camphorsulfonate, 3,3-dimethyl-2-oxobutylthiacyclohexanium camphorsulfonate,

2-cyclohexyl-2-oxoethyl
Thiacyclohexanium camphorsulfonate, 2
-Cyclopentyl-2-oxoethyl thiacyclohexanium camphorsulfonate, 2-oxopropyl (1,4-thioxanium) camphorsulfonate, 2-oxobutyl (1,4-thioxanium)
Camphorsulfonate, 2-oxopentyl
(1,4-thioxanium) camphorsulfonate, 2-oxohexyl (1,4-thioxanium)
Camphorsulfonate, 2-oxoheptyl
(1,4-thioxanium) camphorsulfonate, 2-oxooctyl (1,4-thioxanium)
Camphorsulfonate, 3-methyl-2-oxobutyl (1,4-thioxanium) camphorsulfonate, 3,3-dimethyl-2-oxobutyl (1,
4-thioxanium) camphorsulfonate,

2-cyclohexyl-2-oxoethyl
(1,4-thioxanium) camphorsulfonate, 2-cyclopentyl-2-oxoethyl (1,4
-Thioxanium) camphorsulfonate, 2-oxopropyl (4-oxothiacyclohexanium)
Camphorsulfonate, 2-oxobutyl (4-
Oxothiacyclohexanium) camphorsulfonate, 2-oxopentyl (4-oxothiacyclohexanium) camphorsulfonate, 2-oxohexyl (4-oxothiacyclohexanium) camphorsulfonate, 2-oxoheptyl (4 -Oxothiacyclohexanium) camphorsulfonate, 2-oxooctyl (4-oxothiacyclohexanium) camphorsulfonate, 3-methyl-2
-Oxobutyl (4-oxothiacyclohexanium) camphorsulfonate, 3,3-dimethyl-2
-Oxobutyl (4-oxothiacyclohexanium) camphorsulfonate,

2-cyclohexyl-2-oxoethyl
(4-oxothiacyclohexanium) camphorsulfonate, 2-cyclopentyl-2-oxoethyl
(4-oxothiacyclohexanium) camphorsulfonate, 2-oxopropyl (1,4-dithianium) camphorsulfonate, 2-oxobutyl
(1,4-dithianium) camphorsulfonate,
2-oxopentyl (1,4-dithianium) camphorsulfonate, 2-oxohexyl (1,4-
Dithianium) camphorsulfonate, 2-oxoheptyl (1,4-dithianium) camphorsulfonate, 2-oxooctyl (1,4-dithianium) camphorsulfonate, 3-methyl-2-oxobutyl (1,4-dithianium) Camphorsulfonate, 3,3-dimethyl-2-oxobutyl
(1,4-dithianium) camphorsulfonate,
2-cyclohexyl-2-oxoethyl (1,4-dithianium) camphorsulfonate, 2-cyclopentyl-2-oxoethyl (1,4-dithianium)
Camphorsulfonate 2-oxocyclohexyl thiacyclopentanium
Camphorsulfonate and the like.

The sulfonium salt represented by the formula (I) or (I ′) has the effect of improving the line edge roughness when added to a resist composition. In the resist composition according to the present invention, the sulfonium salt represented by the formula (I) and the formula (I ′) are used as an acid generator.
And at least one onium salt selected from a triphenylsulfonium salt represented by the formula (IIa) and a diphenyliodonium salt represented by the formula (IIb). By using such an onium salt-based acid generator in combination, sensitivity and resolution can be further improved as compared with the case where the sulfonium salt-based acid generator of the formula (I) or (I ′) is used alone. Further, compared with a case where at least one onium salt-based acid generator selected from the formulas (IIa) and (IIb) is used alone, a sulfonium salt represented by the formula (I) or (I ′) is used in combination. Thereby, the line edge roughness can be further improved.

Next, the essential components in the present invention,
Liphenylsulfonium salt and diphenyliodonium
A formula representing at least one onium salt selected from salts
In (IIa) and (IIb), P¹, P^Two, P^Three, P^Fouras well as
P^FiveAre each independently of one another hydrogen, hydroxyl,
Represents an alkyl group having 1 to 6 carbon atoms or an alkoxy group having 1 to 6 carbon atoms.
The alkyl group and the alkoxy group have a carbon number of 3 or more.
A bond may be linear or branched. Specific alkyl group
Examples of methyl, ethyl, propyl, iso
Propyl, butyl, tert-butyl, pentyl,
Hexyl group and the like, as examples of the alkoxy group
Represents methoxy, ethoxy, propoxy, butoxy
And the like. In addition, in formulas (IIa) and (IIb)
And P which constitutes an anion⁶SO_Three ^-, P⁷SO _Three ^-Is organic
Represents a sulfonate ion. Where P⁶, P⁷Is it
Independently, any organic group having about 1 to 12 carbon atoms may be used.
For example, a perfluoroalkyl group having 1 to 8 carbon atoms,
An alkyl group having a prime number of 1 to 8, an aromatic group having a carbon number of 6 to 12,
It can be a camphor group. Par with 1 to 8 carbon atoms
Fluoroalkyl group, alkyl group having 1 to 8 carbon atoms, carbon
Specific examples of the aromatic groups of Formulas 6 to 12 include those described above.
And the like.

The triphenylsulfonium salt represented by the formula (IIa) and the diphenyliodonium salt represented by the formula (IIb) can be used as they are, as long as they are commercially available, or can be produced according to a conventional method. It is.
The method for producing triphenylsulfonium salt (IIa) is as follows:
For example, a method in which the corresponding triphenylsulfonium bromide is reacted with the same silver salt of a sulfonic acid as the anion of the target compound, and Chem. Pharm. Bull., Vol. 29, 3
A method of reacting the corresponding diphenylsulfoxide with a benzene compound and a perfluoroalkanesulfonic acid in the presence of trifluoroacetic anhydride according to the description of 753 (1981). Accordingly,
The corresponding aryl Grignard reagent is reacted with thionyl chloride, then with triorganosilyl halide to form triarylsulfonium halide, and then reacted with the same sulfonic acid silver salt as the anion of the target compound. Can be manufactured. Further, P ¹ in the formula (IIa),
The compound wherein P ² and / or P ³ is a hydroxyl group is disclosed in
According to the description in JP-A-8-311018, tert
-A triphenylsulfonium salt having a butoxy group,
Treat with the same sulfonic acid as the compound anion and tert
-Can be produced by removing a butyl group.

