JP2003322964A - Photoacid generator for chemically amplified resist, resist material containing the same and pattern forming method - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an acid generator added resist material excellent in resolution, thermal stability and storage stability and ensuring small line edge roughness. <P>SOLUTION: Disclosed is a photoacid generator for a chemically amplified resist represented by formula (1) wherein R<SP>1</SP>and R<SP>2</SP>each represents a 1-6C linear, branched or cyclic unsubstituted or oxygen substituted alkyl, or R<SP>1</SP>and R<SP>2</SP>together may form a 4-6C unsubstituted or oxygen substituted cyclic structure; R<SP>3</SP>-R<SP>5</SP>each represents H, a 1-6C alkyl or a 6-12C aryl, provided that at least one of R<SP>3</SP>-R<SP>5</SP>represents a 6-12C aryl; and Y<SP>-</SP>is a 1-10C alkyl-sulfonate, a 6-20C aryl-sulfonate, a 2-10C bisalkylsulfonylimide or a 3-12C trisalkylsulfonylmethide. <P>COPYRIGHT: (C)2004,JPO

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention is used for a chemically amplified resist material for producing an integrated circuit sensitive to radiation such as ultraviolet rays, deep ultraviolet rays, electron beams, X-rays, excimer lasers, γ rays and synchrotron radiation. The present invention relates to a photoacid generator for a chemically amplified resist material, a resist material containing the photoacid generator for a chemically amplified resist material, and a pattern forming method using the same.

[0002]

2. Description of the Related Art In recent years, with the higher integration and higher speed of LSIs, finer pattern rules are required, and far-ultraviolet lithography and vacuum-ultraviolet lithography are considered promising as next-generation fine processing techniques. There is. Current,
Photolithography using a KrF excimer laser is used to produce 0.15 μm rule advanced semiconductors, and 0.13 μm rule production is about to start. Photolithography using ArF excimer laser light as a light source is strongly desired to be realized as an indispensable technology for ultrafine processing of 0.13 μm or less.

Particularly, in photolithography using ArF excimer laser light as a light source, a highly sensitive resist material capable of exhibiting sufficient resolution with a small exposure amount is required in order to prevent deterioration of a precise and expensive optical system material. Has been. As a measure for realizing a high-sensitivity resist material, it is most general to select a highly transparent material at a wavelength of 193 nm as each composition. For example, as the base resin, poly (meth) acrylic acid and its derivative, norbornene-maleic anhydride alternating polymer, polynorbornene and metathesis ring-opening polymer have been proposed, and the point of increasing the transparency of the resin alone. So we have achieved some results. However, with regard to acid generators, increasing the transparency lowers the acid generation efficiency, resulting in low sensitivity, or lacking thermal stability or storage stability, which is still practical. The current situation is that nothing has been obtained.

For example, JP-A-7-25846, JP-A-7-28237, JP-A-8-27102 and JP-A-20.
The alkylsulfonium salts proposed in 01-354669, JP-A-2002-40636 and the like have very high transparency, but insufficient acid generation efficiency, and also have poor thermal stability. Not suitable.

[0005]

[Chemical 7] (JP-A-7-25846, JP-A-2001-35466
No. 9, JP-A No. 2002-40636)

The alkylaryl sulfonium salt proposed in Japanese Patent Application Laid-Open No. 10-319581 is
Although it has a good balance between transparency and acid generation efficiency and high sensitivity, it lacks heat stability and storage stability.

[0007]

[Chemical 8] (Example of JP-A-10-319581)

The arylsulfonium salt, which was effective in photolithography using KrF excimer laser light, is excellent in acid generation efficiency, thermal stability and storage stability, but has extremely low transparency, and the pattern after development has a sharp taper shape. Becomes There is a method of thinning the resist in order to supplement the transparency, but in this case, the etching resistance of the resist film is significantly lowered, so that it is not suitable as a pattern forming method. These are mainly cases where the structure on the cation side of the onium salt was changed, and it has been reported that the type of acid generated and the type of acid labile group are closely related in terms of resolution and pattern shape. .

As the miniaturization is promoted, the line edge roughness and the dimensional difference (I / G bias) between the isolated pattern and the dense pattern are becoming problems. It is well known that a dimensional difference occurs between a dense pattern after development and an isolated pattern even if the dimensions on the mask are the same. The above problem is serious especially in the dimension exceeding the wavelength. This is because the optical intensity differs due to the difference in optical interference in the image formation of the dense pattern and the isolated pattern. The resist dimension becomes thinner as the pitch increases (pitch; the sum of the line dimension and the space dimension. In this case, the line dimension does not change and the dimension of the space portion expands), and further becomes smaller due to the increase in acid diffusion. The problem of coarse / dense dependence in which the size of an isolated pattern is smaller than that of a dense pattern is becoming more serious. Although a method of reducing acid diffusion has been proposed as a method of reducing the density dependency, if the acid diffusion is too small, the side wall of the resist pattern after development,
There arises a problem that unevenness and skin roughness occur due to standing waves, or line edge roughness increases. It is shown that the smaller the acid diffusion distance is, the more prominent the unevenness of the side wall due to the standing wave is. The line edge roughness observed from the sky SEM shows the same tendency, that is, the line edge roughness increases as the acid diffusion becomes smaller. In order to reduce the roughness of the line, a method of increasing the acid diffusion distance is generally used, but this cannot improve the density dependence any further. As a method for improving the line edge roughness, there is a method for improving the contrast of light. For example, if the line width dimension is larger at the same exposure wavelength, the line edge roughness becomes smaller, and even if the step wavelength NA is the same, the higher the stepper NA, the more the pattern is deformed than the normal illumination. Illumination (eg annular illumination, quadrupole illumination), usually C
The phase shift mask has a smaller line edge roughness than the r mask. There is a correlation between the line edge contrast of the pattern and the line edge roughness, and the steeper the line edge contrast is, the smaller the line edge roughness is. At the exposure wavelength, it is expected that short-wavelength exposure will result in a smaller line edge roughness.
However, when comparing the line edge roughness between the KrF exposure and the ArF exposure, the optical contrast of the ArF exposure should be higher by the shorter wavelength and the line edge roughness should be smaller, but in reality, the KrF exposure is better. There is a report that it is excellent (SPIE 399
9, 264 (2001)). This is due to the difference in performance between the KrF and ArF resist materials. In particular, it is shown that the line edge roughness due to the material in ArF exposure is serious, and the acid that does not deteriorate the sparse / dense dependence while improving the line edge roughness. A generator is desired.

The 2-allyl-2-oxoethylthiacyclopentanium salt disclosed in Japanese Patent Laid-Open No. 2000-292917 has been proposed as having excellent sensitivity and excellent rectangularity of the resist pattern. It was found that the acid generator is not satisfactory as an acid generator that does not improve the above-mentioned line edge roughness and at the same time does not deteriorate the sparse / dense dependence.

[0011]

[Chemical 9] (Example of JP 2000-292917 A)

As described above, the conventionally proposed photo-acid generator compound has high transparency but low sensitivity for generating an acid necessary for cleavage of an acid labile group in the resin, and has a sufficient resolution. It has been found that there are problems such as low quality, low crystallinity in synthesis, high water solubility and difficulty in purification, and low yield. When the sensitivity is low, there is a problem that the exposure time is increased, the productivity is reduced, and the load on the exposure apparatus is increased.

[0013]

As the photo-acid generator of the resist material, the solubility (compatibility) in the resist solvent and the resin is sufficiently high, the storage stability is good, there is no toxicity, and the coating is performed. Of the conventional photo-acid generator, especially an alkylsulfonium compound, though it is required to have good properties, pattern profile shape, PED stability, high resolution, particularly good sensitivity, and simple synthesis. The photo-acid generator does not meet all of these requirements.

The object of the present invention is to solve the above-mentioned various problems, to provide a chemically amplified resist material which is easy to synthesize and is particularly excellent in sensitivity and resolution, and a photoacid generator for chemically amplified resist material, and the photoacid generator. A resist material and a pattern forming method used are provided.

[0015]

Means for Solving the Problems and Modes for Carrying Out the Invention As a result of intensive studies for achieving the above-mentioned object, the present inventors have found that a sulfonium salt represented by the following general formula (1) as a photoacid generator. By using a compound, particularly a resist material containing a sulfonium salt compound represented by the following formulas (1a) and (1b), excellent solubility, storage stability, and coating property can be achieved.
Even when the PED is for a long time, line width fluctuation and shape deterioration are small, the pattern profile shape after development is excellent, and it has high resolution and sensitivity suitable for microfabrication, and it is extremely effective especially in deep ultraviolet lithography. I found that

Further, as a photo-acid generator, the following general formula (2)
A sulfonium salt compound represented by the following formula (2)
By using the resist material containing the sulfonium salt compound represented by a) or (2b), the solubility, the storage stability and the coatability are excellent, and the line width variation and the shape deterioration are small even when PED is performed for a long time. The inventors have found that they have an excellent pattern profile shape after development, have high resolution and sensitivity suitable for microfabrication, and exert great power particularly in deep-UV lithography, and have completed the present invention.

The present invention will be described in more detail below. The present invention includes the following general formulas (1), (1a) and (1b).
And a photo-acid generator for a chemically amplified resist represented by the following general formulas (2), (2a) and (2b).

[0018]

[Chemical 10] (In the formula, R ¹ and R ² may be the same or different,
Number 1-6 straight, branched or cyclic unsubstituted or alkyl group having an oxygen atom, or R ¹ and R ² form a cyclic structure having an unsubstituted or oxygen atom having 4 to 6 carbon atoms May be. R ^3, R ^4, R ⁵ may be the same or different, a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or a substituted or unsubstituted aryl group having 6 to 12 carbon atoms, R ^3, At least one of R ⁴ and R ⁵ has 6 to 1 carbon atoms
2 represents a substituted or unsubstituted aryl group. Y ⁻ is a substituted or unsubstituted alkyl sulfonate having 1 to 10 carbon atoms, a substituted or unsubstituted aryl sulfonate having 6 to 20 carbon atoms, a substituted or unsubstituted bisalkylsulfonylimide having 2 to 10 carbon atoms, or a carbon number 3-12 substituted or unsubstituted trisalkylsulfonylmethides are shown. . )

[0019]

[Chemical 11] (In the formula, R ¹ and R ² have the same meanings as described above. Ya ⁻ is a perfluoroalkyl sulfonate having 1 to 8 carbon atoms, a bis (perfluoroalkylsulfonyl) imide having 2 to 10 carbon atoms, or a carbon number. 3-12 tris (perfluoroalkylsulfonyl) methides are shown.)

[0020]

[Chemical 12] (In the formula, Ya has the same meaning as above. X is CH.
₂ (methylene) or O (oxygen atom) is shown. m is 0 or 1. )

[0021]

[Chemical 13] (In the formula, R ¹ , R ² and Y ⁻ have the same meanings as described above. R ⁷
Is a hydrogen atom, a linear, branched or cyclic substituted or unsubstituted alkyl group having 1 to 6 carbon atoms, a linear, branched or cyclic alkoxy group having 1 to 6 carbon atoms, a nitro group, a fluorine atom , Or chlorine atom. n is an integer of 1 to 5. )

[0022]

[Chemical 14] (In the formula, R ¹ , R ² and Ya have the same meanings as described above.)

[0023]

[Chemical 15] (In the formula, X, m, and Ya have the same meanings as above.)

The above formula (1) or (1a), (2),
In (2a), R ¹ and R ² may be the same or different and each is a linear, branched or cyclic C 1-6 unsubstituted or oxygen-containing alkyl group, or R ¹ and R ² May form a cyclic structure having 4 to 6 carbon atoms, which is unsubstituted or has an oxygen atom. More specifically, methyl group, ethyl group, n-propyl group, sec-propyl group, n-butyl group, sec-butyl group, iso-butyl group, ter.
A t-butyl group, an n-hexyl group, or a group bonded to R ¹ and R ² to form butylene or pentylene is shown. Of these, methyl group, ethyl group and butylene bonded to each other are preferable. In the above formula (1), R ³ , R ⁴ ,
R ^{5 s} may be the same or different and each represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or a substituted or unsubstituted aryl group having 6 to 12 carbon atoms, and each of R ³ , R ⁴ and R ⁵ At least one of them represents a substituted or unsubstituted aryl group having 6 to 12 carbon atoms. Examples of the alkyl group having 1 to 6 carbon atoms include methyl group, ethyl group, n-propyl group, sec-
Propyl group, n-butyl group, sec-butyl group, iso
-Butyl group, tert-butyl group, n-hexyl group and the like can be mentioned, and examples of the substituted or unsubstituted aryl group having 6 to 12 carbon atoms include phenyl group, 4-methylphenyl group and 4
-Methoxyphenyl group, fluorophenyl group, nitrophenyl group and the like can be mentioned. Of these, R ³ is preferably a hydrogen atom, R ⁴ is a hydrogen atom or a phenyl group, and R ⁵ is a hydrogen atom or a phenyl group.

Y ⁻ is a substituted or unsubstituted alkyl sulfonate having 1 to 10 carbon atoms, a substituted or unsubstituted aryl sulfonate having 6 to 20 carbon atoms, a substituted or unsubstituted bisalkylsulfonyl imide having 2 to 10 carbon atoms,
Alternatively, a substituted or unsubstituted trisalkylsulfonylmethide having 3 to 12 carbon atoms is shown. More specifically, trifluoromethane sulfonate, nonafluorobutane sulfonate, heptadecafluorooctane sulfonate,
2,2,2-trifluoroethane sulfonate, perfluoro-2-ethoxyethane sulfonate, pentafluorobenzene sulfonate, 4-trifluoromethylbenzene sulfonate, 4-fluorobenzene sulfonate, mesitylene sulfonate, 2,4,6-triisopropyl Benzene sulfonate, toluene sulfonate,
Benzenesulfonate, 4- (4'-toluenesulfonyloxy) benzenesulfonate, 6- (4-toluenesulfonyloxy) naphthalene-2-sulfonate, 4
-(4-Toluenesulfonyloxy) naphthalene-1-
Sulfonate, 5- (4-toluenesulfonyloxy)
Naphthalene-1-sulfonate, 8- (4-toluenesulfonyloxy) naphthalene-1-sulfonate, naphthalenesulfonate, camphorsulfonate, octanesulfonate, dodecylbenzenesulfonate, butanesulfonate, methanesulfonate, bis (trifluoromethanesulfonyl) imide, bis ( Examples thereof include perfluoroethanesulfonyl) imide, bis (perfluorobutanesulfonyl) imide, tris (trifluoromethanesulfonyl) methide, and tris (perfluoroethanesulfonyl) methide.

