JP2003261529A - Photo acid generating agent compound, chemical amplification positive type resist material and method for forming pattern - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a high-resolution resist material having high sensitivity and high resolution and small line edge roughness to high energy beam having ≤300 nm wavelength and containing an acid generating agent excellent in heat stability and storage stability, and to provide a pattern-forming method using the resist material. <P>SOLUTION: The chemical amplification positive type resist material comprises a base resin, the acid generating agent generating a fluorine group- containing alkylimidic acid and a solvent. The method for forming the pattern comprises a step for applying the resist material onto a base, a step for exposing the high energy beam having ≤300 nm wavelength through a photo mask after heat treatment to the resist material and a step for heat-treating the exposed material and developing the heat-treated material by a developing agent. <P>COPYRIGHT: (C)2003,JPO

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to an onium salt that generates a specific fluorine group-containing alkylimidic acid, and a resist material for exposure to high energy rays having a wavelength of 300 nm or less, which contains the same, and this resist material. The present invention relates to a pattern forming method using.

[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, for the base resin, poly (meth) acrylic acid and its derivatives, norbornene-maleic anhydride alternating polymer, polynorbornene and metathesis ring-opening polymer, etc. have been proposed, and in terms of increasing the transparency of the resin alone. Has achieved some results. However, with regard to acid generators, increasing the transparency lowers the acid generation efficiency, resulting in low sensitivity, or lacking heat stability and storage stability, which is still not practical. Is not obtained at present.

For example, the alkylsulfonium salts proposed in Patent Document 1, Patent Document 2, Patent Document 3 and the like have very high transparency, but the acid generation efficiency is not sufficient, and the thermal stability is also difficult. Is not preferable. The alkylaryl sulfonium salt proposed in Patent Document 4 and the like has a good balance between transparency and acid generation efficiency and high sensitivity, but lacks heat stability and storage stability. K
The arylsulfonium salt, which was effective in photolithography using rF excimer laser light, has a high acid generation efficiency,
Although it has excellent thermal stability and storage stability, its transparency is extremely low, and the pattern after development has a sharp taper shape.
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 is changed, but there is a close relationship between the type of acid generated and the type of acid labile group in terms of resolution and pattern shape. It has been reported. For example, many studies have been reported on changing the type of acid in polyhydroxystyrene and polyhydroxystyrene / (meth) acrylate copolymer-based resists for KrF lithography. For example, Patent Document 5 reports that a good pattern shape can be obtained when an acid generator that generates camphorsulfonic acid is added. However, the reactivity of acid elimination is low in the polymer for ArF having an alicyclic structure, and even if it is the same as the acid elimination group of polyhydroxystyrene and polyhydroxystyrene / (meth) acrylate copolymer, camphor sulfone The elimination reaction does not proceed with acid. Note that (meth) acrylate means methacrylate and / or acrylate.

On the anion side of the onium salt, a fluorinated alkyl sulfonic acid having a high acidity is mainly applied. As the fluorinated alkyl sulfonic acid, trifluoromethane sulfonic acid, nonafluorobutane sulfonic acid,
Hexadecafluorooctane sulfonic acid may be mentioned.
Moreover, the aryl sulfonic acid which carried out the fluorine substitution or the fluorine alkyl substitution is also mentioned. Specifically, 4-fluorobenzenesulfonic acid, 3-benzenesulfonic acid, 2-
Benzenesulfonic acid, 2,4-difluorobenzenesulfonic acid, 2,3-difluorobenzenesulfonic acid, 3,
4-difluorobenzenesulfonic acid, 2,6-difluorobenzenesulfonic acid, 3,5-difluorobenzenesulfonic acid, 2,3,4-trifluorobenzenesulfonic acid, 3,4,5-trifluorobenzenesulfonic acid,
2,4,6-trifluorobenzenesulfonic acid, 2,
3,4,5,6 pentafluorobenzenesulfonic acid, 4
-Trifluoromethylbenzenesulfonic acid, 5-trifluoromethylbenzenesulfonic acid, 6-trifluoromethylbenzenesulfonic acid, 4-trifluoromethylnaphthyl-2-sulfonic acid and the like can be mentioned.

On the other hand, as the miniaturization is promoted, the line edge roughness and the dimensional difference (I / G bias) between the isolated pattern and the dense pattern have become problems. It is well known that a difference in size between a dense pattern after development and an isolated pattern occurs even if the size on the mask is 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.

For example, in FIG. 1, wavelength 248 nm, NA
The vertical axis represents the dimension of the line when the pitch of the repeating line of 0.18 micron was changed along the horizontal axis under the optical conditions of 0.6 and σ0.75. If the line size is standardized to be 0.18 micron at a pitch of 0.36 micron (0.18 micron line, 0.18 micron space), the size of the optical image becomes thin and thick as the pitch increases. To go. Next, the results of obtaining the resist line dimensions after development are also shown. The resist dimensions and the optical image dimensions are KLA-Tencor (formerly Finli
e Technologies Inc. )) The simulation software PROLIT sold by
H2 Ver. 6.0 was used. The resist size becomes smaller as the pitch increases, and becomes smaller as the acid diffusion increases. The problem of sparse / dense dependence in which the size of an isolated pattern is smaller than that of a dense pattern is becoming more serious. It can be understood from the above simulation results that the method of reducing the acid diffusion is effective as a method of reducing the density dependency.

However, if the acid diffusion is too small, the side wall of the resist pattern after development may have irregularities or skin roughness due to standing waves, or the line edge roughness may increase. For example, the aforementioned KLA-Tencor simulation software PROLITH
Ver. FIG. 2 shows the calculation results of the resist cross-sectional shape of 0.18 μm line and space pattern when the acid diffusion distance was changed on the Si substrate using 6.0. It is shown that the smaller the acid diffusion distance, the more prominent the unevenness of the sidewall due to the standing wave. The line edge roughness observed from the sky SEM shows the same tendency, that is, the line edge roughness increases as the acid diffusion decreases. In order to reduce the roughness of the line, it is common to increase the acid diffusion distance, but this cannot improve the sparse-dense dependence. In FIG.
The larger the acid diffusion distance, the larger the dimensional difference between the dense pattern with a small pitch and the sparse pattern with a large pitch. That is, it is shown that the sparse-dense dependence becomes large. There is a trade-off relationship between the reduction of line edgeness and the reduction of sparse / dense dependence, and it can be considered that it is difficult to achieve both at the same time.

As a method of improving the line edge roughness, there is a method of 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 and the stepper NA is higher, the line pattern is more deformed than normal illumination. Illumination (for example, ring illumination, quadrupole illumination), or a phase shift mask usually has smaller line edge roughness than a Cr mask. There is a correlation between the optical contrast of the line edge of the pattern and the line edge roughness, and the steeper the optical contrast of the line edge, the smaller the line edge roughness. At the exposure wavelength, it is expected that short-wavelength exposure has 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. There is a report that it is excellent (Non-patent document 1). 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.

[0011]

[Patent Document 1] JP-A-7-25846

[Patent Document 2] JP-A-7-28237

[Patent Document 3] Japanese Patent Application Laid-Open No. 8-27102

[Patent Document 4] Japanese Patent Laid-Open No. 10-319581

[Patent Document 5] US Pat. No. 5,744,537

[Non-Patent Document 1] SPIE 3999, 264, (20
01)

[0012]

SUMMARY OF THE INVENTION The present invention has been made in view of the above circumstances, and it is highly sensitive to high energy rays of 300 nm or less, has a high resolution, a small line edge roughness, thermal stability, and storage stability. It is an object of the present invention to provide a novel acid generator having excellent stability, a high resolution resist material containing the same, and a pattern forming method using the resist material.

[0013]

Means for Solving the Problems As a result of intensive studies to achieve the above object, the present inventor generates a fluorine group-containing alkylimidic acid, preferably the following general formula (1):
Alternatively, the sulfonium salt or iodonium salt represented by (2) is highly sensitive to high-energy rays of 300 nm or less and has sufficient thermal stability and storage stability, and a chemistry prepared by blending this It has been found that the amplified positive resist material has high resolution and can improve line edge roughness and sparse / dense dependence, and is extremely effective for precise fine processing.

That is, the present invention provides a photoacid generating compound represented by the general formula (1).

[Chemical 3] (R ¹ is an alkylene group having 2 to 8 carbon atoms, R ² is a single bond, an oxygen atom, a nitrogen atom or an alkylene group having 1 to 4 carbon atoms. R ³ is a linear chain having 1 to 8 carbon atoms. A branched or cyclic alkyl group, or an aryl group having 6 to 10 carbon atoms, the alkyl group having 1 to 4 carbon atoms, the fluorinated alkyl group having 1 to 4 carbon atoms, and the alkoxy group having 1 to 4 carbon atoms groups, fluorinated alkoxy group having 1 to 4 carbon atoms, a nitro group, a cyano group, a fluorine atom, a phenyl group, a substituted phenyl group, an acetyl group, or a benzoyloxy group may be substituted with .Rf1, Rf ₂ Either one or both have 1 to 20 carbon atoms containing at least one or more fluorine atoms.
Is a linear, branched, or cyclic alkyl group, and may contain a hydroxy group, a carbonyl group, an ester group, an ether group, or an aryl group, and only _one of Rf _{1 and} Rf ₂ is at least one. When it is a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms containing the above fluorine atom, the other is a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms. , A hydroxy group, a carbonyl group, an ester group, an ether group, or an aryl group. Rf ₁ and Rf ₂ may combine to form a ring. ) Further, the present invention provides a chemically amplified positive resist composition containing a base resin, an acid generator and a solvent, wherein the acid generator generates a fluorine group-containing alkylimidic acid. Amplified positive resist material,
And a pattern including a step of applying the resist material on a substrate, a step of exposing with a high energy ray having a wavelength of 300 nm or less through a photomask after heat treatment, and a step of developing with a developing solution after heat treatment A forming method is provided.

[0015]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be described in more detail below. The acid generator used in the present invention is characterized by generating a fluorine group-containing alkylimidic acid, and is preferably an onium salt represented by the above general formula (1) or the following general formula (2).

[Chemical 4]

In the general formula (1), R ¹ is preferably an alkylene group having 4 or 5 carbon atoms. General formula (1)
In, R ³ is preferably a phenyl group or a naphthyl group.

In the general formula (1) or (2), Rf1,
One or both of Rf _{2 is} a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms containing at least one fluorine atom, and is a hydroxy group, a carbonyl group, an ester group, an ether group or an aryl group. When Rf ₁ or Rf _{2 is} a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms and containing at least one or more fluorine atom, the other Is a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms and may contain a hydroxy group, a carbonyl group, an ester group, an ether group or an aryl group. Rf ₁ and R
f ₂ may combine with each other to form a ring. R ¹ is the same or non-identical straight-chain, branched or cyclic alkyl group having 1 to 12 carbon atoms, a carbonyl group, an ester group, an ether group,
It may contain a thioether group or a double bond,
Alternatively, it represents an aryl group having 6 to 12 carbon atoms or an aralkyl group having 7 to 20 carbon atoms, M ⁺ represents iodonium or sulfonium, and n is 2 or 3.