Further, diphenyliodonium salt (IIb)
For example, J. Am. Chem. Soc., Vol. 81,
342 According to the description in (1959), a method in which iodyl sulfate and the corresponding aryl compound are reacted and then the same sulfonic acid as the anion of the target compound is added, or iodine is added to a mixed solution of acetic anhydride and fuming nitric acid And reacting the corresponding aryl compound with the reaction product obtained by adding trifluoroacetic acid and then adding the same sulfonic acid as the anion of the desired compound, according to the description in JP-A-9-179302. ,
Concentrated sulfuric acid is added dropwise to a mixture of the corresponding aryl compound, acetic anhydride, and potassium iodate to cause a reaction, and then the same sulfonic acid as the anion of the target compound is added.

Specific examples of triphenylsulfonium salts and diphenyliodonium salts corresponding to formulas (IIa) and (IIb) include the following compounds.

Triphenylsulfonium methanesulfonate, triphenylsulfonium ethanesulfonate, triphenylsulfonium butanesulfonate,
Triphenylsulfonium perfluorobutanesulfonate, triphenylsulfonium p-toluenesulfonate, triphenylsulfonium camphorsulfonate, 4-methylphenyldiphenylsulfonium methanesulfonate, 4-methylphenyldiphenylsulfonium ethanesulfonate, 4-methylphenyldiphenyl Sulfonium butanesulfonate, 4-
Methylphenyldiphenylsulfonium benzenesulfonate, 4-methylphenyldiphenylsulfonium p-toluenesulfonate, 4-methylphenyldiphenylsulfonium camphorsulfonate, 4-methylphenyldiphenylsulfonium perfluorooctanesulfonate, 4-hydroxyphenyldiphenylsulfonium perfluoro Butanesulfonate, 4
-Methoxyphenyldiphenylsulfonium perfluorobutanesulfonate, tris (4-methylphenyl) sulfonium perfluorobutanesulfonate,
Tris (4-methoxyphenyl) sulfonium perfluorobutanesulfonate, 4-methylphenyldiphenylsulfonium perfluorooctanesulfonate, 4-hydroxyphenyldiphenylsulfonium
Perfluorooctanesulfonate, 4-methoxyphenyldiphenylsulfonium perfluorooctanesulfonate, tris (4-methylphenyl) sulfonium Perfluorooctanesulfonate, tris (4-
Methoxyphenyl) sulfonium perfluorooctanesulfonate,

Diphenyliodonium perfluorobutanesulfonate, di (4-methoxyphenyl) iodonium perfluorooctanesulfonate, di (4-
tert-butylphenyl) iodonium perfluorooctanesulfonate, di (4-tert-butylphenyl)
Iodonium methanesulfonate, di (4-tert-butylphenyl) iodonium ethanesulfonate, di (4-tert-butylphenyl) iodonium butanesulfonate, di (4-tert-butylphenyl) iodonium benzenesulfonate, di (4 -Tert-butylphenyl) iodonium p-toluenesulfonate, di (4-tert-butylphenyl) iodonium camphorsulfonate, and the like.

Next, the resin component constituting the resist composition of the present invention will be described. This resin has polymerized units having acid labile groups. The resin for the chemically amplified positive resist is insoluble or hardly soluble in alkali by itself, but some groups are cleaved by the action of an acid and become alkali-soluble after cleaving. The acid-labile group in the present invention can be any of various conventionally known groups. Specific examples of the acid-labile group include various esters of carboxylic acids, for example, alkyl esters represented by methyl esters and tert-butyl esters, methoxymethyl esters, ethoxymethyl esters, 1-ethoxyethyl esters, 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] acetal esters such as ethyl ester, tetrahydro-2-furyl ester and tetrahydro-2-pyranyl ester, isobornyl ester and 2-alkyl-2-adamantyl ester, 1- (1-adamantyl) And alicyclic esters such as 1) -alkylalkyl esters. The monomer leading to such a carboxylic acid ester-containing polymerization unit may be a (meth) acrylic monomer such as a methacrylic acid ester or an acrylic acid ester, or a norbornene carboxylic acid ester, a tricyclodecene carboxylic acid ester, or a tetracyclocarboxylic acid. As in the case of decene carboxylic acid ester, carboxylic acid ester group bonded to alicyclic monomer may be used.

Among these monomers, bulky groups containing an alicyclic group such as 2-alkyl-2-adamantyl and 1- (1-adamantyl) -1-alkylalkyl as a group which is cleaved by the action of an acid. It is preferable to use a compound having a group because the resolution is excellent. Examples of monomers containing such a bulky group include 2-alkyl-2-adamantyl (meth) acrylate and 1- (1) (meth) acrylate.
-Adamantyl) -1-alkylalkyl, 2-alkyl-2-adamantyl 5-norbornene-2-carboxylate, 1- (1-adamantyl) -1-alkylalkyl 5-norbornene-2-carboxylate, and the like.
In particular, the use of 2-alkyl-2-adamantyl (meth) acrylate as a monomer is preferable because the resolution is excellent. Representative examples of such 2-alkyl-2-adamantyl (meth) acrylates include, for example, 2-methyl-2-adamantyl acrylate, methacrylic acid 2
-Methyl-2-adamantyl, 2-ethyl acrylate-
Examples thereof include 2-adamantyl, 2-ethyl-2-adamantyl methacrylate, and 2-n-butyl-2-adamantyl acrylate. Among these, particularly when 2-ethyl-2-adamantyl (meth) acrylate is used,
It is preferable because the balance between sensitivity and heat resistance is good. Of course, if necessary, another monomer having a group that can be cleaved by the action of an acid may be used in combination.

The 2-alkyl-2-adamantyl (meth) acrylate can be usually produced by reacting a 2-alkyl-2-adamantanol or a metal salt thereof with an acrylic acid halide or a methacrylic acid halide.

The resin of the present invention may contain, in addition to the above polymer units having an acid-labile group, other polymer units which are not cleaved or hardly cleaved by the action of an acid. Of course it is possible. Examples of other polymerization units that may be contained include, for example, polymerization units of a monomer having a free carboxylic acid group such as acrylic acid and methacrylic acid, and aliphatic unsaturated dicarboxylic anhydrides such as maleic anhydride and itaconic anhydride. , A polymer unit of 2-norbornene, a polymer unit of (meth) acrylonitrile, a polymer unit of various (meth) acrylates, and the like. In the case of ArF exposure, light absorption is large, which is not preferable. However, in the case of KrF exposure, there is no problem of light absorption, so that a polymerized unit of hydroxystyrene can be used.

In particular, a polymerization unit of p-hydroxystyrene, a polymerization unit of m-hydroxystyrene, a polymerization unit of 3-hydroxy-1-adamantyl (meth) acrylate,
(Meth) acrylic acid 3,5-dihydroxy-1-adamantyl polymerized unit, lactone ring optionally substituted with alkyl (meth) acryloyloxy-γ-butyrolactone polymerized unit, the following formulas (IIIa) and (IIIb) It is preferable to copolymerize the polymerized unit of the alicyclic lactone represented by the formula from the viewpoint of the adhesiveness of the resist to the substrate.