Further, the above general formulas (1a), (1b),
In (2a) and (2b), Ya ⁻ is a C 1-8 perfluoroalkyl sulfonate, a C 2-10 bis (perfluoroalkylsulfonyl) imide, or a C 3-12 tris (perfluoroalkyl). Sulfonyl) methide, and more specifically trifluoromethanesulfonate, perfluorobutanesulfonate, perfluorooctanesulfonate, bis (trifluoromethanesulfonyl) imide, bis (perfluoroethanesulfonyl) imide, bis (perfluorobutanesulfonyl) imide , Tris (trifluoromethanesulfonyl) methide, tris (perfluoroethanesulfonyl)
Methide, tris (perfluorobutanesulfonyl) methide are shown. In addition, in (1b) and (2b), X is C
H ₂ (methylene) or O (oxygen atom) is shown, and m is 0 or 1.

More specifically, the cation skeletons of the sulfonium salts (1), (1a) and (1b) of the present invention are shown below.

[0028]

[Chemical 16]

Further, the above general formulas (2) and (2
The cation skeleton of the sulfonium salt represented by a) and (2b) is specifically shown below.

[0030]

[Chemical 17]

The sulfonium salt of the present invention is not particularly limited, but more preferable ones include a combination of the above cation and the above anion, that is, sulfonate, bisalkylsulfonylimide, trisalkylsulfonylmethide and the like.

As a method for synthesizing the sulfonium salt of the present invention, an existing method can be used, but specifically, it can be synthesized by a reaction of a sulfide compound and a substituted alkyl halide.

[0033]

[Chemical 18] (R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁷ , Y ⁻ , Ya ⁻ , X,
n and m are as defined above, and Hal represents a chlorine atom, a bromine atom or an iodine atom. )

The reaction of the sulfide with the alkyl halide is preferably carried out in a solvent such as nitromethane, acetonitrile or methanol. More specific sulfides include dimethyl sulfide, diethyl sulfide, tetrahydrothiophene, 1,4-thioxane, pentamethylene sulfide, 2-methyl-tetrahydrothiophene and the like. Examples of the alkyl halide include cinnamyl bromide, methoxycinnamyl bromide, benzyl bromide, α-bromomethylstyrene and the like.

The cinnamyl bromide may be either cis or trans, but trans is more preferable. Also,
Cinnamyl bromide can be synthesized by a known method, for example, by a conventional method from cinnamic acid or various substituted cinnamic acid. Y or Ya may be reacted in the acid state such as sulfonic acid, imidic acid and methide acid, or in the state where salts such as sodium salt, potassium salt, silver salt and ammonium salt are formed.

The present invention further provides the following chemically amplified resist material containing a photo-acid generator for a chemically amplified resist and a pattern forming method. [I] A chemically amplified resist material containing (A) a resin whose solubility in an alkali developing solution is changed by the action of an acid, and (B) the above photoacid generator. [II] A chemically amplified positive resist composition containing (A) a resin whose solubility in an alkali developing solution is changed by the action of an acid, and (B) the above photoacid generator. [III] A resist material further containing (C) a compound other than the component (B) which generates an acid upon irradiation with radiation. The resist composition as described above, wherein the resin of the component (IV) (A) is a resin having a substituent whose solubility in an alkali developing solution changes when the C—O—C bond is cleaved by the action of an acid. [V] The resist material as described above, which further comprises (D) a basic compound. [VI] (i) a step of applying the above resist material on a substrate, and (ii) a step of performing heat treatment and then exposing with a high energy beam or an electron beam having a wavelength of 250 nm or less through a photomask, and (iii) 3.) A pattern forming method, which comprises a step of performing a heat treatment if necessary and then developing with a developing solution.

The resist material containing the photo-acid generator for a chemically amplified resist of the present invention can be used either as a positive type or a negative type, but is preferably used as a positive type resist material from the viewpoint of resolution. Specific embodiments are as follows. <1> (A) Resin whose solubility in an alkaline developer is changed by the action of acid (B) In the above general formulas (1), (1a), (1b) or (2), (2a), (2b) A chemically amplified positive type resist material containing the photoacid generator (F) organic solvent shown. <2> Further, (C) generates an acid by irradiation with radiation (B)
The chemically amplified positive resist composition as described in <1>, which further comprises a photoacid generator other than the components. <3> The chemically amplified positive resist material as described in <1> or <2>, further comprising (D) a basic compound. <4> The chemically amplified positive resist composition as described in <1> to <3>, further comprising (E) an organic acid derivative. <5> The chemically amplified positive resist composition as described in <1> to <4>, further comprising (G) a compound having a molecular weight of 3,000 or less whose solubility in an alkali developing solution is changed by the action of an acid. . <6> (B) Photoacid generator (F) Organic solvent (H) Alkali-soluble resin represented by the general formula (1), (1a), (1b) or (2), (2a), (2b) (I) A chemically amplified negative resist material containing an acid crosslinking agent that forms a crosslinked structure by the action of an acid. <7> Further, it is characterized by containing the above component (C) <
6> The chemically amplified negative resist material as described above. <8> Further, it is characterized by containing the component (D)
6>, <7> chemically amplified negative resist material

Each component will be described in detail below.
The resin whose solubility in an alkali developing solution is changed by the action of the acid of the component (A) is not particularly limited, but a part or all of the hydrogen atoms of the carboxyl group are protected by an acid-labile protecting group (acid group). Examples of the resin include a resin protected with a stable group.
A resin in which some or all of the phenolic hydroxyl groups are protected by an acid-labile protecting group (acid-labile group) can also be used and can be favorably used in KrF excimer laser exposure. This is not appropriate because the transmittance of the resist film is too low during laser exposure.

As a base resin having a protecting group (acid-labile group) which is released by an acid, as a resist for KrF excimer laser, polyhydroxystyrene (PH) is used.
S), and a copolymer of PHS and styrene, a (meth) acrylic acid ester, a maleimide N-carboxylic acid ester, and a resist for ArF excimer laser, a (meth) acrylic acid ester type, norbornene and maleic anhydride. Examples thereof include an alternating copolymerization system, an alternating copolymerization system of tetracyclododecene and maleic anhydride, a polynorbornene system, and a metathesis polymerization system by ring-opening polymerization, but the present invention is not limited to these polymerization polymers.

Polyhydroxystyrene-containing resins are described in JP-A-2001-122850 and 2001-32481.
JP-A No. 2001-337448 and JP-A No. 2002-2 can be referred to as JP-A No. 2001-337448 and JP-A No.
No. 3354, etc., and the above-mentioned JP-A-7-25846,
JP-A-7-28237, JP-A-8-27102, JP-A-2001-354669, JP-A-2002-4063
6, JP-A-10-319581, and JP-A-2000-2.
Reference can be made to Japanese Patent No. 92917.

Here, as the acid labile group, a part of the phenolic hydroxyl group of the alkali-soluble resin and a part or all of the carboxyl group are protected by an acid labile substituent represented by a C--O--C bond. In this case, various types of acid labile groups are selected, but particularly groups represented by the following general formulas (4) to (7), tertiary alkyl groups having 4 to 20 carbon atoms, preferably 4 to 15 carbon atoms, An alkyl group is a C1-6 trialkylsilyl group, a C4-20 oxoalkyl group,
It is preferably an aryl group-substituted alkyl group having 7 to 20 carbon atoms.

[0042]

[Chemical 19]

In the formula, R ¹⁰ and R ¹¹ are hydrogen atoms or have 1 carbon atom.
To 18, preferably 1 to 10 linear, branched or cyclic alkyl groups, specifically a methyl group, an ethyl group,
Propyl group, isopropyl group, n-butyl group, sec-
Examples thereof include a butyl group, a tert-butyl group, a cyclopentyl group, a cyclohexyl group, a 2-ethylhexyl group, and an n-octyl group. R ¹² represents a monovalent hydrocarbon group having 1 to 18 carbon atoms, preferably 1 to 10 which may have a hetero atom such as an oxygen atom, and is a linear, branched or cyclic alkyl group, Some of the hydrogen atoms are hydroxyl groups, alkoxy groups,
Examples thereof include those substituted with an oxo group, an amino group, an alkylamino group and the like, and specific examples include the following substituted alkyl groups.

[0044]

[Chemical 20]

R ¹⁰ and R ¹¹ , R ¹⁰ and R ¹² , and R ¹¹ and R ¹² may form a ring. When a ring is formed, R ¹⁰ and
R ¹¹ and R ¹² each have 1 to 18 carbon atoms, preferably 1 to
10 represents a linear or branched alkylene group.

R ¹³ has 4 to 20 carbon atoms, preferably 4 to 1 carbon atoms.
5 tertiary alkyl groups, each alkyl group has 1 carbon atom
To a trialkylsilyl group, a C4 to C20 oxoalkyl group, or a group represented by the above general formula (4),
Specific examples of the tertiary alkyl group include tert-butyl group, tert-amyl group, 1,1-diethylpropyl group, 1-ethylcyclopentyl group, 1-butylcyclopentyl group, 1-ethylcyclohexyl group, 1-butylcyclohexyl group. Group, 1-ethyl-2-cyclopentenyl group, 1-ethyl-2-cyclohexenyl group, 2-methyl-2-adamantyl group, 2-ethyl-2-adamantyl group, 1-adamantyl-1-methyl-ethyl group And the like. Specific examples of the trialkylsilyl group include a trimethylsilyl group, a triethylsilyl group, and dimethyl-ter.
Examples thereof include a t-butylsilyl group, and specific examples of the oxoalkyl group include a 3-oxocyclohexyl group, a 4-methyl-2-oxooxan-4-yl group, and a 5-methyl- group.
Examples include 5-oxooxolan-4-yl group. z
Is an integer of 0 to 6.

R ¹⁴ represents a linear, branched or cyclic alkyl group having 1 to 8 carbon atoms or an optionally substituted aryl group having 6 to 20 carbon atoms, which may be linear, branched or cyclic. As the alkyl group, specifically, a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, a tert-butyl group, a tert-amyl group, an n-pentyl group, an n-hexyl group, Examples thereof include a cyclopentyl group, a cyclohexyl group, a cyclopentylmethyl group, a cyclopentylethyl group, a cyclohexylmethyl group, and a cyclohexylethyl group. Specific examples of the optionally substituted aryl group include a phenyl group, a methylphenyl group, a naphthyl group, and anthryl. Examples thereof include a group, a phenanthryl group and a pyrenyl group. h is 0 or 1, i is 0, 1, 2, or 3, and is a number satisfying 2h + i = 2 or 3.

R ¹⁵ represents a linear, branched or cyclic alkyl group having 1 to 8 carbon atoms or an optionally substituted aryl group having 6 to 20 carbon atoms, and specifically, the same as R ¹⁴ . The thing can be illustrated. R ^{16 to} R ²⁵ each independently represent a hydrogen atom or a monovalent hydrocarbon group which may contain a hetero atom having 1 to 15 carbon atoms, such as a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, sec-butyl group, te
rt-butyl group, tert-amyl group, n-pentyl group, n-hexyl group, n-octyl group, n-nonyl group,
n-decyl group, cyclopentyl group, cyclohexyl group,
Cyclopentylmethyl group, cyclopentylethyl group, cyclopentylbutyl group, cyclohexylmethyl group, cyclohexylethyl group, linear, branched or cyclic alkyl group such as cyclohexylbutyl group, a part of these hydrogen atoms is a hydroxyl group, an alkoxy group, Examples thereof include those substituted with a carboxy group, an alkoxycarbonyl group, an oxo group, an amino group, an alkylamino group, a cyano group, a mercapto group, an alkylthio group, a sulfo group and the like. R ^{16 to} R ²⁵ may form a ring with each other (for example, R ¹⁶ and R ¹⁷ , R ¹⁶
And R ¹⁸ , R ¹⁷ and R ¹⁹ , R ¹⁸ and R ¹⁹ , R ²⁰ and R ²¹ , R ²² and R ^23, etc.), and in that case, divalent carbonization which may contain a hetero atom having 1 to 15 carbon atoms. A hydrogen group is shown, and examples thereof include ones obtained by removing one hydrogen atom from those exemplified as the above monovalent hydrocarbon group. In addition, R ^{16 to} R ²⁵ may bond to adjacent carbons without any intervening bond to form a double bond (for example, R ¹⁶ and R ¹⁸ , R ¹⁸ and R ²⁴ , R ²² and R
²⁴ etc.).

Among the acid labile groups represented by the above formula (4), specific examples of the linear or branched group include the following groups.

[0050]

[Chemical 21]

The cyclic acid-labile group represented by the above formula (4) is specifically tetrahydrofuran-
Examples thereof include a 2-yl group, a 2-methyltetrahydrofuran-2-yl group, a tetrahydropyran-2-yl group, a 2-methyltetrahydropyran-2-yl group and the like.

Specific examples of the acid labile group of the above formula (5) include tert-butoxycarbonyl group, tert-butoxycarbonylmethyl group, tert-amyloxycarbonyl group, tert-amyloxycarbonylmethyl group,
1,1-diethylpropyloxycarbonyl group, 1,1
-Diethylpropyloxycarbonylmethyl group, 1-ethylcyclopentyloxycarbonyl group, 1-ethylcyclopentyloxycarbonylmethyl group, 1-ethyl-
2-cyclopentenyloxycarbonyl group, 1-ethyl-2-cyclopentenyloxycarbonylmethyl group, 1
Examples include -ethoxyethoxycarbonylmethyl group, 2-tetrahydropyranyloxycarbonylmethyl group, 2-tetrahydrofuranyloxycarbonylmethyl group and the like.

Specific examples of the acid labile group of the above formula (6) include 1-methylcyclopentyl, 1-ethylcyclopentyl, 1-n-propylcyclopentyl, 1-isopropylcyclopentyl, 1-n-butylcyclopentyl, 1 -Sec-butylcyclopentyl, 1-methylcyclohexyl, 1-ethylcyclohexyl, 3-methyl-1-cyclopenten-3-yl, 3-ethyl-1-cyclopenten-3-yl, 3-methyl-1-cyclohexene-3- Yl, 3-ethyl-1-cyclohexene-3
Examples include -yl, 1-cyclohexyl-cyclopentyl and the like. Specific examples of the acid labile group of the above formula (7) include the following groups.

