JP2001255647A - Fluoroalkylonium salt type cation or acid generating agent which generates cation or acid when irradiated with energy beam - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a cation or acid generating agent suitable for use in a chemical amplification type resist material, having high sensitivity to energy beams and capable of generating a cation or acid. SOLUTION: The cation or acid generating agent comprises an energy beam sensitive fluoroalkylonium salt of formula (1) in which groups R1-R3 (alkyl, aryl or the like) and a group Rf (fluoroalkyl) combine with the central element A (I, S, Se, Te, N or P). The chemical amplification type resist material is obtained by blending the acid generating agent.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a fluoroalkylonium salt type cation or acid generator which generates a cation or an acid upon irradiation with energy rays.

[0002]

2. Description of the Related Art Conventionally, onium salts such as sulfonium and iodonium have been used as actinic rays such as ultraviolet rays, electron beams, X-rays and lasers (in this specification, these are referred to as "energy rays").
) Is widely known to absorb and decompose to generate a strong acid. These are important as cations or acid generators, which are components of chemically amplified resist materials composed of energy-sensitive curable resins such as chemically amplified photoresists used in semiconductor manufacturing or base resins having acid labile groups. Substance.

An example of the use of a chemically amplified resist of an onium salt is described in (Ito et al., "Polymer Engineering and Science", 1983, Vol. 23, 101
2). However, many onium salts that have been announced as components of chemically amplified resists still have low sensitivity to energy rays, and have the disadvantage that it takes a long time to irradiate a necessary energy dose.

[0004]

SUMMARY OF THE INVENTION Accordingly, the present inventors
When a high-sensitivity acid generator capable of improving the above performance was studied, a fluoroalkylonium salt having a fluoroalkyl group introduced therein was found. Accordingly, an object of the present invention is to provide a compound which is effective as a cation or an acid generator denatured by energy rays in the field of photoresists and the like, and a chemically amplified resist material containing the compound.

[0005]

SUMMARY OF THE INVENTION The above-mentioned object of the present invention is as follows.
Generate cations or acids by energy ray irradiation,
Equation (1):

[0006]

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Wherein A is an element selected from iodine, sulfur, selenium, tellurium, nitrogen or phosphorus; when A is iodine, R ² and R ³ are absent and R ¹ has ¹ carbon atom
An alkyl group having from 15 to 15 or an aryl group having from 6 to 15 carbon atoms; when A is sulfur, selenium or tellurium, R ³
Is not present, and R ¹ and R ² are each independently an alkyl group having 1 to 15 carbon atoms, an aryl group having 6 to 20 carbon atoms,
Dialkylamino group having 2 to 30 carbon atoms, 7 to 35 carbon atoms
Or a diarylamino group having 12 to 40 carbon atoms, R ¹ and R ² may be bonded to each other to form a ring; when A is nitrogen or phosphorus, R ¹ and R 2 ² and R ³ each independently have 1 carbon atom
15 alkyl group, an aryl group having 6 to 20 carbon atoms, a dialkylamino group having 2 to 30 carbon atoms, a diarylamino group alkyl arylamino group, or 12 to 40 carbon atoms 7-35 carbon atoms, R ¹ And R ² and R ³ may be bonded to each other to form one or more rings;
³ is absent, and R ¹ and R ² may combine to form an aromatic ring containing A; provided that the alkyl group, the alkyl group of the dialkylamino group and the alkyl group of the alkylarylamino group are An aryl group, a halogen atom, an oxygen atom, a nitrogen atom, a sulfur atom or a silicon atom, which may be substituted or branched or may form a ring; And the aryl group of the diarylamino group is an alkyl group, a haloalkyl group, a halogen atom, an alkoxyl group, an aryloxy group, a nitro group, an amide group, a cyano group, an alkanoyl group, an aroyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, or an acyloxy group. Rf may be branched or may form a ring Is intended a portion of the fluorine perfluoroalkyl group or said perfluoroalkyl group prime 1-15 is substituted with hydrogen; X ^- or is represented by a is) conjugate base of a Bronsted acid or (2, ):

[0008]