The anion moiety in the general formula (1) or (2) is a fluorine group-containing alkylimide anion,
There are various combinations by changing the combination of Rf ₁ and Rf ₂ , and it is not possible to show all of them.
For example, it can be illustrated below.

[0019]

[Chemical 5]

In general, in order to control the acid diffusion distance, it is common to control by the molecular weight of the generated acid. For example, when increasing the acid diffusion distance, an acid generator that generates a sulfonic acid with a short chain length of the perfluoroalkyl group is added, and conversely, when shortening the acid diffusion distance, the chain length of the perfluoroalkyl group is changed. An acid generator that generates long sulfonic acid is added. However, the conventionally used perfluoroalkylsulfonic acid or perfluoroarylsulfonic acid controls the acid diffusion distance by the length of one alkyl group or aryl group, so that the strict acid diffusion distance can be controlled. It was difficult to control.
However, since the fluorine group-containing alkylimidic acid mentioned in the present invention has two alkyl groups, various combinations of two alkyl groups having different chain lengths are possible and strict control of the acid diffusion distance is possible. It was Furthermore,
It was confirmed that the fluorine-containing alkylimidic acid had a shorter acid diffusion distance than the perfluoroalkylsulfonic acid even with the same alkyl chain length.

Specific examples of the onium salt compound represented by the general formula (1) are shown below.

[Chemical 6]

The onium salt of the present invention limits the structure of the acid generated, that is, the anion side, but the cation side is not particularly limited. In the general formula (2), M includes a sulfur atom and an iodine atom, and the general formula (2) can be represented by the general formulas (2) -s and (2) -i. Specifically, the following structures can be exemplified.

[Chemical 7] Here, R ⁵ , R ⁶ and R ⁷ are the same or non-identical carbon atoms 1
To 20 linear, branched or cyclic alkyl group, aryl group or aralkyl group, wherein R ⁵ and R ⁶ or R ⁶ and R ⁷ , R ⁵ and R ⁷ are respectively bonded to form a ring. May be. R ⁸ and R ⁹ are the same or non-identical aryl groups having 6 to 20 carbon atoms, and R ⁸ and R ⁹ may be bonded to each other to form a ring.

Specific examples of the general formula (2) -s include the following structures.

[Chemical 8]

Where R¹¹, R¹², R¹³Independently,
Hydrogen atom, halogen atom, straight chain having 1 to 20 carbon atoms,
Branched or cyclic alkyl group, straight chain having 1 to 20 carbon atoms
-Shaped, branched or cyclic alkoxy groups, having 6 to 2 carbon atoms
An aryl group of 0, or a straight chain having 1 to 20 carbon atoms,
A branched or cyclic alkyl group which is an ester group,
Carbonyl group, alkyl group which may contain lactone ring
is there. R¹⁴, R¹⁵, R ¹⁶Are independently C1-C10
A linear, branched or cyclic alkyl group,
It may contain a ring group, an ester group, or a lactone ring. R
¹⁷Is a methylene group, R¹⁸Is a straight chain of 1 to 10 carbon atoms
A chain, branched or cyclic alkyl group, R¹⁷And R¹⁸
May combine with each other to form a ring. a, b, c are independent
Is an integer of 0-5.

[0025]

[Chemical 9]

[0026]

[Chemical 10]

Specific examples of the general formula (2) -i can include the following structures.

[Chemical 11]

The sulfonium salt represented by the general formula (1) can be synthesized by, for example, a reaction between a thiophene compound and an acetyl bromide compound (Step 1) or an ion exchange reaction (St).
ep2). In Step 1, the reaction is completed by stirring in nitromethane at room temperature for several hours. The amounts of thiophene compound and acetyl bromide compound are equimolar. The compound 1 obtained is washed with diethyl ether and water and extracted into the aqueous phase. Next, a fluorine group-containing imide acid is added in an equimolar amount to the compound 1, dichloromethane or chloroform is added, and anion exchange is performed while stirring at room temperature for several minutes to several tens of minutes to extract the organic phase of the final compound. The final phase is obtained by concentrating the organic phase, crystallizing with diethyl ether and purifying.

[0029]

[Chemical 12]

The amount of the onium salt represented by the above formula (1) or (2) is preferably 0.1 to 15 parts by weight, more preferably 0.5 to 10 parts by weight, based on 100 parts by weight of the base resin.
If the blending amount is too small, the sensitivity may be low, and if it is too large, the transparency may be lowered and the resolution performance of the resist material may be lowered.

The base resin used in the present invention is preferably insoluble or sparingly soluble in a developing solution and made soluble in the developing solution by an acid. Insoluble or sparingly soluble in a developing solution means that the solubility in a 2.38 wt% TMAH (tetramethylammonium hydroxide) aqueous solution is 0 to 2
It is 0Å / sec, and the solubility in the developing solution is 20 to 300Å / sec.

The base resin used in the chemically amplified positive resist composition of the present invention includes polyhydroxystyrene and a polyhydroxystyrene derivative in which a part or all of the hydroxyl groups thereof are substituted with an acid labile group, poly (meth) acryl. Acids and esters thereof (including copolymers of acrylic acid and methacrylic acid and esters thereof), copolymers of cycloolefin and maleic anhydride, copolymers of cycloolefin and maleic anhydride and acrylic acid ester, cycloolefin And maleic anhydride and methacrylic acid copolymer, cycloolefin and maleic anhydride and acrylic acid ester and methacrylic acid ester copolymer, cycloolefin and maleimide copolymer, cycloolefin and maleimide and acrylic acid ester copolymer With copolymer, cycloolefin One or more high molecular weight polymers selected from the group consisting of a copolymer of reimide and methacrylic acid ester, a copolymer of cycloolefin, maleimide, acrylic acid ester and methacrylic acid ester, polynorbornene, and metathesis ring-opening polymer. An example is coalescence. The base resin used in the present invention is preferably polyhydroxystyrene (PHS), a hydroxystyrene in which a part or all of the hydroxyl groups are substituted with an acid labile group, and styrene for a resist for KrF excimer laser. Copolymers, copolymers of hydroxystyrene and (meth) acrylic acid ester, copolymers of hydroxystyrene and maleimide N carboxylic acid ester, and resists for ArF excimer laser include poly (meth) acrylic acid ester-based, norbornene And maleic anhydride alternating copolymerization system, tetracyclododecene and maleic anhydride alternating copolymerization system, polynorbornene system, metathesis polymerization system by ring-opening polymerization, but are limited to these polymerized polymers. There is no such thing. In the case of a positive type resist, it is general that the dissolution rate of the unexposed portion is reduced by substituting the hydroxyl group of the phenol or carboxyl group with an acid labile group. The acid labile group in the base polymer is selected variously, but in particular, the following formula (AL10),
A group represented by (AL11), a tertiary alkyl group having 4 to 40 carbon atoms represented by the following formula (AL12), a trialkylsilyl group having 1 to 6 carbon atoms, an oxoalkyl group having 4 to 20 carbon atoms, and the like. It is preferable. In addition, (meth) acrylic acid means methacrylic acid and / or acrylic acid.

[0033]

[Chemical 13]

R in the formulas (AL10) and (AL11)
¹⁹ , R ²² is independently a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms and may contain a hetero atom such as oxygen, sulfur, nitrogen or fluorine. R ²⁰ and R ²¹ are independently a hydrogen atom, a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms, and may contain a hetero atom such as oxygen, sulfur, nitrogen or fluorine, d is an integer of 0-10. R ²⁰ and R ²¹ , R ²⁰ and R ²² , and R ²¹ and R ²² may be bonded to each other to form a ring.

Specific examples of the compound represented by the formula (AL10) include tert-butoxycarbonyl group and te.
rt-butoxycarbonylmethyl group, tert-amyloxycarbonyl group, tert-amyloxycarbonylmethyl group, 1-ethoxyethoxycarbonylmethyl group, 2
-Tetrahydropyranyloxycarbonylmethyl group, 2
-Tetrahydrofuranyloxycarbonylmethyl group, etc.
Further, the following general formulas (AL10) -1 to (AL10) -10
And a substituent represented by.

[0036]

[Chemical 14]

Formulas (AL10) -1 to (AL10) -10
Wherein R ²⁶ is the same or non-identical straight chain having 1 to 8 carbon atoms,
A branched or cyclic alkyl group, or 6 to 2 carbon atoms
0 represents an aryl group or an aralkyl group. R ²⁷ is absent or represents a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms. R ²⁸ represents an aryl group or an aralkyl group having 6 to 20 carbon atoms. d is an integer of 0-6.

Examples of the acetal compound represented by the formula (AL11) are (AL11) -1 to (AL11) -23.

[0039]

[Chemical 15]

Further, one of the hydrogen atoms of the hydroxyl group of the base resin is
% Or more is general formula (AL11a) or (AL11b)
It may be crosslinked intermolecularly or intramolecularly with an acid labile group represented by.

[0041]

[Chemical 16]

In the formula, R ²⁹ and R ^{30 each} independently represent a hydrogen atom or a linear, branched or cyclic alkyl group having 1 to 8 carbon atoms. Alternatively, R ²⁹ and R ³⁰ may combine to form a ring, and in the case of forming a ring, R ²⁹ and R ³⁰ have 1 carbon atoms.
The straight-chain or branched alkylene groups of -8 are shown. R
³¹ is a linear, branched or cyclic alkylene group having 1 to 10 carbon atoms. f is an integer of 0-10. A is e
+1 represents an aliphatic or alicyclic saturated hydrocarbon group having 1 to 50 carbon atoms, an aromatic hydrocarbon group or a heterocyclic group, and these groups may have a heteroatom therebetween, or at the carbon atom thereof. A part of the hydrogen atoms bonded may be substituted with a hydroxyl group, a carboxyl group, a carbonyl group or a fluorine atom. B represents -CO-O-, -NHCO-O- or NHCONH-. e is an integer of 1 to 7.

General formulas (AL11-a), (AL11-
The cross-linking acetal shown in b) can be specifically mentioned in the following (AL11) -24 to (AL11) -31.

[0044]

[Chemical 17]

The tertiary alkyl group represented by the formula (AL12) includes tert-butyl group, triethylcarbyl group, 1-ethylnorbornyl group, 1-methylcyclohexyl group, 1-ethylcyclopentyl group, 2- ( 2-methyl) adamantyl group, 2- (2-ethyl) adamantyl group, tert-amyl group or the like or the following general formula (AL1
2) -1 to (AL12) -18 can be mentioned.

[0046]

[Chemical 18]

In the above formula, R ³² represents the same or non-identical straight-chain, branched or cyclic alkyl group having 1 to 8 carbon atoms, or an aryl group or aralkyl group having 6 to 20 carbon atoms. R ³³ and R ³⁵ are absent or independently represent a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms. R ³⁴ represents an aryl group or an aralkyl group having 6 to 20 carbon atoms.