[0093]

(Wherein R ¹ and R ² are each independently hydrogen,
Represents methyl or trifluoromethyl, and n represents a number of 1 to 3. )

3-Hydroxy-1- (meth) acrylate
Adamantyl and 3,5-dihydroxy-1-adamantyl (meth) acrylate are commercially available, but can also be produced, for example, by reacting the corresponding hydroxyadamantane with (meth) acrylic acid or a halide thereof. Further, (meth) acryloyloxy-γ-butyrolactone is obtained by reacting α- or β-bromo-γ-butyrolactone, in which the lactone ring may be substituted with alkyl, with acrylic acid or methacrylic acid, or when the lactone ring is alkyl. It can be produced by reacting an optionally substituted α- or β-hydroxy-γ-butyrolactone with an acrylic acid halide or a methacrylic acid halide. The monomer for leading to the polymerized unit of the alicyclic lactone represented by the formula (IIIa) or (IIIb) is specifically, for example, a (meth) acrylic acid ester of an alicyclic lactone having a hydroxyl group as follows: And mixtures thereof. These esters can be produced, for example, by reacting the corresponding alicyclic lactone having a hydroxyl group with (meth) acrylic acid (for example, JP-A-2000-26446).

[0096]

3-hydroxy-1- (meth) acrylate
Adamantyl, polymerized units of 3,5-dihydroxy-1-adamantyl (meth) acrylate, polymerized units of α- (meth) acryloyloxy-γ-butyrolactone, polymerized units of β- (meth) acryloyloxy-γ-butyrolactone, formula ( The polymerized units of the alicyclic lactones represented by IIIa) and (IIIb) each have a high polarity, and the presence of any of them in the resin improves the adhesion of the resist containing the same to the substrate. . These polymerized units also contribute to improving the resolution of the resist.

Here, (meth) acryloyloxy-γ-
Examples of a monomer for leading a polymerized unit of butyrolactone include 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-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 when a polymerized unit of hydroxystyrene is used as a polymerized unit of the resin. Specifically, a p- or m-hydroxystyrene copolymer resin as shown below is exemplified. When such a copolymer resin is obtained, it can be obtained by subjecting the corresponding (meth) acrylate monomer to acetoxystyrene and styrene by radical polymerization, followed by deacetylation with an acid.

[0100]

[0101]

[0102]

In these cases, the acid labile group includes
The use of 2-alkyl-2-adamantyl and 1- (1-adamantyl) -1-alkylalkyl is more advantageous in terms of dry etching resistance.

Further, a resin containing a polymerized unit of 2-norbornene has a strong structure since it has an alicyclic group directly in its main chain, and exhibits characteristics of excellent dry etching resistance. The polymerized unit of 2-norbornene is, for example, the corresponding 2
-It can be introduced into the main chain by radical polymerization using an aliphatic unsaturated dicarboxylic anhydride such as maleic anhydride or itaconic anhydride in addition to norbornene. Therefore, 2-
The norbornene polymerization unit is formed by opening the double bond, and can be represented by the formula (IV). Further, the polymerized unit of maleic anhydride, which is a polymerized unit of aliphatic unsaturated dicarboxylic anhydride, and the polymerized unit of itaconic anhydride are formed by opening their double bonds, and each of the formulas (V) and (V) (VI).

[0105]

Here, R in the formula (IV)^ThreeAnd R^FourAre each other
Independently, hydrogen, alkyl having 1 to 3 carbons, 1 to 3 carbons
Of hydroxyalkyl, carboxyl, cyano or
Represents a group -COOZ (Z is an alcohol residue),
Or R^ThreeAnd R^FourTogether, indicated by -C (= O) OC (= O)-
Carboxylic anhydride residues can also be formed. R ^Three
And / or R^FourIs a specific example when is alkyl
Is, for example, methyl, ethyl, propyl, etc.
Specific examples of hydroxyalkyl include hydrido
Loxymethyl, 2-hydroxyethyl and the like.
You. R^ThreeAnd / or R^FourIs a group -COOZ,
Ruboxyl is an ester, equivalent to Z
As the alcohol residue, for example,
Alkyl having a good number of carbon atoms of about 1 to 8, 2-oxooxola
-3- or -4-yl and the like.
Examples of the alkyl substituent include a hydroxyl group and an alicyclic hydrocarbon.
Residues and the like. Then, R^ThreeAnd / or R^FourBut-
When the carboxylic acid ester residue is represented by COOZ
Specific examples of methoxycarbonyl, ethoxycal
Bonyl, 2-hydroxyethoxycarbonyl, tert-butyl
Toxoxycarbonyl, 2-oxooxolan-3-ylo
Xycarbonyl, 2-oxooxolan-4-yloxo
Cicarbonyl, 1,1,2-trimethylpropoxy
Bonyl, 1-cyclohexyl-1-methylethoxycal
Bonyl, 1- (4-methylcyclohexyl) -1-methyl
Ruethoxycarbonyl, 1- (1-adamantyl) -1
-Methylethoxycarbonyl and the like.

Further, specific examples of the monomer for leading to the polymerized unit of 2-norbornene represented by the formula (IV) include the following compounds.

2-norbornene 2-hydroxy-5-norbornene 5-norbornene-2-carboxylic acid methyl 5-norbornene-2-carboxylate 5-norbornene-2-carboxylic acid-t-butyl 5-norbornene-2-carboxylic acid 1-cyclohexyl-1-methylethyl, 5-norbornene-2-carboxylate 1- (4-methylcyclohexyl) -1-methylethyl, 5-norbornene-2-carboxylate 1- (4-hydroxycyclohexyl) -1- Methyl ethyl, 1-methyl-1- (4-oxocyclohexyl) ethyl 5-norbornene-2-carboxylate, 1- (1-adamantyl) -1-methylethyl 5-norbornene-2-carboxylate, 5-norbornene- 1-methylcyclohexyl 2-carboxylate, 5-norbornene-2-carbo Acid 2-methyl-2-adamantyl 5-norbornene-2-carboxylate, 2-ethyl-2-adamantyl 5-norbornene-2-carboxylic acid 2-hydroxy-1
-Ethyl, 5-norbornene-2-methanol, 5-norbornene-2,3-dicarboxylic anhydride and the like.