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Wherein A ¹ and A ² are the same or different and are both elements selected from iodine, sulfur, selenium, tellurium, nitrogen or phosphorus; when A ¹ or A ² is iodine, ⁴ , R ⁵ , R ⁷ and R ⁸ are not present; when A ¹ or A ² is sulfur, selenium or tellurium, R ⁵ and R ⁸ are absent and R ⁴ and R ⁷ are each independently ,
An alkyl group having 1 to 15 carbon atoms, an aryl group having 6 to 20 carbon atoms, a dialkylamino group having 2 to 30 carbon atoms, and 7 carbon atoms
-35 alkylarylamino groups or 12-carbon atoms
When A ¹ or A ² is nitrogen or phosphorus, R ⁴ , R ⁵ , R ⁷ and R ⁸ are each independently an alkyl group having 1 to 15 carbon atoms, 6 carbon atoms; ~
An aryl group having 20 carbon atoms, a dialkylamino group having 2 to 30 carbon atoms, an alkylarylamino group having 7 to 35 carbon atoms or a diarylamino group having 12 to 40 carbon atoms, and R ⁴ and R ⁵ , or R ⁷ and R ⁸ May be bonded to each other to form a ring; provided that the alkyl group, the alkyl group of the dialkylamino group and the alkyl group of the alkylarylamino group include an aryl group, a halogen atom, an oxygen atom,
A nitrogen atom, a sulfur atom or a silicon atom may be substituted or branched or may form a ring, and the aryl group, the aryl group of the alkylarylamino group and the aryl group of the diarylamino group are Alkyl group, haloalkyl group, halogen atom, alkoxyl group,
Aryloxy group, nitro group, amide group, cyano group, alkanoyl group, aroyl group, alkoxycarbonyl group,
R ⁶ may be substituted with an aryloxycarbonyl group or an acyloxy group; R ⁶ may be substituted with an aryl group, a halogen atom, an oxygen atom, a nitrogen atom, a sulfur atom or a silicon atom, and may be a branched or unsubstituted ring. An alkylene group having 1 to 15 carbon atoms which may be formed; Rf may have 1 to 15 carbon atoms which may be branched or may form a ring;
X is a perfluoroalkyl group represented by the formula: or a part of the fluorine of the perfluoroalkyl group is substituted by hydrogen;
^- relates to fluoroalkyl onium salt type cationic or acid generator represented by a is) conjugate base of a Bronsted acid.

Rf in the above formula (1) or (2) is -CH ₂ Rf ¹ (Rf ¹ is a perfluoroalkyl having 1 to 14 carbon atoms which may be branched or form a ring. in which some of the fluorine group or the perfluoroalkyl group is substituted with _{^{hydrogen), - Rf 2 CF 2 H}} (R
f ² is in which a part of the fluorine perfluoroalkylene group or the perfluoroalkylene group branched carbon atoms which may be well form a ring optionally 1-14 are substituted with hydrogen) or -CH2Rf ³ CF ₂ H (Rf ³ may have a carbon number of 1 to 1 which may be branched or form a ring)
3) or a perfluoroalkylene group in which a part of fluorine of the perfluoroalkylene group is substituted with hydrogen), and X ⁻ is preferably a conjugated base of a fluoroalkylsulfonic acid.

By blending the fluoroalkylonium salt type cation or acid generator of the present invention with a negative resist resin or a positive resist resin, a highly sensitive chemically amplified resist material can be produced.

[0012]

DESCRIPTION OF THE PREFERRED EMBODIMENTS In general, a cation or an acid generator is such that the central element A and one of the parts (substituents) bonded thereto are cut by irradiation energy, and the cut substituent becomes a cation. A counter anion takes a hydrogen atom to become an acid group to generate a cation or an acid (J. Polym. Sci. Part A: Po
lym. chem. 30 , 2365-2369 (199)
2); Macromolecules, 24 , 2137
-2139 (1991)).

The fluoroalkylonium salt used in the present invention is characterized in that the fluoroalkyl group, which is a strong electron-withdrawing group, is directly linked to the central element A, A ¹ or A ² (iodine, sulfur, selenium, tellurium, nitrogen or phosphorus). A typical onium salt is a trialkylsulfonium salt derivative, a tribenzylsulfonium salt derivative (JP-A-8-208597), and a triphenylsulfonium salt derivative. As compared with an acid generator such as diphenyliodonium salt (Japanese Patent Application Laid-Open No. H11-305440, etc.), the cationic property of the central element A is higher, the reactivity is further improved, and the sensitivity to energy rays is significantly higher. It can be a cation generator or an acid generator. Hammett's substituent constant (σ
m) is -0.06 for the methyl group and 0.0 for the phenyl group.
4. The benzyl group is -0.05, the trifluoromethyl group is 0.46 (edited by The Chemical Society of Japan, "Basic Chemistry Handbook II", 34
It is known that fluoroalkyl groups have a higher electron withdrawing property than these. For example, in the examples of the present invention to be described later, the amount of decomposition of the S- (fluoroalkyl) diphenylsulfonium salt having a trifluoromethyl group or a trifluoroethyl group of Examples 2 and 3 by light is the same as that of Comparative Example 1. It is higher than that of the phenylsulfonium salt, and it is understood that introduction of the fluoroalkyl group into the onium salt serves as a highly sensitive cation or acid generator.

By the way, when a cation or acid generator is added to a resist in particular, it is not preferable that some gas is generated along with generation of the cation or acid. Such a gas is generated when a component desorbed by photolysis of a cation or an acid generator has a low molecular weight. Therefore, in order to prevent generation of gas, it is effective to prevent low molecular weight compounds from being generated by decomposition. For this purpose, the compound which is decomposed and desorbed from the central element A by decomposition should be made less likely to be gasified, or if the bond is broken, it must be bonded to the remaining portion and not desorbed. Therefore, for example, when the central element A is sulfur, selenium or tellurium, if the alkyl group R ¹ and the aryl group or the alkyl group R ² are bonded to each other to form a ring, the generation of gas will occur. No cation or acid generator. The same is true when A is nitrogen or phosphorus. In addition, substituents other than the fluoroalkyl group Rf of the fluoroalkylonium salt (R ¹ , R ^2, etc .; sometimes simply referred to as R hereinafter)
Are all aryl groups, the bond between the fluoroalkyl group Rf and the central element A is usually cleaved (Tetr
ahedron Letters, 31 , 3579 (1
990)), it has been reported that if at least one of the substituents R has an alkyl group, the bond between the alkyl group and the central element A is broken (J. Org. Chem. USS).
R, 20 , 103 (1984)).