[0048]

[Chemical 19]

Further, (AL12) -19, (AL12)-
As shown in 20, the polymer may be crosslinked in the molecule or between the molecules by including R ³⁶ which is a divalent or higher valent alkylene group or arylene group. R in formula (12) -19
³² is the same as above, R ³⁶ is a straight chain having 1 to 20 carbon atoms,
It represents a branched or cyclic alkylene group or an arylene group, and may contain a hetero atom such as an oxygen atom, a sulfur atom, or a nitrogen atom. g is an integer of 1 to 3.

Further, R ³² , R ³³ , R ³⁴ and R ³⁵ are oxygen,
It may have a hetero atom such as nitrogen or sulfur, and specifically, it can be shown in the following (13) -1 to (13) -7.

[0051]

[Chemical 20]

The base resin used in the present invention is preferably a polymer structure containing a silicon atom. As the silicon-containing polymer, a polymer containing silicon as an acid labile group is first mentioned. Examples of the acid labile group containing silicon include trialkylsilyl groups having 1 to 6 carbon atoms, such as trimethylsilyl group, triethylsilyl group and dimethyl-tert-butylsilyl group. Also,
The following silicon-containing acid labile groups can be used.

[0053]

[Chemical 21] In the above formula, R ³⁷ and R ³⁸ are independently a hydrogen atom or a carbon number of 1.
To 20 alkyl groups. R ³⁹ , R ⁴⁰ and R ⁴¹ are the same or non-identical C 1-20 alkyl group or haloalkyl group, C 6-20 aryl group, or a silicon atom in the formula with a siloxane bond or a silethylene bond. It is a silicon-containing group or a trimethylsilyl group which is bonded. R ³⁷ and R ³⁸ may combine with each other to form a ring.

Specific examples of (A-4), (A-5) and (A-6) are shown below.

[0055]

[Chemical formula 22]

The general formula (A-7) or (A-
A cyclic silicon-containing acid labile group represented by 8) can also be used.

[Chemical formula 23]

Here, R ⁴² and R ⁵⁴ independently have 1 carbon atom.
To 20 linear, branched or cyclic alkyl groups.
^{R 43, R 44, R 47} , R 48, R 51, R 52, R 53 are independently hydrogen atom or a straight, a branched or cyclic alkyl group. R ⁴⁵ , R ⁴⁶ , R ⁴⁹ , R
⁵⁰ is a hydrogen atom, a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms, a fluorinated alkyl group having 1 to 20 carbon atoms, or an aryl group having 6 to 20 carbon atoms.
p, q, r, and s are integers of 0 to 10, and 1 ≦ p + q
+ S ≦ 20.

Specific examples of (A-7) and (A-8) can be shown below.

[0059]

[Chemical formula 24]

Examples of the trialkylsilyl group having an acid labile group having 1 to 6 carbon atoms include trimethylsilyl group, triethylsilyl group and dimethyl-tert-butylsilyl group.

Secondly, as the silicon-containing polymer used in the present invention, an acid-stable silicon-containing repeating unit can be used. The acid-containing stable silicon-containing repeating unit can be shown below.

[0062]

[Chemical 25]

Here, R ⁵⁵ is a hydrogen atom, a methyl group, a fluorine atom or a trifluoromethyl group, and R ⁵⁶ is a divalent hydrocarbon group having 3 to 10 carbon atoms. R ⁵⁷ , R ⁵⁸ ,
R ⁵⁹ is the same or non-identical hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an aryl group, an alkyl group containing a fluorine atom, a hydrocarbon group containing a silicon atom, or a group containing a siloxane bond, R ⁵⁷ And R ⁵⁸ , R ⁵⁸ and R ⁵⁹ , or R ⁵⁷ and R
⁵⁹ may be bonded to each other to form a ring. R ²⁵ is a single bond or an alkylene group having 1 to 4 carbon atoms. h is 0 or 1. For example, a more specific example of (9) -5 is as follows.

[0064]

[Chemical formula 26]

[0065]

[Chemical 27]

The base resin used in the present invention is not limited to one kind, and may be two or more kinds of polymer compounds. 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 molecular weight of the polymer compound used for the base resin can be determined in terms of polystyrene using gas permeation chromatography (GPC). The preferred weight average molecular weight is 5,000 to 100,000. If it is less than 5,000, the film formability and resolution may be inferior.
If it exceeds 000, the resolution may be poor. The same applies to the preferred weight average molecular weight range of the silicon-containing polymer when the silicon-containing polymer is used as the base resin.

The resist composition of the present invention may contain a conventionally proposed acid generator different from the sulfonium salt and iodonium salt represented by the above general formula (1). Examples of the compound to be added as the acid generator include i. An onium salt of the following general formula (P1a-1), (P1a-2) or (P1b), ii. A diazomethane derivative represented by the following general formula (P2), iii. A glyoxime derivative represented by the following general formula (P3), iv. A bissulfone derivative represented by the following general formula (P4), v. A sulfonic acid ester of an N-hydroxyimide compound represented by the following general formula (P5), vi. β-ketosulfonic acid derivative, vii. A disulfone derivative, viii. A nitrobenzyl sulfonate derivative, ix. Examples thereof include sulfonate ester derivatives.

[0068]

[Chemical 28] (In the above formula, R ^101a , R ^101b and R ^101c are each independently a linear, branched or cyclic alkyl group, alkenyl group, oxoalkyl group or oxoalkenyl group having 1 to 12 carbon atoms, and It represents an aryl group having 6 to 20, an aralkyl group having 7 to 12 carbon atoms or an aryloxoalkyl group, and some or all of the hydrogen atoms of these groups may be substituted with an alkoxy group, etc. Further, R
^101b and R ^{10 1c} and may also form a ring, when they form a ring, each R ^101b, R ^101c are alkylene groups of 1 to 6 carbon atoms. K ⁻ represents a non-nucleophilic counter ion other than (1), (2) and (3). )

The above R ^101a , R ^101b and R ^101c may be the same or different from each other. Specifically, examples of the alkyl group include a methyl group, an ethyl group, a propyl group, an isopropyl group and n-butyl. Group, sec-butyl group, tert
-Butyl group, pentyl group, hexyl group, heptyl group, octyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclopropylmethyl group, 4-methylcyclohexyl group, cyclohexylmethyl group, norbornyl group, adamantyl group and the like. . Examples of the alkenyl group include a vinyl group, an allyl group, a propenyl group, a butenyl group, a hexenyl group and a cyclohexenyl group. Examples of the oxoalkyl group include a 2-oxocyclopentyl group and a 2-oxocyclohexyl group.
-Oxopropyl group, 2-cyclopentyl-2-oxoethyl group, 2-cyclohexyl-2-oxoethyl group,
Examples thereof include a 2- (4-methylcyclohexyl) -2-oxoethyl group. Examples of the aryl group include phenyl group, naphthyl group, p-methoxyphenyl group, m
-Methoxyphenyl group, o-methoxyphenyl group, ethoxyphenyl group, p-tert-butoxyphenyl group,
Alkoxyphenyl group such as m-tert-butoxyphenyl group, 2-methylphenyl group, 3-methylphenyl group, 4-methylphenyl group, ethylphenyl group, 4-t
ert-butylphenyl group, 4-butylphenyl group, alkylphenyl group such as dimethylphenyl group, alkylnaphthyl group such as methylnaphthyl group, ethylnaphthyl group, alkoxynaphthyl group such as methoxynaphthyl group and ethoxynaphthyl group, dimethylnaphthyl group And a dialkylnaphthyl group such as a diethylnaphthyl group, a dialkoxynaphthyl group such as a dimethoxynaphthyl group, and a diethoxynaphthyl group. Examples of the aralkyl group include a benzyl group, a phenylethyl group and a phenethyl group. As the aryloxoalkyl group, a 2-phenyl-2-oxoethyl group, a 2- (1-naphthyl) -2-oxoethyl group, 2
Examples thereof include 2-aryl-2-oxoethyl groups such as-(2-naphthyl) -2-oxoethyl group. As the non-nucleophilic counter ion of K ⁻ , chloride ion, halide ion such as bromide ion, triflate, fluoroalkyl sulfonate such as 1,1,1-trifluoroethane sulfonate, nonafluorobutane sulfonate, tosylate, benzene sulfonate. Examples include aryl sulfonates such as 4-fluorobenzene sulfonate and 1,2,3,4,5-pentafluorobenzene sulfonate, and alkyl sulfonates such as mesylate and butane sulfonate.

[0070]

[Chemical 29] (In the above formula, R ^102a and R ^102b each independently represent a linear, branched or cyclic alkyl group having 1 to 8 carbon atoms.
R ¹⁰³ represents a linear, branched or cyclic alkylene group having 1 to 10 carbon atoms. R ^104a and R ^104b each independently represent a 2-oxoalkyl group having 3 to 7 carbon atoms. K ^-
Represents a non-nucleophilic counter ion. )

Specific examples of R ^102a and R ^102b include methyl group, ethyl group, propyl group, isopropyl group and n-
Examples thereof include a butyl group, a sec-butyl group, a tert-butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a cyclopentyl group, a cyclohexyl group, a cyclopropylmethyl group, a 4-methylcyclohexyl group and a cyclohexylmethyl group. R ¹⁰³ is a methylene group,
Ethylene group, propylene group, butylene group, pentylene group, hexylene group, heptylene group, octylene group, nonylene group, 1,4-cyclohexylene group, 1,2-cyclohexylene group, 1,3-cyclopentyl group Len group, 1,4-
Examples thereof include a cyclooctylene group and a 1,4-cyclohexanedimethylene group. ^{Examples of} R ^104a and R ^104b include a 2-oxopropyl group, a 2-oxocyclopentyl group, a 2-oxocyclohexyl group, and a 2-oxocycloheptyl group. K ^- is represented by the formulas (P1a-1) and (P1a-
The same thing as what was demonstrated by 2) can be mentioned.

[0072]

[Chemical 30] (In the above formula, R ¹⁰⁵ and R ¹⁰⁶ are independently a linear, branched or cyclic alkyl group having 1 to 12 carbon atoms or a halogenated alkyl group, an aryl group having 6 to 20 carbon atoms or an aryl halide. A group or an aralkyl group having 7 to 12 carbon atoms is shown.)

Examples of the alkyl group for R ¹⁰⁵ and R ¹⁰⁶ include 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 pentyl group, a hexyl group, a heptyl group, Examples thereof include an octyl group, an amyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a norbornyl group and an adamantyl group. As the halogenated alkyl group, trifluoromethyl group, 1,1,1-trifluoroethyl group, 1,1,1
-Trichloroethyl group, nonafluorobutyl group, etc. are mentioned. As the aryl group, a phenyl group, a p-methoxyphenyl group, an m-methoxyphenyl group, an o-methoxyphenyl group, an ethoxyphenyl group, an alkoxyphenyl group such as a p-tert-butoxyphenyl group and an m-tert-butoxyphenyl group, Examples thereof include alkylphenyl groups such as 2-methylphenyl group, 3-methylphenyl group, 4-methylphenyl group, ethylphenyl group, 4-tert-butylphenyl group, 4-butylphenyl group and dimethylphenyl group. Examples of the halogenated aryl group include fluorophenyl group, chlorophenyl group, 1,2,3,4,5
-Pentafluorophenyl group and the like. Examples of the aralkyl group include a benzyl group and a phenethyl group.