The resin used in the present invention varies depending on the type of radiation for patterning exposure, the type of an acid-labile group, and the like. It is preferable to contain it in the range of mol%.
Particularly, when a polymerized unit of 2-alkyl-2-adamantyl (meth) acrylate or 1- (1-adamantyl) -1-alkylalkyl (meth) acrylate is used as the acid-labile group, The unit is 1 of the whole resin
Advantageously, it is at least 5 mol%. Also,
In addition to polymer units having an acid-labile group, other polymer units that are not easily cleaved by the action of an acid, for example, polymer units of 3-hydroxy-1-adamantyl (meth) acrylate, (meth) acrylic acid 3,5-dihydroxy-1-adamantyl, polymerized units of α- (meth) acryloyloxy-γ-butyrolactone, polymerized units of β- (meth) acryloyloxy-γ-butyrolactone, and oils represented by formulas (IIIa) and (IIIb) A polymer unit of a cyclic lactone, a polymer unit of hydroxystyrene, a polymer unit of 2-norbornene represented by the formula (IV), and a maleic anhydride represented by the formula (V), which is a polymer unit of an aliphatic unsaturated dicarboxylic anhydride. Polymerized units of
When polymerized units of itaconic anhydride represented by the formula (VI) are present, their total is 20% of the total resin.
It is preferable that the content be in the range of ~ 90 mol%.

When 2-norbornenes and aliphatic unsaturated dicarboxylic anhydrides are used as copolymer monomers,
Since these tend to hardly polymerize, it is preferable to use them in excess in consideration of this point.

In the chemically amplified positive resist composition of the present invention, a basic compound, especially a basic nitrogen-containing organic compound, for example, an amine, is added as a quencher, so that it can be left behind after exposure. The performance degradation due to the accompanying deactivation of the acid can be improved. Specific examples of the basic compound used for the quencher include those represented by the following formulas.

[0112]

[0113]

In the formula, R ¹¹ , R ¹² and R ¹⁷ each independently represent hydrogen, alkyl, cycloalkyl or aryl. The alkyl, cycloalkyl or aryl may be each independently substituted with a hydroxyl group, an amino group, or an alkoxy group having 1 to 6 carbon atoms. The amino group is
It may be substituted by an alkyl group having 1 to 4 carbon atoms. The alkyl preferably has about 1 to 6 carbon atoms, the cycloalkyl preferably has about 5 to 10 carbon atoms, and the aryl preferably has about 6 to 10 carbon atoms. R ¹³ , R ¹⁴
And R ¹⁵ each independently represent hydrogen, alkyl, cycloalkyl, aryl or alkoxy. The alkyl, cycloalkyl, aryl, or alkoxy may be each independently substituted with a hydroxyl group, an amino group, or an alkoxy group having 1 to 6 carbon atoms. The amino group may be substituted with an alkyl group having 1 to 4 carbon atoms. The alkyl preferably has about 1 to 6 carbon atoms, the cycloalkyl preferably has about 5 to 10 carbon atoms, the aryl preferably has about 6 to 10 carbon atoms, and the alkoxy has About 6 is preferable. R ¹⁶ is
Represents alkyl or cycloalkyl. The alkyl or cycloalkyl is each independently a hydroxyl group, an amino group,
It may be substituted by an alkoxy group having 1 to 6 carbon atoms. The amino group may be substituted with an alkyl group having 1 to 4 carbon atoms. The alkyl preferably has about 1 to 6 carbon atoms, and the cycloalkyl preferably has about 5 to 10 carbon atoms. A represents alkylene, carbonyl, imino, sulfide or disulfide. The alkylene preferably has about 2 to 6 carbon atoms. Also, R
Any of ^{11 to} R ¹⁷ that can have both a linear structure and a branched structure may be used.

The resist composition of the present invention contains about 80 to 99.9% by weight of a resin and about 0.1 to 20% by weight of an acid generator based on the total solid content. preferable. In the present invention, when a sulfonium salt of the formula (I) and at least one onium salt selected from a triphenylsulfonium salt of the formula (IIa) and an iodonium salt of the formula (IIb) are used in combination as an acid generator, both are used. Usually, it is preferable to use the composition in a weight ratio of about 9: 1 to 1: 9, more preferably about 8: 2 to 2: 8. When a basic compound is used as the quencher, 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 composition may also contain small amounts of various additives such as sensitizers, dissolution inhibitors, other resins, surfactants, stabilizers, and dyes, if necessary.

The resist composition of the present invention is usually made into a resist composition in which each of the above components is dissolved in a solvent, and is applied to a substrate such as a silicon wafer by a conventional method such as spin coating. 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 is evaporated, and a solvent generally used in this field is used. Can. For example, glycol ether esters such as ethyl cellosolve acetate, methyl cellosolve acetate and propylene glycol monomethyl ether acetate, esters such as ethyl lactate, butyl acetate, amyl acetate and ethyl pyruvate, acetone, methyl isobutyl ketone, 2-heptanone And ketones such as cyclohexanone, and cyclic esters such as γ-butyrolactone. These solvents can be used alone or in combination of two or more.

The resist film applied on the substrate and dried is subjected to an exposure treatment for patterning, and then to a heat treatment for accelerating the deprotection group reaction, and then developed with an alkali developing solution. You. The alkaline developer used here may be any of various alkaline aqueous solutions used in this field, and generally, an aqueous solution of tetramethylammonium hydroxide or (2-hydroxyethyl) trimethylammonium hydroxide (commonly called choline) is used. Often used.

[0118]

Next, the present invention will be described more specifically with reference to examples, but the present invention is not limited to these examples. In the examples, percentages and parts representing the content or the use amount are based on weight unless otherwise specified. The weight average molecular weight is a value determined by gel permeation chromatography using polystyrene as a standard.

Synthesis Example 1 of Acid Generator: Synthesis of Acid Generator B1 (1) Tetrahydrothiophene 7 in a four-necked flask
0.17 parts and 750 parts of acetone were charged, and 150 parts of 1-bromopinacolone was added dropwise thereto, followed by stirring at room temperature for 24 hours. The precipitated crystals were collected by filtration, washed with 100 parts of tert-butyl methyl ether, and dried to give 3,3-
161.3 parts of dimethyl-2-oxobutyl thiacyclopentanium bromide were obtained. (2) A four-necked flask was charged with 80 parts of 3,3-dimethyl-2-oxobutylthiacyclopentanium bromide obtained in (1) and 3200 parts of acetonitrile, and 56.33 parts of potassium trifluoromethanesulfonate was added thereto. Was added dropwise and stirred at room temperature for 18 hours. The precipitated potassium bromide was separated by filtration, and the filtrate was concentrated. Acetone was added thereto, and the mixture was stirred at room temperature for 16 hours, and insoluble materials were separated by filtration. The filtrate was further concentrated, acetone was added, and the mixture was charged into tert-butyl methyl ether to obtain the desired compound 94.
73 parts were obtained. This compound is represented by the following formula: 3,3-dimethyl-2-oxobutyl thiacyclopentanium
The fact that the compound is trifluoromethanesulfonate is ¹ H-
Confirmed by NMR (JEOL “GX-270”).