Some of the fluoroalkylonium salts used in the present invention have already been reported.

For example, in the formula (1), A is iodine and R is
^{When 1} is an aryl group, Chemistry L
eters, 1663 (1981), Synthetic Organic Chemistry Society, Vol. 41, No. 3, page 251 or JP-A-55-162.
No. 763, JP-A-57-24319, JP-A-58-1
No. 67527, JP-A-60-172959, JP-A-6
It is reported in each of the gazettes of 1-25492.

In the formula (1), when A is sulfur, R ¹ and R ² are both aryl groups and the Rf group is CF ₃ , see J. Am.
Org. Chem. USSR, 20 , 103 (198
4) or J. Org. Chem. 63 , 2656 (1
998), wherein A is sulfur, selenium or tellurium, R ¹ and R ² are both aryl groups, and R ¹ and R ²
Are linked to each other to form a ring. Am.
Chem. Soc. 115 , 2156 (1993) or JP-A-3-197479 and JP-A-6-56821. All of these fluoroalkylonium salts are only disclosed for use in the field of synthetic organic chemistry as reagents for introducing fluoroalkyl groups into various organic compounds. In the formula (1), when A is sulfur, selenium or tellurium, R ¹ is an alkyl group or an aryl group, and R ² is an alkyl group, Zh. Org. Khim. , 15 , 24
32 (1979); Org. Chem. USSR,
15 , 2201 (1979). In the formula (1), when Rf is —CH ₂ Rf ¹ , A is sulfur and the Rf ¹ group is CF ₃ , R ¹ and R ² are both methyl groups, and both are phenyl groups. And those in which the phenyl groups are bonded to each other to form a ring, have been reported (Bull. Chem. Soc. J.
pn. 64 , 2008 (1991)). Formula (1) wherein A is sulfur and R ¹ and R ² are both dialkylamino groups is described in Chem. Ber. , 124 , 31 (199
Reported in 1).

Further, in the formula (1), those wherein A is nitrogen and R ¹ , R ² and R ³ are an alkyl group or an aryl group are described in J. Am. Org. Chem. USSR, 16 , 213
9 (1980), R ³ does not exist, and R ¹ and R ² combine to form an aromatic ring containing A (nitrogen). Proceedings of the Lectures P-44 (p. 182) and the 73rd Symposium on Organic Synthesis, Abstracts, p. 1 In the formula (1), when Rf is —CH ₂ Rf ¹ , A is nitrogen and R ^{1 is}
When R ² and R ³ are an alkyl group or an aryl group, or when R ³ is absent and R ¹ and R ² combine to form an aromatic ring containing A (nitrogen), see Bull. Chem.
Soc. Jpn. 64 , 2008 (1991).

In the formula (1), A is phosphorus and R ¹ , R ² ,
Those in which R ³ is an aryl group are described in J. Am. Am. Chem.
Soc. 115 , 2156 (1993), wherein R ¹ , R ² and R ³ are dialkylamino groups are described in J. Am. Fluorine Chem. , 70 , 271
(1995). Further, R ¹ in the case Rf in formula (1) is -CH ₂ Rf ^1, A is a phosphorus,
When R ² and R ³ are aryl groups, see Bull. Che
m. Soc. Jpn. 64 , 2008 (1991).

Even in these known fluoroalkylonium salts, there is no report on the use as a cation generator or acid generator in which cations or acids are generated by irradiation with energy rays.

Next, the fluoroalkylonium salts that can be used in the present invention are listed below, but are not limited thereto, and the fluoroalkylonium salts described in the above-mentioned documents other than those exemplified are also listed. Can be used.

Fluoroalkylonium salts wherein the central element is iodine:

[0023]

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Fluoroalkylonium salts wherein the central element is sulfur:

[0025]

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[0026]

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[0027]

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[0028]

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[0029]

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[0030]

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A fluoroalkylonium salt in which the central element is selenium:

[0032]

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Fluoroalkylonium salts wherein the central element is tellurium:

[0034]

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Fluoroalkylonium salts wherein the central element is nitrogen:

[0036]

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Fluoroalkylonium salt whose central element is phosphorus:

[0038]

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[0039]