[0074]

[Chemical 31] (In the above formula, R ¹⁰⁷ , R ¹⁰⁸ , and R ¹⁰⁹ independently have 1 carbon atom.
To C12 linear, branched or cyclic alkyl group or halogenated alkyl group, C6 to C20 aryl group or halogenated aryl group, or C7 to C12
The aralkyl group of is shown. R ¹⁰⁸ and R ¹⁰⁹ may combine with each other to form a ring structure, and in the case of forming a ring structure,
R ¹⁰⁸ and R ¹⁰⁹ each represent a linear or branched alkylene group having 1 to 6 carbon atoms. )

Examples of the alkyl group, halogenated alkyl group, aryl group, halogenated aryl group and aralkyl group for R ¹⁰⁷ , R ¹⁰⁸ and R ¹⁰⁹ include the same groups as those described for R ¹⁰⁵ and R ¹⁰⁶ . ^Examples of the alkylene group for R ¹⁰⁸ and R ¹⁰⁹ include a methylene group, an ethylene group, a propylene group, a butylene group and a hexylene group.

[0076]

[Chemical 32] (In the above formula, R ^101a and R ^101b are the same as above.)

[0077]

[Chemical 33]

(In the above formula, R ¹¹⁰ is an arylene group having 6 to 10 carbon atoms, an alkylene group having 1 to 6 carbon atoms or 2 carbon atoms.
To 6 alkenylene groups, and a part or all of the hydrogen atoms of these groups are further a straight-chain or branched alkyl group having 1 to 4 carbon atoms, a straight-chain or branched alkyl group having 1 to 4 carbon atoms. It may be substituted with an alkoxy group, a nitro group, an acetyl group or a phenyl group. R ¹¹¹ has 1 to 8 carbon atoms
Linear, branched or substituted alkyl group having 1 carbon atom
To a linear, branched or substituted alkenyl group having 1 to 8 carbon atoms, a linear, branched or substituted alkoxyalkyl group having 1 to 8 carbon atoms, a phenyl group, or a naphthyl group. Some or all of them have 1 to 4 carbon atoms.
Or an alkoxy group having 1 to 4 carbon atoms; or an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a phenyl group which may be substituted with a nitro group or an acetyl group; 3-5 heteroaromatic groups;
Alternatively, it may be substituted with a chlorine atom or a fluorine atom. )

Here, as the arylene group of R ¹¹⁰ ,
1,2-phenylene group, 1,8-naphthylene group and the like, and as the alkylene group, methylene group, 1,2-ethylene group, 1,3-propylene group, 1,4-butylene group, 1-
Phenyl-1,2-ethylene group, norbornane-2,3
Examples of the alkenylene group such as -diyl group include 1,2-vinylene group, 1-phenyl-1,2-vinylene group, and 5-norbornene-2,3-diyl group. R ¹¹¹
As the alkyl group of R ^{101a to} R ^101c, and as the alkenyl group, vinyl group, 1-propenyl group, allyl group, 1-butenyl group, 3-butenyl group, isoprenyl group, 1-pentenyl group. , 3-pentenyl group, 4
-Pentenyl group, dimethylallyl group, 1-hexenyl group, 3-hexenyl group, 5-hexenyl group, 1-heptenyl group, 3-heptenyl group, 6-heptenyl group, 7-octenyl group and the like are alkoxyalkyl groups. , Methoxymethyl group, ethoxymethyl group, propoxymethyl group, butoxymethyl group, pentyloxymethyl group, hexyloxymethyl group, heptyloxymethyl group, methoxyethyl group, ethoxyethyl group, propoxyethyl group, butoxyethyl group, pliers Roxyethyl group, hexyloxyethyl group, methoxypropyl group, ethoxypropyl group, propoxypropyl group, butoxypropyl group, methoxybutyl group, ethoxybutyl group, propoxybutyl group, methoxypentyl group, ethoxypentyl group, methoxyhexyl group, methoxy Heptyl Etc. The.

The number of carbon atoms which may be further substituted is 1
As the alkyl group of 4 to 4, a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a tert-butyl group and the like, and as an alkoxy group having 1 to 4 carbon atoms, a methoxy group, ethoxy group. A group, a propoxy group, an isopropoxy group, an n-butoxy group, an isobutoxy group, a tert-butoxy group and the like are substituted with an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a nitro group or an acetyl group. As the phenyl group which may be present, a phenyl group, a tolyl group, a p-tert-butoxyphenyl group, a p-acetylphenyl group, a p-nitrophenyl group and the like are listed as a heteroaromatic group having 3 to 5 carbon atoms. Examples thereof include pyridyl group and furyl group.

Specifically, as onium salts, for example, diphenyliodonium trifluoromethanesulfonate,
Trifluoromethanesulfonic acid (p-tert-butoxyphenyl) phenyliodonium, p-toluenesulfonic acid diphenyliodonium, p-toluenesulfonic acid (p-tert-butoxyphenyl) phenyliodonium, trifluoromethanesulfonic acid triphenylsulfonium, trifluoromethanesulfone Acid (p-te
rt-Butoxyphenyl) diphenylsulfonium, bis (p-tert-butoxyphenyl) phenylsulfonium trifluoromethanesulfonate, tris (p-tert-butoxyphenyl) sulfonium trifluoromethanesulfonate, triphenylsulfonium p-toluenesulfonate, p- Toluenesulfonic acid (p-ter
t-butoxyphenyl) diphenylsulfonium, p-
Bis (p-tert-butoxyphenyl) phenylsulfonium toluenesulfonate, tris (p-tert-butoxyphenyl) sulfonium p-toluenesulfonate, triphenylsulfonium nonafluorobutanesulfonate, triphenylsulfonium butanesulfonate,
Trimethylsulfonium trifluoromethanesulfonate, trimethylsulfonium p-toluenesulfonate,
Cyclohexylmethyl (2-oxocyclohexyl) sulfonium trifluoromethanesulfonate, cyclohexylmethyl (2-oxocyclohexyl) sulfonium p-toluenesulfonate, dimethylphenylsulfonium trifluoromethanesulfonate, dimethylphenylsulfonium p-toluenesulfonate, trifluoromethanesulfonic acid Dicyclohexylphenylsulfonium, dicyclohexylphenylsulfonium p-toluenesulfonate, trinaphthylsulfonium trifluoromethanesulfonate, cyclohexylmethyl (2-oxocyclohexyl) sulfonium trifluoromethanesulfonate, (2-norbonyl) methyl trifluoromethanesulfonate (2-oxocyclohexyl) ) Sulfonium, ethylene bis [meth] (2-oxo-cyclopentyl) sulfonium trifluoromethanesulfonate],
1,2'-naphthylcarbonylmethyl tetrahydrothiophenium triflate and the like can be mentioned.

As the diazomethane derivative, bis (benzenesulfonyl) diazomethane, bis (p-toluenesulfonyl) diazomethane, bis (xylenesulfonyl) diazomethane, bis (cyclohexylsulfonyl) diazomethane, bis (cyclopentylsulfonyl) diazomethane, bis (n-butylsulfonyl) ) Diazomethane, bis (isobutylsulfonyl) diazomethane, bis (sec
-Butylsulfonyl) diazomethane, bis (n-propylsulfonyl) diazomethane, bis (isopropylsulfonyl) diazomethane, bis (tert-butylsulfonyl) diazomethane, bis (n-amylsulfonyl) diazomethane, bis (isoamylsulfonyl) diazomethane, bis (sec) -Amylsulfonyl) diazomethane,
Bis (tert-amylsulfonyl) diazomethane, 1
-Cyclohexylsulfonyl-1- (tert-butylsulfonyl) diazomethane, 1-cyclohexylsulfonyl-1- (tert-amylsulfonyl) diazomethane, 1-tert-amylsulfonyl-1- (tert
-Butylsulfonyl) diazomethane and the like.

As a glyoxime derivative, bis-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- (p-toluenesulfonyl) -2-methyl-3,4-pentanedione glyoxime, bis-O- (n-butanesulfonyl) ) -Α-Dimethylglyoxime, bis-O- (n-butanesulfonyl)
-Α-diphenylglyoxime, bis-O- (n-butanesulfonyl) -α-dicyclohexylglyoxime,
Bis-O- (n-butanesulfonyl) -2,3-pentanedione glyoxime, bis-O- (n-butanesulfonyl) -2-methyl-3,4-pentanedione glyoxime, bis-O- (methane Sulfonyl) -α-dimethylglyoxime, bis-O- (trifluoromethanesulfonyl) -α-dimethylglyoxime, bis-O- (1,
1,1-trifluoroethanesulfonyl) -α-dimethylglyoxime, bis-O- (tert-butanesulfonyl) -α-dimethylglyoxime, bis-O- (perfluorooctanesulfonyl) -α-dimethylglyoxime, Bis-O- (cyclohexanesulfonyl) -α-
Dimethylglyoxime, bis-O- (benzenesulfonyl) -α-dimethylglyoxime, bis-O- (p-fluorobenzenesulfonyl) -α-dimethylglyoxime, bis-O- (p-tert-butylbenzenesulfonyl) -Α-dimethylglyoxime, bis-O- (xylenesulfonyl) -α-dimethylglyoxime, bis-
Examples thereof include O- (camphorsulfonyl) -α-dimethylglyoxime.

As the bissulfone derivative, bisnaphthylsulfonylmethane, bistrifluoromethylsulfonylmethane, bismethylsulfonylmethane, bisethylsulfonylmethane, bispropylsulfonylmethane, bisisopropylsulfonylmethane, bis-p-toluenesulfonylmethane, bisbenzenesulfonylmethane. Etc.

As the β-ketosulfone derivative, 2-cyclohexylcarbonyl-2- (p-toluenesulfonyl) propane, 2-isopropylcarbonyl-2- (p
-Toluenesulfonyl) propane and the like.

Examples of the disulfone derivative include diphenyldisulfone and dicyclohexyldisulfone.

Examples of the nitrobenzyl sulfonate derivative include 2,6-dinitrobenzyl p-toluenesulfonate and 2,4-dinitrobenzyl p-toluenesulfonate.

As the sulfonate derivative, 1,
2,3-tris (methanesulfonyloxy) benzene,
1,2,3-tris (trifluoromethanesulfonyloxy) benzene, 1,2,3-tris (p-toluenesulfonyloxy) benzene and the like can be mentioned.