[0120]

¹ H-NMR (chloroform-d, internal standard tetramethylsilane): δ (ppm) 1.24 (s, 9H); 2.
26−2.33 (m, 2H); 2.42−2.52 (m, 2H); 3.45−3.55
(m, 2H); 3.61-3.71 (m, 2H); 4.96 (s, 2H).

Acid Generator Synthesis Example 1-2: Synthesis of Acid Generator B1 (Alternative Method) In (2) of Acid Generator Synthesis Example 1, the 3,3- obtained in (1) in a four-necked flask. After 169.58 parts of dimethyl-2-oxobutyl thiacyclopentanium bromide and 3391.59 parts of acetonitrile were charged, 100 parts of trifluoromethanesulfonic acid was added dropwise thereto after cooling to 5 ° C, and the mixture was stirred at 5 ° C for 1.5 hours. The solution was concentrated to 270 parts, to which was added ethyl acetate 680, and with stirring.
300 parts of tert-butyl methyl ether was added, and the precipitate was separated by filtration. The residue is further dissolved in 500 parts of ethyl acetate, concentrated to 420 parts, 50 parts of tert-butyl methyl ether is added with stirring, and the precipitate is filtered and dried to obtain 156.22 parts of the desired product. Was.

Acid Generator Synthesis Examples 2 and 3: Synthesis of Acid Generators B2 and B3 In the acid generator synthesis example 1 (2), potassium perfluorobutanesulfonate and perfluorooctane were used instead of potassium trifluoromethanesulfonate. Except for using potassium sulfonate, the reaction was carried out according to (2) of Synthesis Example 1 of an acid generator, and 3,3-dimethyl-2-oxobutyl thiacyclopentanium perfluorobutanesulfonate and 3,3-dimethyl were used. -2-oxobutyl
Thiacyclopentanium perfluorooctanesulfonate was obtained.

¹ H-NMR of 3,3-dimethyl-2-oxobutyl thiacyclopentanium perfluorobutanesulfonate (dimethylsulfoxide-d6, internal standard tetramethylsilane): δ (ppm) 1.15 (s, 9H) ; 2.
13−2.23 (m, 4H); 3.33−3.38 (m, 2H); 3.47−3.54
(m, 2H); 4.85 (s, 2H).

¹ H-NMR of 3,3-dimethyl-2-oxobutyl thiacyclopentanium perfluorooctanesulfonate (chloroform-d, internal standard tetramethylsilane): δ (ppm) 1.25 (s, 9H); 2.24-2.
32 (m, 2H); 2.49−2.56 (m, 2H); 3.56−3.69 (m, 4H);
5.05 (s, 2H).

Synthesis example 4 of acid generator B4: Synthesis of acid generator B4 2.3 parts of 3,3-dimethyl-2-oxobutylthiacyclopentanium bromide and 92 parts of acetonitrile were charged into a four-necked flask. A solution prepared by dissolving 2.4 parts of silver toluenesulfonate in 7.2 parts of acetonitrile was added dropwise, and the mixture was stirred at room temperature for 22 hours. The precipitated silver bromide was separated by filtration and washed with 30 parts of acetonitrile. The combined filtrate and washings were concentrated to 3.3 parts, to which 30 parts of acetonitrile was added, stirred at room temperature for 2 hours, and the insolubles were filtered off. The filtrate was concentrated to 2.75 parts. The concentrated residue was recrystallized from a mixed solvent of ethyl acetate and tert-butyl methyl ether to obtain 0.68 parts of a desired product. This compound is represented by the following formula:
¹ -N-dimethyl-2-oxobutyl thiacyclopentanium p-toluenesulfonate
Confirmed with MR (JEOL “GX-270”).

[0127]

¹ H-NMR (dimethyl sulfoxide-d6,
Internal standard substance tetramethylsilane): δ (ppm) 1.12 (s,
9H); 2.05--2.29 (m, 4H); 2.29 (s, 3H); 3.32-3.56
(m, 4H); 4.89 (s, 2H); 7.12 (d, 2H); 7.48 (d, 2H).

Synthesis example 5 of acid generator: Synthesis of acid generator B5 2.3 parts of 3,3-dimethyl-2-oxobutylthiacyclopentanium bromide and 92 parts of acetonitrile were charged into a four-necked flask, and camphorsulfone was added thereto. A solution prepared by dissolving 2.9 parts of silver acid in 8.8 parts of acetonitrile was added dropwise, and the mixture was stirred at room temperature for 18 hours. The precipitated silver bromide was separated by filtration and washed with 30 parts of acetonitrile. The combined filtrate and washings were concentrated to 3.2 parts, to which 10 parts of acetonitrile was added, stirred at room temperature for 2 hours, and the insolubles were filtered off. The filtrate was concentrated to 2.92 parts. The concentrated residue was recrystallized from a mixed solvent of ethyl acetate and tert-butyl methyl ether to obtain 2.46 parts of a desired product. This compound is represented by the following formula:
-Dimethyl-2-oxobutyl thiacyclopentanium camphorsulfonate was identified as ¹ H-NM
R (JEOL “GX-270”).

[0130]

¹ H-NMR (dimethylsulfoxide-d6,
Internal standard substance tetramethylsilane): δ (ppm) 0.74 (s,
3H); 1.05 (s, 3H); 1.15 (s, 9H); 1.20-1.39 (m, 2
H); 1.76-1.95 (m, 3H); 2.10-2.28 (m, 5H); 2.36
(d, 1H); 2.66-2.74 (m, 1H); 2.86 (d, 1H); 3.33-3.58
(m, 4H); 4.90 (s, 2H).

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.
The mixture was charged at a molar ratio of 2.5 (20.0 parts: 9.5 parts: 7.3 parts), and methylisobutyl ketone was added in an amount of 2 times by weight based on all monomers to prepare a solution. Thereto, azobisisobutyronitrile as an initiator was added at 2 mol% based on the total amount of monomers, and the mixture was heated at 80 ° C. for about 8 hours. Thereafter, an operation of pouring the reaction solution into a large amount of heptane and precipitating was performed three times,
Purified. As a result, a copolymer having a weight average molecular weight of about 9,200 was obtained. This copolymer is referred to as a resin A1.

Resin Synthesis Example 2: Synthesis of Resin A2 2-Ethyl-2-adamantyl methacrylate, 3-hydroxy-1-adamantyl acrylate, norbornene and maleic anhydride in a molar ratio of 2: 2: 3: 3 (10 .0
Parts: 9.0 parts: 5.7 parts: 5.9 parts), and after adding methyl isobutyl ketone in an amount of 2 times by weight of all monomers,
The temperature was raised to 80 ° C. in a nitrogen atmosphere. Then, azobisisobutyronitrile was used as an initiator in an amount of 3% based on the total amount of monomers.
Mol% and heated at 80 ° C. for about 15 hours. afterwards,
The operation of pouring the reaction solution into a large amount of methanol to precipitate
This was repeated to obtain a copolymer having a weight average molecular weight of about 12160 and a dispersion of 1.90 (17.1 parts). This copolymer is referred to as a resin A2.