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Among these specific fluoroalkylonium salts, the following compounds are novel substances. Compounds I-4, I-8, I-10, I-11, I-1
2, I-13 Compounds S-2 to S-13, S-17 to S-40, S-4
4-S-145 Compound Se-1 to Se-9, Se-11, Se-13 to
Se-22 Compounds Te-1 to Te-9, Te-11, Te-13 to
Te-22 Compounds N-1 to N-14, N-19, N-21 to N-2
X in fluoroalkyl onium salt used in the 4 compound P-1 to 26 present invention ^- is the conjugate base of a Bronsted acid. Examples of Bronsted acids include trifluoromethanesulfonic acid, tetrafluoroethanesulfonic acid, perfluorobutanesulfonic acid, perfluoropentanesulfonic acid, perfluorohexanesulfonic acid, perfluorooctanesulfonic acid, and fluoroalkylsulfonic acids such as difluoromethanesulfonic acid. methanesulfonic acid, trichloromethane sulfonic acid, benzenesulfonic acid, toluenesulfonic acid, sulfuric acid, fluorosulfonic acid, chlorosulfonic _{acid, HBF 4, HSbF 6, HPF} 6, HSbCl 5 F, H
Examples include, but are not limited to, SbCl ₆ , HAsF ₆ , HBCl ₃ F, HACl ₄ . Particularly, a fluoroalkylsulfonic acid is preferred because it is a strong acid and does not generate hydrogen fluoride or hydrogen chloride.

The cation or acid generator of the present invention is basically composed of the above fluoroalkylonium salt, but may be used in combination with other conventionally known cation or acid generators, if necessary.

The energy beam capable of generating a cation or an acid from the cation or acid generator is not particularly limited, but is preferably an ultra-high, high, medium, low-pressure mercury lamp, a xenon lamp, a carbon arc lamp, a metal halide lamp. , Fluorescent lamp, tungsten lamp, excimer lamp, germicidal lamp, excimer laser, nitrogen laser, argon ion laser, helium cadmium laser, helium neon laser, krypton ion laser, KrF excimer laser, ArF excimer laser, F2 laser, various semiconductor lasers, Electromagnetic wave energy obtained from a YAG laser, a light emitting diode, a CRT light source, and the like, and high energy rays such as an electron beam, an X-ray, and a radiation.

The cation or acid generator of the present invention is highly sensitive to these energy rays and can generate cations or acids with a smaller irradiation dose than conventional acid generators.

By combining the fluoroalkylonium salt type cation or acid generator of the present invention with a sensitizer, the activity with respect to energy rays can be further enhanced, and a supersensitive cation or acid generator can be obtained. Examples of the sensitizer include naphthalene derivatives, anthracene derivatives, phenanthrene derivatives, pyrene derivatives, naphthacene derivatives, perylene derivatives, pentacene derivatives, hexacene derivatives, fused polycyclic aromatic derivatives such as heptacene derivatives, fluorene derivatives, naphthoquinone derivatives, anthraquinone derivatives, Benzoin derivatives, xanthene derivatives,
Thioxanthene derivatives, xanthone derivatives, thioxanthone derivatives, coumarin derivatives, cyanine derivatives, merocyanine derivatives, acridine derivatives, indoline derivatives,
Examples thereof include an azulene derivative, a porphyrin derivative, a phthalocyanine derivative, a benzothiazole derivative, a spiropyran derivative, and the like. These may be used in any proportion as needed, and may be used as a mixture of two or more kinds.

The cation or acid generator of the present invention can be used in the field of generating cations or acids by irradiation with energy rays and utilizing the generated cations or acids.
In particular, it is useful as a cation or acid generator of a chemically amplified resist material for converting a functional group-containing resist resin into a form soluble or insoluble in a developer using the generated cation or acid as a catalyst.

The cation or acid generator of the present invention can be used with a chemically amplified negative resist material when a resin of the type which becomes insoluble in a developer by being crosslinked or condensed by the cation or acid generated as a resist resin is used. Become. Examples of such a resist resin include a cyclized isoprene-based negative resist, a polyvinyl alcohol-based negative resist,
Polyvinyl cinnamate-based negative resists, copolymers of polymethacrylic acid esters and hydroxystyrene and the like can be mentioned.

When a resin of a type in which a functional group portion is decomposed or dissociated by a cation or an acid generated as a resist resin and becomes soluble in a developer is used, a chemically amplified positive resist material is obtained. As such a resist resin, as an alkali-soluble resin serving as a base resin, for example, novolak resin; polyvinylphenol resin; polyisopropenylphenol resin; vinylphenol and acrylic acid, methacrylic acid, acrylonitrile,
Methyl methacrylate, methyl acrylate, maleic acid, maleic anhydride, isopropenylphenol, copolymer of styrene or α-methylstyrene; isopropenylphenol and acrylic acid, methacrylic acid, acrylonitrile, methyl methacrylate, methyl acrylate, maleic acid, Examples include maleic anhydride, isopropenylphenol, copolymers with styrene or α-methylstyrene. In vinylphenol and isopropenylphenol, the positional relationship between the hydroxyl group and the vinyl group or isopropenyl group is not particularly limited, but p-vinylphenol or p-isopropenylphenol is generally preferred. These resins may be partially hydrogenated in order to improve transparency. Further, an alkyl group, an alkoxy group, or the like may be introduced into the phenol nucleus of the resin as long as it is soluble in alkali. Among these alkali-soluble resins, a polyvinylphenol-based resin, that is, a homopolymer of vinylphenol or a copolymer of vinylphenol and another monomer is preferable.