[0054]

[Chemical formula 22]

The tertiary alkyl group having 4 to 20 carbon atoms, preferably 4 to 15 carbon atoms includes tert-butyl group and tert.
-Amyl group, 3-ethyl-3-pentyl group, dimethylbenzyl group and the like can be mentioned.

Examples of the trialkylsilyl group in which each alkyl group has 1 to 6 carbon atoms include trimethylsilyl group, triethylsilyl group and tert-butyldimethylsilyl group.

Examples of the oxoalkyl group having 4 to 20 carbon atoms include a 3-oxocyclohexyl group and a group represented by the following formula.

[0058]

[Chemical formula 23]

Examples of the aryl group-substituted alkyl group having 7 to 20 carbon atoms include benzyl group, methylbenzyl group, dimethylbenzyl group, diphenylmethyl group and 1,1-diphenylethyl group.

In addition to the above acid labile group, part of the phenolic hydroxyl group is intramolecularly //
Alternatively, a resin that is cross-linked between molecules can be used. Reference can be made to JP-A No. 11-190904 for specific examples and synthesis of crosslinked polymers having an acid labile group.

The above-mentioned polymer compounds are not limited to one kind, and two or more kinds can be added. The performance of the resist material can be adjusted by using plural kinds of polymer compounds. It is also possible to use a plurality of types of polymer compounds having different molecular weights and dispersities.

The amount of the above resin added to the resist composition of the present invention is arbitrary, but the solid content in the resist is 1
65-99 parts by weight in 00 parts by weight, preferably 65-98
Parts by weight. The above-mentioned solid content means "all components except the solvent of the resist material of the present invention".

The component (B) of the resist composition of the present invention is a photoacid generator of the above formula (1), (1a), (1b), (2), (2a) or (2b), and its blending. The amount is 0.1 to 10 parts by weight, and particularly 1 to 5 parts by weight based on 100 parts by weight of the solid content in the resist.

Further, the photo-acid generators (1), (1
a), (1b), (2), (2a), (2b),
When the photoacid generator of the component (C) is added, it is a compound that generates an acid by irradiation with high energy rays such as ultraviolet rays, far ultraviolet rays, electron beams, X rays, excimer lasers, γ rays, and synchrotron radiation. It doesn't matter. Suitable photoacid generators include sulfonium salts, iodonium salts,
There are sulfonyldiazomethane, N-sulfonyloxydicarboximide type acid generator and the like. As detailed below,
These may be used alone or in combination of two or more.

The sulfonium salt is a salt of a sulfonium cation and a sulfonate. As the sulfonium cation, triphenylsulfonium, (4-tert-butoxyphenyl) diphenylsulfonium and bis (4-ter) are used.
t-butoxyphenyl) phenylsulfonium, tris (4-tert-butoxyphenyl) sulfonium,
(3-tert-butoxyphenyl) diphenylsulfonium, bis (3-tert-butoxyphenyl) phenylsulfonium, tris (3-tert-butoxyphenyl) sulfonium, (3,4-ditert-butoxyphenyl) diphenylsulfonium, bis ( 3,4-
Ditert-butoxyphenyl) phenylsulfonium, tris (3,4-ditert-butoxyphenyl)
Sulfonium, diphenyl (4-thiophenoxyphenyl) sulfonium, (4-tert-butoxycarbonylmethyloxyphenyl) diphenylsulfonium, tris (4-tert-butoxycarbonylmethyloxyphenyl) sulfonium, (4-tert-butoxyphenyl) bis ( 4-dimethylaminophenyl) sulfonium, tris (4-dimethylaminophenyl) sulfonium, 4-methylphenyldiphenylsulfonium, 4
-Tert-butylphenyldiphenylsulfonium,
Bis (4-methylphenyl) phenylsulfonium, bis (4-tet-butylphenyl) phenylsulfonium, tris (4-methylphenyl) sulfonium, tris (4-tert-butylphenyl) sulfonium, tris (phenylmethyl) sulfonium, 2 -Naphthyldiphenylsulfonium, dimethyl-2-naphthylsulfonium, 4-hydroxyphenyldimethylsulfonium, 4-methoxyphenyldimethylsulfonium, trimethylsulfonium, 2-oxocyclohexylcyclohexylmethylsulfonium, trinaphthylsulfonium, tribenzylsulfonium, diphenylmethylsulfonium, dimethyl Phenylsulfonium, 2-oxopropylthiacyclopentanium, 2-oxobutylthiacyclopentanium , 2-oxo-3,3 dimethylbutylthiacyclopentanium, 2-oxo-2-phenylethylthiacyclopentanium, and the like. Examples of the sulfonate include trifluoromethanesulfonate, nonafluorobutanesulfonate, heptadecafluorooctanesulfonate. , 2,2,2-trifluoroethane sulfonate, pentafluorobenzene sulfonate,
4-trifluoromethylbenzene sulfonate, 4-fluorobenzene sulfonate, mesitylene sulfonate, 2,4,6-triisopropylbenzene sulfonate, toluene sulfonate, benzene sulfonate, 4
-(4'-toluenesulfonyloxy) benzenesulfonate, 6- (4-toluenesulfonyloxy) naphthalene-2-sulfonate, 4- (4-toluenesulfonyloxy) naphthalene-1-sulfonate, 5- (4-
Toluenesulfonyloxy) naphthalene-1-sulfonate, 8- (4-toluenesulfonyloxy) naphthalene-1-sulfonate, naphthalenesulfonate, camphorsulfonate, octanesulfonate, dodecylbenzenesulfonate, butanesulfonate, methanesulfonate, bis (trifluoromethanesulfonyl) Imide, bis (perfluoroethanesulfonyl) imide,
Examples thereof include bis (perfluorobutanesulfonyl) imide, tris (trifluoromethanesulfonyl) methide, tris (perfluoroethanesulfonyl) methide, and the like, and sulfonium salts of combinations thereof.

The iodonium salt is a salt of an iodonium cation and a sulfonate, and includes diphenyliodonium, bis (4-tert-butylphenyl) iodonium and 4
-Tert-butoxyphenylphenyliodonium,
Examples of aryliodonium cations such as 4-methoxyphenylphenyliodonium and sulfonates include trifluoromethanesulfonate, nonafluorobutanesulfonate, heptadecafluorooctanesulfonate, and
2,2,2-trifluoroethane sulfonate, pentafluorobenzene sulfonate, 4-trifluoromethylbenzene sulfonate, 4-fluorobenzene sulfonate, mesitylene sulfonate, 2,4,6-triisopropylbenzene sulfonate, toluene sulfonate, benzene sulfonate, 4- (4'-toluenesulfonyloxy) benzenesulfonate, 6- (4-toluenesulfonyloxy) naphthalene-2-sulfonate, 4- (4-toluenesulfonyloxy) naphthalene-1-sulfonate, 5- (4-toluenesulfonyl) (Oxy) naphthalene-1-sulfonate, 8- (4-toluenesulfonyloxy) naphthalene-1-sulfonate, naphthalenesulfonate, camphorsulfonate, octanesulfonate , Dodecylbenzenesulfonate, butanesulfonate, methanesulfonate bis (trifluoromethanesulfonyl) imide, bis (perfluoroethanesulfonyl) imide, bis (perfluorobutanesulfonyl) imide, tris (trifluoromethanesulfonyl) methide, tris (perfluoroethanesulfonyl) ) Methide and the like, and iodonium salts of these combinations can be mentioned.

Examples of the sulfonyldiazomethane include bis (ethylsulfonyl) diazomethane, bis (1-methylpropylsulfonyl) diazomethane, bis (2-methylpropylsulfonyl) diazomethane, bis (1,1-dimethylethylsulfonyl) diazomethane and bis (cyclohexyl). Sulfonyl) diazomethane, bis (perfluoroisopropylsulfonyl) diazomethane, bis (phenylsulfonyl) diazomethane, bis (4-methylphenylsulfonyl) diazomethane, bis (2,4-dimethylphenylsulfonyl) diazomethane, bis (4-acetyloxyphenylsulfonyl) ) Diazomethane, bis (4-methanesulfonyloxyphenylsulfonyl) diazomethane, bis (4- (4-toluenesulfonyloxy) phenylsulfoni ) Diazomethane, bis (2-naphthylsulfonyl) diazomethane, 4-methylphenyl sulfonyl benzoyl diazomethane, tert- butyl-4- methylphenyl sulfonyl diazomethane, 2-naphthylsulfonyl benzoyl diazomethane,
4-methylphenylsulfonyl-2-naphthoyldiazomethane, methylsulfonylbenzoyldiazomethane, t
Examples include bissulfonyldiazomethane and sulfonylcarbonyldiazomethane such as ert butoxycarbonyl-4-methylphenylsulfonyldiazomethane.

Examples of the N-sulfonyloxydicarboximide type photoacid generator include succinimide, naphthalene dicarboximide, phthalic acid imide, cyclohexyldicarboximide, 5-norbornene-2,3-dicarboximide and 7-. Oxabicyclo [2.2.1] -5
-Imide skeleton such as heptene-2,3-dicarboximide and trifluoromethanesulfonate, nonafluorobutanesulfonate, heptadecafluorooctanesulfonate, 2,2,2-trifluoroethanesulfonate, pentafluorobenzenesulfonate, 4-trifluoro Methylbenzene sulfonate, 4-fluorobenzene sulfonate, mesitylene sulfonate, 2,4
6-triisopropylbenzene sulfonate, toluene sulfonate, benzene sulfonate, naphthalene sulfonate, camphor sulfonate, octane sulfonate, dodecyl benzene sulfonate, butane sulfonate, methane sulfonate and the like are mentioned as a combination of compounds.

Benzoin sulfonate type photoacid generators include benzoin tosylate, benzoin mesylate,
Examples thereof include benzoin butane sulfonate.

As the pyrogallol trisulfonate-type photoacid generator, all the hydroxyl groups of pyrogallol, phloroglysin, catechol, resorcinol, hydroquinone are trifluoromethanesulfonate, nonafluorobutanesulfonate, heptadecafluorooctanesulfonate, 2,2,2. -Trifluoroethane sulfonate, pentafluorobenzene sulfonate, 4-trifluoromethylbenzene sulfonate, 4-fluorobenzene sulfonate, toluene sulfonate, benzene sulfonate, naphthalene sulfonate, camphor sulfonate, octane sulfonate, dodecyl benzene sulfonate, butane sulfonate, methane sulfonate, etc. The compound substituted by is mentioned.

Examples of the nitrobenzyl sulfonate type photoacid generator include 2,4-dinitrobenzyl sulfonate and 2
-Nitrobenzyl sulfonate, 2,6-dinitrobenzyl sulfonate, and the sulfonate includes
Specifically, trifluoromethane sulfonate, nonafluorobutane sulfonate, heptadecafluorooctane sulfonate, 2,2,2-trifluoroethane sulfonate, pentafluorobenzene sulfonate, 4-trifluoromethylbenzene sulfonate, 4-fluorobenzene sulfonate, toluene sulfonate , Benzene sulfonate, naphthalene sulfonate, camphor sulfonate, octane sulfonate, dodecyl benzene sulfonate, butane sulfonate, methane sulfonate and the like. Further, a compound in which the nitro group on the benzyl side is replaced with a trifluoromethyl group can be used as well.

Examples of sulfone type photoacid generators include bis (phenylsulfonyl) methane, bis (4-methylphenylsulfonyl) methane, bis (2-naphthylsulfonyl) methane, and 2,2-bis (phenylsulfonyl) propane. , 2,2-bis (4-methylphenylsulfonyl)
Propane, 2,2-bis (2-naphthylsulfonyl) propane, 2-methyl-2- (p-toluenesulfonyl)
Propiophenone, 2- (cyclohexylcarbonyl)
-2- (p-toluenesulfonyl) propane, 2,4-
Dimethyl-2- (p-toluenesulfonyl) pentane-
3-on and the like can be mentioned.

Examples of the glyoxime derivative type photoacid generator include compounds described in Japanese Patent No. 2906999 and Japanese Patent Application Laid-Open No. 9-301948.
O- (p-toluenesulfonyl) -α-dimethylglyoxime, bis-O- (p-toluenesulfonyl) -α-
Diphenylglyoxime, bis-O- (p-toluenesulfonyl) -α-dicyclohexylglyoxime, bis-O- (p-toluenesulfonyl) -2,3-pentanedione glyoxime, bis-O- (n-butanesulfonyl) ) -Α-Dimethylglyoxime, bis-O- (n-butanesulfonyl) -α-diphenylglyoxime, bis-O- (n-butanesulfonyl) -α-dicyclohexylglyoxime, bis-O- (methanesulfonyl) -Α
-Dimethylglyoxime, bis-O- (trifluoromethanesulfonyl) -α-dimethylglyoxime, bis-
O- (2,2,2-trifluoroethanesulfonyl)-
α-dimethylglyoxime, bis-O- (10-camphorsulfonyl) -α-dimethylglyoxime, bis-
O- (benzenesulfonyl) -α-dimethylglyoxime, bis-O- (p-fluorobenzenesulfonyl)-
α-dimethylglyoxime, bis-O- (p-trifluoromethylbenzenesulfonyl) -α-dimethylglyoxime, bis-O- (xylenesulfonyl) -α-dimethylglyoxime, bis-O- (trifluoromethanesulfonyl) -Nioxime, bis-O- (2,2,2-trifluoroethanesulfonyl) -nioxime, bis-O
-(10-camphorsulfonyl) -nioxime, bis-O- (benzenesulfonyl) -nioxime, bis-O
-(P-fluorobenzenesulfonyl) -nioxime,
Bis-O- (p-trifluoromethylbenzenesulfonyl) -nioxime, bis-O- (xylenesulfonyl)
-Nioxime and the like can be mentioned.

Further, oxime sulfonates described in US Pat. No. 6,0047,24, especially (5- (4-toluenesulfonyl) oxyimino-5H-thiophen-2-ylidene) phenylacetonitrile, (5- (10-camphorsulfonyl) oxyimino- 5H-thiophene-
2-ylidene) phenylacetonitrile, (5-n-octanesulfonyloxyimino-5H-thiophene-2)
-Ylidene) phenylacetonitrile, (5- (4-toluenesulfonyl) oxyimino-5H-thiophene-
2-ylidene), (2-methylphenyl) acetonitrile, (5- (10-camphorsulfonyl) oxyimino-5H-thiophen-2-ylidene), (2-methylphenyl) acetonitrile, (5-n-octanesulfonyloxyimino) -5H-thiophene-2-ylidene), (2-methylphenyl) acetonitrile and the like.