Resin Synthesis Example 3: Synthesis of Resin A3 2-ethyl-2-adamantyl methacrylate, 5-methacryloyloxy-2,6-norbornene lactone and α-methacryloyloxy-γ-butyrolactone in a molar ratio of 2: 1: 1 The mixture was mixed at a ratio (11.1 g: 5.0 g: 3.8 g), and 50 g of 1.4-dioxane was added to obtain a solution. Thereto was added 0.30 g of azobisisobutyronitrile as an initiator, the temperature was raised to 85 ° C., and stirring was continued for 5 hours. Then a large amount of n
Purification was performed by repeating the operation of pouring into heptane for crystallization three times to obtain a copolymer having a molecular weight of 9100 and a dispersion of 1.72. This is called resin A3.

Resin Synthesis Example 4: Synthesis of Resin A4 1- (1-adamantyl) acrylate was placed in a 4-neck flask.
10.5 g (42 mmol) of 1-methylethyl, 9.4 g of 3-hydroxy-1-adamantyl acrylate (42
mmol), 6.0 g of 2-norbornene (63 mmol)
l), 6.2 g (63 mmol) of maleic anhydride was added, and dissolved with 64.2 g of methyl isobutyl ketone.
After bubbling by blowing nitrogen for minutes, the temperature was raised to 80 ° C. A solution of 1.0 g (6.3 mmol) of 2,2′-azobis (isobutyronitrile) dissolved in 16.0 g of methyl isobutyl ketone was added dropwise to the solution, and the mixture was kept at 80 ° C. for 15 hours. The obtained reaction mass was cooled and poured into 1134 g of methanol. Then, white crystals were precipitated, and the crystals were taken out by filtration. The crystals were washed with methanol and dried under reduced pressure at 30 ° C. for 15 hours. The crystals of the copolymer of 1- (1-adamantyl) -1-methylethyl acrylate, 3-hydroxy-1-adamantyl acrylate, 2-norbornene and maleic anhydride thus obtained were 16.4 g, and had a molecular weight of 16.4 g. Was 6900 in terms of polystyrene. This is designated as resin A4.

Resin Synthesis Example 5: Synthesis of Resin A5 (1) A flask was charged with 16.4 g (0.07 mol) of 2-methyl-2-adamantyl methacrylate and 45.4 g (0.28 mol) of p-acetoxystyrene. And 123.6 g of isopropanol were charged and purged with nitrogen, and the temperature was raised to 75 ° C. Add dimethyl 2'2-azobis (2-
4.84 g (0.021 mol) of methyl propionate)
Was dissolved in 9.7 g of isopropanol and added dropwise.
After aging at 75 ° C. for about 0.5 hours and under reflux for about 11 hours, the mixture was diluted with acetone, charged into heptane, crystallized, crystals were taken out by filtration, and the obtained crystals were dried. The obtained crystals of 2-methyl-2-adamantyl methacrylate and p-acetoxystyrene copolymer were 54.2.
g.

(2) Into a flask, 53.0 g (0.30 mol as a monomer unit) of 2-methyl-2-adamantyl methacrylate and p-acetoxystyrene copolymer (20:80) obtained above were added. -Dimethylaminopyridine 5.3 g (0.043 mol) and methanol 159.0
g, and aged for 20 hours under reflux. After cooling, the mixture was neutralized with 3.13 g (0.052 mol) of glacial acetic acid, charged in water, crystallized, and crystals were taken out by filtration. Thereafter, the crystals were dissolved in acetone, charged in water, crystallized, and the crystals were taken out by filtration.
After repeating twice, the obtained crystals were dried. The crystals of the obtained 2-methyl-2-adamantyl methacrylate and p-hydroxystyrene copolymer weighed 37.8 g. The weight average molecular weight is about 7900, and the degree of dispersion is 1.72 (G
PC method: converted to polystyrene), and the copolymerization ratio was determined to be about 20:80 by a nuclear magnetic resonance (< ¹³ > C-NMR) spectrometer. This resin is referred to as resin A5.

Resin A6: 4-hydroxystyrene / styrene / t-butyl acrylate (60/20/20) copolymer, weight average molecular weight 11,000 (manufactured by Maruzen Petrochemical Co., Ltd., TSM
4)

Next, an example in which a resist composition was prepared using the following acid generators B1 to B3, C1 and C2 and evaluated was shown.

Acid generator B1: 3,3-dimethyl-2-oxobutyl thiacyclopentanium trifluoromethanesulfonate Acid generator B2: 3,3-dimethyl-2-oxobutyl
Thiacyclopentanium perfluorobutanesulfonate acid generator B3: 3,3-dimethyl-2-oxobutyl
Thiacyclopentanium perfluorooctanesulfonate acid generator B4: 3,3-dimethyl-2-oxobutyl
Thiacyclopentanium p-toluenesulfonate, acid generator B5: 3,3-dimethyl-2-oxobutyl
Thiacyclopentanium camphorsulfonate, acid generator C1: 4-methylphenyldiphenylsulfonium perfluorooctanesulfonate Acid generator C2: di-p-tert-butylphenyliodonium camphorsulfonate

Examples 1 to 6 and Comparative Examples 1 to 4 Resins and acid generators shown in Table 1 were mixed with the following components, and further filtered through a fluororesin filter having a pore diameter of 0.2 μm to form a resist solution. Was prepared. Resin: 10 parts (type is as shown in Table 1) Acid generator: Type and amount are as shown in Table 1. Quencher: 0.015 part of 2,6-diisopropylhydroaniline (0.008 part only in Example 6) Solvent: 57 parts of propylene glycol monomethyl ether acetate 3 parts of γ-butyrolactone

[0142] "DUV-30J" manufactured by Brewer was applied and applied.
The resist solution was spin-coated on a silicon wafer on which an organic anti-reflection film having a thickness of 1,600 ° was formed by baking at 5 ° C. for 60 seconds so that the film thickness after drying was 0.335 μm. . After the application of the resist solution, prebaking was performed on a direct hot plate at a temperature shown in Table 1 for 60 seconds. The wafer on which the resist film was formed in this way,
ArF excimer stepper [“NSR Ar” manufactured by Nikon Corporation
F ”, NA = 0.55, σ = 0.6], and the line-and-space pattern was exposed while changing the exposure amount in steps. Jarbake and 2.38% more
Paddle development was performed for 60 seconds with an aqueous solution of tetramethylammonium hydroxide. The pattern after development was observed with a scanning electron microscope to examine the effective sensitivity and resolution. The resist solution was applied on a quartz glass wafer, and a resist film was formed so as to have a thickness of 0.335 μm after prebaking under the same conditions as described above. Was measured with a spectrophotometer. Table 2 shows the evaluation results.