As the group which is introduced into the alkali-soluble resin and has a dissolution inhibiting ability in an alkali developer but is unstable to an acid, various known protecting groups can be employed. For example, tert-butoxycarbonyl, tert-butoxycarbonylmethyl, 1-ethoxyethyl, 1-methoxyethyl,
1-propoxyethyl, 1-isopropoxyethyl, 1
-Tert-butoxyethyl, 1-isobutoxyethyl, 1
-Butoxyethyl, 1-pentyloxyethyl, 1-cyclopentyloxyethyl, 1-hexyloxyethyl, 1-
Cyclohexyloxyethyl, 1-heptyloxyethyl,
1-alkoxyalkyl groups such as 1-cycloheptyloxyethyl, 1-methoxypropyl or 1-methoxy-1-methylethyl; tetrahydro-2-pyranyl, 6-
Methoxytetrahydro-2-pyranyl, 6-ethoxytetrahydro-2-pyranyl, tetrahydro-2-furyl, 5-methoxytetrahydro-2-furyl or 5-
And 2-residues of a cyclic saturated ether such as ethoxytetrahydro-2-furyl. These groups will replace the hydrogen atoms of the phenolic hydroxyl groups.

In the chemically amplified resist material of the present invention, since the cation or acid generator of the present invention is highly sensitive to energy rays, the amount of the cation or acid generator added may be smaller than in the conventional case. For example, resist resin 100
0.01 to 20 parts by weight, more preferably 0.1 to 20 parts by weight
-10 parts by weight is preferred. Further, the above-mentioned other acid generators and / or sensitizers may be used in combination.

In addition, it is generally known that, in a chemically amplified positive photoresist, the deterioration of performance due to the deactivation of an acid due to withdrawal after exposure can be improved by adding an organic base compound as a quencher. In the present invention, it is preferable to blend such an organic base compound. As the organic base compound used here,
For example, hexylamine, heptylamine, octylamine, nonylamine, decylamine, aniline, 2-,
3- or 4-methylaniline, 4-nitroaniline,
1 such as 1-naphthylamine or 2-naphthylamine
Secondary amines: dibutylamine, dipentylamine, dihexylamine, diheptylamine, dioctylamine,
Secondary amines such as dinonylamine, didecylamine, N-methylaniline, piperidine or diphenylamine; triethylamine, trimethylamine, tripropylamine, tributylamine, tripentylamine,
Trihexylamine, triheptylamine, trioctylamine, trinonylamine, tridecylamine, methyldibutylamine, methyldipentylamine, methyldihexylamine, methyldicyclohexylamine, methyldiheptylamine, methyldioctylamine, methyldinonylamine, Methyldidecylamine, ethyldibutylamine, ethyldipentylamine, ethyldihexylamine, ethyldiheptylamine, ethyldioctylamine, ethyldinonylamine, ethyldidecylamine,
Tertiary amines such as tris [2- (2-methoxyethoxy) ethyl] amine, triisopropanolamine or N, N-dimethylaniline; diamines such as ethylenediamine, tetramethylenediamine or hexamethylenediamine; imidazole, pyridine, Unsaturated cyclic amines such as -methylpyridine, 4-methylimidazole and bipyridine. These organic base compounds can be used alone or in combination of two or more.

[0051]

EXAMPLES The present invention will be described in detail below with reference to examples, but the present invention is not limited to these examples.

Example 1 30 mg of (1H, 1H-heptafluorobutyl) phenyliodonium triflate was dissolved in a solvent (deuterated acetonitrile:
Water = 10: 1) 0.66 ml was dissolved in, packed into an NMR tube, then irradiated for 1 hour a low pressure mercury lamp at room temperature, ¹⁹ F
NMR was measured to determine the degree of decomposition. Further, this solution was transferred to a sample bottle using 1 ml of acetonitrile, 8 ml of pure water was added, and the mixture was stirred. After 1 minute, the measurement of the pH of the solution was started using a pH meter. The measurement was performed, and the average value was obtained. Table 1 shows the results.
Shown in

Examples 2-3 and Comparative Example 1 20 mg of each onium salt shown in Table 1 was dissolved in 0.72 ml of a solvent (deuterated acetonitrile: water = 5: 1), and NM was added.
R tubes were then irradiated with a low-pressure mercury lamp at room temperature for 2 hours, and NMR (in the case of Examples 2 and 3, ¹⁹ F-NMR,
In the case of Comparative Example 1, ¹ H-NMR was measured to determine the degree of decomposition. Further, this solution was transferred to a sample bottle using 1 ml of acetonitrile, 8 ml of pure water was added and stirred, and after 1 minute, measurement of the pH of the solution was started using a pH meter,
A total of three measurements were performed within 2 minutes, and the average was determined. Table 1 shows the results.

[0054]

[Table 1]

Comparative Example 2 When irradiating with a low-pressure mercury lamp, 30 mg of (1H, 1H-heptafluorobutyl) phenyliodonium triflate was used.
The same operation as in Example 1 was carried out in the same manner as in Example 1 except that an NMR tube containing a solution of 10: 1 (0.66 ml) of deuterated acetonitrile: water was wrapped with aluminum foil and completely shielded from light. The amount of decomposition and pH by NMR were measured.
Table 2 shows the results.