US Pat. No. 6,261,738, JP-A-200
Oxime sulfonate described in JP-A 0-314956,
In particular, 2,2,2-trifluoro-1-phenyl-ethanone oxime-O-methyl sulfonate; 2,2,2-
Trifluoro-1-phenyl-ethanone oxime-O-
(10-camphoryl sulfonate); 2,2,2-trifluoro-1-phenyl-ethanone oxime-O- (4
-Methoxyphenyl sulfonate); 2,2,2-trifluoro-1-phenyl-ethanone oxime-O- (1
-Naphthyl sulfonate); 2,2,2-trifluoro-1-phenyl-ethanone oxime-O- (2-naphthyl sulfonate); 2,2,2-trifluoro-1-phenyl-ethanone oxime- O- (2,4,6-trimethylphenyl sulfonate); 2,2,2-trifluoro-1- (4-methylphenyl) -ethanone oxime-
O- (10-camphoryl sulfonate); 2,2,2-
Trifluoro-1- (4-methylphenyl) -ethanone oxime-O- (methyl sulfonate); 2,2,2-
Trifluoro-1- (2-methylphenyl) -ethanone oxime-O- (10-camphoryl sulfonate);
2,2,2-Trifluoro-1- (2,4-dimethylphenyl) -ethanone oxime-O- (10-camphoryl sulfonate); 2,2,2-trifluoro-1-
(2,4-Dimethylphenyl) -ethanone oxime-O
-(1-naphthylsulfonate); 2,2,2-trifluoro-1- (2,4-dimethylphenyl) -ethanone oxime-O- (2-naphthylsulfonate); 2,
2,2-Trifluoro-1- (2,4,6-trimethylphenyl) -ethanone oxime-O- (10-camphoryl sulfonate); 2,2,2-trifluoro-1-
(2,4,6-Trimethylphenyl) -ethanone oxime-O- (1-naphthyl sulfonate); 2,2,2-
Trifluoro-1- (2,4,6-trimethylphenyl) -ethanone oxime-O- (2-naphthyl sulfonate); 2,2,2-trifluoro-1- (4-methoxyphenyl) -ethanone Oxime-O-methyl sulfonate; 2,2,2-trifluoro-1- (4-methylthiophenyl) -ethanone oxime-O-methyl sulfonate; 2,2,2-trifluoro-1- (3. 4-dimethoxyphenyl) -ethanone oxime-O-methyl sulfonate; 2,2,3,3,4,4,4-heptafluoro-1-phenyl-butanone oxime-O- (10-camphoryl sulfonate) 2,2,2-trifluoro-
1- (phenyl) -ethanone oxime-O-methyl sulfonate; 2,2,2-trifluoro-1- (phenyl) -ethanone oxime-O-10-camphoryl sulfonate; 2,2,2- Trifluoro-1- (phenyl)
-Ethanone oxime-O- (4-methoxyphenyl) sulfonate; 2,2,2-trifluoro-1- (phenyl) -ethanone oxime-O- (1-naphthyl) sulfonate; 2,2,2-tri Fluoro-1- (phenyl)
-Ethanone oxime-O- (2-naphthyl) sulfonate; 2,2,2-trifluoro-1- (phenyl) -ethanone oxime-O- (2,4,6-trimethylphenyl) sulfonate; 2,2 , 2-trifluoro-1-
(4-Methylphenyl) -ethanone oxime-O- (1
0-camphoryl) sulfonate; 2,2,2-trifluoro-1- (4-methylphenyl) -ethanone oxime-O-methyl sulfonate; 2,2,2-trifluoro-1- (2-methylphenyl) ) -Ethanone oxime-O
-(10-camphoryl) sulfonate; 2,2,2-trifluoro-1- (2,4-dimethylphenyl) -ethanone oxime-O- (1-naphthyl) sulfonate;
2,2,2-Trifluoro-1- (2,4-dimethylphenyl) -ethanone oxime-O- (2-naphthyl) sulfonate; 2,2,2-trifluoro-1- (2
4,6-Trimethylphenyl) -ethanone oxime-O
-(10-camphoryl) sulfonate; 2,2,2-trifluoro-1- (2,4,6-trimethylphenyl)
-Ethanone oxime-O- (1-naphthyl) sulfonate; 2,2,2-trifluoro-1- (2,4,6-trimethylphenyl) -ethanone oxime-O- (2-naphthyl) sulfonate; 2 , 2,2-trifluoro-1
-(4-Methoxyphenyl) -ethanone oxime-O-
Methyl sulfonate; 2,2,2-trifluoro-1-
(4-Thiomethylphenyl) -ethanone oxime-O-
Methyl sulfonate; 2,2,2-trifluoro-1-
(3,4-dimethoxyphenyl) -ethanone oxime-
O-methyl sulfonate; 2,2,2-trifluoro-
1- (4-methoxyphenyl) -ethanone oxime-O
-(4-methylphenyl) sulfonate; 2,2,2-
Trifluoro-1- (4-methoxyphenyl) -ethanone oxime-O- (4-methoxyphenyl) sulfonate; 2,2,2-trifluoro-1- (4-methoxyphenyl) -ethanone oxime-O- (4-dodecylphenyl) sulfonate; 2,2,2-trifluoro-1-
(4-Methoxyphenyl) -ethanone oxime-O-octyl sulfonate; 2,2,2-trifluoro-1-
(4-Thiomethylphenyl) -ethanone oxime-O-
(4-Methoxyphenyl) sulfonate; 2,2,2-
Trifluoro-1- (4-thiomethylphenyl) -ethanone oxime-O- (4-dodecylphenyl) sulfonate; 2,2,2-trifluoro-1- (4-thiomethylphenyl) -ethanone oxime- O-octyl sulfonate; 2,2,2-trifluoro-1- (4-thiomethylphenyl) -ethanone oxime-O- (2-naphthyl) sulfonate; 2,2,2-trifluoro-1-
(2-Methylphenyl) -ethanone oxime-O-methylsulfonate; 2,2,2-trifluoro-1- (4
-Methylphenyl) -ethanone oxime-O-phenylsulfonate; 2,2,2-trifluoro-1- (4-
Chlorophenyl) -ethanone oxime-O-phenyl sulfonate; 2,2,3,3,4,4,4-heptafluoro-1- (phenyl) -butanone oxime-O- (1
0-camphoryl) sulfonate; 2,2,2-trifluoro-1-naphthyl-ethanone oxime-O-methyl sulfonate; 2,2,2-trifluoro-2-naphthyl-ethanone oxime-O-methyl sulfo Nart; 2,
2,2-trifluoro-1- [4-benzylphenyl]
-Ethanone oxime-O-methyl sulfonate; 2,
2,2-trifluoro-1- [4- (phenyl-1,4
-Dioxa-but-1-yl) phenyl] -ethanone oxime-O-methyl sulfonate; 2,2,2-trifluoro-1-naphthyl-ethanone oxime-O-propyl sulfonate; 2,2,2 -Trifluoro-2-naphthyl-ethanone oxime-O-propyl sulfonate;
2,2,2-trifluoro-1- [4-benzylphenyl] -ethanone oxime-O-propyl sulfonate;
2,2,2-Trifluoro-1- [4-methylsulfonylphenyl] -ethanone oxime-O-propyl sulfonate; 1,3-bis [1- (4-phenoxyphenyl) -2,2,2- Trifluoroethanone oxime-O
-Sulfonyl] phenyl; 2,2,2-trifluoro-
1- [4-methylsulfonyloxyphenyl] -ethanone oxime-O-propyl sulfonate; 2,2,2-
Trifluoro-1- [4-methylcarbonyloxyphenyl] -ethanone oxime-O-propyl sulfonate; 2,2,2-trifluoro-1- [6H, 7H-
5,8-Dioxonaphth-2-yl] -ethanone oxime-O-propyl sulfonate; 2,2,2-trifluoro-1- [4-methoxycarbonylmethoxyphenyl] -ethanone oxime-O-propyl sulfonate ;
2,2,2-Trifluoro-1- [4- (methoxycarbonyl)-(4-amino-1-oxa-pent-1-yl) -phenyl] -ethanone oxime-O-propyl sulfonate; 2, 2,2-trifluoro-1- [3,5
-Dimethyl-4-ethoxyphenyl] -ethanone oxime-O-propyl sulfonate; 2,2,2-trifluoro-1- [4-benzyloxyphenyl] -ethanone oxime-O-propyl sulfonate; 2, 2,2-trifluoro-1- [2-thiophenyl] -ethanone oxime-O-propyl sulfonate; and 2,2,2-trifluoro-1- [1-dioxa-thiophen-2-yl)]- Ethanone oxime-O-propyl sulfonate.

JP-A-9-95479, JP-A-9-23
Oxime sulfonate α- (p-toluenesulfonyloxyimino) -phenylacetonitrile, α- (p-chlorobenzenesulfonyloxyimino) -phenylacetonitrile, α- (4-nitrobenzenesulfonyloxyimino) described in JP-A No. 0588 or the prior art. ) -Phenylacetonitrile, α- (4-nitro-2-trifluoromethylbenzenesulfonyloxyimino) -phenylacetonitrile, α- (benzenesulfonyloxyimino) -4-chlorophenylacetonitrile, α- (benzenesulfonyloxyimino) -2 ，
4-dichlorophenylacetonitrile, α- (benzenesulfonyloxyimino) -2,6-dichlorophenylacetonitrile, α- (benzenesulfonyloxyimino) -4-methoxyphenylacetonitrile, α- (2
-Chlorobenzenesulfonyloxyimino) -4-methoxyphenylacetonitrile, α- (benzenesulfonyloxyimino) -2-thienylacetonitrile, α-
(4-dodecylbenzenesulfonyloxyimino) -phenylacetonitrile, α-[(4-toluenesulfonyloxyimino) -4-methoxyphenyl] acetonitrile, α-[(dodecylbenzenesulfonyloxyimino) -4-methoxyphenyl] acetonitrile, α-
(Tosyloxyimino) -3-thienylacetonitrile, α- (methylsulfonyloxyimino) -1-cyclopentenylacetonitrile, α- (ethylsulfonyloxyimino) -1-cyclopentenylacetonitrile, α- (isopropylsulfonyloxyimino)- 1
-Cyclopentenylacetonitrile, α- (n-butylsulfonyloxyimino) -1-cyclopentenylacetonitrile, α- (ethylsulfonyloxyimino)-
1-cyclohexenyl acetonitrile, α- (isopropylsulfonyloxyimino) -1-cyclohexenylacetonitrile, α- (n-butylsulfonyloxyimino) -1-cyclohexenylacetonitrile and the like can be mentioned.

As the bisoxime sulfonate, compounds described in JP-A-9-208554, particularly bis (α- (4-toluenesulfonyloxy) imino) -p
-Phenylene diacetonitrile, bis (α- (benzenesulfonyloxy) imino) -p-phenylene diacetonitrile, bis (α- (methanesulfonyloxy) imino) -p-phenylene diacetonitrile bis (α- (butanesulfonyloxy) imino ) -P-phenylenediacetonitrile, bis (α- (10-camphorsulfonyloxy) imino) -p-phenylenediacetonitrile, bis (α- (4-toluenesulfonyloxy) imino) -p-phenylenediacetonitrile, bis ( α-
(Trifluoromethanesulfonyloxy) imino) -p
-Phenylenediacetonitrile, bis (α- (4-methoxybenzenesulfonyloxy) imino) -p-phenylenediacetonitrile, bis (α- (4-toluenesulfonyloxy) imino) -m-phenylenediacetonitrile, bis (α- (Benzenesulfonyloxy) imino) -m-phenylenediacetonitrile, bis (α-
(Methanesulfonyloxy) imino) -m-phenylenediacetonitrile bis (α- (butanesulfonyloxy) imino) -m-phenylenediacetonitrile, bis (α- (10-camphorsulfonyloxy) imino)
-M-phenylenediacetonitrile, bis (α- (4-
Toluenesulfonyloxy) imino) -m-phenylenediacetonitrile, bis (α- (trifluoromethanesulfonyloxy) imino) -m-phenylenediacetonitrile, bis (α- (4-methoxybenzenesulfonyloxy) imino) -m-phenyl Range acetonitrile and the like can be mentioned.

Among these, photoacid generators preferably used include sulfonium salts, bissulfonyldiazomethane,
N-sulfonyloxydicarboximide. Specifically, triphenyl sulfonium p-toluene sulfonate, triphenyl sulfonium camphor sulfonate, triphenyl sulfonium pentafluorobenzene sulfonate, triphenyl sulfonium nonafluorobutane sulfonate, triphenyl sulfonium 4-
(4′-toluenesulfonyloxy) benzenesulfonate, triphenylsulfonium, 2,4,6-triisopropylbenzenesulfonate, 4-tert-butoxyphenyldiphenylsulfonium p-toluenesulfonate, 4-tert-butoxyphenyldiphenylsulfonium camphorsulfonate, 4-tert-
Butoxyphenyl diphenylsulfonium 4- (4'-
Toluenesulfonyloxy) benzenesulfonate, tris (4-methylphenyl) sulfonium, camphorsulfonate, tris (4-tert-butylphenyl) sulfonium camphorsulfonate, bis (te
rt-Butylsulfonyl) diazomethane, bis (cyclohexylsulfonyl) diazomethane, bis (2,4-dimethylphenylsulfonyl) diazomethane, bis (4-)
tert-butylphenylsulfonyl) diazomethane,
N-camphorsulfonyloxy-5-norbornene-
2,3-carboxylic acid imide, Np-toluenesulfonyloxy-5-norbornene-2,3-carboxylic acid imide and the like can be mentioned.

The amount of the photo-acid generator (C) added to the chemically amplified resist material of the present invention may be any amount so long as the effect of the present invention is not impaired, but it is 0 per 100 parts by weight of the solid content in the resist material. -10 parts by weight, preferably 0-5 parts by weight. When the proportion of the photo-acid generator (C) is too large, there is a possibility that the resolution may be deteriorated and the problem of foreign matter during development / resist stripping may occur. The photo-acid generator (C) may be used alone or in combination of two or more. Further, it is also possible to use a photo-acid generator having a low transmittance at the exposure wavelength and to control the transmittance in the resist film by the addition amount thereof.