As the sulfonic acid ester derivative of the N-hydroxyimide compound, N-hydroxysuccinimide methanesulfonic acid ester, N-hydroxysuccinimide trifluoromethanesulfonic acid ester, N-hydroxysuccinimide ethanesulfonic acid ester, N-
Hydroxysuccinimide 1-propanesulfonic acid ester, N-hydroxysuccinimide 2-propanesulfonic acid ester, N-hydroxysuccinimide 1-pentanesulfonic acid ester, N-hydroxysuccinimide 1-octanesulfonic acid ester, N-hydroxysuccinimide p-toluene sulfone Acid ester, N-
Hydroxysuccinimide p-methoxybenzenesulfonic acid ester, N-hydroxysuccinimide 2-chloroethanesulfonic acid ester, N-hydroxysuccinimide benzenesulfonic acid ester, N-hydroxysuccinimide 2,4,6-trimethylbenzenesulfonic acid ester, N-hydroxysuccinimide 1-naphthalenesulfonic acid ester, N-hydroxysuccinimide 2-naphthalenesulfonic acid ester, N-hydroxy-2-phenylsuccinimide methanesulfonic acid ester, N-hydroxymaleimide methanesulfonic acid ester, N-hydroxymaleimidoethanesulfonic acid ester, N -Hydroxy-2-phenylmaleimide methanesulfonate, N-hydroxyglutarimide methanesulfonate Le, N- hydroxy glutarimide benzenesulfonate ester, N- hydroxyphthalimide methanesulfonate ester, N- hydroxyphthalimide benzenesulfonate ester, N- hydroxyphthalimide trifluoromethanesulfonate ester, N
-Hydroxyphthalimide p-toluenesulfonic acid ester, N-hydroxynaphthalimide methanesulfonic acid ester, N-hydroxynaphthalimidebenzenesulfonic acid ester, N-hydroxy-5-norbornene-
2,3-Dicarboximidomethanesulfonic acid ester, N-hydroxy-5-norbornene-2,3-dicarboximidotrifluoromethanesulfonic acid ester, N-hydroxy-5-norbornene-2,3-dicarboximide p- Examples thereof include toluene sulfonic acid ester.

Preferably, triphenylsulfonium trifluoromethanesulfonate, (p-tert-butoxyphenyl) diphenylsulfonium trifluoromethanesulfonate, tris (p-tert-butoxyphenyl) sulfonium trifluoromethanesulfonate, p
-Triphenylsulfonium Toluenesulfonate, p-
Toluenesulfonate (p-tert-butoxyphenyl) diphenylsulfonium, p-toluenesulfonate tris (p-tert-butoxyphenyl) sulfonium, trifluoromethanesulfonate trinaphthylsulfonium, trifluoromethanesulfonate cyclohexylmethyl (2-oxocyclohexyl) Sulfonium, (2-norbornyl) methyl (2-oxocyclohexyl) sulfonium trifluoromethanesulfonate, 1,2 ′
-Onium salts such as naphthylcarbonylmethyltetrahydrothiophenium triflate, bis (benzenesulfonyl) diazomethane, bis (p-toluenesulfonyl)
Diazomethane, bis (cyclohexylsulfonyl) diazomethane, bis (n-butylsulfonyl) diazomethane, bis (isobutylsulfonyl) diazomethane, bis (sec-butylsulfonyl) diazomethane, bis (n
-Propylsulfonyl) diazomethane, bis (isopropylsulfonyl) diazomethane, bis (tert-butylsulfonyl) diazomethane and other diazomethane derivatives,
Bis-O- (p-toluenesulfonyl) -α-dimethylglyoxime, bis-O- (n-butanesulfonyl)-
Glyoxime derivatives such as α-dimethylglyoxime, bissulfone derivatives such as bisnaphthylsulfonylmethane,
N-hydroxysuccinimide methanesulfonic acid ester, N-hydroxysuccinimide trifluoromethanesulfonic acid ester, N-hydroxysuccinimide 1
-Propanesulfonic acid ester, N-hydroxysuccinimide 2-propanesulfonic acid ester, N-hydroxysuccinimide 1-pentanesulfonic acid ester,
Sulfonic acid ester derivatives of N-hydroxyimide compounds such as N-hydroxysuccinimide p-toluenesulfonic acid ester, N-hydroxynaphthalimide methanesulfonic acid ester and N-hydroxynaphthalimidebenzenesulfonic acid ester are used.

The above-mentioned acid generators may be used alone or in combination.
A combination of two or more species can be used. Since the onium salt is excellent in the rectangularity improving effect and the diazomethane derivative and the glyoxime derivative are excellent in the standing wave reducing effect, it is possible to finely adjust the profile by combining them.

The amount of the acid generator added is preferably 0.1 to 15 parts by weight, more preferably 0.5 to 100 parts by weight as the total amount of the sulfonium salt of the formula (1). ~ 8 parts by weight. If it is less than 0.1 parts by weight, the sensitivity may be low, and if it is more than 15 parts by weight, the transparency may be lowered and the resolution performance of the resist material may be lowered.

The organic solvent used in the present invention may be any organic solvent in which the base resin, the acid generator, other additives and the like can be dissolved. Examples of such an organic solvent include ketones such as cyclohexanone and methyl-2-n-amyl ketone, 3-methoxybutanol, and 3
-Methyl-3-methoxybutanol, 1-methoxy-2
-Alcohols such as propanol and 1-ethoxy-2-propanol, propylene glycol monomethyl ether, ethylene glycol monomethyl ether, propylene glycol monoethyl ether, ethylene glycol monoethyl ether, propylene glycol dimethyl ether, diethylene glycol dimethyl ether and other ethers, propylene glycol Monomethyl ether acetate, propylene glycol monoethyl ether acetate, ethyl lactate, ethyl pyruvate, butyl acetate, methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, tert-butyl acetate, tert-butyl propionate, propylene glycol monoter.
Examples thereof include esters such as t-butyl ether acetate, and one of these may be used alone or two or more of them may be used in combination, but the present invention is not limited thereto.

In the present invention, among these organic solvents, diethylene glycol dimethyl ether and 1-ethoxy-2, which have the highest solubility of the acid generator in the resist component, are used.
In addition to propanol, propylene glycol monomethyl ether acetate, which is a safe solvent, and a mixed solvent thereof are preferably used.

The amount of the organic solvent used is 200 to 1,000 parts by weight, particularly 400 to 1,000 parts by weight, based on 100 parts by weight of the base resin.
800 parts by weight is preferred.

A dissolution control agent can be further added to the resist material of the present invention. The dissolution control agent has a weight average molecular weight of 100 to 1,000, preferably 150 to
A compound having a mean number of 800 and a carboxylic group in the molecule of the phenolic hydroxyl group hydrogen atom of the compound having two or more phenolic hydroxyl groups in the molecule at an average of 0 to 100 mol% as a whole. The hydrogen atom of the carboxy group of 80 is averaged as a whole by the acid labile group
Compounds substituted at a ratio of -100 mol% are blended. The substitution ratio of the hydrogen atom of the phenolic hydroxyl group or the carboxy group with the acid labile group is 0 mol% or more of the entire phenolic hydroxyl group or the carboxy group on average, preferably 30%.
It is at least mol%, and its upper limit is 100 mol%, more preferably 80 mol%. In this case, as the compound having two or more phenolic hydroxyl groups or the compound having a carboxy group, those represented by the following formulas (D1) to (D14) are preferable.

[0097]

[Chemical 34]

(In the above formula, R ²⁰¹ and R ²⁰² each independently represent a hydrogen atom or a linear or branched alkyl group or alkenyl group having 1 to 8 carbon atoms.
²⁰³ is a hydrogen atom, a linear or branched alkyl group or alkenyl group having 1 to 8 carbon atoms, or-(R
²⁰⁷ ) Indicates _k COOH (k is 0 or 1). R
_{^204, - (CH 2) i -} (. I is an integer of 2 to 10), indicating an arylene group having 6 to 10 carbon atoms, a carbonyl group, a sulfonyl group, an oxygen atom or a sulfur atom. R
²⁰⁵ is an alkylene group having 1 to 10 carbon atoms, 6 to 1 carbon atoms
And 0 represents an arylene group, a carbonyl group, a sulfonyl group, an oxygen atom or a sulfur atom. R ²⁰⁶ is hydrogen atom, carbon number 1
~ 8 linear or branched alkyl or alkenyl groups, or a phenyl group or naphthyl group substituted with a hydroxyl group, respectively. R ²⁰⁷ represents a linear or branched alkylene group having 1 to 10 carbon atoms. R ²⁰⁸ represents a hydrogen atom or a hydroxyl group. j is an integer of 0-5. u is 0
Or 1. s, t, s ', t', s ", and t" are s + t = 8, s '+ t' = 5, s "+ t", respectively.
= 4 and has at least one hydroxyl group in each phenyl skeleton. α is the formula (D8),
The number of the compound (D9) is 100 to 1,000. )

In the above formula, R ²⁰¹ and R ²⁰² are, for example, hydrogen atom, methyl group, ethyl group, butyl group, propyl group,
Examples thereof include ethynyl group and cyclohexyl group. R ^{203
Are the} same as R ²⁰¹ , R ²⁰² , or
Examples of COOH, —CH ₂ COOH and R ²⁰⁴ include an ethylene group, a phenylene group, a carbonyl group, a sulfonyl group, an oxygen atom and a sulfur atom. Examples of R ²⁰⁵ include a methylene group, or a group similar to R ²⁰⁴ , R
Examples of ²⁰⁶ include a hydrogen atom, a methyl group, an ethyl group, a butyl group, a propyl group, an ethynyl group, a cyclohexyl group,
Examples thereof include a phenyl group and a naphthyl group each substituted with a hydroxyl group.

Examples of the acid labile group of the dissolution inhibitor include the same acid labile groups as the base polymer.
It may be the same as or different from the base polymer. It is also possible to add two or more different dissolution inhibitors.

The amount of the dissolution inhibitor blended is such that the base resin 1
0 to 50 parts by weight, preferably 5 to 5 parts by weight
The amount is 0 parts by weight, more preferably 10 to 30 parts by weight, and they can be used alone or in combination of two or more kinds. If the blending amount is less than 5 parts by weight, the resolution may not be improved, and if it exceeds 50 parts by weight, the pattern film may be reduced and the resolution may be lowered.

The above-mentioned dissolution inhibitors are, for compounds having a phenolic hydroxyl group or a carboxy group,
Synthesized by introducing acid labile groups using organic chemistry recipes.

Further, a basic compound can be added to the resist material of the present invention. As the basic compound, a compound that can suppress the diffusion rate when the acid generated from the acid generator diffuses in the resist film is suitable. By compounding a basic compound, the diffusion rate of acid in the resist film is suppressed and resolution is improved, sensitivity change after exposure is suppressed, and the dependency on the substrate and environment is reduced, and the exposure margin and pattern profile are reduced. Etc. can be improved.

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,
Examples include nonylamine, decylamine, dodecylamine, cetylamine, methylenediamine, ethylenediamine, tetraethylenepentamine and the like.