Effective sensitivity: Displayed at the minimum exposure amount at which a 0.18 μm line and space pattern was 1: 1.

Resolution: Displayed with the minimum size of the line and space pattern separated by the exposure amount of the effective sensitivity.

Smoothness of pattern wall surface: The wall surface of the isolated line pattern was observed with a scanning electron microscope.

[0146]

[Table 1] ━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━ Example No. Resin Acid generator Free break (° C) PEB (° C ) ━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━ Example 1 A1 B1 (0.5 parts) + C1 (0.2 parts) 110 115 Example 2 A1 B2 (0.5 parts) + C1 (0.2 parts) 110 115 Example 3 A1 B3 (0.5 parts) + C1 (0.2 parts) 110 125 Example 4 A2 B3 (0.5 parts) + C1 (0.2 parts) 110 125 Example 5 A3 B3 (0.5 parts) + C1 (0.2 parts) 100 125 Example 6 A4 B1 (0.25 parts) + C1 (0.2 parts) 110 125 ───────────────比較 Comparative Example 1 A1 C1 (0.2 parts) 110 125 Comparative Example 2 A2 C1 (0.2 parts) 110 125 Comparative Example 3 A3 C1 (0.2 parts) 100 125 Comparative Example 4 A4 C1 (0.2 parts) 100 125 ━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━

[0147]

[Table 2] ━━━━━━━━━━━━━━━━━━━━━━━━━━━━━ Example No. Effective sensitivity Resolution Transmittance mJ / cm ² μm smoothness on pattern wall Properties ━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━ Example 1 48 0.16 68 ○ Example 2 57 0.15 68 ○ Example 3 41 0.16 67 ○ Example 4 41 0.16 67 ○ Example 5 70 0.16 68 ○ Example 6 29 0.16 65 ○ ─── Comparative Example 1 53 0.15 64-Comparative Example 2 76 0.16 64-Comparative Example 3 88 0.16 65-Comparative Example 4 44 0.16 67-━━━━━━━━━━━━━━━━━━━ ━━━━━━━━━━━

As shown in Table 2, the resist compositions of the examples had better line edge roughness than the comparative examples, did not lower the transmittance, and had good sensitivity and resolution.

Examples 7 to 12 and Comparative Examples 5 and 6 The resins and acid generators shown in Table 1 were mixed with the following components, and further filtered through a fluororesin filter having a pore diameter of 0.2 μm to form a resist solution. Was prepared. Resin: 13.5 parts (type is as shown in Table 3) Acid generator: Type and amount are as shown in Table 1. Quencher: 0.07 parts of triisopropanolamine Solvent: 60 parts of ethyl lactate

In Examples 7 to 10 and Comparative Examples 5 and 6,
In Examples 11 and 12, Brewer's “DUV-30J” was applied and baked at 215 ° C. for 60 seconds to form an organic antireflection film having a thickness of 1600 °. "DUV-42", applied at 215 ℃, 6
The resist solution was spin-coated on a silicon wafer on which an organic anti-reflection film having a thickness of 600 ° was formed by baking under a condition of 0 second so that the film thickness after drying was 0.49 μm. After the application of the resist solution, prebaking was performed on a direct hot plate at a temperature shown in Table 3 for 60 seconds. A KrF excimer stepper [“NSR 2205EX12B” manufactured by Nikon Corporation, NA = 0.55, 2 /
A three-zone illumination] was used to expose the line and space pattern while changing the exposure stepwise. After the exposure, post-exposure baking was performed on a hot plate at the temperature shown in Table 3 for 60 seconds, and paddle development was performed with a 2.38% tetramethylammonium hydroxide aqueous solution for 60 seconds. The pattern after development was observed with a scanning electron microscope to examine the effective sensitivity and resolution. Further, the above-mentioned resist solution was applied on a quartz glass wafer, and a resist film was formed so as to have a film thickness of 0.49 μm after pre-baking under the same conditions as described above. Was measured with a spectrophotometer. Table 4 shows the evaluation results.
It was shown to.

Effective sensitivity: Displayed with the minimum exposure amount at which a 0.20 μm line and space pattern was 1: 1.

Resolution: The minimum size of the line and space pattern separated by the exposure amount of the effective sensitivity was displayed.

Smoothness of pattern wall surface: The wall surface of the isolated line pattern was observed with a scanning electron microscope.

[0154]

[Table 3] ━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━ Example No. Resin Acid generator Free break (° C) PEB (° C ) ━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━ Example 7 A5 B2 (0.35 parts) + C2 (0.7 parts) 120 140 Example 8 A6 B1 (0.35 part) + C2 (0.35 part) 130 140 Example 9 A6 B2 (0.35 part) + C2 (0.35 part) 130 140 Example 10 A6 B3 (0.35 part) + C2 (0.35 part) 130 140 Example 11 A6 B4 (0.35 part) + C2 (0.35 part) 130 140 Example 12 A6 B5 (0.35 part) + C2 (0.35 part) 130 140 ─────────────── ───────────────── Comparative Example 5 A5 C2 (0.7 parts) 120 140 Comparative Example 6 A6 C2 (0.35 parts) 130 140 ━━━━━━━━━ ━━━━━━━━━━━━━━━━━━━━━━━

[0155]

[Table 4] ━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━ Example No. Effective sensitivity Resolution Transmittance mJ / cm ² μm of pattern wall Smoothness ━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━ Example 7 50 0.16 72 ○ Example 8 78 0.16 76 ○ Example 9 82 0.16 76 ○ Example 10 90 0.16 76 ○ Example 11 82 0.16 75 ○ Example 12 96 0.16 75 ○ ────────────────────────── ──── Comparative Example 5 48 0.16 72-Comparative Example 6 120 0.19 77-━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━

As shown in Table 4, the resist compositions of the examples had better line edge roughness than the comparative examples, did not lower the transmittance, and had good sensitivity and resolution.

[0157]

The chemically amplified positive resist composition of the present invention provides a resist pattern having significantly improved line edge roughness, and has excellent dry etching resistance and sensitivity.
Resist performance such as resolution is also good. Therefore, this composition is suitable for lithography using a KrF excimer laser, an ArF excimer laser, or the like, thereby giving a high-performance resist pattern.