COMPARATIVE EXAMPLES 3-5 When irradiating a low-pressure mercury lamp, the onium salts 20 shown in Table 2 were used.
The same operation as in Examples 2-3 and Comparative Example 1 was performed except that an NMR tube containing a solution of 5 mg (0.72 ml) of deuterated acetonitrile: water was wrapped with aluminum foil and completely shielded from light. In the same manner as in Example 1, the amount of decomposition by NMR and the pH were measured. Table 2 shows the results.

[0057]

[Table 2]

Next, the synthesis of a fluoroalkylonium salt will be described with reference to Examples. The fluoroalkylonium salt used in the present invention can be synthesized by various methods described in the above-mentioned known documents, or by a novel method combining those methods with various organic chemical techniques.

Examples will be described below, but the present invention is not limited to these examples. The fluoroalkylonium salts synthesized in Examples 4 to 6 are novel compounds.

Embodiment 4

[0061]

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441 mg (5 mmo) of tetrahydrothiophene
l) in a solution of 8 ml of methylene chloride under stirring at room temperature,
2.18 g (5 mmol) of (2,2,2-trifluoroethyl) phenyliodonium triflate was added and stirred for 3 hours. 40 ml of diethyl ether was added to the reaction mixture,
The separated oil was separated by decantation, washed five times with diethyl ether, recrystallized from ethyl acetate-diethyl ether, and dried under reduced pressure to obtain the desired (2,2,2-trifluoroethyl). 1.43 g (89% yield) of tetrahydrothiophenium triflate were obtained.

Melting point: 55.5-56.0 ° C. ¹ H-NMR (CD ₃ CN); δ 2.34 (4H, m), 3.56 (2H, m), 3.72
(2H, m), 4.07 (2H, q, J = 9Hz) ¹⁹ F-NMR (CD ₃ CN, internal standard CFCl ₃ ); δ -62.1 (3F, t, J
= 9Hz),-78.1 (3F, s) IR (KBr); ν3010, 1340, 1259, 1159, 1094, 1031, 63
7, 517 cm ^-1 Mass (FAB); m / e 171 (M ⁺ -OSO ₂ CF ₃ ) accurate mass spectrometry; calculated value of M-OSO ₂ CF ₃ (C ₆ H ₁₀ F ₃ S), 171.04
528, measured 171.04570

Embodiment 5

[0065]

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220 mg of tetrahydrothiophene (2.5 m
mol) in 5 ml of methylene chloride at room temperature under stirring.
1.34 g (2.5 mmol) of (1H, 1H-perfluorobutyl) phenyliodonium triflate was added and stirred for 4 hours. 30 ml of diethyl ether was added to the reaction mixture, and the precipitated crystals were collected by filtration, recrystallized from acetonitrile-diethyl ether, and dried under reduced pressure to obtain 860 mg of the desired (1H, 1H-perfluorobutyl) tetrahydrothiophenium triflate ( (82% yield).

Melting point: 122.5 to 123.5 ° C. ¹ H-NMR (CD ₃ CN); δ 2.26-2.45 (4H, m), 3.59 (2H, m),
3.76 (2H, m), 4.09 (2H, t, J = 17 Hz) ¹⁹ F-NMR (CD ₃ CN, internal standard CFCl ₃ ); δ -78.1 (3F, s),
-79.9 (3F, t, J = 9.6Hz), -109.3 (2F, m), -125.8 (2
F, m) IR (KBr); ν3001, 2950, 1355, 1274, 1230, 1163, 11
20, 1090, 1033,940, 702, 642, 576, 517 cm ^-1 Mass (FAB); m / e 271 (M ⁺ -OSO ₂ CF ₃ ) accurate mass spectrometry; calculated value of M ⁺ -OSO ₂ CF ₃ (C ₈ H ₁₀ F ₇ S), 271.0
3890, measured 271.03844

Embodiment 6

[0069]

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Sodium hydride (62.5% in oil)
A suspension of 2.02 g (53 mmol) in 50 ml of DMF was cooled on ice.
4.43 ml (50 mmol) of benzeneethanethiol under stirring
Was added dropwise. After stirring at room temperature for 30 minutes, the inside of the reaction system was degassed and replaced with nitrogen gas, the temperature was lowered to -5 ° C, and the reaction system was degassed again, and the inside of the reaction system was replaced with trifluoromethyl iodide gas. . After stirring for 30 minutes under ice cooling and further for 30 minutes at room temperature, the reaction mixture was poured into 200 ml of water, extracted with hexane three times, and the organic layer was washed with water and saturated saline, and then washed.
The extract was dried over anhydrous magnesium sulfate and concentrated under reduced pressure to obtain 6.74 g of a yellow oily substance. According to gas chromatography, this oil was a mixture of trifluoromethylphenethyl sulfide: phenethyl disulfide = 9: 1.