As the secondary aliphatic amines, 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-
Examples include dimethyltetraethylenepentamine.

As tertiary aliphatic amines, trimethylamine, triethylamine, tri-n-propylamine, triisopropylamine, tri-n-butylamine, triisobutylamine, tri-sec-butylamine, tripentylamine, tricyclopentyl. Amine,
Trihexylamine, tricyclohexylamine, triheptylamine, trioctylamine, trinonylamine, tridecylamine, tridodecylamine, tricetylamine, N, N, N ', N'-tetramethylmethylenediamine, N, N , N ′, N′-tetramethylethylenediamine, N, N, N ′, N′-tetramethyltetraethylenepentamine and the like are exemplified.

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, etc.), 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 derivative (eg, oxazole, isoxazole, etc.), thiazole derivative (eg, thiazole, isothiazole, etc.), imidazole derivative (eg, imidazole, 4-methylimidazole, 4-methyl-2-) Phenylimidazole, etc.), pyrazole derivative, furazan derivative, pyrroline derivative (eg, pyrroline, 2-methyl-1)
-Pyrroline etc.), pyrrolidine derivative (e.g. pyrrolidine, N-methylpyrrolidine, pyrrolidinone, N-methylpyrrolidone etc.), imidazoline derivative, imidazolidine derivative, pyridine derivative (e.g. pyridine, methylpyridine, ethylpyridine, propylpyridine, butylpyridine, 4- (1-butylpentyl) pyridine, dimethylpyridine, trimethylpyridine, triethylpyridine,
Phenylpyridine, 3-methyl-2-phenylpyridine, 4-tert-butylpyridine, diphenylpyridine, benzylpyridine, methoxypyridine, butoxypyridine, dimethoxypyridine, 1-methyl-2-pyridone, 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 (for example, quinoline, 3-quinolinecarbonitrile, etc.), isoquinoline derivative, cinnoline derivative, quinazoline derivative, quinoxaline derivative, phthalazine derivative, Purine derivatives, pteridine derivatives, carbazole derivatives, phenanthridine derivatives, acridine derivatives, phenazine derivatives, 1,10
-Phenanthroline derivative, adenine derivative, adenosine derivative, guanine derivative, guanosine derivative, uracil derivative, uridine derivative and the like are exemplified.

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) and the like.

Examples of the nitrogen-containing compound having a sulfonyl group include 3-pyridinesulfonic acid, pyridinium p-toluenesulfonate and the like.

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, 2,4-quinolinediol, 3-indolemethanol hydrate, and mono. Ethanolamine, diethanolamine, triethanolamine, N-ethyldiethanolamine, N, N-diethylethanolamine, triisopropanolamine, 2,2'-iminodiethanol, 2-aminoethanol, 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 , Piperizi Ethanol, 1- (2-hydroxyethyl) pyrrolidine, 1- (2-hydroxyethyl)
2-pyrrolidinone, 3-piperidino-1,2-propanediol, 3-pyrrolidino-1,2-propanediol, 8-hydroxyurolidine, 3-cuinuclidinol, 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 and N
-Methylformamide, N, N-dimethylformamide, acetamide, N-methylacetamide, N, N-
Examples thereof include dimethylacetamide, propionamide, benzamide and the like.

Examples of the imide derivative include phthalimide, succinimide, maleimide and the like.

Further, one kind or two or more kinds selected from the basic compounds represented by the following general formula (B) -1 can be added.

[Chemical 35] In the above formula, m = 1, 2 or 3. The side chains X may be the same or different and have the following general formulas (X) -1 to (X) -3.
Can be expressed as The side chain Y is the same or different and represents a hydrogen atom or a linear, branched or cyclic C1-C20 alkyl group, and the alkyl group may include an ether group or a hydroxyl group. In addition, Xs may combine with each other to form a ring.

Here, R ³⁰⁰ , R ³⁰² , and R ³⁰⁵ are independently a linear or branched alkylene group having 1 to 4 carbon atoms, and R ³⁰¹ and R ³⁰⁴ are independently a hydrogen atom, or Carbon number 1
To 20 linear, branched, or cyclic alkyl groups, and may contain one or more hydroxy groups, ether groups, ester groups, and lactone rings. R ³⁰³ is a single bond,
Alternatively, it is a linear or branched alkylene group having 1 to 4 carbon atoms. R ³⁰⁶ is a linear, branched, or cyclic alkyl group having 1 to 20 carbon atoms, and may contain one or more hydroxy group, ether, ester group, or lactone ring.

[0117]

[Chemical 36]

Specific examples of the compound represented by formula (B) -1 are shown below. Tris (2-methoxymethoxyethyl) amine, 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-pivaloyloxyxyethyl) amine, N, N-bis (2-acetoxyethyl) 2
-(Acetoxyacetoxy) ethylamine, tris (2
-Methoxycarbonyloxyethyl) amine, tris (2-tert-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 (2-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) Screw [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- Examples of (diethylamino) -δ-valerolactone include
It is not limited to these.

Further, one kind or two or more kinds of basic compounds having a cyclic structure represented by the following general formula (B) -2 can be added.

[Chemical 37] (In the above formula, X is as described above, R ³⁰⁷ has 2 to 20 carbon atoms.
Is a linear or branched alkylene group and may contain one or more carbonyl groups, ether groups, ester groups, and sulfides.

B-2 is specifically 1- [2- (methoxymethoxy) ethyl] pyrrolidine, 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, 2- (1-pyrrolidinyl) ethyl acetate, 2-piperidinoethyl acetate , 2-morpholinoethyl acetate, 2- (1-pyrrolidinyl) formate
Ethyl, 2-piperidinoethyl propionate, 2-morpholinoethyl acetoxyacetic 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, methyl 3-morpholinopropionate, methyl 3- (thiomorpholino) propionate, 2-methyl-3- (1-pyrrolidinyl) Methyl propionate, ethyl 3-morpholinopropionate, methoxycarbonylmethyl 3-piperidinopropionate, 2- (1-pyrrolidinyl) propionate 2-
Hydroxyethyl, 2-acetoxyethyl 3-morpholinopropionate, 2-oxotetrahydrofuran-3-yl 3- (1-pyrrolidinyl) propionate, tetrahydrofurfuryl 3-morpholinopropionate, glycidyl 3-piperidinopropionate, 3 -2-Methoxyethyl morpholinopropionate, 3- (1-pyrrolidinyl)
2- (2-methoxyethoxy) ethyl propionate, 3
-Butyl morpholino propionate, cyclohexyl 3-piperidinopropionate, α- (1-pyrrolidinyl) methyl-γ-butyrolactone, β-piperidino-γ-butyrolactone, β-morpholino-δ-valerolactone, 1
-Methyl pyrrolidinyl acetate, methyl piperidinoacetate, methyl morpholino acetate, methyl thiomorpholino acetate, 1-
Examples thereof include ethyl pyrrolidinyl acetate and 2-methoxyethyl morpholino acetate.

Further, a basic compound containing a cyano group represented by the general formulas (B) -3 to (B) -6 can be added.

[Chemical 38] (In the above formula, X, R ³⁰⁷ and m are as described above, R ³⁰⁸ and R ^309.
Are independently the same or different straight-chain or branched alkylene groups having 1 to 4 carbon atoms. )

The base containing a cyano group is specifically 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-methylaminopropionate, N- (2-cyanoethyl)-
Methyl N- (2-hydroxyethyl) -3-aminopropionate, N- (2-acetoxyethyl) -N- (2-
Methyl 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] amino Acetonitrile, N-cyanomethyl-N-
Methyl (2-methoxyethyl) -3-aminopropionate, N-cyanomethyl-N- (2-hydroxyethyl)
Methyl-3-aminopropionate, N- (2-acetoxyethyl) -N-cyanomethyl-3-aminopropionate methyl, 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-piperidinepropiononitrile, 4-morpholinepropiononitrile, 1-pyrrolidineacetonitrile, 1-piperidine acetonitrile, 4-morpholine acetonitrile,
Cyanomethyl 3-diethylaminopropionate, N, N
-Bis (2-hydroxyethyl) -3-aminopropionate cyanomethyl, 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-diethylaminopropionate 2-cyanoethyl, N, N-bis (2-hydroxyethyl) -3-aminopropionate 2-cyanoethyl, N, 2-Cyanoethyl N-bis (2-acetoxyethyl) -3-aminopropionate, N, N-bis (2-
Formyloxyethyl) -3-aminopropionic acid 2-
Cyanoethyl, N, N-bis (2-methoxyethyl)-
2-Cyanoethyl 3-aminopropionate, N, N-bis [2- (methoxymethoxy) ethyl] -3-cyanoethylaminopropionate, 2-cyanoethyl 1-pyrrolidine propionate, 1-piperidine cyanomethyl propionate, 4-morpholine Cyanomethyl propionate, 1
Examples include 2-cyanoethyl pyrrolidine propionate, 2-cyanoethyl 1-piperidine propionate, and 2-cyanoethyl 4-morpholine propionate.

The amount of the above basic compound to be added depends on the amount of the acid generator 1 used.
The amount is 0.001 to 10 parts by weight, preferably 0.01 to 1 part by weight. If the blending amount is less than 0.001 part by weight, the effect as an additive may not be sufficiently obtained, and if it exceeds 10 parts by weight, the resolution and sensitivity may decrease.

Further, the resist material of the present invention may contain a compound (organic acid) having a group represented by ≡C-COOH in the molecule. ≡C-COOH in the molecule
As the compound having a group represented by, for example, one or more compounds selected from the following Group I and Group II can be used, but the compound is not limited thereto. By blending this component, the PED stability of the resist is improved and the edge roughness on the nitride film substrate is improved. [Group I] Some or all of the hydrogen atoms of the phenolic hydroxyl group of the compounds represented by the following general formulas (A1) to (A10) are -R ⁴⁰¹ -COOH (R ⁴⁰¹ is a straight chain having 1 to 10 carbon atoms or A branched alkylene group), and the molar ratio of the phenolic hydroxyl group (C) in the molecule to the group (D) represented by ≡C—COOH is C / (C + D) = 0.1.
A compound that is ˜1.0. [Group II] Compounds represented by the following general formulas (A11) to (A15).

[0125]

[Chemical Formula 39]

(In the above formula, R ⁴⁰⁸ represents a hydrogen atom or a methyl group. R ⁴⁰² and R ⁴⁰³ are each independently a hydrogen atom, a linear or branched alkyl group having 1 to 8 carbon atoms, Or a linear or branched alkenyl group having 1 to 8 carbon atoms, R ⁴⁰⁴ represents a hydrogen atom, a linear or branched alkyl group having 1 to 8 carbon atoms, or a linear chain having 1 to 8 carbon atoms Or branched alkenyl group, ^or- ( ^R409 ) _k-
COOR 'group (R' is a hydrogen atom or -R ⁴⁰⁹ -COOH
And k is 0 or 1. ) Is shown. R ^{405 is-}
_{(CH 2) i - (.} I is an integer of 2 to 10), indicating an arylene group having 6 to 10 carbon atoms, a carbonyl group, a sulfonyl group, an oxygen atom or a sulfur atom. R ⁴⁰⁶ has 1 carbon atom
It represents an alkylene group having 10 to 10, an arylene group having 6 to 10 carbon atoms, a carbonyl group, a sulfonyl group, an oxygen atom or a sulfur atom. R ⁴⁰⁷ is a hydrogen atom, a linear or branched alkyl group having 1 to 8 carbon atoms, a linear or branched alkenyl group having 1 to 8 carbon atoms, or a phenyl group or naphthyl substituted with a hydroxyl group. Indicates a group. R ⁴⁰⁹
Represents a linear or branched alkylene group having 1 to 10 carbon atoms. R ⁴¹⁰ represents a hydrogen atom, a linear or branched alkyl group having 1 to 8 carbon atoms, a linear or branched alkenyl group having 1 to 8 carbon atoms, or a —R ⁴¹¹ —COOH group. R ⁴¹¹ represents a linear or branched alkylene group having 1 to 10 carbon atoms. j is an integer of 0-5. u is 0 or 1. s1, t1, s2, t2, s3, t
3, s4 and t4 are s1 + t1 = 8 and s2 + t2, respectively.
= 5, s3 + t3 = 4, s4 + t4 = 6, and each phenyl skeleton has at least one hydroxyl group. κ is the number that gives the compound of formula (A6) a weight average molecular weight of 1,000 to 5,000. λ is the formula (A
The compound of 7) is added to have a weight average molecular weight of 1,000 to 10,000.
It is a number to be 0. )

[0127]

[Chemical 40]

(In the above formula, R ⁴⁰² , R ⁴⁰³ , and R ⁴¹¹ have the same meanings as described above. R ⁴¹² represents a hydrogen atom or a hydroxyl group. S5 and t5 are s5 ≧ 0 and t5 ≧ 0. , S5 + t
It is a number that satisfies 5 = 5. h ′ is 0 or 1. )

As this component, specifically, the following general formula AI
Examples thereof include compounds represented by -1 to 14 and AII-1 to 10, but are not limited thereto.

[0130]

[Chemical 41]

(In the above formula, R ″ is a hydrogen atom or CH ₂ C
OOH group is shown, and in each compound, R '' is 10 to 10
0 mol% is a CH ₂ COOH group. α and κ have the same meanings as above. )

[0132]

[Chemical 42]

The compounds having a group represented by ≡C-COOH in the molecule may be used alone or in combination of two or more.

The addition amount of the compound having a group represented by ≡C-COOH in the molecule is 0 to 5 parts by weight, preferably 0.1 to 5 parts by weight, more preferably 100 parts by weight of the base resin. 0.1 to 3 parts by weight, more preferably 0.1
~ 2 parts by weight. If it is more than 5 parts by weight, the resolution of the resist material may deteriorate.

Further, the resist material of the present invention can contain an acetylene alcohol derivative as an additive, and thereby the storage stability can be improved.
As the acetylene alcohol derivative, the following general formula (S
What is shown by 1) and (S2) can be used conveniently.

[0136]

[Chemical 43] (In the above formula, R ⁵⁰¹ , R ⁵⁰² , R ⁵⁰³ , R ⁵⁰⁴ , and R ⁵⁰⁵ are each independently a hydrogen atom, or a straight chain having 1 to 8 carbon atoms,
It is a branched or cyclic alkyl group, X and Y represent 0 or a positive number, and 0 ≦ X ≦ 30, 0 ≦ Y ≦ 30, 0 ≦ X + Y.
Satisfies ≦ 40. )

The acetylene alcohol derivative is preferably Surfynol 61, Surfynol 82, Surfynol 104, Surfynol 104E, Surfynol 104H, Surfynol 104A, Surfynol TG, Surfynol PC, Surfynol 44.
0, Surfynol 465, Surfynol 485 (A
ir Products and Chemicals
Inc. Manufactured by Nisshin Chemical Industry Co., Ltd., and the like.

The amount of the acetylene alcohol derivative added is 0.01 to 2% by weight, more preferably 0.02 to 1% by weight based on 100% by weight of the resist composition. 0.0
If it is less than 1% by weight, the effect of improving the coating property and storage stability may not be sufficiently obtained, and if it is more than 2% by weight, the resolution of the resist material may deteriorate.

In addition to the above components, the resist composition of the present invention may contain, as an optional component, a surfactant which is commonly used for improving the coating property. In addition, the addition amount of the optional component can be a normal amount within a range that does not impair the effects of the present invention.

The surfactant is preferably a nonionic one, such as perfluoroalkyl polyoxyethylene ethanol, fluorinated alkyl ester, perfluoroalkylamine oxide, perfluoroalkyl EO adduct (wherein EO is ethylene oxide). Abbreviation),
Examples thereof include fluorine-containing organosiloxane compounds.
For example, Florard "FC-430", "FC-431"
(All manufactured by Sumitomo 3M), Surflon "S-1
41 "," S-145 "(all manufactured by Asahi Glass Co., Ltd.), Unidyne" DS-401 "," DS-403 "," DS- "
451 ”(all manufactured by Daikin Industries, Ltd.), Megafac“ F-8151 ”(manufactured by Dainippon Ink and Chemicals, Inc.),“ X-7
0-092 "," X-70-093 "(all manufactured by Shin-Etsu Chemical Co., Ltd.) and the like can be mentioned. Preferably, Florard "FC-430" (manufactured by Sumitomo 3M Ltd.),
"X-70-093" (made by Shin-Etsu Chemical Co., Ltd.) is mentioned.

A pattern can be formed using the resist material of the present invention by employing a known lithography technique. For example, a film such as a silicon wafer or the like can be spin coated or the like to have a film thickness of 0. .3 to 2.0 μ
m so that it becomes 60 m on a hot plate.
~ 180 ° C, 1 to 10 minutes, preferably 80 to 150
Prebak at 1 ° C for 1 to 5 minutes. Next, a mask for forming a desired pattern is held over the resist film, and a KrF or ArF excimer laser is used for an exposure amount of 1 to 1.
About 00 mJ / cm ² , preferably 5 to 50 mJ / cm ^2.
After irradiating to a certain degree, 60 on the hot plate
~ 180 ° C, 1 to 5 minutes, preferably 80 to 150 ° C,
Post exposure bake (PEB) for 1-3 minutes. Furthermore, 0.1 to 5% by weight, preferably 2 to 3% by weight
Using an alkaline aqueous solution developer such as tetramethylammonium hydroxide (TMAH) for 0.1 to 3 minutes, preferably 0.5 to 2 minutes, dipping method, paddle method, spray method A desired pattern is formed on the substrate by developing by a conventional method such as a method. If the above range is out of the upper and lower limits, the desired pattern may not be obtained in some cases.

[0142]

EXAMPLES The present invention will be specifically described below by showing synthesis examples, examples and comparative examples, but the present invention is not limited to the following examples. Synthesis Example 1 Synthesis of 2-oxo-2-phenylethylthiacyclopentanium bromide aqueous solution 2-bromoacetophenone 4.
97 g (0.025 mol) were dissolved in 9.5 g nitromethane. 2.2 g (0.025 mol) of tetrahydrothiophene was added at room temperature, and the mixture was aged at room temperature for 2 hours.
The reaction solution solidified as the reaction proceeded. 70 g of water and 50 g of diethyl ether were added to dissolve the solid matter. The aqueous layer was separated and further washed with 50 g of diethyl ether to remove lipophilic impurities. Anion exchange with various bisperfluoroalkylsulfonimides was performed using this aqueous solution.

Synthesis of 2-oxo-2-phenylethylthiacyclopentanium bis (perfluoroethylsulfonyl) imide Bis (perfluoroethylsulfonyl) imide was added to the above aqueous solution of 2-oxo-2-phenylethylthiacyclopentanium bromide. An oily substance separated upon the addition of 9.5 g (0.025 mol). This oil was added to dichloromethane 100
Extracted with g. The organic layer was washed 4 times with 50 g of water, and the organic layer was concentrated with a rotary evaporator to give an oily substance 15
got g. 50 g of diethyl ether was added to this oil to crystallize, and the crystals were filtered under reduced pressure and dried to give 13 g of white crystals.
Got Yield 66%.

TOF-MS analysis of the obtained sample was performed. Measuring device is Kratos Kompact Pr
ob MALDI-TOFMS, positive and negative accelerating voltages of 5 kV, mass calibration was C ₆₀ , and straight flight was performed. 207.3 mass peak as cation,
An anion peak of 379.9 was obtained, the mass of the cation matched with that of 2-oxo-2-phenylethylthiacyclopentanium, and the anion matched the mass of bis (perfluoroethylsulfonyl) imide.

The analysis results of IR and ¹ H-NMR are as follows. IR (thin film): ν = 3077, 3031, 2975,
2929, 1687, 1598, 1583, 1452,
1430, 1386, 1351, 1332, 1230,
1174, 1141, 1083, 995, 975, 90
6, 883, 775, 755, 740, 684, 64
0,613,568,536,524cm ^{-1 1} H-NM
R (300 MHz in CDCl ₃ ): δ = 7.61
7-7.666 ppm (Ha, 1H, triplet), 7.4
24-7.482 ppm (Hb, 2H, triplet), 7.
911-7.935 ppm (Hc, 2H, doublet),
5.117 ppm (Hd, 2H, singlet), 3.473
-3.720 ppm (He, 4H, multiplet), 2.25
6-2.500 (Hf, 4H, multiplet)

[Chemical 44]

Synthesis Example 2 Synthesis of 2-oxo-2-phenylethylthiacyclopentanium bis (perfluoro-n-butylsulfonyl) imide Bis (was added to the above aqueous solution of 2-oxo-2-phenylethylthiacyclopentanium bromide. Addition of 14.5 g (0.025 mol) of perfluoro-n-butylsulfonyl) imide separated the oil. The oil was extracted with 150 g of dichloromethane. The organic layer was washed 4 times with 80 g of water, and the organic layer was concentrated with a rotary evaporator to obtain 18 g of an oily substance. 50g of diethyl ether in this oil
Was crystallized, and the crystals were filtered under reduced pressure and dried to obtain 13.5 g of white crystals. Yield 68% TO of the obtained sample
F-MS analysis was performed. As a cation, a mass peak of 207.3 and an anion peak of 579.9 were obtained. The mass of the cation was the same as that of 2-oxo-2-phenylethylthiacyclopentanium, and the anion was bis (perfluoro-n). -Butylsulfonyl) imide mass matched.