A compound which decomposes with an acid to generate an acid (acid-proliferating compound) may be added to the resist material of the present invention. For these compounds, see J. Photopo
lym. Sci. and Tech. , 8.43-4
4, 45-46 (1995), J. Photopoly
m. Sci. and Tech. , 9.29-30 (1
996).

Examples of acid multiplying compounds include tert-butyl-2-methyl-2-tosyloxymethyl acetoacetate, 2-phenyl 2- (2-tosyloxyethyl)-
Examples thereof include 1,3-dioxolane, but are not limited thereto. Of the known photo-acid generators, compounds having poor stability, particularly poor thermal stability, often show properties like acid-proliferating compounds.

The amount of the acid multiplication compound added to the resist material of the present invention is 2 parts by weight or less, preferably 1 part by weight or less based on 100 parts by weight of the solid content in the resist material.
If the added amount is too large, it is difficult to control diffusion, resulting in deterioration of resolution and deterioration of pattern shape.

As the basic compound as the component (D), a compound which can suppress the diffusion rate when the acid generated from the photo-acid generator diffuses in the resist film is suitable. With the combination of, the acid diffusion rate in the resist film is suppressed and the resolution is improved, the sensitivity change after exposure is suppressed, the dependency on the substrate and the environment is reduced, and the exposure margin and pattern profile are improved. can do.

Examples of such a basic compound include primary, secondary and tertiary aliphatic amines, mixed amines,
Aromatic amines, heterocyclic amines, nitrogen-containing compounds having a carboxy group, nitrogen-containing compounds having a sulfonyl group,
Examples thereof include nitrogen-containing compounds having a hydroxyl group, nitrogen-containing compounds having a hydroxyphenyl group, alcoholic nitrogen-containing compounds, amide derivatives and imide derivatives.

Specifically, as primary aliphatic amines, ammonia, methylamine, ethylamine, n-propylamine, isopropylamine, n-butylamine, isobutylamine, sec-butylamine, ter.
t-butylamine, pentylamine, tert-amylamine, cyclopentylamine, hexylamine, cyclohexylamine, heptylamine, octylamine,
Nonylamine, decylamine, dodecylamine, cetylamine, methylenediamine, ethylenediamine, tetraethylenepentamine, etc. are exemplified, and secondary aliphatic amines include dimethylamine, diethylamine, di-n.
-Propylamine, diisopropylamine, di-n-butylamine, diisobutylamine, di-sec-butylamine, dipentylamine, dicyclopentylamine,
Dihexylamine, dicyclohexylamine, diheptylamine, dioctylamine, dinonylamine, didecylamine, didodecylamine, dicetylamine, N, N
-Dimethylmethylenediamine, N, N-dimethylethylenediamine, N, N-dimethyltetraethylenepentamine and the like are exemplified, and as tertiary aliphatic amines, trimethylamine, triethylamine, tri-n-propylamine, triisopropylamine. , Tri-n-butylamine, triisobutylamine, tri-sec-butylamine, tripentylamine, tricyclopentylamine, trihexylamine, tricyclohexylamine,
Triheptylamine, trioctylamine, trinonylamine, tridecylamine, tridodecylamine, tricetylamine, N, N, N ', N'-tetramethylmethylenediamine, N, N, N', N'-tetra Examples include methylethylenediamine, N, N, N ′, N′-tetramethyltetraethylenepentamine, and the like.

Examples of the mixed amines include dimethylethylamine, methylethylpropylamine, benzylamine, phenethylamine, benzyldimethylamine and the like. Specific examples of aromatic amines and heterocyclic amines include aniline derivatives (eg, aniline,
N-methylaniline, N-ethylaniline, N-propylaniline, N, N-dimethylaniline, 2-methylaniline, 3-methylaniline, 4-methylaniline, ethylaniline, propylaniline, trimethylaniline, 2-nitroaniline , 3-nitroaniline, 4-nitroaniline, 2,4-dinitroaniline, 2,6-dinitroaniline, 3,5-dinitroaniline, N, N-
Dimethyltoluidine), diphenyl (p-tolyl) amine, methyldiphenylamine, triphenylamine,
Phenylenediamine, naphthylamine, diaminonaphthalene, pyrrole derivatives (eg pyrrole, 2H-pyrrole, 1-methylpyrrole, 2,4-dimethylpyrrole,
2,5-dimethylpyrrole, N-methylpyrrole, etc.),
Oxazole derivatives (such as oxazole and isoxazole), thiazole derivatives (such as thiazole and isothiazole), imidazole derivatives (such as imidazole, 4-methylimidazole and 4-methyl-2-phenylimidazole), pyrazole derivatives, furazan derivatives, Pyrroline derivative (for example, pyrroline, 2-methyl-1-pyrroline, etc.), Pyrrolidine derivative (for example, pyrrolidine, N-methylpyrrolidine, pyrrolidinone, N-methylpyrrolidone, etc.), imidazoline derivative, imidazolidine derivative, pyridine derivative (for example, pyridine, methyl) Pyridine, ethyl pyridine, propyl pyridine, butyl pyridine, 4- (1-butylpentyl) pyridine, dimethyl pyridine, trimethyl pyridine, triethyl pyridine, phenyl pyridi , 3-methyl-2-phenylpyridine, 4-tert-butylpyridine, diphenylpyridine, benzylpyridine, methoxypyridine, butoxypyridine, dimethoxypyridine, 1-methyl-2-pyridine, 4-pyrrolidinopyridine, 1-methyl- 4-phenylpyridine, 2- (1-ethylpropyl) pyridine,
Aminopyridine, dimethylaminopyridine, etc.), pyridazine derivative, pyrimidine derivative, pyrazine derivative, pyrazoline derivative, pyrazolidine derivative, piperidine derivative, piperazine derivative, morpholine derivative, indole derivative, isoindole derivative, 1H-indazole derivative, indoline derivative, quinoline derivative (Eg, quinoline, 3-quinolinecarbonitrile, etc.), isoquinoline derivative, cinnoline derivative, quinazoline derivative, quinoxaline derivative, phthalazine derivative, purine derivative, pteridine derivative, carbazole derivative, phenanthridine derivative, acridine derivative, phenazine derivative, 1,1
Examples thereof include 0-phenanthroline derivative, adenine derivative, adenosine derivative, guanine derivative, guanosine derivative, uracil derivative and uridine derivative.

Further, examples of the nitrogen-containing compound having a carboxy group include aminobenzoic acid, indolecarboxylic acid, amino acid derivatives (eg, nicotinic acid, alanine, arginine, aspartic acid, glutamic acid, glycine,
Histidine, isoleucine, glycylleucine, leucine, methionine, phenylalanine, threonine, lysine, 3-aminopyrazine-2-carboxylic acid, methoxyalanine, etc.) are exemplified, and 3-pyridinesulfonic acid is used as the nitrogen-containing compound having a sulfonyl group. , Pyridinium p-toluenesulfonate, and the like, and examples of the nitrogen-containing compound having a hydroxyl group, the nitrogen-containing compound having a hydroxyphenyl group, and the alcoholic nitrogen-containing compound include 2-hydroxypyridine, aminocresol, and 2,4-quinolinediol. , 3-indole methanol hydrate, monoethanolamine, diethanolamine, triethanolamine, N-ethyldiethanolamine, N, N-diethylethanolamine, triisopropanolamine,
2,2'-iminodiethanol, 2-aminoethano-
3-amino-1-propanol, 4-amino-1-
Butanol, 4- (2-hydroxyethyl) morpholine, 2- (2-hydroxyethyl) pyridine, 1- (2
-Hydroxyethyl) piperazine, 1- [2- (2-hydroxyethoxy) ethyl] piperazine, piperidine ethanol, 1- (2-hydroxyethyl) pyrrolidine,
1- (2-hydroxyethyl) -2-pyrrolidinone, 3
-Piperidino-1,2-propanediol, 3-pyrrolidino-1,2-propanediol, 8-hydroxyjulolidine, 3-cuinclidinol, 3-tropanol,
1-Methyl-2-pyrrolidine ethanol, 1-aziridine ethanol, N- (2-hydroxyethyl) phthalimide, N- (2-hydroxyethyl) isonicotinamide and the like are exemplified. Examples of the amide derivative include formamide, N-methylformamide, N, N-dimethylformamide, acetamide, N-methylacetamide, N,
Examples include N-dimethylacetamide, propionamide, benzamide and the like. Examples of the imide derivative include phthalimide, succinimide, and maleimide.

Further, one or more selected from the basic compounds represented by the following general formula (D1) can be blended. N (X ') _w (YY) _3-w (D1) (In the formula, w = 1, 2 or 3. YY is independently a hydrogen atom or a linear, branched or cyclic carbon atom number 1 to It represents an alkyl group of 20 and may contain a hydroxyl group or an ether structure, and X'is independently of the following general formulas (X'1) to (X '.
It represents a group represented by 3), and two or three X ′'s may combine to form a ring. )

[0089]

[Chemical formula 24] (In the formula, R ³⁰⁰ , R ³⁰² , and R ³⁰⁵ represent a linear or branched alkylene group having 1 to 4 carbon atoms. R ³⁰¹ , R ³⁰⁴ , R
³⁰⁶ represents a hydrogen atom or a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms, and may contain one or more hydroxy groups, ether structures, ester structures or lactone rings. R ³⁰³ is a single bond or 1 to 4 carbon atoms
Represents a linear or branched alkylene group. )

Specific examples of the basic compound represented by the above general formula (B1) include tris (2-methoxymethoxyethyl) amine and tris {2- (2-methoxyethoxy).
Ethyl} amine, tris {2- (2-methoxyethoxymethoxy) ethyl} amine, tris {2- (1-methoxyethoxy) ethyl} amine, tris {2- (1-ethoxyethoxy) ethyl} amine, tris {2 -(1-Ethoxypropoxy) ethyl} amine, tris [2- {2
-(2-hydroxyethoxy) ethoxy} ethyl] amine, 4,7,13,16,21,24-hexaoxa-
1,10-diazabicyclo [8.8.8] hexacosane, 4,7,13,18-tetraoxa-1,10-diazabicyclo [8.5.5] eicosane, 1,4,1
0,13-tetraoxa-7,16-diazabicyclooctadecane, 1-aza-12-crown-4, 1-aza-15-crown-5, 1-aza-18-crown-
6, tris (2-formyloxyethyl) amine, tris (2-acetoxyethyl) amine, tris (2-propionyloxyethyl) amine, tris (2-butyryloxyethyl) amine, tris (2-isobutyryloxy) Ethyl) amine, tris (2-valeryloxyethyl) amine, tris (2-pivaloyloxyethyl) amine, N, N-bis (2-acetoxyethyl) 2- (acetoxyacetoxy) ethylamine, tris (2- Methoxycarbonyloxyethyl) amine, tris (2-t
ert-butoxycarbonyloxyethyl) amine, tris [2- (2-oxopropoxy) ethyl] amine,
Tris [2- (methoxycarbonylmethyl) oxyethyl] amine, tris [2- (tert-butoxycarbonylmethyloxy) ethyl] amine, tris [2- (cyclohexyloxycarbonylmethyloxy) ethyl]
Amine, tris (2-methoxycarbonylethyl) amine, tris (2-ethoxycarbonylethyl) amine,
N, N-bis (2-hydroxyethyl) 2- (methoxycarbonyl) ethylamine, N, N-bis (2-acetoxyethyl) 2- (methoxycarbonyl) ethylamine, N, N-bis (2-hydroxyethyl) 2 -(Ethoxycarbonyl) ethylamine, N, N-bis (2-acetoxyethyl) 2- (ethoxycarbonyl) ethylamine, N, N-bis (2-hydroxyethyl) 2- (2
-Methoxyethoxycarbonyl) ethylamine, N, N
-Bis (2-acetoxyethyl) 2- (2-methoxyethoxycarbonyl) ethylamine, N, N-bis (2-
Hydroxyethyl) 2- (2-hydroxyethoxycarbonyl) ethylamine, N, N-bis (2-acetoxyethyl) 2- (2-acetoxyethoxycarbonyl) ethylamine, N, N-bis (2-hydroxyethyl) 2
-[(Methoxycarbonyl) methoxycarbonyl] ethylamine, N, N-bis (2-acetoxyethyl) 2-
[(Methoxycarbonyl) methoxycarbonyl] ethylamine, N, N-bis (2-hydroxyethyl) 2-
(2-oxopropoxycarbonyl) ethylamine,
N, N-bis (2-acetoxyethyl) 2- (2-oxopropoxycarbonyl) ethylamine, N, N-bis (2-hydroxyethyl) 2- (tetrahydrofurfuryloxycarbonyl) ethylamine, N, N-bis ( Two
-Acetoxyethyl) 2- (tetrahydrofurfuryloxycarbonyl) ethylamine, N, N-bis (2-hydroxyethyl) 2-[(2-oxotetrahydrofuran-3-yl) oxycarbonyl] ethylamine, N,
N-bis (2-acetoxyethyl) 2-[(2-oxotetrahydrofuran-3-yl) oxycarbonyl] ethylamine, N, N-bis (2-hydroxyethyl) 2
-(4-Hydroxybutoxycarbonyl) ethylamine, N, N-bis (2-formyloxyethyl) 2-
(4-formyloxybutoxycarbonyl) ethylamine, N, N-bis (2-formyloxyethyl) 2-
(2-Formyloxyethoxycarbonyl) ethylamine, N, N-bis (2-methoxyethyl) 2- (methoxycarbonyl) ethylamine, N- (2-hydroxyethyl) bis [2- (methoxycarbonyl) ethyl] amine, N -(2-acetoxyethyl) bis [2- (methoxycarbonyl) ethyl] amine, N- (2-hydroxyethyl) bis [2- (ethoxycarbonyl) ethyl] amine, N- (2-acetoxyethyl) bis [2 -(Ethoxycarbonyl) ethyl] amine, N- (3-hydroxy-1-propyl) bis [2- (methoxycarbonyl)
Ethyl] amine, N- (3-acetoxy-1-propyl) bis [2- (methoxycarbonyl) ethyl] amine, N- (2-methoxyethyl) bis [2- (methoxycarbonyl) ethyl] amine, N-butylbis [2-
(Methoxycarbonyl) ethyl] amine, N-butylbis [2- (2-methoxyethoxycarbonyl) ethyl]
Amine, N-methylbis (2-acetoxyethyl) amine, N-ethylbis (2-acetoxyethyl) amine,
N-methylbis (2-pivaloyloxyethyl) amine, N-ethylbis [2- (methoxycarbonyloxy) ethyl] amine, N-ethylbis [2- (tert.
-Butoxycarbonyloxy) ethyl] amine, tris (methoxycarbonylmethyl) amine, tris (ethoxycarbonylmethyl) amine, N-butylbis (methoxycarbonylmethyl) amine, N-hexylbis (methoxycarbonylmethyl) amine, β- (diethylamino) Examples thereof include -δ-valerolactone.