 ────────────────────────────────────────────────── ─── Continued on the front page (72) Inventor Akira Kamabuchi 3-1-198 Kasuganaka, Konohana-ku, Osaka City Sumitomo Chemical Co., Ltd. F-term (reference) 2H025 AA01 AA02 AA03 AA09 AB16 AC04 AC08 AD03 BE00 BE07 BG00 FA03 FA12 FA17 4H006 AA01 AA03 AB80

Claims (10)

[Claims] 1. A sulfonium salt represented by the following formula (I) and a sulfonium salt represented by the following formula (I ′) (Wherein, Q ¹ and Q ² independently represent an alkyl group having 1 to 6 carbon atoms or a cycloalkyl group having 3 to 10 carbon atoms. Q ³ represents a hydrogen atom, and Q ⁴ represents a carbon atom. Represents an alkyl group of numbers 1 to 6, a cycloalkyl group of 3 to 10 carbon atoms,
Or Q ³ and Q ⁴ together with an adjacent CHC (O) group
-Represents an oxocycloalkyl group. Q ⁵ SO ₃ ^- represents an organic sulfonate ions. However, when Q ⁵ represents a perfluoroalkyl group having 1 to 8 carbon atoms, the case where Q ³ and Q ⁴ together with an adjacent CHC (O) group represent a 2-oxocyclohexyl group is excluded. ) (In the formula, Q represents an alicyclic hydrocarbon group having 3 to 7 carbon atoms that completes a ring together with the described S ⁺ . The alicyclic hydrocarbon group may have a ketone group, Further, at least one —CH ₂ — of the alicyclic hydrocarbon group may be substituted with an oxygen atom or a sulfur atom, Q ³ represents a hydrogen atom, and Q ⁴ represents an alkyl having 1 to 6 carbon atoms. Group, having 3 to 1 carbon atoms
0 represents a cycloalkyl group, or Q ³ and Q ⁴ together with an adjacent CHC (O) group represent a 2-oxocycloalkyl group. Q ⁵ SO ₃ ^- represents an organic sulfonate ions. At least one sulfonium salt selected from the group consisting of a triphenylsulfonium salt represented by the following formula (IIa) and a diphenyliodonium salt represented by the following formula (IIb) (Wherein, P ^{1 to} P ³ independently represent hydrogen, a hydroxyl group, an alkyl group having 1 to 6 carbon atoms or an alkoxy group having 1 to 6 carbon atoms, and P ⁶ SO ₃ ⁻ represents an organic sulfonate ion. Represents.) (In the formula, P ⁴ and P ⁵ independently represent hydrogen, a hydroxyl group, an alkyl group having 1 to 6 carbon atoms or an alkoxy group having 1 to 6 carbon atoms, and P ⁷ SO ₃ ⁻ represents an organic sulfonate ion. And an acid generator containing at least one onium salt selected from the group consisting of an onium salt and a polymerized unit having an acid-labile group, which itself is insoluble or hardly soluble in alkali, A chemically amplified positive resist composition comprising a resin which becomes soluble in alkali by the action of the above. (2) Q ⁵ in the formula (I), Q ^{5 in} the formula (I ′), P ⁶ in the formula (IIa) and P ^{5 in} the formula (IIb).
The composition according to claim 1, wherein ⁷ independently represents a perfluoroalkyl group having 1 to 8 carbon atoms, an alkyl group having 1 to 8 carbon atoms, an aromatic group having 6 to 12 carbon atoms, or a camphor group. 3. A sulfonium salt represented by the formula (I) and a sulfonium salt represented by the formula (I ′), a triphenylsulfonium salt represented by the formula (IIa) and a sulfonium salt represented by the formula (IIb): 3. The composition according to claim 1, wherein at least one onium salt selected from diphenyliodonium salt) is present in a weight ratio of 9: 1 to 1: 9. 4. The composition according to claim 1, wherein the content of the polymerized unit having an acid-labile group in the resin is 10 to 80 mol%. 5. The polymer unit having an acid-labile group in the resin is 2-alkyl-2-adamantyl (meth) acrylate or 1- (1-adamantyl) -1 (meth) acrylate.
The composition according to claim 1, which is a polymerized unit of an alkylalkyl. 6. The resin further comprises polymerized units of p-hydroxystyrene, polymerized units of m-hydroxystyrene, polymerized units of 3-hydroxy-1-adamantyl (meth) acrylate, and 3,5- (meth) acrylic acid. Dihydroxy-1
A polymer unit of adamantyl, a polymer unit of (meth) acryloyloxy-γ-butyrolactone in which the lactone ring may be substituted with alkyl, and the following formulas (IIIa), (III)
The composition according to any one of claims 1 to 5, further comprising at least one polymer unit selected from polymer units of an alicyclic lactone represented by b). (In the formula, R ¹ and R ² independently represent hydrogen, methyl or trifluoromethyl, and n represents a number of 1 to ^3. ) 7. The composition according to claim 6, wherein the resin further has a polymerized unit of 2-norbornene and a polymerized unit of an aliphatic unsaturated dicarboxylic anhydride. 8. The composition according to claim 1, further comprising an amine as a quencher. 9. The formula (Ia) (Wherein, Q ⁶ is perfluoroalkyl group having 1 to 8 carbon atoms, an alkyl group having 1 to 8 carbon atoms, .Q ⁶ which represents an aromatic group or a camphor group having 6 to 12 carbon atoms, 1 to 4 carbon atoms When it represents a perfluoroalkyl group having from 8 to 8, Q ¹ and Q ² each independently represent an alkyl group having 1 to 6 carbon atoms and 3 to 1 carbon atoms.
Represents a cycloalkyl group of 0. Q ³ represents a hydrogen atom, and Q ⁴ represents an alkyl group having 1 to 6 carbon atoms and a cycloalkyl group having 3 to 10 carbon atoms. Q ⁶ is an alkyl group having 1 to 8 carbon atoms,
When representing an aromatic group having 6 to 12 carbon atoms or a camphor group, Q ¹ and Q ² independently represent an alkyl group having 1 to 6 carbon atoms or a cycloalkyl group having 3 to 10 carbon atoms. Q ³
Represents a hydrogen atom, Q ⁴ represents an alkyl group having 1 to 6 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, or Q ³ and Q ⁴
Represents a 2-oxocycloalkyl group together with an adjacent CHC (O) group. ). 10. The formula (I'a) (In the formula, Q represents an alicyclic hydrocarbon group having 3 to 7 carbon atoms that completes a ring together with the described S ⁺ . The alicyclic hydrocarbon group may have a ketone group, Further, at least one —CH ₂ — of the alicyclic hydrocarbon group may be substituted with an oxygen atom or a sulfur atom, Q ³ represents a hydrogen atom, and Q ⁴ represents an alkyl having 1 to 6 carbon atoms. Group, having 3 to 1 carbon atoms
0 represents a cycloalkyl group, or Q ³ and Q ⁴ together with an adjacent CHC (O) group represent a 2-oxocycloalkyl group. Q ⁵ SO ₃ ^- represents an organic sulfonate ions. ).