The analysis results of IR and ¹ H-NMR are as follows. IR (thin film): ν = 3066, 3043, 3023,
2966, 2921, 1685, 1598, 1583,
1452, 1430, 1386, 1359, 1326,
1290, 1257, 1214, 1197, 1153,
1062, 1035, 991, 887, 875, 80
6, 738, 721, 701, 688, 651, 63
^{6,615,595,576,536,512cm -1 1 H-NMR (300MHz} in CDCl 3): δ
= 7.617-7.666 ppm (Ha, 1H, triplet), 7.424-7.482 ppm (Hb, 2H, 3)
Multiplet), 7.911-7.935 ppm (Hc, 2H,
Doublet), 5.117 ppm (Hd, 2H, singlet),
3.473-3.720 ppm (He, 4H, multiplet), 2.256-2.500 (Hf, 4H, multiplet)

[Chemical formula 45]

Examples Sulfonium salts and iodonium salts (P
AG1 to 9) were evaluated for sensitivity and resolution when used as a resist.

[0149]

[Chemical formula 46]

[0150]

[Chemical 47]

Examples 1 to 40 Evaluation of Resolution of Resists Sulfonium salts and iodonium salts (P
AG1-9) is used as an acid generator, and a polymer (Polymer 1-26) represented by the following formula is used as a base resin, and a dissolution control agent (DRR1-1) represented by the following formula is used.
4), a basic compound, a compound having a group represented by ≡C—COOH in the molecule represented by the formula as an organic acid (ACC
1, 2) are dissolved in a solvent containing 0.01% by weight of FC-430 (manufactured by Sumitomo 3M Ltd.) in the composition shown in the table to prepare resist materials. Each resist solution was prepared by filtering with a trademark (trademark) filter.

[0152]

[Chemical 48]

[0153]

[Chemical 49]

[0154]

[Chemical 50]

[0155]

[Chemical 51]

[0156]

[Chemical 52]

[0157]

[Chemical 53]

ArF Exposure Examples ArF for resists using Polymers 1-18
Exposure (wavelength 193 nm) was performed. An antireflection film solution (AR19, Shipley Co., Ltd.) is applied on a silicon substrate, and then 200
Antireflection film (82 nm)
(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 Ar
F excimer laser microstepper (N manufactured by Nikon Corporation
A = 0.55, σ0.7) was used for exposure, baking was performed at 110 ° C. for 90 seconds (PEB), and development was performed for 30 seconds with an aqueous solution of 2.38 wt% 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 ). A value obtained by subtracting the line width of the isolated line from the line width of the group line by setting the minimum line width (μm) as the resolution of the evaluation resist, measuring the line width of the line and space 1:10 with the same exposure amount, and measuring the line width of the isolated line. Is the dimensional difference (I / G bias) between the isolated pattern and the dense pattern. Also, measure the unevenness of the group line,
Line edge roughness was used. The results are shown in Table 1.

KrF Exposure Example For the resists using the polymers 19 to 26, KrF was used.
Exposure (wavelength 248 nm) was performed. Antireflection coating solution on a silicon substrate (DUV-3 manufactured by Brewer Science)
0) is applied, and the resist solution is spin-coated on the base of an antireflection film (film thickness of 55 nm) prepared by baking at 200 ° C. for 60 seconds and using a hot plate at 100 ° C.
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. For resist evaluation, the exposure dose for resolving the 0.18 μm group line and space at a ratio of 1: 1 was determined as the optimum exposure dose (Eop, mJ
/ Cm ² ), the minimum line width (μm) of the separated line and space in this exposure amount is taken as the resolution of the evaluation resist, and the line and space of the same exposure amount 1:
The line width of 10 isolated lines was measured, and the value obtained by subtracting the line width of the isolated line from the line width of the group line was taken as the dimensional difference (I / G bias) between the isolated pattern and the dense pattern. In addition, the unevenness of the group line was measured and used as the line edge roughness.
The results are shown in Table 2.

Table 1 shows the composition of each resist and the evaluation results. In addition, in Table 1, 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, a sulfonium salt represented by the following formula (PAG
Regarding 10 to 15), the sensitivity and resolution when used as a resist were evaluated.

[Chemical 54]

Comparative Examples 1 to 6 Sulfonium salts represented by the above formula (PAGs 10 to 15)
Was used to prepare a resist having the composition shown in Table 3 in the same manner as described above, and the resist was exposed to light using an ArF microstepper in the same manner as described above to evaluate sensitivity and resolution. Table 3 shows the composition of each resist and the evaluation results.

From the results shown in 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. .

[0164]

The resist material containing the acid generator of the present invention is particularly excellent in resolution, has a small dimensional difference between an isolated pattern and a dense pattern, and has a small line edge roughness.

[0165]

[Table 1]

[0166]

[Table 2]

[0167]

[Table 3]

[0168]

[Table 4]

[0169]

[Table 5]

[Brief description of drawings]

FIG. 1 is a simulation calculation result showing a change in line size when a line pitch and an acid diffusion distance are changed, and 25 to 70 nm represents an acid diffusion distance.

FIG. 2 is a simulation calculation result of a resist cross-sectional shape when the acid diffusion distance is changed to 18 to 70 nm.

Front page continuation (51) Int.Cl. ⁷ Identification code FI theme code (reference) H01L 21/027 H01L 21/30 502R (72) Inventor Tomohiro Kobayashi 1 of 28 Fukushima Nishibukushima Shin-Etsu Chemical Co., Ltd. New Functional Material Technology Research Laboratory (72) Inventor Yoichi Osawa 1 of 28 Fukushima, Nishifukushima, Kubiki-mura, Nakakubiki-gun, Niigata Prefecture Shin-Etsu Chemical Co., Ltd. F-Term (Reference) 2H025 AA01 AA02 AA03 AB16 AC04 AC08 AD03 BE00 BE07 BG00 CC20 FA03 FA12 FA17 4C023 JA05 4H006 AA01 AA03 AB92

Claims (11)

[Claims] 1. A photoacid-generating compound represented by the general formula (1). [Chemical 1] (R ¹ is an alkylene group having 2 to 8 carbon atoms, R ² is a single bond, an oxygen atom, a nitrogen atom or an alkylene group having 1 to 4 carbon atoms. R ³ is a linear chain having 1 to 8 carbon atoms. A branched or cyclic alkyl group, or an aryl group having 6 to 10 carbon atoms, the alkyl group having 1 to 4 carbon atoms, the fluorinated alkyl group having 1 to 4 carbon atoms, and the alkoxy group having 1 to 4 carbon atoms groups, fluorinated alkoxy group having 1 to 4 carbon atoms, a nitro group, a cyano group, a fluorine atom, a phenyl group, a substituted phenyl group, an acetyl group, or a benzoyloxy which may be substituted with a group .Rf _1, Rf ₂ has 1 to 20 carbon atoms, one or both of which contains at least one or more fluorine atom
Is a linear, branched, or cyclic alkyl group, and may contain a hydroxy group, a carbonyl group, an ester group, an ether group, or an aryl group, and only _one of Rf _{1 and} Rf ₂ is at least one. When it is a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms containing the above fluorine atom, the other is a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms. , A hydroxy group, a carbonyl group, an ester group, an ether group, or an aryl group. Rf ₁ and Rf ₂ may combine to form a ring. ) 2. The photoacid generating compound according to claim 1, wherein R ¹ is an alkylene group having 4 or 5 carbon atoms. 3. The photoacid generating compound according to claim 1, wherein R ³ is a phenyl group or a naphthyl group. 4. A chemically amplified positive resist material containing a base resin, an acid generator and a solvent, wherein the acid generator generates a fluorine group-containing alkylimidic acid. Type resist material. 5. The chemically amplified positive resist composition according to claim 4, wherein the acid generator is an onium salt represented by the following general formula (1) or general formula (2). [Chemical 2] (In the formula, Rf1, Rf ₂ of either or both of 1 to 20 carbon atoms containing one or more fluorine atoms linear, branched or cyclic alkyl group, hydroxy group, a carbonyl group, an ester A group, an ether group or an aryl group may be included, and only _one of Rf _{1 and} Rf ₂ contains at least one or more fluorine atoms and has 1 to 2 carbon atoms.
When it is a linear, branched or cyclic alkyl group of 0, the other is a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms, a hydroxy group, a carbonyl group, an ester group, It may contain an ether group or an aryl group. Rf ₁ and Rf ₂ may combine to form a ring. R ¹
Is an alkylene group having 2 to 8 carbon atoms, and R ² is a single bond or an oxygen atom, a nitrogen atom, or an alkylene group having 1 to 4 carbon atoms. R ³ is a linear, branched, or cyclic alkyl group having 1 to 8 carbon atoms, or an aryl group having 6 to 10 carbon atoms, an alkyl group having 1 to 4 carbon atoms, or a fluorinated one having 1 to 4 carbon atoms. Alkyl group, C1-4 alkoxy group, C1
4 to 4 may be substituted with a fluorinated alkoxy group, nitro group, cyano group, fluorine atom, phenyl group, substituted phenyl group, acetyl group, or benzoyloxy group. R ⁴ is the same or non-identical straight-chain having 1 to 12 carbon atoms,
It is a branched or cyclic alkyl group and may contain a carbonyl group, an ester group, an ether group, a thioether group or a double bond, or an aryl group having 6 to 12 carbon atoms or an aralkyl group having 7 to 20 carbon atoms. Represents M
⁺ Represents iodonium or sulfonium, and n is 2 or 3. ) 6. The chemically amplified positive resist composition according to claim 4, wherein the base resin is insoluble or slightly soluble in a developing solution and becomes soluble in the developing solution with an acid. 7. The base resin comprises polyhydroxystyrene and a polyhydroxystyrene derivative in which a part or all of hydroxyl groups thereof are substituted with an acid labile group, polyacrylic acid and its ester, polymethacrylic acid and its ester, Acrylic acid and methacrylic acid copolymer and its ester, cycloolefin and maleic anhydride copolymer, cycloolefin and maleic anhydride and acrylic acid ester copolymer, cycloolefin and maleic anhydride and methacrylic acid ester Copolymer, cycloolefin / maleic anhydride / acrylic acid ester / methacrylic acid ester copolymer, cycloolefin / maleimide copolymer, cycloolefin / maleimide / acrylic acid ester copolymer, cycloolefin / maleimide Methacrylic acid S A polymer of one or more selected from the group consisting of a copolymer of ter, a copolymer of cycloolefin, maleimide, acrylic acid ester and methacrylic acid ester, polynorbornene, and a metathesis ring-opening polymer. Item 7. A chemically amplified positive resist material according to any one of Items 4 to 6. 8. The chemically amplified positive resist composition according to claim 4, wherein the base resin is a polymer structure containing a silicon atom. 9. The method according to claim 4, further comprising a basic compound.
9. The chemically amplified positive resist material as described in any of 8 to 8. 10. The method according to claim 4, further comprising a dissolution inhibitor.
10. The chemically amplified positive resist material as described in any one of 1 to 9 above. 11. A step of applying the resist material according to claim 4 on a substrate, a step of exposing with a high energy ray having a wavelength of 300 nm or less through a photomask after the heat treatment, and a heat treatment. And then developing with a developing solution.