6.66 g of this mixture (29 mmol of trifluoromethylphenethyl sulfide) was dissolved in 30 ml of acetic acid, and 3.80 g of 31% aqueous hydrogen peroxide was added dropwise at 80 ° C.
After stirring at the same temperature for 1.5 hours, 20 ml of acetic acid and 1.91 g of aqueous hydrogen peroxide were added, and the mixture was further heated and stirred for 1 hour. The reaction mixture was returned to room temperature, poured into 250 ml of water, extracted three times with ethyl acetate, washed with water and saturated saline, dried over anhydrous magnesium sulfate, and concentrated under reduced pressure.
6.47 g of a pale brown oil were obtained. This was purified by silica gel column chromatography (developing solvent; ethyl acetate: hexane = 1: 10) to obtain 4.09 g of trifluoromethylphenethyl sulfoxide as a pale yellow oil (37% in two steps). [Identification data of trifluoromethylphenethyl sulfoxide] ¹ H-NMR (CDCl ₃ ); δ 3.08-3.25 (3H, m), 3.32-3.38 (1
H, m), 7.25 (2H, dm, J = 7Hz), 7.29 (1H, tm, J = 7H
z), 7.35 (2H, tm, J = 7Hz) ¹⁹ F-NMR (CDCl ₃ , internal standard CFCl ₃ ); δ -73.8 (3F, s) IR (neat); ν 3031, 2361, 1735, 1498, 1456 , 1179,
1146, 1082, 1070, 749, 701, 463 cm ^-1 Mass; m / e 223 (M ⁺ + H), 154 (M ⁺ + H-CF ₃ ) Exact mass spectrometry; Calculated value (C ₉ H ₁₀ F ₃ (OS), 223.04020, measured 223.04064

To a solution of 2.89 g (13 mmol) of trifluoromethylphenethyl sulfoxide in 16 ml of methylene chloride was added:
Under ice cooling, trifluoromethanesulfonic anhydride 2.41m
l (14.3 mmol) was added, and the mixture was stirred under ice cooling for 20 minutes and further at room temperature for 14 hours. The reaction mixture was concentrated under reduced pressure at room temperature,
The obtained residue was washed three times with diethyl ether to obtain a black oily substance. This oil was purified by silica gel column chromatography (developing solvent: acetonitrile: methylene chloride =
1: 3 → 1: 2 → 1: 1), and further washed with a mixed solvent of acetonitrile-diethyl ether.
2.55 g (yield 55%) of the desired S- (trifluoromethyl) -2,3-dihydro-1-benzothiophenium triflate was obtained as a pale brown oil.

[S- (trifluoromethyl) -2,3-
Identification data of dihydro-1-benzothiophenium triflate] ¹ H-NMR (CD ₃ CN); δ 3.79-3.92 (2H, m), 4.43-4.55 (2
H, m), 7.72 (1H, t, J = 8Hz), 7.78 (1H, d, J = 8Hz),
7.91 (1H, t, J = 8 Hz), 8.13 (1H, d, J = 8 Hz) ¹⁹ F-NMR (CD ₃ CN, internal standard CFCl ₃ ); δ -52.9 (3F, s),
-78.1 (3F, s) IR (neat); ν1257, 1174, 1116, 1033, 760, 643, 520
cm ^-1 Mass (FAB); m / e 205 (M ⁺ -OSO ₂ CF ₃ ), 136 (M ⁺ -OSO ₂ CF _3-
CF ₃ ) accurate mass spectrometry; calculated value of M ⁺ -OSO ₂ CF ₃ (C ₉ H ₈ F ₃ S), 205.02
968, measured 205.02926

[0074]

According to the present invention, a cation or acid generator having high sensitivity to energy rays can be provided. When this cation or acid generator is incorporated into the resist resin, the irradiation time of the energy beam can be reduced because the amount of irradiation of the energy beam can be reduced, and the resist can be processed only by irradiating the high energy beam for a very short time. Fine processing can be achieved.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) C08L 101/00 C08L 101/00 C09K 3/00 C09K 3/00 K G03F 7/038 601 G03F 7/038 601 7/039 601 7/039 601 H01L 21/027 C07D 333/46 // C07D 333/46 333/54 333/54 H01L 21/30 502R F-term (reference) 2H025 AA01 AB16 AC01 AD01 AD03 BE07 BG00 CB52 CC20 4H006 AA03 AB80 EA02 TA04 TB14 4H050 AA03 AB76 AB80 AB99 4J002 AA001 EB106 EV176 EV296 FD206

Claims (8)