Further, one or more kinds selected from the basic compounds having a cyclic structure represented by the following general formula (D2) can be blended.

[Chemical 25] (In the formula, X ′ is the same as above. R ³⁰⁷ has 2 to 2 carbon atoms.
It is a linear or branched alkylene group of 20 and may contain one or more carbonyl groups, ether structures, ester structures or sulfide structures. )

Specific examples of the basic compound having a cyclic structure represented by the general formula (D2) include 1- [2- (methoxymethoxy) ethyl] pyrrolidine and 1- [2- (methoxymethoxy) ethyl] piperidine. , 4- [2- (methoxymethoxy) ethyl] morpholine, 1- [2-
[(2-Methoxyethoxy) methoxy] ethyl] pyrrolidine, 1- [2-[(2-methoxyethoxy) methoxy] ethyl] piperidine, 4- [2-[(2-methoxyethoxy) methoxy] ethyl] morpholine, acetic acid 2-
(1-pyrrolidinyl) ethyl, 2-piperidinoethyl acetate, 2-morpholinoethyl acetate, 2- (1-pyrrolidinyl) ethyl formate, 2-piperidinoethyl propionate,
Acetoxyacetic acid 2-morpholinoethyl, methoxyacetic acid 2
-(1-Pyrrolidinyl) ethyl, 4- [2- (methoxycarbonyloxy) ethyl] morpholine, 1- [2-
(T-Butoxycarbonyloxy) ethyl] piperidine, 4- [2- (2-methoxyethoxycarbonyloxy) ethyl] morpholine, methyl 3- (1-pyrrolidinyl) propionate, methyl 3-piperidinopropionate, 3- Methyl morpholino propionate, methyl 3- (thiomorpholino) propionate, 2-methyl-3- (1
-Methyl pyrrolidinyl) propionate, ethyl 3-morpholinopropionate, methoxycarbonylmethyl 3-piperidinopropionate, 2-hydroxyethyl 3- (1-pyrrolidinyl) propionate, 2-acetoxyethyl 3-morpholinopropionate, 3 -(1-Pyrrolidinyl) propionic acid 2-oxotetrahydrofuran-3-
Yl, tetrahydrofurfuryl 3-morpholinopropionate, glycidyl 3-piperidinopropionate, 2-methoxyethyl 3-morpholinopropionate, 3- (1-
2- (2-methoxyethoxy) ethyl pyrrolidinyl) propionate, butyl 3-morpholinopropionate, 3-
Cyclohexyl piperidinopropionate, α- (1-pyrrolidinyl) methyl-γ-butyrolactone, β-piperidino-γ-butyrolactone, β-morpholino-δ-valerolactone, methyl 1-pyrrolidinyl acetate, methyl piperidinoacetate, methyl morpholinoacetate , Methyl thiomorpholino acetate, ethyl 1-pyrrolidinyl acetate, and 2-methoxyethyl morpholino acetate.

Further, one or more selected from the basic compounds having a cyano group represented by the following general formulas (D3) to (D6) may be blended.

[Chemical formula 26] (In the formula, X ′, R ³⁰⁷ , and w are the same as above. R ³⁰⁸ ,
R ³⁰⁹ is independently a linear or branched alkylene group having 1 to 4 carbon atoms. )

Specific examples of the basic compound having a cyano group represented by the above general formulas (D3) to (D6) include 3- (diethylamino) propiononitrile,
N, N-bis (2-hydroxyethyl) -3-aminopropiononitrile, N, N-bis (2-acetoxyethyl) -3-aminopropiononitrile, N, N-bis (2-formyloxyethyl) -3-Aminopropiononitrile, N, N-bis (2-methoxyethyl) -3-
Aminopropiononitrile, N, N-bis [2- (methoxymethoxy) ethyl] -3-aminopropiononitrile, N- (2-cyanoethyl) -N- (2-methoxyethyl) -3-aminopropionic acid methyl ester , Methyl N- (2-cyanoethyl) -N- (2-hydroxyethyl) -3-aminopropionate, methyl N- (2-acetoxyethyl) -N- (2-cyanoethyl) -3-aminopropionate, N -(2-Cyanoethyl) -N-ethyl-
3-aminopropiononitrile, N- (2-cyanoethyl) -N- (2-hydroxyethyl) -3-aminopropiononitrile, N- (2-acetoxyethyl) -N-
(2-Cyanoethyl) -3-aminopropiononitrile, N- (2-cyanoethyl) -N- (2-formyloxyethyl) -3-aminopropiononitrile, N-
(2-Cyanoethyl) -N- (2-methoxyethyl)-
3-Aminopropiononitrile, N- (2-cyanoethyl) -N- [2- (methoxymethoxy) ethyl] -3-
Aminopropiononitrile, N- (2-cyanoethyl)
-N- (3-hydroxy-1-propyl) -3-aminopropiononitrile, N- (3-acetoxy-1-propyl) -N- (2-cyanoethyl) -3-aminopropiononitrile, N- ( 2-cyanoethyl) -N- (3-
Formyloxy-1-propyl) -3-aminopropiononitrile, N- (2-cyanoethyl) -N-tetrahydrofurfuryl-3-aminopropiononitrile, N,
N-bis (2-cyanoethyl) -3-aminopropiononitrile, diethylaminoacetonitrile, N, N-bis (2-hydroxyethyl) aminoacetonitrile,
N, N-bis (2-acetoxyethyl) aminoacetonitrile, N, N-bis (2-formyloxyethyl) aminoacetonitrile, N, N-bis (2-methoxyethyl) aminoacetonitrile, N, N-bis [2 -(Methoxymethoxy) ethyl] aminoacetonitrile, methyl N-cyanomethyl-N- (2-methoxyethyl) -3-aminopropionate, methyl N-cyanomethyl-N- (2-hydroxyethyl) -3-aminopropionate, N
-(2-acetoxyethyl) -N-cyanomethyl-3-
Methyl aminopropionate, N-cyanomethyl-N-
(2-hydroxyethyl) aminoacetonitrile, N-
(2-acetoxyethyl) -N- (cyanomethyl) aminoacetonitrile, N-cyanomethyl-N- (2-formyloxyethyl) aminoacetonitrile, N-cyanomethyl-N- (2-methoxyethyl) aminoacetonitrile, N-cyanomethyl- N- [2- (methoxymethoxy) ethyl] aminoacetonitrile, N- (cyanomethyl) -N- (3-hydroxy-1-propyl) aminoacetonitrile, N- (3-acetoxy-1-propyl)
-N- (cyanomethyl) aminoacetonitrile, N-cyanomethyl-N- (3-formyloxy-1-propyl) aminoacetonitrile, N, N-bis (cyanomethyl) aminoacetonitrile, 1-pyrrolidinepropiononitrile, 1-piperidinepropionate Ononitrile, 4-morpholine propiononitrile, 1-pyrrolidine acetonitrile, 1-piperidine acetonitrile, 4-morpholine acetonitrile, cyanomethyl 3-diethylaminopropionate, N, N-bis (2-hydroxyethyl)-
Cyanomethyl 3-aminopropionate, N, N-bis (2-acetoxyethyl) -3-aminopropionate cyanomethyl, N, N-bis (2-formyloxyethyl) -3-aminopropionate cyanomethyl, N, N-
Bis (2-methoxyethyl) -3-aminopropionate cyanomethyl, N, N-bis [2- (methoxymethoxy) ethyl] -3-aminopropionate cyanomethyl,
3-Diethylaminopropionic acid (2-cyanoethyl), N, N-bis (2-hydroxyethyl) -3-aminopropionic acid (2-cyanoethyl), N, N-bis (2-acetoxyethyl) -3-aminopropion Acid (2-cyanoethyl), N, N-bis (2-formyloxyethyl) -3-aminopropionic acid (2-cyanoethyl), N, N-bis (2-methoxyethyl) -3-aminopropionic acid (2 -Cyanoethyl), N, N-bis [2- (methoxymethoxy) ethyl] -3-aminopropionic acid (2-cyanoethyl), 1-pyrrolidine cyanomethyl propionate, 1-piperidine cyanomethyl propionate, 4-morpholine cyanomethyl propionate ,
1-pyrrolidine propionic acid (2-cyanoethyl), 1
-Piperidine propionic acid (2-cyanoethyl), 4-
Morpholine propionic acid (2-cyanoethyl) etc. can be illustrated.

The basic compounds may be used alone or in combination of two or more, and the compounding amount thereof is 0 to 2 parts by weight, especially 0% by weight based on 100 parts by weight of the solid content in the resist material. A mixture of 0.01 to 1 part by weight is suitable. If the blending amount exceeds 2 parts by weight, the sensitivity may be lowered too much.

Examples of the organic acid derivative which is the component (E) are not particularly limited, but specifically, phenol, cresol, catechol, resorcinol, pyrogallol, phloroglycine, bis (4-hydroxyphenyl) methane. , 2,2-bis (4'-hydroxyphenyl) propane, bis (4-hydroxyphenyl) sulfone, 1,1,1-tris (4'-hydroxyphenyl)
Ethane, 1,1,2-tris (4′-hydroxyphenyl) ethane, hydroxybenzophenone, 4-hydroxyphenylacetic acid, 3-hydroxyphenylacetic acid, 2-hydroxyphenylacetic acid, 3- (4-hydroxyphenyl) propionic acid, 3- (2-hydroxyphenyl) propionic acid, 2,5-dihydroxyphenylacetic acid, 3,
4-dihydroxyphenylacetic acid, 1,2-phenylenediacetic acid, 1,3-phenylenediacetic acid, 1,4-phenylenediacetic acid, 1,2-phenylenedioxydiacetic acid, 1,4-
Phenylenedipropanoic acid, benzoic acid, salicylic acid, 4,
4-bis (4'-hydroxyphenyl) valeric acid, 4-t
ert-butoxyphenylacetic acid, 4- (4-hydroxyphenyl) butyric acid, 3,4-dihydroxymandelic acid, 4
-Hydroxymandelic acid and the like can be mentioned, and salicylic acid and 4,4-bis (4'-hydroxyphenyl) valeric acid are particularly preferable. These can be used alone or in combination of two or more.

The amount of the organic acid derivative added to the chemically amplified resist material of the present invention is 10% of the solid content in the resist material.
It is 5 parts by weight or less, preferably 1 part by weight or less in 0 parts by weight. If the added amount is more than 5 parts by weight, the resolution may be deteriorated. The organic acid derivative may not be added depending on the combination of compositions in the resist.

Examples of the organic solvent of the component (F) include butyl acetate, amyl acetate, cyclohexyl acetate, 3-methoxybutyl acetate, methyl ethyl ketone, methyl amyl ketone,
Cyclohexanone, cyclopentanone, 3-ethoxyethylpropionate, 3-ethoxymethylpropionate, 3-methoxymethylpropionate, methyl acetoacetate, ethyl acetoacetate, diacetone alcohol, methyl pyruvate, ethyl pyruvate, Propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monomethyl ether propionate, propylene glycol monoethyl ether propionate, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, 3- Methyl-3-methoxybutanol, N-methylpyrrolidone, dimethylsulfoxide, γ-butyrrola Tons, propylene glycol methyl ether acetate, propylene glycol ethyl ether acetate, propylene glycol propyl ether acetate, methyl lactate, ethyl lactate, propyl lactate, and tetramethylene sulfone, and the like, but is not limited thereto. Particularly preferred are propylene glycol alkyl ether acetate and alkyl lactate. These solvents may be used alone or in combination of two or more. Examples of preferred mixed solvents are propylene glycol alkyl ether acetate and alkyl lactate. The alkyl group of the propylene glycol alkyl ether acetate in the present invention includes those having 1 to 4 carbon atoms, such as a methyl group, an ethyl group, a propyl group and the like. Among them, a methyl group and an ethyl group are preferable. Further, this propylene glycol alkyl ether acetate has 1,2-substitution products and 1,3-substitution products,
There are three types of isomers depending on the combination of substitution positions, but they may be used alone or in combination.

The alkyl group of the alkyl lactate ester may be one having 1 to 4 carbon atoms, such as a methyl group, an ethyl group, a propyl group and the like. Among them, a methyl group and an ethyl group are preferable.

The amount of these solvents added is 300 to 2,000 relative to 100 parts by weight of the solid content of the chemically amplified resist material.
The weight is preferably 400 to 1,000 parts by weight, but is not limited to this as long as it is a concentration that can be achieved by the existing film forming method.

As the compound (dissolution inhibitor) having a molecular weight of 3,000 or less, the solubility of which in the alkali developing solution is changed by the action of the acid of the component (G), a low molecular weight phenol or carboxylic acid derivative having a molecular weight of 2,500 or less can be used. It is also possible to add a compound in which some or all of them are substituted with an acid labile substituent.

As the phenol or carboxylic acid derivative having a molecular weight of 2,500 or less, bisphenol A, bisphenol H, bisphenol S, 4,4-bis (4 '
-Hydroxyphenyl) valeric acid, tris (4-hydroxyphenyl) methane, 1,1,1-tris (4'-hydroxyphenyl) ethane, 1,1,2-tris (4'-
Hydroxyphenyl) ethane, phenolphthalein,
Examples thereof include thymolphthalein, cholic acid, deoxycholic acid, and lithocholic acid, and examples of the acid-labile substituent include those exemplified as the acid labile group of the above-mentioned polymer again.

An example of a dissolution inhibitor which is preferably used is bis (4- (2'-tetrahydropyranyloxy)
Phenyl) methane, bis (4- (2'-tetrahydrofuranyloxy) phenyl) methane, bis (4-tert)
-Butoxyphenyl) methane, bis (4-tert-butoxycarbonyloxyphenyl) methane, bis (4-
tert-butoxycarbonylmethyloxyphenyl)
Methane, bis (4- (1'-ethoxyethoxy) phenyl) methane, bis (4- (1'-ethoxypropyloxy) phenyl) methane, 2,2-bis (4 '-(2'')
-Tetrahydropyranyloxy)) propane, 2,2-
Bis (4 '-(2''-tetrahydrofuranyloxy)
Phenyl) propane, 2,2-bis (4'-tert-
Butoxyphenyl) propane, 2,2-bis (4'-t
ert-butoxycarbonyloxyphenyl) propane, 2,2-bis (4-tert-butoxycarbonylmethyloxyphenyl) propane, 2,2-bis (4 ′)
-(1 ''-ethoxyethoxy) phenyl) propane,
2,2-bis (4 '-(1''-ethoxypropyloxy) phenyl) propane, 4,4-bis (4'-
(2 ″ -Tetrahydropyranyloxy) phenyl) tert-butyl valerate, 4,4-bis (4 ′-(2 ″-
Tetrahydrofuranyloxy) phenyl) valeric acid ter
t-butyl, 4,4-bis (4'-tert-butoxyphenyl) tert-butyl valerate, 4,4-bis (4-t
ert-Butoxycarbonyloxyphenyl) valeric acid t
tert-butyl, 4,4-bis (4'-tert-butoxycarbonylmethyloxyphenyl) valerate tert-butyl, 4,4-bis (4 '-(1''-ethoxyethoxy) phenyl) valerate tert-butyl, 4 , 4-Bis (4 ′-(1 ″ -ethoxypropyloxy) phenyl) valerate tert-butyl, tris (4- (2′-tetrahydropyranyloxy) phenyl) methane, tris (4- (2′-tetrahydrofura) Nyloxy) phenyl) methane, tris (4-tert-butoxyphenyloxy) methane, tris (4-tert-butoxycarbonyloxyphenyl) methane, tris (4-tert-butoxycarbonyloxymethylphenyl) methane, tris (4- ( 1'-ethoxyethoxy) phenyl) methane, tris (4- (1'-ethoxypropyl) ) Phenyl) methane, 1,1,2-tris (4 '- (2''
-Tetrahydropyranyloxy) phenyl) ethane,
1,1,2-Tris (4 ′-(2 ″ -tetrahydrofuranyloxy) phenyl) ethane, 1,1,2-Tris (4′-tert-butoxyphenyl) ethane, 1,
1,2-tris (4'-tert-butoxycarbonyloxyphenyl) ethane, 1,1,2-tris (4'-
tert-butoxycarbonylmethyloxyphenyl)
Ethane, 1,1,2-tris (4 '-(1'-ethoxyethoxy) phenyl) ethane, 1,1,2-tris (4'-(1'-ethoxypropyloxy) phenyl)
Examples include ethane, cholic acid t-butyl ester, deoxycholic acid t-butyl ester, lithocholic acid t-butyl ester and the like.

The amount of the dissolution inhibitor (G) added to the resist material of the present invention is 10% of the solid content in the resist material.
It is 20 parts by weight or less, preferably 15 parts by weight or less in 0 parts by weight. If the amount is more than 20 parts by weight, the monomer component increases and the heat resistance of the resist material decreases.

When the photo-acid generator of the present invention is used as a negative resist material, the resin is not particularly limited, but the base resin before substitution of the acid labile group of the above resin is used. It is suitable.

For example, poly p-hydroxystyrene, poly m-hydroxystyrene, poly 4-hydroxy 2-methylstyrene, poly 4-hydroxy-3-methylstyrene, poly α-methyl p-hydroxystyrene, partially hydrogenated poly p. -Hydroxystyrene copolymer, poly (p-
Hydroxystyrene-α-methyl p-hydroxystyrene) copolymer, poly (p-hydroxystyrene-α-
Methyl styrene) copolymer, poly (p-hydroxystyrene-styrene) copolymer, poly (p-hydroxystyrene-m-hydroxystyrene) copolymer, poly (p-hydroxystyrene-styrene) copolymer, poly (p-hydroxystyrene-acrylic acid) ) Copolymer, poly (p-hydroxystyrene-methacrylic acid) copolymer, poly (p-hydroxystyrene-methyl acrylate) copolymer, poly (p-hydroxystyrene-acrylic acid-methyl methacrylate) copolymer, poly (p-hydroxystyrene-methyl) Acrylate) copolymer, poly (p-hydroxystyrene-methacrylic acid-methyl methacrylate) copolymer, polymethacrylic acid, polyacrylic acid, poly (acrylic acid-methyl acrylate) copolymer , Poly (methacrylic acid - methyl methacrylate) copolymer, poly (acrylic acid - maleimide) copolymer, poly (methacrylic acid - maleimide)
Examples thereof include copolymers, poly (p-hydroxystyrene-acrylic acid-maleimide) copolymers, poly (p-hydroxystyrene-methacrylic acid-maleimide) copolymers, and the like, but are not limited to these combinations.

Further, in order to have various functions, a substituent may be introduced into a part of the phenolic hydroxyl group or the carboxyl group of the above acid labile group-protected polymer. For example, a substituent for improving the adhesiveness to the substrate or a substituent for improving the etching resistance, particularly acid for controlling the dissolution rate of the unexposed portion and the low-exposed portion in the alkali developing solution so as not to be too high. It is preferable to introduce a relatively stable substituent into alkali. Examples of the substituent include, for example, 2-hydroxyethyl group, 2-hydroxypropyl group, methoxymethyl group, methoxycarbonyl group, ethoxycarbonyl group, methoxycarbonylmethyl group, ethoxycarbonylmethyl group, 4
-Methyl-2-oxo-4-oxolanyl group, 4-methyl-2-oxo-4-oxanyl group, methyl group, ethyl group, n-propyl group, iso-propyl group, n-butyl group, sec-butyl group , Acetyl group, pivaloyl group, adamantyl group, isobornyl group, cyclohexyl group and the like, but are not limited thereto. Further, an acid-decomposable substituent, for example, a t-butoxycarbonyl group, or a t-butyl group, a t-butoxycarbonylmethyl group, or a comparatively difficult acid-decomposable substituent can be introduced.

The amount of the above resin added to the resist composition of the present invention is arbitrary, but the solid content in the resist is 1%.
65-99 parts by weight in 00 parts by weight, preferably 65-98
Parts by weight.

Examples of the acid crosslinking agent which forms a crosslinked structure by the action of the acid as the component (I) include compounds having two or more hydroxymethyl groups, alkoxymethyl groups, epoxy groups or vinyl ether groups in the molecule. , Substituted glycouril derivatives, urea derivatives, hexa (methoxymethyl) melamine, etc. are preferably used as the acid crosslinking agent of the chemically amplified negative resist composition of the present invention. For example, N, N,
Tetraalkoxymethyl-substituted glycolurils, such as N ', N'-tetramethoxymethylurea and hexamethoxymethylmelamine, tetrahydroxymethyl-substituted glycolurils and tetramethoxymethylglycoluril, substituted and unsubstituted bis-hydroxymethylphenols , A phenolic compound such as bisphenol A and a condensate such as epichlorohydrin. Particularly suitable crosslinking agents are 1,3,5,7-tetraalkoxymethylglycoluril or 1,3,5,7-tetrahydroxymethylglycoluril, such as 1,3,5,7-tetramethoxymethylglycoluril, 2,6-dihydroxymethyl p-cresol, 2,6-dihydroxymethylphenol, 2,2 ', 6,6'-tetrahydroxymethyl-bisphenol A and 1,4-bis- [2- (2-
Hydroxypropyl)]-benzene, N, N, N ′,
Examples thereof include N'-tetramethoxymethylurea and hexamethoxymethylmelamine. The addition amount is arbitrary, but it is 1 to 20 parts by weight, preferably 5 to 15 parts by weight based on 100 parts by weight of the solid content in the resist material. These crosslinking agents may be used alone or in combination of two or more kinds.

Into the chemically amplified resist material of the present invention, an additive such as a surfactant for improving the coating property and a light absorbing material for reducing diffuse reflection from the substrate can be added.

Examples of the surfactant include, but are not limited to, polyoxyethylene lauryl ether, polyoxyethylene steryl ether, polyoxyethylene cetyl ether, polyoxyethylene olein ether, and other polyoxyethylene alkyls. Ethers, polyoxyethylene octylphenol ether,
Polyoxyethylene alkyl allylic ethers such as polyoxyethylene nonylphenol ether, polyoxyethylene polyoxypropylene block copolymers,
Sorbitan monolaurate, sorbitan monopalmitate, sorbitan fatty acid esters such as sorbitan monostearate, polyoxyethylene sorbitan monolaurate, polyoxyethylene sorbitan monopalmitate, polyoxyethylene sorbitan monostearate,
Nonionic surfactants of polyoxyethylene sorbitan fatty acid ester such as polyoxyethylene sorbitan trioleate and polyoxyethylene sorbitan tristearate, Ftop EF301, EF303, EF35
2 (Tochem Products), Megafac F171, F
172, F173 (Dainippon Ink and Chemicals), Florard FC430, FC431 (Sumitomo 3M), Asahi Guard AG710, Surflon S-381, S-38
2, SC101, SC102, SC103, SC10
4, SC105, SC106, Surfynol E100
4, KH-10, KH-20, KH-30, KH-40
(Asahi Glass) and other fluorine-based surfactants, organosiloxane polymer KP341, X-70-092, X-70-0
93 (Shin-Etsu Chemical Co., Ltd.), acrylic acid-based or methacrylic acid-based Polyflow No. 75, No. 95 (Kyoeisha Yushi Kagaku Kogyo), among them FC430, Surflon S
-381, Surfynol E1004, KH-20, K
H-30 is preferred. These can be used alone or in combination of two or more.

The addition amount of the surfactant in the chemically amplified resist material of the present invention is 2 parts by weight or less, preferably 1 part by weight or less based on 100 parts by weight of the solid content in the resist material composition.

Further, an ultraviolet absorber can be added to the chemically amplified resist material of the present invention. Although not particularly limited, those described in JP-A No. 11-190904 can be used, preferably bis (4-hydroxyphenyl) sulfoxide, bis (4-tert-butoxyphenyl) sulfoxide, bis (4-). tert-
Diaryl sulfoxide derivatives such as butoxycarbonyloxyphenyl) sulfoxide, bis [4- (1-ethoxyethoxy) phenyl] sulfoxide, bis (4-hydroxyphenyl) sulfone, bis (4-tert-butoxyphenyl) sulfone, bis (4- tert-butoxycarbonyloxyphenyl) sulfone, bis [4-
(1-ethoxyethoxy) phenyl] sulfone, bis [4- (1-ethoxypropoxy) phenyl] sulfone and other diarylsulfone derivatives, benzoquinonediazide, naphthoquinonediazide, anthraquinonediazide,
Diazo compounds such as diazofluorene, diazotetralone and diazophenanthrone, complete or partial ester compounds of naphthoquinone-1,2-diazide-5-sulfonic acid chloride and 2,3,4-trihydroxybenzophenone, naphthoquinone-1 , 2-diazido-4-sulfonic acid chloride and quinonediazide group-containing compounds such as complete or partial ester compounds of 2,4,4'-trihydroxybenzophenone, 9-anthracenecarboxylic acid t
tert-Butyl, 9-anthracenecarboxylic acid tert
-Amyl, 9-anthracenecarboxylic acid tert-methoxymethyl, 9-anthracenecarboxylic acid tert-ethoxyethyl, 9-anthracenecarboxylic acid 2-ter
Examples thereof include t-tetrahydropyranyl and 2-tert-tetrahydrofuranyl 9-anthracenecarboxylic acid. The amount of the ultraviolet absorber blended may or may not be added depending on the type of the resist material, but when added, it is 0 to 10 parts by weight, more preferably 0.5 to 100 parts by weight of the base resin. 10 parts by weight, more preferably 1 to 5 parts by weight.

A pattern can be formed by using the resist material of the present invention by using a known lithography technique. For example, a film such as a silicon wafer can be formed by spin coating or the like to a film thickness of 0. .3 to 2.0 μ
m so that it becomes 60 m on a hot plate.
~ 150 ° C, 1 to 10 minutes, preferably 80 to 130
Prebak at 1 ° C for 1 to 5 minutes. Next, a mask for forming a target pattern is held over the resist film, and an ArF excimer laser is used for an exposure amount of 1 to 100 mJ /
cm ^2, preferably about after irradiation so that the 5～50MJ / cm ^2, on a hot plate at 60 to 150
Post exposure bake (PEB) is performed at 1 ° C. for 1 to 5 minutes, preferably 80 to 130 ° C. for 1 to 3 minutes. Furthermore,
0.1 to 5%, preferably 2 to 3% tetramethylammonium hydroxide (TMAH) or the like aqueous alkaline developer is used for 0.1 to 3 minutes, preferably 0.5 to 2
Min., Dip method, paddle method,
A desired pattern is formed on the substrate by developing by a conventional method such as a spray method. If the above range is out of the upper and lower limits, the desired pattern may not be obtained.

[0115]

The resist material containing the acid generator of the present invention is excellent in resolution, thermal stability and storage stability.
The line edge roughness is also small.

[0116]

EXAMPLES The present invention will be specifically described below with reference to Examples and Comparative Examples, but the present invention is not limited to the following Examples. [Synthesis Example 1] Synthesis of 3-phenyl-2-propenylthiacyclopentanium perfluorobutanesulfonate 2.2 g (0.025 mol) of tetrahydrothiophene and 8 g of nitromethane were added to 4.9 g of cinnamyl bromide (0.
(025 mol) was added, and the mixture was stirred at room temperature for 30 minutes. 40 g of water
And 40 g of diethyl ether were added for liquid separation, and 8.5 g of potassium perfluorobutanesulfonate (0.02
5 mol) and 100 g of dichloromethane were added, and the mixture was stirred at room temperature for 1 hour. The separated organic layer was washed 3 times with 50 g of water and then the solvent was removed on a rotary evaporator. The obtained oily substance was recrystallized from diethyl ether, filtered and dried to obtain 10.2 g of the target 3-phenyl-2-propenylthiacyclopentanium perfluorobutanesulfonate (yield 81%).