[Claims] 1. A cation or an acid which is generated by irradiation with an energy beam, a formula (1): (Where A is an element selected from iodine, sulfur, selenium, tellurium, nitrogen or phosphorus; when A is iodine,
R ² and R ³ are not present; R ¹ is an alkyl group having 1 to 15 carbon atoms or an aryl group having 6 to 15 carbon atoms; when A is sulfur, selenium or tellurium, R ³ is not present; ,
R ¹ and R ² are each independently an alkyl group having 1 to 15 carbon atoms, an aryl group having 6 to 20 carbon atoms,
0 is a dialkylamino group, an alkylarylamino group having 7 to 35 carbon atoms or a diarylamino group having 12 to 40 carbon atoms, and R ¹ and R ² may be bonded to each other to form a ring; In the case of nitrogen or phosphorus, R ¹ , R ² and R ³ are each independently an alkyl group having 1 to 15 carbon atoms, an aryl group having 6 to 20 carbon atoms, a dialkylamino group having 2 to 30 carbon atoms, An alkylarylamino group having 7 to 35 or a diarylamino group having 12 to 40 carbon atoms, wherein R ¹ , R ² and R ³ are each bonded to each other to form 1
One or more rings may be formed, or R ³ is absent;
R ¹ and R ² may combine to form an aromatic ring containing A; provided that the alkyl group, the alkyl group of the dialkylamino group and the alkyl group of the alkylarylamino group include an aryl group, a halogen atom, Oxygen atom, nitrogen atom,
The aryl group, the aryl group of the alkylarylamino group and the aryl group of the diarylamino group may be substituted with a sulfur atom or a silicon atom, or may be branched or may form a ring. Rf may be substituted with a haloalkyl group, a halogen atom, an alkoxyl group, an aryloxy group, a nitro group, an amide group, a cyano group, an alkanoyl group, an aroyl group, an alkoxycarbonyl group, an aryloxycarbonyl group or an acyloxy group; A perfluoroalkyl group having 1 to 15 carbon atoms which may form a ring or a perfluoroalkyl group in which part of fluorine of the perfluoroalkyl group is substituted by hydrogen; X ^- is a conjugate of a Bronsted acid Cation or acid generation of a fluoroalkylonium salt represented by . 2. Formula (2) which generates a cation or an acid by irradiation with energy rays. Wherein A ¹ and A ² are the same or different and are both elements selected from iodine, sulfur, selenium, tellurium, nitrogen or phosphorus; when A ¹ or A ² is iodine,
⁴ , R ⁵ , R ⁷ and R ⁸ are not present; when A ¹ or A ² is sulfur, selenium or tellurium, R ⁵ and R ⁸ are absent and R ⁴ and R ⁷ are each independently , Having 1 to 1 carbon atoms
5 alkyl group, an aryl group having 6 to 20 carbon atoms, a dialkylamino group having 2 to 30 carbon atoms, be a diarylamino group alkyl arylamino group, or 12 to 40 carbon atoms 7-35 carbon atoms; A ¹ or When A ² is nitrogen or phosphorus, R ⁴ , R ⁵ , R ⁷ and R ⁸ are each independently:
An alkyl group having 1 to 15 carbon atoms, an aryl group having 6 to 20 carbon atoms, a dialkylamino group having 2 to 30 carbon atoms, and 7 carbon atoms
-35 alkylarylamino groups or 12-carbon atoms
40 diarylamino groups, R ⁴ and R ⁵ , or R
⁷ and R ⁸ may be bonded to each other to form a ring;
However, the alkyl group, the alkyl group of the dialkylamino group and the alkyl group of the alkylarylamino group are
An aryl group, a halogen atom, an oxygen atom, a nitrogen atom, a sulfur atom or a silicon atom, which may be substituted or branched or may form a ring;
The aryl group of the alkylarylamino group and the aryl group of the diarylamino group are an alkyl group, a haloalkyl group, a halogen atom, an alkoxyl group, an aryloxy group, a nitro group, an amide group, a cyano group, an alkanoyl group,
R ⁶ may be substituted with an aroyl group, an alkoxycarbonyl group, an aryloxycarbonyl group or an acyloxy group; R ⁶ may be substituted with an aryl group, a halogen atom, an oxygen atom, a nitrogen atom, a sulfur atom or a silicon atom, and may be branched. An alkylene group having 1 to 15 carbon atoms which may be branched or form a ring; Rf is a perfluoroalkyl group having 1 to 15 carbon atoms which may be branched or may form a ring, or it is intended a portion of the fluorine in an alkyl group substituted by hydrogen; X ^- fluoroalkyl onium salt type cationic or acid generator represented by is a conjugate base of Brønsted acid). 3. Rf in the formula (1) or the formula (2)
There, -CH ₂ Rf ¹ (Rf ¹ is part of the fluorine perfluoroalkyl group or said perfluoroalkyl group branched carbon atoms and optionally also good to form a ring optionally 1-14 are substituted with hydrogen 1 or 2).
A cation or acid generator as described. 4. Rf in the formula (1) or the formula (2)
_{^{There, -Rf 2 CF 2 H (Rf}} 2 is a part of the fluorine perfluoroalkylene group or the perfluoroalkylene group branched carbon atoms and optionally also good to form a ring optionally 1-14 are substituted with hydrogen The cation or acid generator according to claim 1 or 2, wherein 5. Rf in the formula (1) or the formula (2)
_{^{There, -CH2Rf 3 CF 2 H (Rf}} 3 is part of the fluorine perfluoroalkylene group or the perfluoroalkylene group branched carbon atoms and optionally also good to form a ring optionally 1-13 are substituted with hydrogen The cation or acid generator according to claim 1 or 2, wherein 6. The compound according to claim 1, wherein X ⁻ in the formula (1) or (2) is a conjugate base of a fluoroalkylsulfonic acid.
The cation or acid generator according to any one of claims 1 to 5, wherein 7. A chemically amplified resist material comprising the fluoroalkylonium salt type cation or acid generator according to claim 1 and a negative resist resin. 8. A chemically amplified resist material comprising the fluoroalkylonium salt-type cation or acid generator according to claim 1 and a positive resist resin.