The results of nuclear magnetic resonance spectrum (NMR), infrared absorption spectrum (IR) and time-of-flight mass spectrometry (TOF-MS) of the obtained sulfonium salt are shown below. ( ¹ H-NMR (CDCl ₃ ); ppm)

[Chemical 27] 2.20-2.45 (4H, m, Ha) 3.45-3.65 (4H, m, Hb) 4.23-4.26 (2H, d, Hc) 6.09-6.19 ( 1H, m, Hd) 6.91-6.97 (1H, d, He) 7.30-7.40 (5H, m, Hf) (IR; cm ^-1 ) 1356, 1273, 1259, 1207, 1190 ，
1132, 1059, 1049, 974, 804, 75
4,737,698,658,638,619,60
0,532,522 (TOF-MS) Positive electrode (+) M ⁺ ; 205 (PhCH = CH-CH ₂ S ⁺ C ₄
Corresponds to H ₈₎ cathode ^{(-) M -; 299 (} C 4 F 9 SO 3 - equivalent to)

[Synthesis Example 2] Synthesis of phenylmethylthiacyclopentanium perfluorobutanesulfonate 8.8 g (0.1 mol) of tetrahydrothiophene and 30 g of nitromethane were added with 8.6 g (0.05 g of benzyl bromide).
Mol) was added and the mixture was stirred at room temperature for 1 hour. 50 g of water and 50 g of diethyl ether were added for liquid separation, and 19.4 g (0.05 mol) of potassium perfluorobutanesulfonate and 100 g of dichloromethane were added to the aqueous layer, followed by stirring at room temperature for 1 hour. The separated organic layer was washed 3 times with 50 g of water,
The solvent was then removed on a rotary evaporator. The obtained oily substance was recrystallized from diethyl ether, filtered and dried to obtain 22.4 g of the desired phenylmethylthiacyclopentanium perfluorobutane sulfonate (yield 94%).

The results of nuclear magnetic resonance spectrum (NMR), infrared absorption spectrum (IR) and time-of-flight mass spectrometry (TOF-MS) of the obtained sulfonium salt are shown below. ( ¹ H-NMR (CDCl ₃ ); ppm)

[Chemical 28] 2.20-2.35 (4H, m, Ha) 3.40-3.60 (4H, m, Hb) 4.63 (2H, s, Hc) 7.34-7.47 (5H, m, Hd) (IR; cm ^-1 ) 1456, 1421, 1356, 1255, 1211
1190, 1134, 1061, 1049, 1004
847, 804, 739, 710, 700, 657, 6
(Corresponding to _{^{Ph-CH 2 S + C 4}} H 8) 179 cathode ^{(-) M -;; 40,619,600,532,523} (TOF-MS) positive ^{(+) M + 299 (C} 4 F 9 SO ₃ ^- equivalent to)

[Synthesis Example 3] Synthesis of sodium 4- (4'-methylphenylsulfonyloxy) benzenesulfonate 208 g (1.0 mol) of 4-phenolsulfonic acid hydrate and 191 g (1 of p-toluenesulfonic acid chloride) ．
0 mol) was dissolved in 400 g of tetrahydrofuran and 250 g of water. An aqueous sodium hydroxide solution (80 g (2.0 mol) of sodium hydroxide and 125
g) was added dropwise at a temperature not exceeding 20 ° C., and after completion of the addition, aging was carried out at room temperature for 2 hours. 700 g of dichloromethane was added to this reaction solution to crystallize sodium 4- (4′-methylphenylsulfonyloxy) benzenesulfonate, and the obtained crystals were filtered.
It was washed with 0 g and dried under reduced pressure at 60 ° C. for 12 hours. Yield 3
30 g (94% yield).

[Synthesis Example 4] Synthesis of 3-phenyl-2-propenylthiacyclopentanium 4- (4-methylphenylsulfonyloxy) benzenesulfonate In place of the potassium perfluorobutanesulfonate used in Synthesis Example 1, a synthesis example The target compound was synthesized in the same manner as in Synthesis Example 1 except that sodium 4- (4′-methylphenylsulfonyloxy) benzenesulfonate of 2 was used.

Synthesis Example 5 Synthesis of 3-phenyl-2-propenylthiacyclopentanium bis (perfluoroethanesulfonyl) imide Instead of potassium perfluorobutanesulfonate used in Synthesis Example 1, bis (perfluoroethanesulfonyl) was used. ) A target compound was synthesized in the same manner as in Synthesis Example 1 except that imide acid was used.

[Synthesis Example 6] Synthesis of phenylmethylthiacyclopentanium bis (perfluoroethanesulfonyl) imide Bis (perfluoroethanesulfonyl) imidic acid is used in place of the potassium perfluorobutanesulfonate used in Synthesis Example 2. The target compound was synthesized in the same manner as in Synthesis Example 2 except for the above.

[Evaluation Example] The photoacid generators (PAG1-10) represented by the following formulas were evaluated for sensitivity and resolution when used as resists.

[0125]

[Chemical 29]

[Examples 1 to 40] Evaluation of resist resolution The photoacid generators (PAG1 to 10) represented by the above formulas were used as acid generators, and the polymers represented by the following formula (Pol) were used.
Ymer1 to 28) as a base resin, and a dissolution inhibitor (DRR1 to 4) represented by the following formula, a basic compound, and an organic acid derivative (ACC1,2) represented by the following formula in the composition shown in the table. 430 (Sumitomo 3M) 0.
A resist material was prepared by dissolving it in a solvent containing 01% by weight, and each composition was further coated with 0.2 μm Teflon (registered trademark).
Each resist solution was prepared by filtering with a filter made by a manufacturer.

[0127]

[Chemical 30]

[0128]

[Chemical 31]

[0129]

[Chemical 32]

[0130]

[Chemical 33]

[0131]

[Chemical 34]

[0132]

[Chemical 35]

ArF Exposure Example For resists using polymers 1-20, ArF
Exposure (wavelength 193 nm) was performed. An antireflection film solution (AR19, Shipley Co., Ltd.) is coated on a silicon substrate, and then 200
Antireflection film (82nm)
(Thickness) Spin coating the resist solution on the substrate,
Bake at 110 ° C for 60 seconds using a hot plate,
A resist film having a film thickness of 300 nm was formed. This is ArF
Excimer laser microstepper (NA made by Nikon Corporation
= 0.55, σ0.7) and exposed at 110 ° C. for 9
Baking (PEB) was performed for 0 seconds, and development was performed for 30 seconds with an aqueous solution of 2.38% tetramethylammonium hydroxide.

The resist was evaluated by setting the exposure amount for resolving the line and space of the 0.20 μm group at 1: 1 as the optimum exposure amount (Eop, mJ / cm ² ), and separating the lines in this exposure amount. The minimum line width (μm) of the AND space is used as the resolution of the evaluation resist, and the line width of the isolated line of the line and space 1:10 with the same exposure amount is measured to change the line width of the group line from the line width of the isolated line. Subtracted value,
The dimensional difference (I / G bias) between the isolated pattern and the dense pattern was used. In addition, the unevenness of the group line was measured and used as the line edge roughness.

The storage stability was judged by the precipitation of foreign matters or the change in sensitivity with the passage of time. Particles can be kept for up to 100 days with a particle counter (KL-20, KL-20
It is preferable that the number of particles of 0.3 μm or more contained in 1 ml of the resist solution in A) is 5 or less, or that the variation with time of the sensitivity (Eop described above) immediately after production is within 5%. And anything more than that was marked as evil.

KrF Exposure Example For the resist using the polymers 21 to 28, KrF is used.
Exposure (wavelength 248 nm) was performed. Antireflection film solution on a silicon substrate (DUV-3 manufactured by Brewer Science Co., Ltd.
0) is applied, and the resist solution is spin-coated on an antireflection film (55 nm film thickness) substrate formed by baking at 200 ° C. for 60 seconds, and then 100 ° C. using a hot plate.
And baked for 60 seconds to form a resist film having a film thickness of 400 nm. This is a KrF excimer laser scanner (Nikon S203B, NA = 0.68 s = 0.75)
Exposure using Bake at 110 ℃ for 90 seconds (PEB)
And developed for 60 seconds with an aqueous solution of 2.38% tetramethylammonium hydroxide.

The resist was evaluated by setting the exposure amount for resolving the 0.18 μm group line and space at 1: 1 as the optimum exposure amount (Eop, mJ / cm ² ), and separating the lines in this exposure amount. The minimum line width (μm) of the AND space is set as the resolution of the evaluation resist, the line width of the isolated line of the line and space 1:10 of the same exposure amount is measured, and the line width of the group line is changed to the line width of the isolated line. Subtracted value,
The dimensional difference (I / G bias) between the isolated pattern and the dense pattern was used. In addition, the unevenness of the group line was measured and used as the line edge roughness.

The storage stability was judged by the precipitation of foreign substances or the change in sensitivity over time. Particles can be kept for up to 100 days with a particle counter (KL-20, KL-20
It is preferable that the number of particles of 0.3 μm or more contained in 1 ml of the resist solution in A) is 5 or less, or that the variation with time of the sensitivity (Eop described above) immediately after production is within 5%. And anything more than that was marked as evil.

The composition of each resist and the evaluation results are shown in Tables 1 and 2.
Shown in. In addition, in Tables 1 and 2, the solvent and the basic compound are as follows. PGMEA: Propylene glycol methyl ether acetate CyHO: Cyclohexanone PG / EL: PGMEA 70% and ethyl lactate 30% mixed solvent TBA: Tributylamine TEA: Triethanolamine TMMEA: Trismethoxymethoxyethylamine TMEMEA: Trismethoxyethoxymethoxyethylamine AAA: Tris ( 2-acetoxyethyl) amine AACN: N, N-bis (2-acetoxyethyl) -3
-Aminopropiononitrile

[Comparative Example] For comparison, the sulfonium salt (PAG6, 7) and the sulfonium salts represented by the following formulas (PAG11 to 13) were evaluated for sensitivity and resolution when used as resists. .

[0141]

[Chemical 36]

[Comparative Examples 1 to 6] The above sulfonium salt (P
AG6, 7 and PAG11 to 13) were used to prepare resists having the compositions shown in Table 3 in the same manner as described above, and the resist was exposed to ArF microstepper in the same manner as described above to obtain sensitivity and resolution,
The storage stability was evaluated.

Table 3 shows the composition of each resist and the evaluation results. From the results of Tables 1, 2 and 3, it was confirmed that the resist material of the present invention had higher sensitivity and higher resolution than the conventional product, and was excellent in line edge roughness and I / G bias.

[0144]

[Table 1]

[0145]

[Table 2]

[0146]

[Table 3]

   ─────────────────────────────────────────────────── ─── Continued front page    (72) Inventor Tsunehiro Nishi             28-1 Nishifukushima, Kubiki Village, Nakakubiki District, Niigata Prefecture             Shin-Etsu Chemical Co., Ltd.Research on new functional materials technology             In-house (72) Inventor Tomohiro Kobayashi             28-1 Nishifukushima, Kubiki Village, Nakakubiki District, Niigata Prefecture             Shin-Etsu Chemical Co., Ltd.Research on new functional materials technology             In-house F term (reference) 2H025 AA02 AB16 AC01 AC03 AC04                       AC05 AC06 AC08 AD03 BE00                       BG00 FA03 FA12 FA17

Claims (12)

[Claims] 1. A photo-acid generator for a chemically amplified resist represented by the following general formula (1). [Chemical 1] (In the formula, R ¹ and R ² may be the same or different,
Number 1-6 straight, branched or cyclic unsubstituted or alkyl group having an oxygen atom, or R ¹ and R ² form a cyclic structure having an unsubstituted or oxygen atom having 4 to 6 carbon atoms May be. R ^3, R ^4, R ⁵ may be the same or different, a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or a substituted or unsubstituted aryl group having 6 to 12 carbon atoms, R ^3, At least one of R ⁴ and R ⁵ has 6 to 1 carbon atoms
2 represents a substituted or unsubstituted aryl group. Y ⁻ is a substituted or unsubstituted alkyl sulfonate having 1 to 10 carbon atoms, a substituted or unsubstituted aryl sulfonate having 6 to 20 carbon atoms, a substituted or unsubstituted bisalkylsulfonylimide having 2 to 10 carbon atoms, or a carbon number 3-12 substituted or unsubstituted trisalkylsulfonylmethides are shown. . ) 2. A photoacid generator for a chemically amplified resist represented by the following general formula (1a). [Chemical 2] (In the formula, R ¹ and R ² have the same meanings as described above. Ya ⁻ is a perfluoroalkyl sulfonate having 1 to 8 carbon atoms, a bis (perfluoroalkylsulfonyl) imide having 2 to 10 carbon atoms, or a carbon number. 3-12 tris (perfluoroalkylsulfonyl) methides are shown.) 3. A photo-acid generator for a chemically amplified resist represented by the following general formula (1b). [Chemical 3] (In the formula, Ya has the same meaning as above. X is CH.
₂ (methylene) or O (oxygen atom) is shown. m is 0 or 1. ) 4. A photoacid generator for a chemically amplified resist represented by the following general formula (2). [Chemical 4] (In the formula, R ¹ , R ² and Y ⁻ have the same meanings as described above. R ⁷
Is a hydrogen atom, a linear, branched or cyclic substituted or unsubstituted alkyl group having 1 to 6 carbon atoms, a linear, branched or cyclic alkoxy group having 1 to 6 carbon atoms, a nitro group, a fluorine atom , Or chlorine atom. n is an integer of 1 to 5. ) 5. A photoacid generator for a chemically amplified resist represented by the following general formula (2a). [Chemical 5] (In the formula, R ¹ , R ² and Ya have the same meanings as described above.) 6. A photoacid generator for a chemically amplified resist represented by the following general formula (2b). [Chemical 6] (In the formula, X, m, and Ya have the same meanings as above.) 7. A chemistry comprising (A) a resin whose solubility in an alkali developing solution is changed by the action of an acid, and (B) a photoacid generator according to any one of claims 1 to 6. Amplified resist material. 8. A chemistry comprising (A) a resin whose solubility in an alkali developing solution is changed by the action of an acid, and (B) a photoacid generator according to any one of claims 1 to 6. Amplified positive resist material. 9. The method according to claim 7, further comprising (C) a compound which generates an acid upon irradiation with radiation, other than the component (B).
The described resist material. 10. The resin of component (A) is C-by the action of acid.
10. The resist material according to claim 7, 8 or 9, which is a resin having a substituent whose solubility in an alkali developing solution changes when the O—C bond is broken. 11. The resist material according to claim 7, further comprising (D) a basic compound. 12. (i) Any one of claims 7 to 11
A step of applying the resist material according to the item 1 above on a substrate,
(Ii) Next, after the heat treatment, a step of exposing with a high-energy beam or an electron beam having a wavelength of 250 nm or less through a photomask, and (iii) a step of performing a heat treatment as necessary and developing with a developing solution. And a pattern forming method comprising: