JP4905667B2 - Novel sulfonate and derivative thereof, photoacid generator, resist material and pattern forming method using the same - Google Patents

Description

  The present invention relates to a novel sulfonic acid salt and derivatives thereof suitably used as a photoacid generator for a resist material, a photoacid generator, a resist material using the same, and a pattern forming method.

  In recent years, with the high integration and high speed of LSIs, there is a demand for miniaturization of pattern rules, and far-ultraviolet lithography and vacuum ultraviolet lithography are promising as next-generation microfabrication technologies. Among them, photolithography using ArF excimer laser light as a light source is an indispensable technique for ultrafine processing of 0.13 μm or less.

ArF lithography began to be used in part from the fabrication of 130 nm node devices and became the main lithography technology from 90 nm node devices. As lithography technology for the next 45nm node, initially 157nm lithography using F ₂ laser is promising, its development was retarded by several problems have been pointed out, water between the projection lens and the wafer, ethylene glycol, glycerin, etc. ArF immersion lithography that can design the numerical aperture (NA) of the projection lens to 1.0 or higher and achieve high resolution by inserting a liquid having a higher refractive index than air has rapidly emerged (for example, Non-patent literature 1: Journal of photopolymer Science and Technology Vol. 17, No. 4, p587 (2004)).

  In ArF lithography, in order to prevent deterioration of precise and expensive optical system materials, a resist material with high sensitivity that can exhibit sufficient resolution with a small exposure amount is required. It is most common to select a highly transparent material at a wavelength of 193 nm. For example, for the base resin, polyacrylic acid and its derivatives, norbornene-maleic anhydride alternating polymer, polynorbornene and ring-opening metathesis polymer, ring-opening metathesis polymer hydrogenated product, etc. have been proposed. Some achievements have been achieved in terms of raising the nature.

  Various studies have also been made on photoacid generators. When a photoacid generator that generates alkane or arenesulfonic acid as used in a chemically amplified resist material using a conventional KrF excimer laser beam as a light source is used as a component of the ArF chemically amplified resist material. It has been found that the acid strength for cleaving the acid labile group of the resin is not sufficient, the resolution is not possible at all, or the sensitivity is low and it is not suitable for device production.

  For this reason, as the photoacid generator for the ArF chemically amplified resist material, one that generates perfluoroalkanesulfonic acid with high acid strength is generally used. These photoacid generators that generate perfluoroalkanesulfonic acid have already been developed as KrF resist materials. For example, Patent Document 1: Japanese Patent Laid-Open No. 2000-122296 and Patent Document 2: Japanese Patent Laid-Open No. 11-282168. The publication describes a photoacid generator that generates perfluorohexanesulfonic acid, perfluorooctanesulfonic acid, perfluoro-4-ethylcyclohexanesulfonic acid, and perfluorobutanesulfonic acid. Further, as novel acid generators, perfluoroalkyl ether sulfonic acids are generated in Patent Documents 3 to 5: JP-A No. 2002-214774, JP-A No. 2003-140332, and US Patent Application Publication No. 2002/0197558. An acid generator has been proposed.

  On the other hand, perfluorooctane sulfonic acid, or its derivative, is known as PFOS after its acronym, and is an eco-concentration derived from stability (non-degradable) derived from C—F bond, hydrophobicity, and lipophilicity. And accumulation are problems. The US Environment Agency (EPA) has enacted 13 PFOS-related substances in the Significant New Use Rule, and the 75 substances are exempted from use in the photoresist field. (Non-Patent Documents 2 and 3: Federal Register / Vol. 67, No. 47 page 11008 / Monday, March 11, 2002, Federal Register / Vol. 67, No. 236 page 72854 / Monday, December 9, 2002).

  In order to deal with such problems related to PFOS, partial fluorine-substituted alkanesulfonic acids having a reduced fluorine substitution rate have been developed by various companies. For example, Patent Document 6: JP-T-2004-531749 discloses that an α, α-difluoroalkanesulfonate is developed from an α, α-difluoroalkene and a sulfur compound, and this sulfonic acid is generated by exposure to light. A resist material containing an agent, specifically, di (4-tert-butylphenyl) iodonium 1,1-difluoro-1-sulfonate-2- (1-naphthyl) ethylene has been disclosed, and Patent Document 7 JP-A-2004-2252 discloses the development of α, α, β, β-tetrafluoroalkane sulfonate using α, α, β, β-tetrafluoro-α-iodoalkane and a sulfur compound and the sulfonic acid. A photoacid generator and a resist material for generating selenium are disclosed. Patent Document 8: Japanese Patent Application Laid-Open No. 2004-307387 discloses 2- (bicyclo [2.2.1] hept-2-yl) -1,1-difluoroethanesulfonic acid salt and a production method thereof, Further, JP-A-2005-266766 discloses a photosensitive composition containing a compound that generates a partially fluorinated alkanesulfonic acid having a sulfonylamide structure derived from perfluoroalkylenesulfonyl difluoride. Yes.

  However, although the substances in the above-mentioned patent documents both have a low fluorine substitution rate, they have a large hydrocarbon skeleton that is difficult to decompose, and there are limitations on the molecular design for changing the size of the alkanesulfonic acid, In addition, there are problems such as expensive fluorine-containing starting materials.

  In addition, there are problems such as defective resist pattern shape due to defects due to minute water droplets remaining on the resist wafer after exposure in immersion exposure, collapse of the resist pattern after development, and T-top shape formation. There is also a need for a pattern forming method capable of obtaining a good resist pattern after development in immersion lithography.

JP 2000-122296 A JP-A-11-282168 JP 2002-214774 A JP 2003-140332 A US Patent Application Publication No. 2002/0197558 JP-T-2004-531749 Japanese Patent Laid-Open No. 2004-2252 JP 2004-307387 A JP 2005-266766 A Journal of photopolymer Science and Technology Vol. 17, no. 4, p587 (2004) Federal Register / Vol. 67, no. 47 page 11008 / Monday, March 11, 2002 Federal Register / Vol. 67, no. 236 page 72854 / Monday, December 9, 2002

  The acid generated by the photoacid generator is that it has sufficient acid strength to cleave the acid labile group in the resist material, that there is appropriate diffusion in the resist material, that it has low volatility, and water. It is hoped that there will be little elution of the resin, no foreign matter will be generated after resist stripping after development, and good degradability without impacting the environment after the end of lithography use. The acid generated does not satisfy these.

  The present invention solves the above-mentioned problems of conventional photoacid generators, and is particularly excellent in resolution and pattern profile shape during ArF exposure, and is suitable as a photoacid generator for resist materials and sulfonates. It is an object to provide a derivative thereof, a resist material using the derivative, and a pattern forming method.

  As a result of intensive studies on the above problems, the present inventors have found that substituted or unsubstituted derivatives derived from 1,1,1,3,3,3-hexafluoro-2-propanol, which are industrially easily available. 1,1,3,3,3 by reaction of an aliphatic or aromatic carboxylic acid 1,1,3,3,3-pentafluoropropen-2-yl ester with a sulfur-containing compound such as sodium sulfite and sodium bisulfite -Pentafluoro-2-acyloxypropane-1-sulfonic acid salt is obtained, and this sulfonic acid is used as a raw material to prepare compounds represented by onium salts, oxime sulfonates, and sulfonyloxyimides, and then hydrolyze the ester. The present inventors have found that these compounds are effective as a photoacid generator for chemically amplified resist materials, and have made the present invention.

（式中、Ｒ⁴は置換もしくは非置換の炭素数１〜２０の直鎖状、分岐状又は環状のアルキル基又はアルケニル基、又は置換もしくは非置換の炭素数６〜１４のアリール基を示す。ｍは１〜５、ｎは０又は１を示す。）
請求項５：
下記一般式（２ｂ）で示されるヨードニウム塩。

（式中、Ｒ⁴は置換もしくは非置換の炭素数１〜２０の直鎖状、分岐状又は環状のアルキル基又はアルケニル基、又は置換もしくは非置換の炭素数６〜１４のアリール基を示す。ｎは０又は１を示す。）
請求項６：
下記一般式（３ａ）で示されるＮ−スルホニルオキシイミド化合物。

（式中、Ｘ、Ｙは相互に独立に水素原子又は置換もしくは非置換の炭素数１〜６のアルキル基を示すか、あるいはＸ及びＹが相互に結合してそれらが結合している炭素原子と共に飽和もしくは不飽和の炭素数６〜１２の環を形成してもよい。Ｚは単結合、二重結合、メチレン基、又は酸素原子を示す。）
請求項７：
下記一般式（３ｂ）で示されるオキシムスルホネート化合物。

（式中、ｑは０又は１を示すが、ｑが０の場合、ｐは単結合、置換もしくは非置換の炭素数１〜２０のアルキル基、又は置換もしくは非置換の炭素数６〜１５のアリール基を示し、ｑが１の場合にはｐは置換もしくは非置換の炭素数１〜２０のアルキレン基、又は置換もしくは非置換の炭素数６〜１５のアリーレン基を示す。ＥＷＧはシアノ基、トリフルオロメチル基、パーフルオロエチル基、パーフルオロプロピル基、５Ｈ−パーフルオロペンチル基、６Ｈ−パーフルオロヘキシル基、ニトロ基又はメチル基を示し、ｑが１の場合、互いのＥＷＧが相互に結合してそれらが結合している炭素原子と共に炭素数６の環を形成してもよい。）
請求項８：
紫外線、遠紫外線、電子線、Ｘ線、エキシマレーザー、γ線、又はシンクロトロン放射線照射の高エネルギー線に感応し、下記一般式（１）で示されるスルホン酸を発生することを特徴とする化学増幅レジスト材料用の光酸発生剤。
ＣＦ ₃ −ＣＨ（ＯＨ）−ＣＦ ₂ ＳＯ ₃ ^- Ｈ ⁺ （１）
請求項９：
下記一般式（２）で示されるスルホニウム塩からなる請求項８記載の光酸発生剤。
Ｒ ¹ Ｒ ² Ｒ ³ Ｓ ⁺ ＣＦ ₃ −ＣＨ（ＯＨ）−ＣＦ ₂ ＳＯ ₃ ^- （２）
（式中、Ｒ ¹ 、Ｒ ² 及びＲ ³ は相互に独立に置換もしくは非置換の炭素数１〜１０の直鎖状又は分岐状のアルキル基、アルケニル基又はオキソアルキル基、又は置換もしくは非置換の炭素数６〜１８のアリール基、アラルキル基又はアリールオキソアルキル基を示すか、あるいはＲ ¹ 、Ｒ ² 及びＲ ³ のうちのいずれか２つ以上が相互に結合して式中の硫黄原子と共に環を形成してもよい。）
請求項１０：
下記一般式（２ａ）で示されるスルホニウム塩からなる請求項８記載の光酸発生剤。

（式中、Ｒ ⁴ は置換もしくは非置換の炭素数１〜２０の直鎖状、分岐状又は環状のアルキル基又はアルケニル基、又は置換もしくは非置換の炭素数６〜１４のアリール基を示す。ｍは１〜５、ｎは０又は１を示す。）
請求項１１：
下記一般式（２ｂ）で示されるヨードニウム塩からなる請求項８記載の光酸発生剤。

（式中、Ｒ ⁴ は置換もしくは非置換の炭素数１〜２０の直鎖状、分岐状又は環状のアルキル基又はアルケニル基、又は置換もしくは非置換の炭素数６〜１４のアリール基を示す。ｎは０又は１を示す。）
請求項１２：
下記一般式（３ａ）で示されるＮ−スルホニルオキシイミド化合物からなる請求項８記載の光酸発生剤。

（式中、Ｘ、Ｙは相互に独立に水素原子又は置換もしくは非置換の炭素数１〜６のアルキル基を示すか、あるいはＸ及びＹが相互に結合してそれらが結合している炭素原子と共に飽和もしくは不飽和の炭素数６〜１２の環を形成してもよい。Ｚは単結合、二重結合、メチレン基、又は酸素原子を示す。）
請求項１３：
下記一般式（３ｂ）で示されるオキシムスルホネート化合物からなる請求項８記載の光酸発生剤。

（式中、ｑは０又は１を示すが、ｑが０の場合、ｐは単結合、置換もしくは非置換の炭素数１〜２０のアルキル基、又は置換もしくは非置換の炭素数６〜１５のアリール基を示し、ｑが１の場合にはｐは置換もしくは非置換の炭素数１〜２０のアルキレン基、又は置換もしくは非置換の炭素数６〜１５のアリーレン基を示す。ＥＷＧはシアノ基、トリフルオロメチル基、パーフルオロエチル基、パーフルオロプロピル基、５Ｈ−パーフルオロペンチル基、６Ｈ−パーフルオロヘキシル基、ニトロ基又はメチル基を示し、ｑが１の場合、互いのＥＷＧが相互に結合してそれらが結合している炭素原子と共に炭素数６の環を形成してもよい。）
請求項１４：
ベース樹脂、酸発生剤及び溶剤を含有してなるレジスト材料において、前記酸発生剤が、請求項８乃至１３のいずれか１項記載の光酸発生剤であることを特徴とするレジスト材料。
請求項１５：
ベース樹脂が、ポリ（メタ）アクリル酸及びその誘導体、シクロオレフィン誘導体−無水マレイン酸交互重合体、シクロオレフィン誘導体と無水マレイン酸とポリアクリル酸又はその誘導体との３あるいは４元以上の共重合体、シクロオレフィン誘導体−α−トリフルオロメチルアクリル酸誘導体共重合体、ポリノルボルネン、開環メタセシス重合体、並びに開環メタセシス重合体水素添加物から選択される１種又は２種以上の高分子重合体であることを特徴とする請求項１４記載のレジスト材料。
請求項１６：
ベース樹脂が、珪素原子を含有する高分子構造体であることを特徴とする請求項１４記載のレジスト材料。
請求項１７：
ベース樹脂が、フッ素原子を含有する高分子構造体であることを特徴とする請求項１４記載のレジスト材料。
請求項１８：
請求項１５，１６又は１７記載のベース樹脂、請求項８乃至１３のいずれか１項記載の光酸発生剤及び溶剤を含有し、上記ベース樹脂が現像液に不溶あるいは難溶であって、酸によって現像液に可溶となる化学増幅ポジ型レジスト材料。
請求項１９：
更に、塩基性化合物を添加してなることを特徴とする請求項１８記載の化学増幅ポジ型レジスト材料。
請求項２０：
更に、溶解阻止剤を含有することを特徴とする請求項１８又は１９記載の化学増幅ポジ型レジスト材料。
請求項２１：
請求項１４乃至２０のいずれか１項記載のレジスト材料を基板上に塗布する工程と、加熱処理後フォトマスクを介して波長３００ｎｍ以下の高エネルギー線で露光する工程と、必要に応じて加熱処理した後、現像液を用いて現像する工程とを含むことを特徴とするパターン形成方法。
請求項２２：
波長１９３ｎｍのＡｒＦエキシマレーザーを用い、レジスト材料を塗布した基板と投影レンズの間に液体を挿入する液浸リソグラフィー法であることを特徴とする請求項２１記載のパターン形成方法。 That is, the present invention provides the following sulfonate and derivatives thereof, a photoacid generator, a resist material, and a pattern forming method.
Claim 1:
A sulfonate represented by the following general formula (1a).
_{CF 3 -CH (OH) -CF 2} SO 3 - M + (1a)
(In the formula, M ⁺ represents lithium ion, sodium ion, potassium ion, ammonium ion, or tetramethylammonium ion.)
Claim 2:
Sulfonic acid represented by the following following general formula (1).
CF ₃ —CH (OH) —CF ₂ SO ₃ ⁻ H ⁺ (1)
Claim 3:
A sulfonium salt represented by the following general formula (2).
R ¹ R ² R ³ S ⁺ CF ₃ —CH (OH) —CF ₂ SO ₃ ⁻ (2)
Wherein R ¹ , R ² and R ³ are each independently substituted or unsubstituted linear or branched alkyl group, alkenyl group or oxoalkyl group having 1 to 10 carbon atoms, or substituted or unsubstituted. An aryl group having 6 to 18 carbon atoms, an aralkyl group or an aryloxoalkyl group, or any two or more of R ¹ , R ² and R ³ are bonded to each other together with the sulfur atom in the formula A ring may be formed.)
Claim 4:
A sulfonium salt represented by the following general formula (2a).

(In the formula, R ⁴ represents a substituted or unsubstituted linear, branched or cyclic alkyl group or alkenyl group having 1 to 20 carbon atoms, or a substituted or unsubstituted aryl group having 6 to 14 carbon atoms . m represents 1 to 5, and n represents 0 or 1.)
Claim 5:
An iodonium salt represented by the following general formula (2b).

(In the formula, R ⁴ represents a substituted or unsubstituted linear, branched or cyclic alkyl group or alkenyl group having 1 to 20 carbon atoms, or a substituted or unsubstituted aryl group having 6 to 14 carbon atoms . n represents 0 or 1.)
Claim 6:
An N-sulfonyloxyimide compound represented by the following general formula (3a).

(In the formula, X and Y each independently represent a hydrogen atom or a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms, or X and Y are bonded to each other and bonded to each other) And may form a saturated or unsaturated ring having 6 to 12 carbon atoms, Z represents a single bond, a double bond, a methylene group, or an oxygen atom.)
Claim 7:
An oxime sulfonate compound represented by the following general formula (3b).

(In the formula, q represents 0 or 1, but when q is 0, p is a single bond, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, or a substituted or unsubstituted carbon group having 6 to 15 carbon atoms. Represents an aryl group, and when q is 1, p represents a substituted or unsubstituted alkylene group having 1 to 20 carbon atoms, or a substituted or unsubstituted arylene group having 6 to 15 carbon atoms, EWG represents a cyano group, A trifluoromethyl group, a perfluoroethyl group, a perfluoropropyl group, a 5H-perfluoropentyl group, a 6H-perfluorohexyl group, a nitro group or a methyl group. When q is 1, the EWGs are bonded to each other. And may form a ring of 6 carbon atoms together with the carbon atom to which they are bonded.)
Claim 8:
A chemistry characterized by generating sulfonic acid represented by the following general formula (1) in response to ultraviolet rays, far ultraviolet rays, electron beams, X-rays, excimer lasers, γ rays, or high energy rays of synchrotron radiation irradiation Photoacid generator for amplified resist material.
CF ₃ —CH (OH) —CF ₂ SO ₃ ⁻ H ⁺ (1)
Claim 9:
The photoacid generator according to claim 8, comprising a sulfonium salt represented by the following general formula (2).
R ¹ R ² R ³ S ⁺ CF ₃ —CH (OH) —CF ₂ SO ₃ ⁻ (2)
Wherein R ¹ , R ² and R ³ are each independently substituted or unsubstituted linear or branched alkyl group, alkenyl group or oxoalkyl group having 1 to 10 carbon atoms, or substituted or unsubstituted. An aryl group having 6 to 18 carbon atoms, an aralkyl group or an aryloxoalkyl group, or any two or more of R ¹ , R ² and R ³ are bonded to each other together with the sulfur atom in the formula A ring may be formed.)
Claim 10:
The photoacid generator according to claim 8, comprising a sulfonium salt represented by the following general formula (2a).

(In the formula, R ⁴ represents a substituted or unsubstituted linear, branched or cyclic alkyl group or alkenyl group having 1 to 20 carbon atoms, or a substituted or unsubstituted aryl group having 6 to 14 carbon atoms. m represents 1 to 5, and n represents 0 or 1.)
Claim 11:
The photoacid generator according to claim 8, comprising an iodonium salt represented by the following general formula (2b).

(In the formula, R ⁴ represents a substituted or unsubstituted linear, branched or cyclic alkyl group or alkenyl group having 1 to 20 carbon atoms, or a substituted or unsubstituted aryl group having 6 to 14 carbon atoms. n represents 0 or 1.)
Claim 12:
The photoacid generator according to claim 8, comprising an N-sulfonyloxyimide compound represented by the following general formula (3a).

(In the formula, X and Y each independently represent a hydrogen atom or a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms, or X and Y are bonded to each other and bonded to each other) And may form a saturated or unsaturated ring having 6 to 12 carbon atoms, Z represents a single bond, a double bond, a methylene group, or an oxygen atom.)
Claim 13:
The photo-acid generator of Claim 8 which consists of an oxime sulfonate compound shown by the following general formula (3b).

(In the formula, q represents 0 or 1, but when q is 0, p is a single bond, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, or a substituted or unsubstituted carbon group having 6 to 15 carbon atoms. Represents an aryl group, and when q is 1, p represents a substituted or unsubstituted alkylene group having 1 to 20 carbon atoms, or a substituted or unsubstituted arylene group having 6 to 15 carbon atoms, EWG represents a cyano group, A trifluoromethyl group, a perfluoroethyl group, a perfluoropropyl group, a 5H-perfluoropentyl group, a 6H-perfluorohexyl group, a nitro group or a methyl group. When q is 1, the EWGs are bonded to each other. And may form a ring of 6 carbon atoms together with the carbon atom to which they are bonded.)
Claim 14 :
Base resin in the resist composition comprising an acid generator and a solvent, the resist material, wherein the acid generator is a photoacid generator of any one of claims 8 to 13.
Claim 15 :
Base resin is poly (meth) acrylic acid and derivatives thereof, cycloolefin derivative-maleic anhydride alternating polymer, copolymer of cycloolefin derivative, maleic anhydride and polyacrylic acid or derivative thereof. , Cycloolefin derivative-α-trifluoromethylacrylic acid derivative copolymer, polynorbornene, ring-opening metathesis polymer, and one or more polymer polymers selected from hydrogenated ring-opening metathesis polymers The resist material according to claim 14 , wherein:
Claim 16 :
The resist material according to claim 14 , wherein the base resin is a polymer structure containing a silicon atom.
Claim 17 :
The resist material according to claim 14 , wherein the base resin is a polymer structure containing a fluorine atom.
Claim 18 :
15., 16 or 17, wherein the base resin contains a photoacid generator and a solvent according to any one of claims 8 to 13, wherein said base resin is insoluble or poorly soluble in the developing solution, acid A chemically amplified positive resist material that becomes soluble in the developer by the above.
Claim 19 :
The chemically amplified positive resist material according to claim 18 , further comprising a basic compound.
Claim 20 :
Furthermore, chemically amplified positive resist composition according to claim 18 or 19, wherein it contains a dissolution inhibitor.
Claim 21 :
A step of applying the resist material according to any one of claims 14 to 20 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 as necessary. And a step of developing using a developing solution.
Claim 22 :
The pattern forming method according to claim 21, wherein the wavelength using an ArF excimer laser of 193 nm, an immersion lithography technique to insert the liquid body between the resist material is applied the substrate and the projection lens.

  Since the sulfonic acid of the present invention has a hydroxyl group that is a polar group in the molecule, the acid diffusion length can be moderately suppressed by hydrogen bonding or the like, and the photoacid generator that generates these sulfonic acids is: It can be used without any problem in the steps of coating, baking before exposure, exposure, baking after exposure, and development in the device production process. Furthermore, it is difficult to be affected by water remaining on the wafer during ArF immersion exposure, and defects can be suppressed. Further, it can be converted to a bulky functional group such as an acyl group or an alkyl group by reacting with an acid halide, acid anhydride, or alkyl halide, and is also very useful as a synthetic intermediate. Furthermore, since it has a low molecular weight and a hydrophilic group, its accumulation in the body is low, and the fluorine substitution rate is low even when it is disposed of by combustion, so that it is highly combustible.

Sulfonate The sulfonate of the present invention is represented by the following general formula (1a).
_{CF 3 -CH (OH) -CF 2} SO 3 - M + (1a)
(In the formula, M ⁺ represents lithium ion, sodium ion, potassium ion, ammonium ion, or tetramethylammonium ion.)

  In addition, lithium salt, sodium salt, potassium salt, ammonium salt, and tetramethylammonium salt were shown for ease of synthesis and ease of isolation of sulfonate, but divalent cation calcium salt, magnesium salt, Other organic amine salts and the like may be used and are not particularly limited as long as they can exist as stable sulfonates.

Photoacid generator The photoacid generator of the present invention is sensitive to high energy rays of ultraviolet rays, far ultraviolet rays, electron beams, X-rays, excimer lasers, γ rays, or synchrotron radiation, and is represented by the following general formula (1). Compounds represented by sulfonium salts, iodonium salts, oxime sulfonates, and sulfonyloxyimides that generate the sulfonic acids shown are used as photoacid generators for chemically amplified resist materials.
CF ₃ —CH (OH) —CF ₂ SO ₃ ⁻ H ⁺ (1)

（式中、Ｒ¹、Ｒ²及びＲ³は相互に独立に置換もしくは非置換の炭素数１〜１０の直鎖状又は分岐状のアルキル基、アルケニル基又はオキソアルキル基、又は置換もしくは非置換の炭素数６〜１８のアリール基、アラルキル基又はアリールオキソアルキル基を示すか、あるいはＲ¹、Ｒ²及びＲ³のうちのいずれか２つ以上が相互に結合して式中の硫黄原子と共に環を形成してもよい。） Sulfonium salt The sulfonium salt according to the present invention is represented by the following general formula (2).

Wherein R ¹ , R ² and R ³ are each independently substituted or unsubstituted linear or branched alkyl group, alkenyl group or oxoalkyl group having 1 to 10 carbon atoms, or substituted or unsubstituted. An aryl group having 6 to 18 carbon atoms, an aralkyl group or an aryloxoalkyl group, or any two or more of R ¹ , R ² and R ³ are bonded to each other together with the sulfur atom in the formula A ring may be formed.)

R ¹ , R ² and R ³ in the above general formula (2) are each independently substituted or unsubstituted C 1-10 linear or branched alkyl group, alkenyl group or oxoalkyl group, or substituted Or an unsubstituted aryl group having 6 to 18 carbon atoms, an aralkyl group, or an aryloxoalkyl group, or any two or more of R ¹ , R ^2, and R ³ are bonded to each other in the formula You may form a ring with a sulfur atom. Specifically, as the alkyl group, methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, sec-butyl group, tert-butyl group, pentyl group, hexyl group, heptyl group, octyl group, cyclopentyl group, Examples include a cyclohexyl group, a cycloheptyl group, a cyclopropylmethyl group, a 4-methylcyclohexyl group, a cyclohexylmethyl group, a norbornyl group, an 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 2-oxocyclopentyl group, 2-oxocyclohexyl group, 2-oxopropyl group, 2-oxoethyl group, 2-cyclopentyl-2-oxoethyl group, 2-cyclohexyl-2-oxoethyl group, 2- ( And 4-methylcyclohexyl) -2-oxoethyl group. As the aryl group, phenyl group, naphthyl group, thienyl group, 4-hydroxyphenyl group, 4-methoxyphenyl group, 3-methoxyphenyl group, 2-methoxyphenyl group, 4-ethoxyphenyl group, 4-tert- Alkoxyphenyl group such as butoxyphenyl group and 3-tert-butoxyphenyl group, 2-methylphenyl group, 3-methylphenyl group, 4-methylphenyl group, 4-ethylphenyl group, 4-tert-butylphenyl group, 4 -Alkylphenyl groups such as butylphenyl group and 2,4-dimethylphenyl group, alkylnaphthyl groups such as methylnaphthyl group and ethylnaphthyl group, alkoxynaphthyl groups such as methoxynaphthyl group and ethoxynaphthyl group, dimethylnaphthyl group and diethylnaphthyl group Dialkyl naphthyl groups such as Group, dialkoxy naphthyl group such as diethoxy naphthyl group. Examples of the aralkyl group include a benzyl group, a 1-phenylethyl group, and a 2-phenylethyl group. As the aryloxoalkyl group, 2-aryl-2-oxoethyl group such as 2-phenyl-2-oxoethyl group, 2- (1-naphthyl) -2-oxoethyl group, 2- (2-naphthyl) -2-oxoethyl group and the like Groups and the like. When any two or more of R ¹ , R ² and R ³ are bonded to each other to form a cyclic structure via a sulfur atom, 1,4-butylene, 3-oxa-1, 5-pentylene and the like can be mentioned. Further examples of the substituent include an aryl group having a polymerizable substituent such as an acryloyloxy group and a methacryloyloxy group. Specific examples include 4- (acryloyloxy) phenyl group, 4- (methacryloyloxy) phenyl group, 4- Examples include (acryloyloxy) -3,5-dimethylphenyl group, 4- (methacryloyl) -3,5-dimethylphenyl group, 4-vinyloxyphenyl group, 4-vinylphenyl group and the like.

  More specifically, the sulfonium cation is represented by triphenylsulfonium, (4-tert-butoxyphenyl) diphenylsulfonium, bis (4-tert-butoxyphenyl) phenylsulfonium, tris (4-tert-butoxyphenyl) sulfonium, (3 -Tert-butoxyphenyl) diphenylsulfonium, bis (3-tert-butoxyphenyl) phenylsulfonium, tris (3-tert-butoxyphenyl) sulfonium, (3,4-ditert-butoxyphenyl) diphenylsulfonium, bis (3 4-ditert-butoxyphenyl) phenylsulfonium, tris (3,4-ditert-butoxyphenyl) sulfonium, diphenyl (4-thiophenoxyphenyl) sulfonium, (4-te t-butoxycarbonylmethyloxyphenyl) diphenylsulfonium, tris (4-tert-butoxycarbonylmethyloxyphenyl) sulfonium, (4-tert-butoxyphenyl) bis (4-dimethylaminophenyl) sulfonium, tris (4-dimethylaminophenyl) ) Sulfonium, 2-naphthyldiphenylsulfonium, dimethyl-2-naphthylsulfonium, 4-hydroxyphenyldimethylsulfonium, 4-methoxyphenyldimethylsulfonium, trimethylsulfonium, 2-oxocyclohexylcyclohexylmethylsulfonium, trinaphthylsulfonium, tribenzylsulfonium, diphenyl Methylsulfonium, dimethylphenylsulfonium, 2-oxo-2-phenylethylthiaci Lopentanium, diphenyl 2-thienylsulfonium, 4-n-butoxynaphthyl-1-thiacyclopentanium, 2-n-butoxynaphthyl-1-thiacyclopentanium, 4-methoxynaphthyl-1-thiacyclopentanium, 2- And methoxynaphthyl-1-thiacyclopentanium. More preferably, triphenylsulfonium, 4-tert-butylphenyldiphenylsulfonium, 4-tert-butoxyphenyldiphenylsulfonium, tris (4-tert-butylphenyl) sulfonium, (4-tert-butoxycarbonylmethyloxyphenyl) diphenylsulfonium, etc. Is mentioned. Further, (4-methacryloyloxyphenyl) diphenylsulfonium, (4-acryloyloxyphenyl) diphenylsulfonium, (4-methacryloyloxy-3,5-dimethylphenyl) diphenylsulfonium, (4-acryloyloxy-3,5-dimethylphenyl) Examples include diphenylsulfonium, (4-methacryloyloxyphenyl) dimethylsulfonium, (4-acryloyloxyphenyl) dimethylsulfonium, and the like. With respect to these polymerizable sulfonium cations, reference can be made to JP-A-4-230645, JP-A-2005-84365, etc., and these polymerizable sulfonium salts can be used as monomers of the constituents of the high molecular weight compounds described later. Can be used.

（式中、Ｒ⁴は置換もしくは非置換の炭素数１〜２０の直鎖状、分岐状又は環状のアルキル基又はアルケニル基、又は置換もしくは非置換の炭素数６〜１４のアリール基を示す。ｍは１〜５、ｎは０又は１を示す。） In this case, examples of the sulfonium salt include those represented by the following general formula (2a).

(In the formula, R ⁴ represents a substituted or unsubstituted linear, branched or cyclic alkyl group or alkenyl group having 1 to 20 carbon atoms, or a substituted or unsubstituted aryl group having 6 to 14 carbon atoms. m represents 1 to 5, and n represents 0 or 1.)

R ⁴ in the general formula (2a) is as described above, m is 1 to 5, and n is 0 (zero) or 1. The substitution position of the R ⁴ — (O) _n — group is not particularly limited, but the 4-position or 3-position of the phenyl group is preferable. More preferably, it is the 4th position. R ⁴ is methyl group, ethyl group, n-propyl group, sec-propyl group, cyclopropyl group, n-butyl group, sec-butyl group, isobutyl group, tert-butyl group, n-pentyl group, cyclopentyl group. N-hexyl group, cyclohexyl group, n-octyl group, n-decyl group, n-dodecyl group, trifluoromethyl group, phenyl group, 4-methoxyphenyl group, 4-tert-butylphenyl group, and n = 1 In this case, an acryloyl group, a methacryloyl group, a vinyl group, and an allyl group may be mentioned.

  Specific examples of the sulfonium cation include 4-methylphenyldiphenylsulfonium, 4-ethylphenyldiphenylsulfonium, 4-tert-butylphenyldiphenylsulfonium, 4-cyclohexylphenyldiphenylsulfonium, 4-n-hexylphenyldiphenylsulfonium, 4-n -Octylphenyldiphenylsulfonium, 4-methoxyphenyldiphenylsulfonium, 4-ethoxyphenyldiphenylsulfonium, 4-tert-butoxyphenyldiphenylsulfonium, 4-cyclohexyloxyphenyldiphenylsulfonium, 4-n-hexyloxyphenyldiphenylsulfonium, 4-n -Octyloxyphenyldiphenylsulfonium, 4-dodecyloxyphenyldiphenylsulfone Ni, 4-trifluoromethylphenyldiphenylsulfonium, 4-trifluoromethyloxyphenyldiphenylsulfonium, 4-tert-butoxycarbonylmethyloxyphenyldiphenylsulfonium, (4-methacryloyloxyphenyl) diphenylsulfonium, (4-acryloyloxyphenyl) Diphenylsulfonium, (4-methacryloyloxy-3,5-dimethylphenyl) diphenylsulfonium, (4-acryloyloxy-3,5-dimethylphenyl) diphenylsulfonium, (4-methacryloyloxyphenyl) dimethylsulfonium, (4-acryloyloxy) Phenyl) dimethylsulfonium and the like.

（式中、Ｒ⁴は置換もしくは非置換の炭素数１〜２０の直鎖状、分岐状又は環状のアルキル基又はアルケニル基、又は置換もしくは非置換の炭素数６〜１４のアリール基を示す。ｎは０又は１を示す。） Iodonium Salt The present invention also provides an iodonium salt. The iodonium salt of the present invention is represented by the following general formula (2b).

(In the formula, R ⁴ represents a substituted or unsubstituted linear, branched or cyclic alkyl group or alkenyl group having 1 to 20 carbon atoms, or a substituted or unsubstituted aryl group having 6 to 14 carbon atoms. n represents 0 or 1.)

R ⁴ in the general formula (2b) is as described above. The substitution position of the R ⁴ — (O) _n — group is not particularly limited, but the 4-position or 3-position of the phenyl group is preferable. More preferably, it is the 4th position. Specific iodonium cations include bis (4-methylphenyl) iodonium, bis (4-ethylphenyl) iodonium, bis (4-tert-butylphenyl) iodonium, bis (4- (1,1-dimethylpropyl) phenyl. ) Iodonium, 4-methoxyphenylphenyliodonium, 4-tert-butoxyphenylphenyliodonium, 4-acryloyloxyphenylphenyliodonium, 4-methacryloyloxyphenylphenyliodonium, among others, bis (4-tert-butylphenyl) Iodonium is preferably used.

（式中、Ｘ、Ｙは相互に独立に水素原子又は置換もしくは非置換の炭素数１〜６のアルキル基を示すか、あるいはＸ及びＹが相互に結合してそれらが結合している炭素原子と共に飽和もしくは不飽和の炭素数６〜１２の環を形成してもよい。Ｚは単結合、二重結合、メチレン基、又は酸素原子を示す。） N-sulfonyloxyimide compound The present invention also provides an N-sulfonyloxyimide compound represented by the following general formula (3a).

(In the formula, X and Y each independently represent a hydrogen atom or a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms, or X and Y are bonded to each other and bonded to each other) And may form a saturated or unsaturated ring having 6 to 12 carbon atoms, Z represents a single bond, a double bond, a methylene group, or an oxygen atom.)

  X and Y in the general formula (3a) each independently represent a hydrogen atom or a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms, or X and Y are bonded to each other to bond them. A saturated or unsaturated ring having 6 to 12 carbon atoms may be formed together with the carbon atoms. Z represents a single bond, a double bond, a methylene group, or an oxygen atom. The imide skeleton excluding the sulfonate part is specifically shown below. JP-A 2003-252855 can be referred to for the imide skeleton.

（式中、ｑは０又は１を示すが、ｑが０の場合、ｐは単結合、置換もしくは非置換の炭素数１〜２０のアルキル基、又は置換もしくは非置換の炭素数６〜１５のアリール基を示し、ｑが１の場合にはｐは置換もしくは非置換の炭素数１〜２０のアルキレン基、又は置換もしくは非置換の炭素数６〜１５のアリーレン基を示す。ＥＷＧはシアノ基、トリフルオロメチル基、パーフルオロエチル基、パーフルオロプロピル基、５Ｈ−パーフルオロペンチル基、６Ｈ−パーフルオロヘキシル基、ニトロ基又はメチル基を示し、ｑが１の場合、互いのＥＷＧが相互に結合してそれらが結合している炭素原子と共に炭素数６の環を形成してもよい。） Oxime sulfonate compound The present invention also provides an oxime sulfonate compound represented by the following general formula (3b).

(In the formula, q represents 0 or 1, but when q is 0, p is a single bond, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, or a substituted or unsubstituted carbon group having 6 to 15 carbon atoms. Represents an aryl group, and when q is 1, p represents a substituted or unsubstituted alkylene group having 1 to 20 carbon atoms, or a substituted or unsubstituted arylene group having 6 to 15 carbon atoms, EWG represents a cyano group, A trifluoromethyl group, a perfluoroethyl group, a perfluoropropyl group, a 5H-perfluoropentyl group, a 6H-perfluorohexyl group, a nitro group or a methyl group. When q is 1, the EWGs are bonded to each other. And may form a ring of 6 carbon atoms together with the carbon atom to which they are bonded.)

  Q in the general formula (3b) is 0 or 1, but when q is 0, p is a single bond, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, or a substituted or unsubstituted carbon number. 6 to 15 aryl groups, and when q is 1, p represents a substituted or unsubstituted alkylene group having 1 to 20 carbon atoms, or a substituted or unsubstituted arylene group having 6 to 15 carbon atoms. EWG represents cyano group, trifluoromethyl group, perfluoroethyl group, perfluoropropyl group, 5H-perfluoropentyl group, 6H-perfluorohexyl group, nitro group or methyl group. EWG may be bonded to each other to form a ring of 6 carbon atoms together with the carbon atom to which they are bonded. The skeletons of these oxime sulfonates are disclosed in U.S. Pat. No. 6,261,738, JP-A-9-95479, JP-A-9-208554, JP-A-9-230588, JP-A-2906999, JP-A-9-301948. This is described in Japanese Patent Laid-Open No. 2000-314956, Japanese Patent Laid-Open No. 2001-233842, and International Publication No. 2004/074242.

A more specific skeleton of oxime sulfonate excluding the sulfonate moiety is shown below.

Here, a method for synthesizing the sulfonium salt, iodonium salt, oxime sulfonate, and sulfonyloxyimide that generates the sulfonic acid represented by the general formula (1) of the present invention will be described.
1,1,3,3,3-hexafluoro-2-propanol developed by Nakai et al. As 1,1,3,3,3-pentafluoropropen-2-ylbenzoate (Tetrahedron. Lett , Vol. 29, 4119 (1988)), 1,1,3,3,3-pentafluoropropen-2-yl aliphatic or aromatic carboxylic acid ester is converted to sodium bisulfite or sodium sulfite and azobis. 2-acyloxy-1,1,3,3,3-pentafluoropropane-1 is reacted in water, alcohol or a mixture thereof as a solvent in the presence of a radical initiator such as isobutyronitrile or benzoyl peroxide. -Synthesis of sulfonates can be carried out (reference: RB Wagner et al., Synthetic Organic Chemistry p813-814, John Wiley & Sons, Inc. (1965). The conversion reaction to a sulfonium salt or an iodonium salt can be performed by a normal anion exchange method using the sulfonate.

  Onium salts are described in The Chemistry of sulfoneum group Part 1 John-Wiley & Sons (1981), Advanced Photochemistry, vol. 17 John-Wiley & Sons (1992); Org. Chem. , 1988.8.53.5571-5573, or JP-A-8-311018, JP-A-9-15848, JP-A-2001-122850, JP-A-7-25846, JP-A-2001-181221, The compound can be synthesized with reference to Japanese Unexamined Patent Publication No. 2002-193887 and Japanese Patent Application Laid-Open No. 2002-193925.

  Further, an onium cation having an acryloyloxy group or a methacryloyloxy group as a polymerizable substituent is obtained by converting an existing hydroxyphenyldiphenylsulfonium halide into a base by a method described in JP-A-4-230645, JP-A-2005-84365, or the like. It can be synthesized by reacting with acryloyl chloride or methacryloyl chloride under sexual conditions.

  Anion exchange can be performed with an alcohol solvent such as methanol or ethanol, or a two-layer system such as dichloromethane-water. Alternatively, as described in JP-A No. 2002-167340, a formulation in which a corresponding sulfonic acid methyl ester is reacted with sulfonium halide or iodonium halide to remove halide ions as methyl halide and anion exchange can be used.

  In addition, by reacting the sulfonate with a chlorinating agent such as thionyl chloride, phosphorus oxychloride, phosphorus pentachloride or the like, the corresponding sulfonyl chloride or sulfonic acid anhydride can be obtained. Imide sulfonate and oxime sulfonate can be synthesized by reacting with carboxyl imide and oximes. The synthesis of imide sulfonate and oxime sulfonate is described in JP-A No. 2003-252855, US Pat. No. 6,261,738, JP-A No. 9-95479, JP-A No. 9-208554, and JP-A No. 9-230588. No. 2,906,999, JP-A-9-301948, JP-A-2000-314956, JP-A-2001-233842, and International Publication No. 2004/074242.

Furthermore, the sulfonium salt, iodonium salt, imide sulfonate, and oxime sulfonate are hydrolyzed or solvolyzed in a water-alcohol or acetone mixed solvent in the presence of a base such as sodium hydroxide by a conventional method to obtain the above general formula ( 2), (2a), (2b), (3a) or (3b) can be synthesized.
More specifically, 2-acyloxy-1,1,3,3,3-pentafluoro-1-sulfonic acid salt is hydrolyzed in water in the presence of a base such as sodium hydroxide or tetrabutylammonium hydroxide. The compound of the general formula (1a) can be synthesized, and its generation can be confirmed by ¹⁹ F nuclear magnetic resonance spectrum ( ¹⁹ F-NMR) and time-of-flight mass spectrometry (TOFMS). Then, the compound of Formula (2), (2a), (2b) is also compoundable by anion exchange by a normal method.

By the way, when the sulfonate is produced, the sulfonate represented by the following general formula (1a ′) or (1a ″) in which hydrogen fluoride is eliminated from the sulfonate of the general formula (1a). May generate.
CF ₃ —C (OH) ═CFSO ₃ ⁻ M ⁺ (1a ′)
CF ₂ ═C (OH) CF ₂ SO ₃ ⁻ M ⁺ (1a ″)
(In the formula, M ⁺ represents lithium ion, sodium ion, potassium ion, ammonium ion, or tetramethylammonium ion.)

  When the sulfonate is obtained as a sulfonate mixture during the production of the sulfonate, the sulfonate represented by the general formula (1a) as the main component and the sulfone represented by the general formula (1a ′) or (1a ″) The ratio (molar ratio) to the acid salt is often from 100 to 0 to 100 to 10.

  In addition, in the sulfonates represented by the above formula (1a ′) or (1a ″), an anion having a mass number of 20 in addition to the main component anion is observed as a minute peak on the NEGATIVE side by time-of-flight mass spectrometry. (However, it depends on the abundance ratio and sensitivity).

  In addition, the sulfonate represented by the general formula (1a ′) or (1a ″) alone or a mixture with the sulfonate represented by the general formula (1a) is a photoacid generator or a sulfonium salt. In addition, an iodonium salt, an N-sulfonyloxyimide compound, or an oxime sulfonate compound may be synthesized, and a photoacid generator using a sulfonate salt represented by the general formula (1a ′) or (1a ″) as a raw material as a resist. It may be contained in a material, a chemically amplified positive resist material, or may be applied to a pattern forming method.

  More specifically, photo acid generators as shown below can be specifically mentioned, and these resist materials and pattern forming methods can be used in the same manner as in the present invention described later.

Responds to high energy rays irradiated with ultraviolet rays, far ultraviolet rays, electron beams, X-rays, excimer lasers, γ rays, or synchrotron radiation, and generates sulfonic acids represented by the following general formula (1 ′) or (1 ″) A photoacid generator for a chemically amplified resist material.
_{CF 3 -C (OH) = CFSO} 3 - H + (1 ')
CF ₂ ═C (OH) CF ₂ SO ₃ ⁻ H ⁺ (1 ″)

A sulfonium salt represented by the following general formula (2 ′) or (2 ″).
R ¹ R ² R ³ S ⁺ CF ₃ —C (OH) ═CFSO ₃ ⁻ (2 ′)
R ¹ R ² R ³ S ⁺ CF ₂ ═C (OH) CF ₂ SO ₃ ⁻ (2 ″)
Wherein R ¹ , R ² and R ³ are each independently substituted or unsubstituted linear or branched alkyl group, alkenyl group or oxoalkyl group having 1 to 10 carbon atoms, or substituted or unsubstituted. An aryl group having 6 to 18 carbon atoms, an aralkyl group or an aryloxoalkyl group, or any two or more of R ¹ , R ² and R ³ are bonded to each other together with the sulfur atom in the formula A ring may be formed.)

A sulfonium salt represented by the following general formula (2a ′) or (2a ″).
_{^{(R 4 - (O) n}} ) m -PhS + Ph 2 CF 3 -C (OH) = CFSO 3 - (2a ')
_{^{(R 4 - (O) n}} ) m -PhS + Ph 2 CF 2 = C (OH) CF 2 SO 3 - (2a '')
(In the formula, R ⁴ represents a substituted or unsubstituted linear, branched or cyclic alkyl group or alkenyl group having 1 to 20 carbon atoms, or a substituted or unsubstituted aryl group having 6 to 14 carbon atoms. Ph represents a phenyl group, m represents 1 to 5, and n represents 0 or 1.)

An iodonium salt represented by the following general formula (2b ′) or (2b ″).
_{^{R 4 (O) n -PhI +}} Ph (O) n -R 4 CF 3 -C (OH) = CFSO 3 -
(2b ')
_{^{R 4 (O) n -PhI +}} Ph (O) n -R 4 CF 2 = C (OH) CF 2 SO 3 -
(2b ″) (wherein R ⁴ , Ph, and n have the same meaning as in the above formula.)

（式中、Ｘ、Ｙは相互に独立に水素原子又は置換もしくは非置換の炭素数１〜６のアルキル基を示すか、あるいはＸ及びＹが相互に結合してそれらが結合している炭素原子と共に飽和もしくは不飽和の炭素数６〜１２の環を形成してもよい。Ｚは単結合、二重結合、メチレン基、又は酸素原子を示す。） N-sulfonyloxyimide compounds represented by the following general formula (3a ′) or (3a ″).

(In the formula, X and Y each independently represent a hydrogen atom or a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms, or X and Y are bonded to each other and bonded to each other) And may form a saturated or unsaturated ring having 6 to 12 carbon atoms, Z represents a single bond, a double bond, a methylene group, or an oxygen atom.)

（式中、ｑは０又は１を示すが、ｑが０の場合、ｐは単結合、置換もしくは非置換の炭素数１〜２０のアルキル基、又は置換もしくは非置換の炭素数６〜１５のアリール基を示し、ｑが１の場合にはｐは置換もしくは非置換の炭素数１〜２０のアルキレン基、又は置換もしくは非置換の炭素数６〜１５のアリーレン基を示す。ＥＷＧはシアノ基、トリフルオロメチル基、パーフルオロエチル基、パーフルオロプロピル基、５Ｈ−パーフルオロペンチル基、６Ｈ−パーフルオロヘキシル基、ニトロ基又はメチル基を示し、ｑが１の場合、互いのＥＷＧが相互に結合してそれらが結合している炭素原子と共に炭素数６の環を形成してもよい。） An oxime sulfonate compound represented by the following general formula (3b ′) or (3b ″).

(In the formula, q represents 0 or 1, but when q is 0, p is a single bond, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, or a substituted or unsubstituted carbon group having 6 to 15 carbon atoms. Represents an aryl group, and when q is 1, p represents a substituted or unsubstituted alkylene group having 1 to 20 carbon atoms, or a substituted or unsubstituted arylene group having 6 to 15 carbon atoms, EWG represents a cyano group, A trifluoromethyl group, a perfluoroethyl group, a perfluoropropyl group, a 5H-perfluoropentyl group, a 6H-perfluorohexyl group, a nitro group or a methyl group. When q is 1, the EWGs are bonded to each other. And may form a ring of 6 carbon atoms together with the carbon atom to which they are bonded.)

  In addition, the sulfonate represented by the above general formula (1a) obtained by the above method or the sulfonate of the above formula (2), (2a), (2b), (3a), (3b) can be obtained in the presence of a base such as triethylamine. By reacting a carboxylic acid halide or carboxylic acid anhydride in a solvent such as methylene chloride or acetonitrile, a sulfonate or sulfonium salt, iodonium salt, imide sulfonate, or oxime sulfonate having a carboxylic acid ester in the molecule. A photoacid generator can be obtained. Further, by reacting a divalent carboxylic acid halide such as adipic acid chloride, a photoacid generator of a divalent sulfonate or sulfonium salt, iodonium salt, imide sulfonate, or oxime sulfonate can be synthesized.

  The present invention firstly provides a photoacid generator for a chemically amplified resist material that generates the sulfonic acid represented by the general formula (1) by irradiation with high energy rays. The second provides sulfonium salts, iodonium salts, dicarboxylimide sulfonates, and oxime sulfonates useful as photoacid generators for chemically amplified resist materials, and the third provides general formula (1) by irradiation with high energy rays. A resist material containing a photoacid generator for a chemically amplified resist material that generates a sulfonic acid represented by the formula (1) and a resin whose solubility in an alkali developer is changed by the action of an acid.

Here, the resist material of the present invention is:
(A) The photoacid generator according to claim 2 (that is, the photoacid generator that generates the sulfonic acid of the formula (1)),
(B) an organic solvent,
(C) a base resin whose solubility in an alkaline developer is changed by the action of an acid,
If necessary (D) a basic compound,
If necessary, (E) a photoacid generator other than the photoacid generator according to claim 2,
If necessary, (F) an organic acid derivative and / or a fluorine-substituted alcohol,
Furthermore, (G) a chemically amplified positive resist material characterized by containing a dissolution inhibitor having a molecular weight of 3,000 or less, if necessary,
Or (A) the photoacid generator according to claim 2,
(B) an organic solvent,
(C ′) an alkali-soluble resin, which is hardly soluble in alkali by a crosslinking agent,
(H) a crosslinking agent that crosslinks with an acid,
If necessary (D) a basic compound,
If necessary, (E) a chemically amplified negative resist material containing a photoacid generator other than the photoacid generator according to claim 2.

  The photoacid generator according to claim 2 of the component (A) of the present invention is as described above. More specifically, the general formula (2), (2a), (2b), (3a) or ( The compound of 3b) is mentioned, The compounding quantity is 0.1-10 parts with respect to 100 parts of base resins in a resist material (mass part, the same hereafter), especially 1-7 parts.

  The organic solvent of the component (B) used in the present invention may be any organic solvent that can dissolve the base resin, acid generator, other additives, and the like. Examples of such organic solvents include ketones such as cyclohexanone and methyl amyl ketone, 3-methoxybutanol, 3-methyl-3-methoxybutanol, 1-methoxy-2-propanol, 1-ethoxy-2-propanol, and the like. Alcohols, 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, 3-ethoxypropio Examples include esters such as ethyl acid, tert-butyl acetate, tert-butyl propionate, propylene glycol mono tert-butyl ether acetate, and lactones such as γ-butyrolactone. These are used alone or in combination of two or more. However, it is not limited to these.

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

  The amount of the organic solvent used is preferably 200 to 3,000 parts, particularly 400 to 2,000 parts, based on 100 parts of the base resin.

The base resin of component (C) or component (C ′) used in the present invention is polyhydroxystyrene (PHS), PHS and styrene, (meth) acrylic acid ester, and other polymerizations for KrF excimer laser resist materials. Copolymers with functional olefin compounds, ArF excimer laser resist materials, (meth) acrylic acid esters, alternating copolymers of cycloolefin and maleic anhydride, and further vinyl ethers or (meth) acrylic esters Copolymer, polynorbornene, cycloolefin ring-opening metathesis polymerization system, cycloolefin ring-opening metathesis polymer hydrogenated product, etc., and fluorine substitution of the above KrF and ArF polymers for F ₂ excimer laser resist materials Body, etc., but these polymerization polymers It is not to be limited. Furthermore, the sulfonium salt and iodonium salt of the present invention having a polymerizable substituent, specifically, (4-acryloyloxyphenyl) diphenylsulfonium cation, (4-methacryloyloxyphenyl) diphenylsulfonium cation, (4-acryloyloxyphenyl) Sulphonium salts, iodonium by combinations of onium cations such as phenyliodonium cation and (4-methacryloyloxyphenyl) phenyliodonium cation and anions such as 1,1,3,3,3-pentafluoro-2-hydroxypropane-1-sulfonate Salts can be used as polymerization components for these base resins. The base resins can be used alone or in combination of two or more. In the case of a positive resist material, the dissolution rate of unexposed areas is generally reduced by substituting phenol or carboxyl groups or hydroxyl groups of fluorinated alkyl alcohols with acid labile groups.

  These base resins are not particularly limited, but include JP-A 2000-159758, JP-A 2000-186118, JP-A 2000-309611, JP-A 2000-327633, and JP-A 2000-330283. JP 2001-329052, JP 2002-202609, JP 2002-161116, JP 2003-28813, JP 2003-20313, JP 2003-26728, JP 2003-34706, JP 2003-64134, JP-A-2003-66612, JP-A-2003-113213, JP-A-2003-316027, JP-A-2003-321466, JP-A-2004-143153, JP-A-2004-124082, JP-A-2004 -115486, JP-A-2004-62175 They include those described in distribution.

  In this case, in particular, the base resin is poly (meth) acrylic acid and derivatives thereof, cycloolefin derivative-maleic anhydride alternating polymer, cycloolefin derivative, maleic anhydride and polyacrylic acid or derivatives thereof. One or more selected from the above copolymers, cycloolefin derivatives-α-trifluoromethylacrylic acid derivative copolymers, polynorbornene, ring-opening metathesis polymers, and ring-opening metathesis polymers hydrogenated products It is preferable that it is a high molecular polymer.

The base resin is preferably a polymer structure containing a silicon atom or a polymer structure containing a fluorine atom.
These are disclosed in JP-A-2005-8765, JP-A-2004-354417, JP-A-2004-352743, JP-A-2004-331854, JP-A-2004-331853, and JP-A-2004-292781. JP-A-2004-252405, JP-A-2004-190036, JP-A-2004-115762, JP-A-2004-83873, JP-A-2004-59844, JP-A-2004-35671, JP-A-2004-83900, JP-A-2004-99689, JP-A-2004-145048, JP-A-2004-217533, JP-A-2004-231815, JP-A-2004-244439, JP-A-2004 JP-A-256562, JP-A-2004-30744 , JP 2004-323422, JP 2005-29527 JP include those described, for example, in JP-A-2005-29539.

  As described above, in the case of a chemically amplified positive resist material, the base resin has an acid labile group, is insoluble or hardly soluble in the developer, and the acid labile group is decomposed by the acid. Those that are soluble in the developer are used. In this case, the acid labile group of the base resin is variously selected, and in particular, an acetal group having 2 to 30 carbon atoms and a tertiary alkyl group having 4 to 30 carbon atoms represented by the following formulas (C1) and (C2). Etc.

In the above formulas (C1) and (C2), R ⁵ and R ⁶ are a hydrogen atom or a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms, and a heteroatom such as oxygen, sulfur, nitrogen or fluorine. R ⁷ , R ⁸ , R ⁹ and R ¹⁰ are each a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 10 carbon atoms, or a 7 to 10 carbon atoms. An aralkyl group, which may contain a heteroatom such as oxygen, sulfur, nitrogen and fluorine. R ⁵ and R ⁶ , R ⁵ and R ⁷ , R ⁶ and R ⁷ , R ⁸ and R ⁹ , R ⁸ and R ¹⁰ , R ⁹ and R ¹⁰ are bonded to each other and the number of carbon atoms together with the carbon atom to which they are bonded. You may form 3-30 rings.

  Specific examples of the acetal group represented by the formula (C1) include methoxymethyl group, ethoxymethyl group, propoxymethyl group, butoxymethyl group, isopropoxymethyl group, t-butoxymethyl group, 1-methoxyethyl group, 1 -Methoxypropyl group, 1-methoxybutyl group, 1-ethoxyethyl group, 1-ethoxypropyl group, 1-ethoxybutyl group, 1-propoxyethyl group, 1-propoxypropyl group, 1-propoxybutyl group, 1-cyclopentyl Oxyethyl group, 1-cyclohexyloxyethyl group, 2-methoxyisopropyl group, 2-ethoxyisopropyl group, 1-phenoxyethyl group, 1-benzyloxyethyl group, 1-phenoxypropyl group, 1-benzyloxypropyl group, 1 -Adamantyloxyethyl group, 1-adamantyloxy Propyl group, 2-tetrahydrofuryl group, 2-tetrahydro-2H-pyranyl group, 1- (2-cyclohexanecarbonyloxyethoxy) ethyl group, 1- (2-cyclohexanecarbonyloxyethoxy) propyl group, 1- [2- ( Examples thereof include, but are not limited to, 1-adamantylcarbonyloxy) ethoxy] ethyl group and 1- [2- (1-adamantylcarbonyloxy) ethoxy] propyl group.

Specific examples of the tertiary alkyl group represented by the above formula (C2) include t-butyl group, t-pentyl group, 1-ethyl-1-methylpropyl group, 1,1-diethylpropyl group, 1,1, 2-trimethylpropyl group, 1-adamantyl-1-methylethyl group, 1-methyl-1- (2-norbornyl) ethyl group, 1-methyl-1- (tetrahydrofuran-2-yl) ethyl group, 1-methyl- 1- (7-oxanalbornan-2-yl) ethyl group, 1-methylcyclopentyl group, 1-ethylcyclopentyl group, 1-propylcyclopentyl group, 1-cyclopentylcyclopentyl group, 1-cyclohexylcyclopentyl group, 1- (2 -Tetrahydrofuryl) cyclopentyl group, 1- (7-oxanalbornan-2-yl) cyclopentyl group, 1-methylcyclo Xyl group, 1-ethylcyclohexyl group, 1-cyclopentylcyclohexyl group, 1-cyclohexylcyclohexyl group, 2-methyl-2-norbornyl group, 2-ethyl-2-norbornyl group, 8-methyl-8-tricyclo [5.2 .1.0 ^2,6 ] decyl group, 8-ethyl-8-tricyclo [5.2.1.0 ^2,6 ] decyl group, 3-methyl-3-tetracyclo [4.4.0.1 ^{2, 5,} 1 ^7,10] dodecyl group, 3-ethyl-3-tetracyclo [4.4.0.1 ^{2, 5,} 1 ^7,10] dodecyl group, 2-methyl-2-adamantyl group, 2-ethyl - 2-adamantyl group, 1-methyl-3-oxo-1-cyclohexyl group, 1-methyl-1- (tetrahydrofuran-2-yl) ethyl group, 5-hydroxy-2-methyl-2-adamantyl group, 5-hydroxy -2-ethyl Although a 2-adamantyl group can be illustrated, it is not limited to these.

  Further, 1 mol% or more of the hydrogen atoms of the hydroxyl group of the base resin may be intermolecularly or intramolecularly crosslinked by an acid labile group represented by the following general formula (C3a) or (C3b).

In said formula, R < ¹¹ >, R < ¹² > shows a hydrogen atom or a C1-C8 linear, branched or cyclic alkyl group. R ¹¹ and R ¹² may combine to form a ring, and when forming a ring, R ¹¹ and R ¹² represent a linear or branched alkylene group having 1 to 8 carbon atoms. R ¹³ is a linear, branched or cyclic alkylene group having 1 to 10 carbon atoms, and b is 0 or an integer of 1 to 10. A represents an a + 1 valent aliphatic or alicyclic saturated hydrocarbon group having 1 to 50 carbon atoms, an aromatic hydrocarbon group or a heterocyclic group, and these groups may intervene a heteroatom, or A part of hydrogen atoms bonded to the carbon atom 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—. a is an integer of 1-7.

  Specific examples of the crosslinked acetal represented by the general formulas (C3a) and (C3b) include the following formulas (C3) -1 to (C3) -8, but are not limited thereto.

  The polystyrene-based weight average molecular weight of the base resin by gel permeation chromatography (GPC) is preferably 2,000 to 100,000, and if it is less than 2,000, the film formability and resolution are poor. If it exceeds 100,000, the resolution may be inferior, or foreign matter may be generated during pattern formation.

  The ratio of the monomer unit containing an acid labile group to the monomer unit (structural unit) of these base resins is 1 to 70%, preferably 20 to 60% in the base resin for ArF excimer laser resist material, and KrF excimer. In the base resin for laser resist material, it is 1 to 50%, preferably 20 to 40%.

  As monomer units other than the above-mentioned monomer units containing acid labile groups, base resins for ArF excimer laser resist materials include polar resins such as alcohols, fluorine-substituted alcohols, ethers, lactones, esters, acid anhydrides, and carboxylic acids. It is preferable that a monomer unit containing a group is introduced. Further, styrene, indene, 4-acetoxystyrene or the like may be introduced into the base resin for the KrF excimer laser resist material in addition to the 4-hydroxystyrene unit into which no acid labile group has been introduced. These monomer units are preferably introduced in one kind or two or more kinds.

  As the basic compound of component (D), a compound capable of suppressing the diffusion rate when the acid generated from the photoacid generator diffuses into the resist film is suitable. By mixing such a basic compound, , The acid diffusion rate in the resist film is suppressed, the resolution is improved, the sensitivity change after exposure is suppressed, the substrate and environment dependency is reduced, and the exposure margin and pattern profile are improved. it can.

  Examples of such basic compounds include primary, secondary, and tertiary aliphatic amines, hybrid amines, aromatic amines, heterocyclic amines, nitrogen-containing compounds having a carboxy group, and sulfonyl groups. A nitrogen-containing compound having a hydroxyl group, a nitrogen-containing compound having a hydroxyl group, a nitrogen-containing compound having a hydroxyphenyl group, an alcoholic nitrogen-containing compound, an amide derivative, an imide derivative, and the like.

  Specifically, primary aliphatic amines include ammonia, methylamine, ethylamine, n-propylamine, isopropylamine, n-butylamine, isobutylamine, sec-butylamine, tert-butylamine, pentylamine, tert- Amylamine, cyclopentylamine, hexylamine, cyclohexylamine, heptylamine, octylamine, nonylamine, decylamine, dodecylamine, cetylamine, methylenediamine, ethylenediamine, tetraethylenepentamine, etc. are exemplified as secondary aliphatic amines. Dimethylamine, diethylamine, di-n-propylamine, diisopropylamine, di-n-butylamine, diisobutylamine, di-sec-butylamine, dipentylamine, disi Lopentylamine, dihexylamine, dicyclohexylamine, diheptylamine, dioctylamine, dinonylamine, didecylamine, didodecylamine, dicetylamine, N, N-dimethylmethylenediamine, N, N-dimethylethylenediamine, N, N-dimethyltetraethylenepenta Examples of tertiary aliphatic amines include trimethylamine, triethylamine, tri-n-propylamine, triisopropylamine, tri-n-butylamine, triisobutylamine, tri-sec-butylamine, and tripentylamine. , Tricyclopentylamine, trihexylamine, tricyclohexylamine, triheptylamine, trioctylamine, trinonylamine, tridecylamine, tridodecylamine, Examples include cetylamine, N, N, N ′, N′-tetramethylmethylenediamine, N, N, N ′, N′-tetramethylethylenediamine, N, N, N ′, N′-tetramethyltetraethylenepentamine and the like. Is done.

  Examples of hybrid amines include dimethylethylamine, methylethylpropylamine, benzylamine, phenethylamine, and benzyldimethylamine. 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-dim Lupyrrole, 2,5-dimethylpyrrole, N-methylpyrrole, etc.), oxazole derivatives (eg oxazole, isoxazole etc.), thiazole derivatives (eg thiazole, isothiazole etc.), imidazole derivatives (eg imidazole, 4-methylimidazole, 4 -Methyl-2-phenylimidazole, etc.), pyrazole derivatives, furazane derivatives, pyrroline derivatives (eg pyrroline, 2-methyl-1-pyrroline etc.), pyrrolidine derivatives (eg pyrrolidine, N-methylpyrrolidine, pyrrolidinone, N-methylpyrrolidone etc.) ), Imidazoline derivatives, imidazolidine derivatives, pyridine derivatives (eg pyridine, methylpyridine, ethylpyridine, propylpyridine, butylpyridine, 4- (1-butylpentyl) pyridine, dimethyl) Lysine, 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 derivatives, pyrimidine derivatives, pyrazine derivatives, pyrazoline derivatives, pyrazolidine derivatives, piperidine Derivatives, piperazine derivatives, morpholine derivatives, indole derivatives, isoindole derivatives, 1H-indazole derivatives, indoline derivatives, quinoline derivatives (eg quinoline, 3-quinoline carbo Nitriles), isoquinoline derivatives, cinnoline derivatives, quinazoline derivatives, quinoxaline derivatives, phthalazine derivatives, purine derivatives, pteridine derivatives, carbazole derivatives, phenanthridine derivatives, acridine derivatives, phenazine derivatives, 1,10-phenanthroline derivatives, adenine derivatives, adenosine Examples include derivatives, guanine derivatives, guanosine derivatives, uracil derivatives, uridine derivatives and the like.

  Furthermore, examples of the nitrogen-containing compound having a carboxy group include aminobenzoic acid, indolecarboxylic acid, amino acid derivatives (for example, 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, and examples of the nitrogen-containing compound having a sulfonyl group include 3-pyridinesulfonic acid, pyridinium p-toluenesulfonate, and the like. Nitrogen-containing compounds having a hydroxyl group, nitrogen-containing compounds having a hydroxyphenyl group, and alcoholic nitrogen-containing compounds include 2-hydroxypyridine, aminocresol, 2,4-quinolinediol, and 3-indolemethanol. Drate, monoethanolamine, 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, piperidineethanol, 1- (2-hydroxyethyl) pyrrolidine, 1- (2-hydroxyethyl) -2-pyrrolidinone, 3-piperidino-1,2-propanediol, 3-pyrrolidino-1,2-propane Diol, 8-hydroxyuroli , 3-cuincridinol, 3-tropanol, 1-methyl-2-pyrrolidineethanol, 1-aziridineethanol, N- (2-hydroxyethyl) phthalimide, N- (2-hydroxyethyl) isonicotinamide, etc. Illustrated. Examples of amide derivatives include formamide, N-methylformamide, N, N-dimethylformamide, acetamide, N-methylacetamide, N, N-dimethylacetamide, propionamide, benzamide and the like. Examples of imide derivatives include phthalimide, succinimide, maleimide and the like.

  Furthermore, 1 type, or 2 or more types chosen from the basic compound shown by the following general formula (Am) -1 can also be added.

N (Rx) _k (Ry) _3-k (Am) -1
(In the formula, k is 1, 2 or 3. The side chains Rx may be the same or different and can be represented by the following general formulas (Rx) -1 to (Rx) -3. The side chain Ry is The same or different hydrogen atom, or a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms, which may contain an ether group or a hydroxyl group, and Rx are bonded to form a ring. You may do it.)

In the above formula, R ³⁰¹ , R ³⁰³ , and R ³⁰⁶ are linear or branched alkylene groups having 1 to 4 carbon atoms, and R ³⁰² and R ³⁰⁵ are hydrogen atoms or linear groups having 1 to 20 carbon atoms, It is a branched or cyclic alkyl group and may contain one or a plurality of hydroxy groups, ether groups, ester groups or lactone rings.
R ³⁰⁴ is a single bond, a linear or branched alkylene group having 1 to 4 carbon atoms, R ³⁰⁷ is a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms, a hydroxy group, One or more ether groups, ester groups or lactone rings may be included.

Specific examples of the compound represented by the general formula (Am) -1 are given 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, 1,4,10,13-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-formyloxyethyl) amine, tris (2-acetoxyethyl) amine, Tris (2-propionyloxyethyl) amine, tris (2-butyryloxyethyl) amine, tris (2-isobutyryloxyethyl) amine, tris (2-valeryloxyethyl) amine, tris (2-pivalloy) Ruoxyxyethyl) 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) Tylamine, 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-acetoxy) Ethyl) 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 ( -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-formyl) Oxyethyl) 2- (2-formyloxyate) Sicarbonyl) ethylamine, N, N-bis (2-methoxyethyl) 2- (methoxycarbonyl) ethylamine, N- (2-hydroxyethyl) bis [2- (methoxycarbonyl) ethyl] amine, N- (2-acetoxy) Ethyl) bis [2- (methoxycarbonyl) ethyl] amine, N- (2-hydroxyethyl) bis [2- (ethoxycarbonyl) ethyl] amine, N- (2-acetoxyethyl) bis [2- (ethoxycarbonyl) Ethyl] amine, N- (3-hydroxy-1-propyl) bis [2- (methoxycarbonyl) ethyl] amine, N- (3-acetoxy-1-propyl) bis [2- (methoxycarbonyl) ethyl] amine, N- (2-methoxyethyl) bis [2- (methoxycarbonyl) ethyl] amine, N-butylbis [2 -(Methoxycarbonyl) ethyl] amine, N-butylbis [2- (2-methoxyethoxycarbonyl) ethyl] amine, N-methylbis (2-acetoxyethyl) amine, N-ethylbis (2-acetoxyethyl) amine, N- Methylbis (2-pivaloyloxyoxyethyl) amine, N-ethylbis [2- (methoxycarbonyloxy) ethyl] amine, N-ethylbis [2- (tert-butoxycarbonyloxy) ethyl] amine, tris (methoxycarbonylmethyl) Examples include, but are not limited to, amine, tris (ethoxycarbonylmethyl) amine, N-butylbis (methoxycarbonylmethyl) amine, N-hexylbis (methoxycarbonylmethyl) amine, and β- (diethylamino) -δ-valerolactone.

（式中、Ｒｘは前述の通り、Ｒ³⁰⁸は炭素数２〜２０の直鎖状又は分岐状のアルキレン基であり、カルボニル基、エーテル基、エステル基又はスルフィドを１個あるいは複数個含んでいてもよい。） Further, one or more basic compounds having a cyclic structure represented by the following general formula (Am) -2 may be added.

(Wherein, Rx is as defined above, R ³⁰⁸ is a straight or branched alkylene group having 2 to 20 carbon atoms, a carbonyl group, an ether group, optionally contain one or more ester or sulfide groups May be good.)

  Specific examples of the formula (Am) -2 include 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) ethyl formate, 2-piperidinoethyl propionate, 2-morpholinoethyl acetoxyacetate, 2- (1-pyrrolidinyl) ethyl methoxyacetate, 4- [2- (methoxycarbonyloxy) ethyl Morpholine, 1- [2- (t-butoxycarbonyloxy) ethyl] piperidine, 4- [2- (2-methoxyethoxycarbonyloxy) ethyl] morpholine, methyl 3- (1-pyrrolidinyl) propionate, 3-piperidi Methyl nopropionate, methyl 3-morpholinopropionate, methyl 3- (thiomorpholino) propionate, methyl 2-methyl-3- (1-pyrrolidinyl) propionate, ethyl 3-morpholinopropionate, 3-piperidinopropion Methoxycarbonylmethyl acid, 2-hydroxyethyl 3- (1-pyrrolidinyl) propionate, 2-acetoxyethyl 3-morpholinopropionate, 2-oxotetrahydrofuran-3-yl 3- (1-pyrrolidinyl) propionate, 3-morpholino Propionic acid tetrahydrofur Ryl, glycidyl 3-piperidinopropionate, 2-methoxyethyl 3-morpholinopropionate, 2- (2-methoxyethoxy) ethyl 3- (1-pyrrolidinyl) propionate, butyl 3-morpholinopropionate, 3-pi Cyclohexyl peridinopropionate, α- (1-pyrrolidinyl) methyl-γ-butyrolactone, β-piperidino-γ-butyrolactone, β-morpholino-δ-valerolactone, methyl 1-pyrrolidinyl acetate, methyl piperidinoacetate, methyl morpholinoacetate, Mention may be made of methyl thiomorpholinoacetate, ethyl 1-pyrrolidinyl acetate, 2-methoxyethyl morpholinoacetate.

（式中、Ｒｘ、Ｒ³⁰⁸、ｋは前述の式（Ａｍ）−１の通り、Ｒ³⁰⁹、Ｒ³¹⁰は同一又は異種の炭素数１〜４の直鎖状又は分岐状のアルキレン基である。） Furthermore, a basic compound containing a cyano group represented by the following general formulas (Am) -3 to (Am) -6 can be added.

(Wherein, Rx, R ^308, k is the aforementioned formula (Am) as -1, R ^309, R ³¹⁰ is a straight or branched alkylene group having the same carbon atoms or a heterologous 1-4. )

  Specific examples of the basic compound containing a cyano group include 3- (diethylamino) propiononitrile, N, N-bis (2-hydroxyethyl) -3-aminopropiononitrile, N, N-bis (2-acetoxy). Ethyl) -3-aminopropiononitrile, N, N-bis (2-formyloxyethyl) -3-aminopropiononitrile, N, N-bis (2-methoxyethyl) -3-aminopropiononitrile, N , N-bis [2- (methoxymethoxy) ethyl] -3-aminopropiononitrile, methyl N- (2-cyanoethyl) -N- (2-methoxyethyl) -3-aminopropionate, N- (2- Cyanoethyl) -N- (2-hydroxyethyl) -3-aminopropionic acid methyl, N- (2-acetoxyethyl) -N- (2-cyanoethyl) -3 Methyl aminopropionate, N- (2-cyanoethyl) -N-ethyl-3-aminopropiononitrile, N- (2-cyanoethyl) -N- (2-hydroxyethyl) -3-aminopropiononitrile, N- (2-acetoxyethyl) -N- (2-cyanoethyl) -3-aminopropiononitrile, N- (2-cyanoethyl) -N- (2-formyloxyethyl) -3-aminopropiononitrile, N- ( 2-cyanoethyl) -N- (2-methoxyethyl) -3-aminopropiononitrile, N- (2-cyanoethyl) -N- [2- (methoxymethoxy) ethyl] -3-aminopropiononitrile, N- (2-cyanoethyl) -N- (3-hydroxy-1-propyl) -3-aminopropiononitrile, N- (3-acetoxy-1-propyl -N- (2-cyanoethyl) -3-aminopropiononitrile, N- (2-cyanoethyl) -N- (3-formyloxy-1-propyl) -3-aminopropiononitrile, N- (2-cyanoethyl) ) -N-tetrahydrofurfuryl-3-aminopropiononitrile, N, N-bis (2-cyanoethyl) -3-aminopropiononitrile, diethylaminoacetonitrile, N, N-bis (2-hydroxyethyl) aminoacetonitrile, N, N-bis (2-acetoxyethyl) aminoacetonitrile, N, N-bis (2-formyloxyethyl) aminoacetonitrile, N, N-bis (2-methoxyethyl) aminoacetonitrile, N, N-bis [2 -(Methoxymethoxy) ethyl] aminoacetonitrile, N-cyanomethyl-N- (2-me Methyl toxiethyl) -3-aminopropionate, methyl N-cyanomethyl-N- (2-hydroxyethyl) -3-aminopropionate, methyl N- (2-acetoxyethyl) -N-cyanomethyl-3-aminopropionate, N-cyanomethyl-N- (2-hydroxyethyl) aminoacetonitrile, N- (2-acetoxyethyl) -N- (cyanomethyl) aminoacetonitrile, N-cyanomethyl-N- (2-formyloxyethyl) aminoacetonitrile, N- Cyanomethyl-N- (2-methoxyethyl) aminoacetonitrile, N-cyanomethyl-N- [2- (methoxymethoxy) ethyl] aminoacetonitrile, N- (cyanomethyl) -N- (3-hydroxy-1-propyl) aminoacetonitrile N- (3-acetoxy-1-propyl Pyr) -N- (cyanomethyl) aminoacetonitrile, N-cyanomethyl-N- (3-formyloxy-1-propyl) aminoacetonitrile, N, N-bis (cyanomethyl) aminoacetonitrile, 1-pyrrolidinepropiononitrile, 1- Piperidine propiononitrile, 4-morpholine propiononitrile, 1-pyrrolidine acetonitrile, 1-piperidine acetonitrile, 4-morpholine acetonitrile, cyanomethyl 3-diethylaminopropionate, N, N-bis (2-hydroxyethyl) -3-aminopropion Cyanomethyl acid, cyanomethyl N, N-bis (2-acetoxyethyl) -3-aminopropionate, cyanomethyl N, N-bis (2-formyloxyethyl) -3-aminopropionate, N, N-bis (2- Meto Cyethyl) -3-aminopropionic acid cyanomethyl, N, N-bis [2- (methoxymethoxy) ethyl] -3-aminopropionic acid cyanomethyl, 3-diethylaminopropionic acid (2-cyanoethyl), N, N-bis (2 -Hydroxyethyl) -3-aminopropionic acid (2-cyanoethyl), N, N-bis (2-acetoxyethyl) -3-aminopropionic acid (2-cyanoethyl), N, N-bis (2-formyloxyethyl) ) -3-Aminopropionic acid (2-cyanoethyl), N, N-bis (2-methoxyethyl) -3-aminopropionic acid (2-cyanoethyl), N, N-bis [2- (methoxymethoxy) ethyl] -3-aminopropionic acid (2-cyanoethyl), cyanomethyl 1-pyrrolidinepropionate, 1-piperidinepropiate Illustrative examples include cyanomethyl onate, cyanomethyl 4-morpholine propionate, 1-pyrrolidinepropionic acid (2-cyanoethyl), 1-piperidinepropionic acid (2-cyanoethyl), 4-morpholine propionic acid (2-cyanoethyl).

  Furthermore, examples of the basic compound include compounds described in JP-A Nos. 2004-347736 and 2004-347738.

  These basic compounds can be used alone or in combination of two or more, and the compounding amount is preferably 0 to 2 parts, particularly 0.05 to 1 part, relative to 100 parts of the base resin.

  In addition to the photoacid generator of the formula (1) of the present invention, when the photoacid generator of component (E) is added, ultraviolet rays, far ultraviolet rays, electron beams, X-rays, excimer lasers, γ rays, synchrotrons are used. Any compound may be used as long as it generates an acid upon irradiation with high energy rays such as Thoron radiation. Suitable photoacid generators include photoacid generators such as sulfonium salts, iodonium salts, sulfonyldiazomethane, N-sulfonyloxydicarboximide, O-arylsulfonyloxime, O-alkylsulfonyloxime, and the like. Although described in detail below, these may be used alone or in combination of two or more.

The sulfonium salt is a salt of a sulfonium cation and a sulfonate or bis (substituted alkylsulfonyl) imide or tris (substituted alkylsulfonyl) methide. As the sulfonium cation, triphenylsulfonium, (4-tert-butoxyphenyl) diphenylsulfonium, bis (4 -Tert-butoxyphenyl) phenylsulfonium, tris (4-tert-butoxyphenyl) sulfonium, (3-tert-butoxyphenyl) diphenylsulfonium, bis (3-tert-butoxyphenyl) phenylsulfonium, tris (3-tert-butoxy Phenyl) sulfonium, (3,4-ditert-butoxyphenyl) diphenylsulfonium, bis (3,4-ditert-butoxyphenyl) phenylsulfo , Tris (3,4-ditert-butoxyphenyl) sulfonium, diphenyl (4-thiophenoxyphenyl) sulfonium, (4-tert-butoxycarbonylmethyloxyphenyl) diphenylsulfonium, tris (4-tert-butoxycarbonylmethyloxy) Phenyl) sulfonium, (4-tert-butoxyphenyl) bis (4-dimethylaminophenyl) sulfonium, tris (4-dimethylaminophenyl) sulfonium, 4-methylphenyldiphenylsulfonium, 4-tert-butylphenyldiphenylsulfonium, bis ( 4-methylphenyl) phenylsulfonium, bis (4-tet-butylphenyl) phenylsulfonium, tris (4-methylphenyl) sulfonium, tris (4-te t-butylphenyl) sulfonium, tris (phenylmethyl) sulfonium, 2-naphthyldiphenylsulfonium, dimethyl-2-naphthylsulfonium, 4-hydroxyphenyldimethylsulfonium, 4-methoxyphenyldimethylsulfonium, trimethylsulfonium, 2-oxocyclohexylcyclohexylmethyl Sulfonium, trinaphthylsulfonium, tribenzylsulfonium, diphenylmethylsulfonium, dimethylphenylsulfonium, 2-oxopropylthiacyclopentanium, 2-oxobutylthiacyclopentanium, 2-oxo-3,3dimethylbutylthiacyclopentanium, 2-oxo-2-phenylethylthiacyclopentanium, 4-n-butoxynaphthyl-1-thiacyclopentaniu , 2-n-butoxynaphthyl-1-thiacyclopentanium, etc., and sulfonates include trifluoromethane sulfonate, pentafluoroethane sulfonate, heptafluoropropane sulfonate, nonafluorobutane sulfonate, tridecafluorohexane sulfonate, hepta Decafluorooctane sulfonate, perfluoro-4-ethylcyclohexane sulfonate, 2,2,2-trifluoroethane sulfonate, pentafluorobenzene sulfonate, 4-trifluoromethylbenzene sulfonate, 4-fluorobenzene sulfonate, mesitylene sulfonate, 2,4 , 6-Triisopropylbenzenesulfonate, toluenesulfonate, benzenesulfonate, 4- (4′-toluenesulfonyloxy) ) Benzenesulfonate, 6- (4-toluenesulfonyloxy) naphthalene-2-sulfonate, 4- (4-toluenesulfonyloxy) naphthalene-1-sulfonate, 5- (4-toluenesulfonyloxy) naphthalene-1-sulfonate, 8 -(4-toluenesulfonyloxy) naphthalene-1-sulfonate, naphthalenesulfonate, camphorsulfonate, octanesulfonate, dodecylbenzenesulfonate, butanesulfonate, methanesulfonate, 1,1-difluoro-2-naphthyl-ethanesulfonate, 1,1, 2,2-tetrafluoro-2- (norbornan-2-yl) ethanesulfonate, 1,1,2,2-tetrafluoro-2- (tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-en-8-yl) ethanesulfonate, etc., and bis (substituted alkylsulfonyl) imide includes bistrifluoromethylsulfonylimide, bispentafluoroethylsulfonylimide, bisheptafluoropropylsulfonylimide 1,3-propylenebissulfonylimide and the like, and tris (substituted alkylsulfonyl) methides include tristrifluoromethylsulfonylmethide, and sulfonium salts of these combinations.

The iodonium salt is a salt of iodonium cation and sulfonate, bis (substituted alkylsulfonyl) imide, tris (substituted alkylsulfonyl) methide, diphenyliodonium, bis (4-tert-butylphenyl) iodonium, 4-tert-butoxyphenylphenyl. Aryl iodonium cations and sulfonates such as iodonium and 4-methoxyphenylphenyl iodonium include trifluoromethane sulfonate, pentafluoroethane sulfonate, heptafluoropropane sulfonate, nonafluorobutane sulfonate, tridecafluorohexane sulfonate, heptadecafluorooctane sulfonate, Fluoro-4-ethylcyclohexanesulfonate, 2,2,2-trifluoroethane Phonate, pentafluorobenzenesulfonate, 4-trifluoromethylbenzenesulfonate, 4-fluorobenzenesulfonate, mesitylenesulfonate, 2,4,6-triisopropylbenzenesulfonate, toluenesulfonate, benzenesulfonate, 4- (4'-toluenesulfonyloxy) ) Benzenesulfonate, 6- (4-toluenesulfonyloxy) naphthalene-2-sulfonate, 4- (4-toluenesulfonyloxy) naphthalene-1-sulfonate, 5- (4-toluenesulfonyloxy) naphthalene-1-sulfonate, 8 -(4-toluenesulfonyloxy) naphthalene-1-sulfonate, naphthalenesulfonate, camphorsulfonate, octanesulfonate, dodecylbenzenesulfonate, Tansulfonate, methanesulfonate, 1,1-difluoro-2-naphthyl-ethanesulfonate, 1,1,2,2-tetrafluoro-2- (norbornan-2-yl) ethanesulfonate, 1,1,2,2- tetrafluoro-2- (tetracyclo [4.4.0.1 ^2,5 .1 ^7,10] dodeca-3-en-8-yl) ethanesulfonate and the like, and the bis (substituted alkylsulfonyl) imide Examples thereof include bistrifluoromethylsulfonylimide, bispentafluoroethylsulfonylimide, bisheptafluoropropylsulfonylimide, 1,3-propylenebissulfonylimide, and tris (substituted alkylsulfonyl) methide is tristrifluoromethylsulfonylmethide. These combinations of iodonium Salt.

  As the sulfonyldiazomethane, bis (ethylsulfonyl) diazomethane, bis (1-methylpropylsulfonyl) diazomethane, bis (2-methylpropylsulfonyl) diazomethane, bis (1,1-dimethylethylsulfonyl) diazomethane, bis (cyclohexylsulfonyl) diazomethane Bis (perfluoroisopropylsulfonyl) diazomethane, bis (phenylsulfonyl) diazomethane, bis (4-methylphenylsulfonyl) diazomethane, bis (2,4-dimethylphenylsulfonyl) diazomethane, bis (4-acetyloxyphenylsulfonyl) diazomethane, Bis (4-methanesulfonyloxyphenylsulfonyl) diazomethane, bis (4- (4-toluenesulfonyloxy) phenylsulfonyl) diazome , Bis (2-naphthylsulfonyl) diazomethane, 4-methylphenylsulfonylbenzoyldiazomethane, tert-butylcarbonyl-4-methylphenylsulfonyldiazomethane, 2-naphthylsulfonylbenzoyldiazomethane, 4-methylphenylsulfonyl-2-naphthoyldiazomethane, Examples thereof include bissulfonyldiazomethane and sulfonylcarbonyldiazomethane such as methylsulfonylbenzoyldiazomethane and tert-butoxycarbonyl-4-methylphenylsulfonyldiazomethane.

Examples of the N-sulfonyloxydicarboximide photoacid generator include succinimide, naphthalene dicarboximide, phthalic imide, cyclohexyl dicarboximide, 5-norbornene-2,3-dicarboximide, 7-oxabicyclo [ 2.2.1] Imido skeletons such as -5-heptene-2,3-dicarboximide and trifluoromethanesulfonate, pentafluoroethanesulfonate, heptafluoropropanesulfonate, nonafluorobutanesulfonate, tridecafluorohexanesulfonate, heptadeca Fluorooctane sulfonate, perfluoro-4-ethylcyclohexane sulfonate, 2,2,2-trifluoroethane sulfonate, pentafluorobenzene sulfonate, 4-trifluoromethylbenzene Lulfonate, 4-fluorobenzenesulfonate, mesitylenesulfonate, 2,4,6-triisopropylbenzenesulfonate, toluenesulfonate, benzenesulfonate, naphthalenesulfonate, camphorsulfonate, octanesulfonate, dodecylbenzenesulfonate, butanesulfonate, methanesulfonate, 1,1 -Difluoro-2-naphthyl-ethanesulfonate, 1,1,2,2-tetrafluoro-2- (norbornan-2-yl) ethanesulfonate, 1,1,2,2-tetrafluoro-2- (tetracyclo [4 .4.0.1 ^2,5 .1 ^7,10] dodeca-3-en-8-yl) compounds of the combination, such as ethane sulfonates.

  Examples of the benzoin sulfonate photoacid generator include benzoin tosylate, benzoin mesylate, and benzoin butane sulfonate.

Pyrogallol trisulfonate photoacid generators include pyrogallol, phloroglysin, catechol, resorcinol, all hydroquinone hydroxyl groups trifluoromethane sulfonate, pentafluoroethane sulfonate, heptafluoropropane sulfonate, nonafluorobutane sulfonate, tridecafluorohexane Sulfonate, heptadecafluorooctane sulfonate, perfluoro-4-ethylcyclohexane sulfonate, 2,2,2-trifluoroethane sulfonate, pentafluorobenzene sulfonate, 4-trifluoromethylbenzene sulfonate, 4-fluorobenzene sulfonate, toluene sulfonate, Benzene sulfonate, naphthalene sulfonate, camphor sulfonate, octane Sulfonate, dodecylbenzenesulfonate, butanesulfonate, methanesulfonate, 1,1-difluoro-2-naphthyl-ethanesulfonate, 1,1,2,2-tetrafluoro-2- (norbornan-2-yl) ethanesulfonate, 1, It includes 1,2,2-tetrafluoro-2- (tetracyclo [4.4.0.1 ^2,5 .1 ^7,10] dodeca-3-en-8-yl) compounds substituted with ethanesulfonate .

Examples of the nitrobenzyl sulfonate photoacid generator include 2,4-dinitrobenzyl sulfonate, 2-nitrobenzyl sulfonate, and 2,6-dinitrobenzyl sulfonate. Specific examples of the sulfonate include trifluoromethane sulfonate and pentafluoroethane. Sulfonate, heptafluoropropane sulfonate, nonafluorobutane sulfonate, tridecafluorohexane sulfonate, heptadecafluorooctane sulfonate, perfluoro-4-ethylcyclohexane sulfonate, 2,2,2-trifluoroethane sulfonate, pentafluorobenzene sulfonate, 4 -Trifluoromethylbenzene sulfonate, 4-fluorobenzene sulfonate, toluene sulfonate, benzene sulfonate, naphth Lensulfonate, camphorsulfonate, octanesulfonate, dodecylbenzenesulfonate, butanesulfonate, methanesulfonate, 1,1-difluoro-2-naphthyl-ethanesulfonate, 1,1,2,2-tetrafluoro-2- (norbornane-2- yl) ethanesulfonate, 1,1,2,2-tetrafluoro-2- (tetracyclo [4.4.0.1 ^2,5 .1 ^7,10] dodeca-3-en-8-yl) ethanesulfonate Is mentioned. A compound in which the nitro group on the benzyl side is replaced with a trifluoromethyl group can also be used.

  Examples of the sulfone photoacid generator include bis (phenylsulfonyl) methane, bis (4-methylphenylsulfonyl) methane, bis (2-naphthylsulfonyl) methane, 2,2-bis (phenylsulfonyl) propane, 2, 2-bis (4-methylphenylsulfonyl) propane, 2,2-bis (2-naphthylsulfonyl) propane, 2-methyl-2- (p-toluenesulfonyl) propiophenone, 2- (cyclohexylcarbonyl) -2- (P-toluenesulfonyl) propane, 2,4-dimethyl-2- (p-toluenesulfonyl) pentan-3-one and the like can be mentioned.

  Examples of O-arylsulfonyloxime compounds or O-alkylsulfonyloxime compounds (oxime sulfonates) include glyoxime derivative-type photoacid generators (compounds described in Japanese Patent No. 2906999 and JP-A-9-301948), thiophene, A long conjugated oxime sulfonate photoacid generator via cyclohexadiene (compound described in US Pat. No. 6,0047,424), an oxime sulfonate having an electron withdrawing group such as a trifluoromethyl group to increase the stability of the compound ( US Pat. No. 6,261,738, a compound described in JP-A No. 2000-314956, a compound described in WO 2004/074242, a phenylacetonitrile, an oxime sulfonate using a substituted acetonitrile derivative (JP-A-9-954). No. 9, JP-A-9-230588 or a compound described as the prior art in the text, and bisoxime sulfonate (compound described in JP-A-9-208554, British Patent (GB) No. 2348644A) And the compounds described in JP-A-2002-278053).

  In the case where the photoacid generator (E) is added to a resist material for KrF excimer laser, sulfonium salts, bissulfonyldiazomethane, N-sulfonyloxydicarboximide, and oxime sulfonate are preferably used. Specifically, triphenylsulfonium p-toluenesulfonate, triphenylsulfonium camphorsulfonate, triphenylsulfonium pentafluorobenzenesulfonate, triphenylsulfonium nonafluorobutanesulfonate, triphenylsulfonium 4- (p-toluenesulfonyloxy) benzenesulfonate, Phenylsulfonium, 2,4,6-triisopropylbenzenesulfonate, 4-tert-butoxyphenyldiphenylsulfonium p-toluenesulfonate, 4-tert-butoxyphenyldiphenylsulfonium camphorsulfonate, 4-tert-butoxyphenyldiphenylsulfonium 4- (p -Toluenesulfonyloxy) benzenesulfonate, tris (4-methylphenol) Nyl) sulfonium, camphorsulfonate, tris (4-tert-butylphenyl) sulfonium camphorsulfonate, bis (tert-butylsulfonyl) diazomethane, bis (cyclohexylsulfonyl) diazomethane, bis (2,4-dimethylphenylsulfonyl) diazomethane, Bis (4-tert-butylphenylsulfonyl) diazomethane, N-camphorsulfonyloxy-5-norbornene-2,3-carboxylic imide, Np-toluenesulfonyloxy-5-norbornene-2,3-carboxylic imide, (5- (10-camphorsulfonyl) oxyimino-5H-thiophen-2-ylidene), (2-methylphenyl) acetonitrile, 5- (4-toluenesulfonyl) oxyimino-5H-thiophene 2-ylidene), and (2-methylphenyl) acetonitrile.

  Furthermore, when adding the photoacid generator of the said (E) component to the resist material for ArF laser, a sulfonium salt or oxime sulfonate is preferable. More specifically, triphenylsulfonium trifluoromethanesulfonate, triphenylsulfonium nonafluorobutanesulfonate, diphenyl 4-methylphenylsulfonium nonafluorobutanesulfonate, 2-oxo-2-phenylethylthiacyclopentanium nonafluorobutanesulfonate, triphenyl Sulfonium perfluoro-4-ethylcyclohexanesulfonate, 4-tert-butylphenyldiphenylsulfonium nonafluorobutanesulfonate, 4-tert-butylphenyldiphenylsulfonium heptadecafluorooctanesulfonate, 2,2,3,3,4,4,5 , 5,6,6,7,7-decafluoro-1- (2-fluorenyl) heptanone oximnonafluorobutanesulfonate, etc. Preferably used.

  In addition, when the photoacid generator (E) is added to the ArF immersion resist material, a sulfonium salt or oxime sulfonate is preferable. More specifically, triphenylsulfonium nonafluorobutanesulfonate, diphenyl 4-methylphenylsulfonium nonafluorobutanesulfonate, triphenylsulfonium perfluoro-4-ethylcyclohexanesulfonate, 4-tert-butylphenyldiphenylsulfonium nonafluorobutanesulfonate, 4 Tert-butylphenyldiphenylsulfonium heptadecafluorooctanesulfonate, 2,2,3,3,4,4,5,5,6,6,7,7-decafluoro-1- (2-fluorenyl) heptanone oxime Nonafluorobutane sulfonate and the like are preferably used.

  The addition amount of the photoacid generator of the component (E) in the chemically amplified resist material of the present invention may be any as long as it does not interfere with the effects of the present invention, but is 0 to 100 parts of the base resin in the resist material. 10 parts, preferably 0 to 5 parts. When the ratio of the photoacid generator (E) is too large, there is a possibility that the resolution is deteriorated and a foreign matter problem occurs during development / resist peeling. The photoacid generator of the above component (E) can be used alone or in combination of two or more. Furthermore, a photoacid generator having a low transmittance at the exposure wavelength can be used, and the transmittance in the resist film can be controlled by the amount of the photoacid generator added.

  In addition, a compound capable of decomposing with an acid to generate an acid (acid-growing compound) may be added to the chemically amplified resist material of the present invention. These compounds are described in J. Am. Photopolym. Sci. and Tech. , 8.43-44, 45-46 (1995), J. Am. Photopolym. Sci. and Tech. , 9.29-30 (1996).

  Examples of the acid-proliferating compound include tert-butyl-2-methyl-2-tosyloxymethyl acetoacetate and 2-phenyl-2- (2-tosyloxyethyl) -1,3-dioxolane. It is not limited to. Of the known photoacid generators, compounds that are inferior in stability, particularly thermal stability, often exhibit the properties of acid-proliferating compounds.

  The addition amount of the acid multiplication compound in the resist material of the present invention is 2 parts or less, preferably 1 part or less, relative to 100 parts of the base resin in the resist material. When the addition amount is too large, it is difficult to control the diffusion, resulting in degradation of resolution and pattern shape.

  Examples of the organic acid derivative as the component (F) are not particularly limited, but specifically, phenol, cresol, catechol, resorcinol, pyrogallol, phloroglysin, bis (4-hydroxyphenyl) methane, 2, 2-bis (4′-hydroxyphenyl) propane, bis (4-hydroxyphenyl) sulfone, 1,1,1-tris (4′-hydroxyphenyl) ethane, 1,1,2-tris (4′-hydroxyphenyl) ) Ethane, hydroxybenzophenone, 4-hydroxyphenylacetic acid, 3-hydroxyphenylacetic acid, 2-hydroxyphenylacetic acid, 3- (4-hydroxyphenyl) propionic acid, 3- (2-hydroxyphenyl) propionic acid, 2,5- Dihydroxyphenylacetic acid, 3,4-dihydroxyphenylacetic acid, 1 2-phenylenediacetic acid, 1,3-phenylenediacetic acid, 1,4-phenylenediacetic acid, 1,2-phenylenedioxydiacetic acid, 1,4-phenylenedipropanoic acid, benzoic acid, salicylic acid, 4,4- Bis (4′-hydroxyphenyl) valeric acid, 4-tert-butoxyphenylacetic acid, 4- (4-hydroxyphenyl) butyric acid, 3,4-dihydroxymandelic acid, 4-hydroxymandelic acid, and the like. Among them, salicylic acid, 4,4-bis (4′-hydroxyphenyl) valeric acid is preferred. These can be used alone or in combination of two or more.

  In addition, as the fluorine-substituted alcohol, a compound in which other than the α-position of the alcohol is substituted with fluorine can be used, and is not particularly limited. A compound having a 2-propanol end is desirable. Specifically, the following compounds can be exemplified.

  In the above formula, R ′ is an acetal group having 2 to 30 carbon atoms, a tertiary alkyl group having 4 to 30 carbon atoms, or the like represented by the formulas (C1) and (C2) described in the above base resin. is there.

  The addition amount of the organic acid derivative or fluorine-substituted alcohol in the chemically amplified resist material of the present invention is 5 parts or less, preferably 1 part or less with respect to 100 parts of the base resin in the resist material. When the addition amount is more than 5 parts, resolution may be deteriorated. The organic acid derivative or the like may not be added depending on the combination of the compositions in the resist.

  (G) As a compound (dissolution inhibitor) having a weight average molecular weight of 3,000 or less whose solubility in an alkali developer is changed by the action of an acid, a low molecular weight phenol or carboxylic acid derivative of 2,500 or less, A compound in which some or all of the hydrogen atoms of the hydroxyl group of the fluorine-substituted alcohol are substituted with an acid-labile substituent can be added.

  The phenol or carboxylic acid derivative having a weight average molecular weight of 2,500 or less includes bisphenol A, bisphenol H, bisphenol S, 4,4-bis (4′-hydroxyphenyl) valeric acid, tris (4-hydroxyphenyl) methane, 1 , 1,1-tris (4′-hydroxyphenyl) ethane, 1,1,2-tris (4′-hydroxyphenyl) ethane, phenolphthalein, thymolphthalein, cholic acid, deoxycholic acid, lithocholic acid, etc. Examples of the fluorine-substituted alcohol include compounds similar to those exemplified in the above [Chemical Formula 16], [Chemical Formula 17], [Chemical Formula 18], and [Chemical Formula 19]. Examples of the acid labile substituent include those exemplified as the acid labile group of the polymer.

  Examples of suitably used dissolution inhibitors include bis (4- (2′-tetrahydropyranyloxy) phenyl) methane, bis (4- (2′-tetrahydrofuranyloxy) phenyl) methane, bis (4-tert -Butoxyphenyl) methane, bis (4-tert-butoxycarbonyloxyphenyl) methane, bis (4-tert-butoxycarbonylmethyloxyphenyl) methane, bis (4- (1'-ethoxyethoxy) phenyl) methane, bis ( 4- (1′-ethoxypropyloxy) phenyl) methane, 2,2-bis (4 ′-(2 ″ -tetrahydropyranyloxy)) propane, 2,2-bis (4 ′-(2 ″-) Tetrahydrofuranyloxy) phenyl) propane, 2,2-bis (4′-tert-butoxyphenyl) propane, 2 2-bis (4′-tert-butoxycarbonyloxyphenyl) propane, 2,2-bis (4-tert-butoxycarbonylmethyloxyphenyl) propane, 2,2-bis (4 ′-(1 ″ -ethoxyethoxy) ) Phenyl) propane, 2,2-bis (4 ′-(1 ″ -ethoxypropyloxy) phenyl) propane, 4,4-bis (4 ′-(2 ″ -tetrahydropyranyloxy) phenyl) valeric acid tert-butyl, 4-tert-butyl 4,4-bis (4 ′-(2 ″ -tetrahydrofuranyloxy) phenyl) valerate, tert-butyl 4,4-bis (4′-tert-butoxyphenyl) valerate, Tert-Butyl 4,4-bis (4-tert-butoxycarbonyloxyphenyl) valerate, 4,4-bis (4′-tert-butyl) Xycarbonylmethyloxyphenyl) tert-butyl valerate, 4,4-bis (4 ′-(1 ″ -ethoxyethoxy) phenyl) tert-butyl valerate, 4,4-bis (4 ′-(1 ″) -Ethoxypropyloxy) phenyl) tert-butylvalerate, tris (4- (2'-tetrahydropyranyloxy) phenyl) methane, tris (4- (2'-tetrahydrofuranyloxy) phenyl) methane, tris (4- tert-butoxyphenyl) methane, tris (4-tert-butoxycarbonyloxyphenyl) methane, tris (4-tert-butoxycarbonyloxymethylphenyl) methane, tris (4- (1′-ethoxyethoxy) phenyl) methane, tris (4- (1′-ethoxypropyloxy) phenyl) methane, 1, 1,2-tris (4 ′-(2 ″ -tetrahydropyranyloxy) phenyl) ethane, 1,1,2-tris (4 ′-(2 ″ -tetrahydrofuranyloxy) phenyl) ethane, 1,1 , 2-tris (4′-tert-butoxyphenyl) ethane, 1,1,2-tris (4′-tert-butoxycarbonyloxyphenyl) ethane, 1,1,2-tris (4′-tert-butoxycarbonyl) Methyloxyphenyl) ethane, 1,1,2-tris (4 ′-(1′-ethoxyethoxy) phenyl) ethane, 1,1,2-tris (4 ′-(1′-ethoxypropyloxy) phenyl) ethane , Cholic acid tert-butyl ester, deoxycholic acid tert-butyl ester, lithocholic acid tert-butyl ester, and the like. Or the compound of Unexamined-Japanese-Patent No. 2003-107706 is mentioned.

  The addition amount of the dissolution inhibitor of the component (G) in the resist material of the present invention is 20 parts or less, preferably 15 parts or less with respect to 100 parts of the base resin in the resist material. If it exceeds 20 parts, the monomer component increases, so the heat resistance of the resist material decreases.

  The (C ′) component alkali-soluble resin used in the negative resist material of the present invention, which is hardly alkali-soluble by a crosslinking agent, includes the acid labile groups of the above-mentioned (C) component resin. It is preferable to use a base resin before substitution.

  For example, poly p-hydroxy styrene, poly m-hydroxy styrene, poly 4-hydroxy 2-methyl styrene, poly 4-hydroxy-3-methyl styrene, poly α-methyl p-hydroxy styrene, partially hydrogenated poly p-hydroxy styrene Copolymer, poly (p-hydroxystyrene-α-methyl p-hydroxystyrene) copolymer, poly (p-hydroxystyrene-α-methylstyrene) copolymer, poly (p-hydroxystyrene-styrene) copolymer, poly (p-hydroxystyrene) -M-hydroxystyrene) copolymer, poly (p-hydroxystyrene-styrene) copolymer, poly (p-hydroxystyrene-acrylic acid) copolymer, poly (p-hydroxystyrene-methacrylic acid) copolymer, poly (p-hydroxys) Len-methyl acrylate) copolymer, poly (p-hydroxystyrene-acrylic acid-methyl methacrylate) copolymer, poly (p-hydroxystyrene-methyl acrylate) copolymer, poly (p-hydroxystyrene-methacrylic acid-methyl methacrylate) copolymer, poly Methacrylic acid, polyacrylic acid, poly (acrylic acid-methyl acrylate) copolymer, poly (methacrylic acid-methyl methacrylate) copolymer, poly (acrylic acid-maleimide) copolymer, poly (methacrylic acid-maleimide) copolymer, poly (p-hydroxy) Styrene-acrylic acid-maleimide) copolymer, poly (p-hydroxystyrene-methacrylic acid-maleimide) copolymer, etc., but are not limited to these combinations. There.

  Moreover, in order to give various functions, you may introduce | transduce a substituent into a part of phenolic hydroxyl group of the said acid labile group protection polymer, and a carboxyl group. For example, a substituent for improving adhesion to the substrate and a substituent for improving etching resistance, particularly an acid for controlling the dissolution rate in an alkaline developer of an unexposed part and a low-exposed part to be not too high. It is preferable to introduce a relatively stable substituent into alkali or alkali. Examples of the substituent include, for example, 2-hydroxyethyl group, 2-hydroxypropyl group, methoxymethyl group, methoxycarbonyl group, ethoxycarbonyl group, methoxycarbonylmethyl group, ethoxycarbonylmethyl group, 4-methyl-2-oxo-4 -Oxolanyl group, 4-methyl-2-oxo-4-oxanyl group, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, acetyl group, pivaloyl group, adamantyl group, Examples thereof include, but are not limited to, an isobornyl group and a cyclohexyl group. In addition, an acid-decomposable substituent such as a tert-butoxycarbonyl group, a tert-butyl group, or a tert-butoxycarbonylmethyl group can be introduced.

  The addition amount of the resin of the component (C ′) in the resist material of the present invention is arbitrary, but it is 65 to 99 parts, preferably 65 to 98 parts with respect to 100 parts of the total solid content in the resist material.

  In addition, examples of the acid crosslinking agent that forms a crosslinked structure by the action of the acid of component (H) include compounds having two or more hydroxymethyl groups, alkoxymethyl groups, epoxy groups, or vinyl ether groups in the molecule, and substituted glycouril. Derivatives, urea derivatives, hexa (methoxymethyl) melamine and the like are suitably used as the acid crosslinking agent for the chemically amplified negative resist material of the present invention. Tetraalkoxymethyl substituted glycolurils, such as N, N, N ′, N′-tetramethoxymethylurea and hexamethoxymethylmelamine, tetrahydroxymethyl substituted glycolurils and tetramethoxymethylglycolurils, substituted and unsubstituted bis -Condensates such as epichlorohydrin and phenolic compounds such as hydroxymethylphenols and bisphenol A. Particularly suitable crosslinking agents are 1,3,5,7-tetraalkoxymethylglycoluril such as 1,3,5,7-tetramethoxymethylglycoluril or 1,3,5,7-tetrahydroxymethylglycoluril, 2,6-dihydroxymethyl p-cresol, 2,6-dihydroxymethylphenol, 2,2 ′, 6,6′-tetrahydroxymethyl-bisphenol A and 1,4-bis- [2- (2-hydroxypropyl) ] -Benzene, N, N, N ′, N′-tetramethoxymethylurea, hexamethoxymethylmelamine and the like.

  The addition amount of the acid crosslinking agent as the component (H) in the chemically amplified resist material of the present invention is arbitrary, but it is 1 to 20 parts, preferably 5 to 15 parts with respect to 100 parts of the base resin in the resist material. These crosslinking agents may be used alone or in combination of two or more.

  In the chemically amplified resist material of the present invention, additives such as a surfactant for improving coatability and a light-absorbing material for reducing irregular reflection from the substrate can be added.

  Examples of surfactants include, but are not limited to, polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene cetyl ether, polyoxyethylene olein ether, Sorbitan fatty acid esters such as polyoxyethylene alkyl allyl ethers such as polyoxyethylene octylphenol ether and polyoxyethylene nonylphenol ether, polyoxyethylene polyoxypropylene block copolymers, sorbitan monolaurate, sorbitan monopalmitate and sorbitan monostearate Polyoxyethylene sorbitan monolaurate, polyoxyethylene sorbitan monopalmitate, polyoxyethylene sorbitan mono Nonionic surfactants of polyoxyethylene sorbitan fatty acid esters such as stearate, polyoxyethylene sorbitan trioleate, polyoxyethylene sorbitan tristearate, F-top EF301, EF303, EF352 (manufactured by Gemco), MegaFuck F171 , F172, F173, R08, R30 (manufactured by Dainippon Ink and Chemicals), Florard FC-430, FC-431, FC-4430, FC-4432 (manufactured by Sumitomo 3M), Asahi Guard AG710, Surflon Fluorine series such as S-381, S-382, SC101, SC102, SC103, SC104, SC105, SC106, Surfynol E1004, KH-10, KH-20, KH-30, KH-40 (Asahi Glass Co., Ltd.) Surface activity Organosiloxane polymer KP341, X-70-092, (manufactured by Shin-Etsu Chemical (Co.)) X-70-093, acrylic acid or methacrylic acid Polyflow No. 75, no. 95 (manufactured by Kyoeisha Yushi Chemical Co., Ltd.), FC-430 (manufactured by Sumitomo 3M Co., Ltd.), Surflon S-381, Surfynol E1004, KH-20, KH-30 (manufactured by Asahi Glass Co., Ltd.). ) Is preferred. These can be used alone or in combination of two or more.

  The addition amount of the surfactant in the chemically amplified resist material of the present invention is 2 parts or less, preferably 1 part or less with respect to 100 parts of the base resin in the resist material.

  Furthermore, an ultraviolet absorber can be blended with the chemically amplified resist material of the present invention. Although not particularly limited, those described in JP-A-11-190904 can be used, and preferably bis (4-hydroxyphenyl) sulfoxide, bis (4-tert-butoxyphenyl) sulfoxide, bis (4 -Tert-butoxycarbonyloxyphenyl) sulfoxide, diaryl sulfoxide derivatives such as bis [4- (1-ethoxyethoxy) phenyl] sulfoxide, bis (4-hydroxyphenyl) sulfone, bis (4-tert-butoxyphenyl) sulfone, bis Diarylsulfone derivatives such as (4-tert-butoxycarbonyloxyphenyl) sulfone, bis [4- (1-ethoxyethoxy) phenyl] sulfone, bis [4- (1-ethoxypropoxy) phenyl] sulfone, benzoquinonediazide, Complete or partial diazo compounds such as toquinonediazide, anthraquinonediazide, diazofluorene, diazotetralone, diazophenantrone, naphthoquinone-1,2-diazide-5-sulfonic acid chloride and 2,3,4-trihydroxybenzophenone Ester compounds, quinonediazide group-containing compounds such as complete or partial ester compounds of naphthoquinone-1,2-diazide-4-sulfonic acid chloride and 2,4,4′-trihydroxybenzophenone, etc., tert-butyl 9-anthracenecarboxylate , 9-anthracenecarboxylic acid tert-amyl, 9-anthracenecarboxylic acid tert-methoxymethyl, 9-anthracenecarboxylic acid tert-ethoxyethyl, 9-anthracenecarboxylic acid 2-tert-tetrahydropyrani , It may be mentioned 9-anthracene carboxylic acid 2-tert-tetrahydrofuranyl and the like.

  The blending amount of the ultraviolet absorber may or may not be added depending on the type of the resist material. Parts, more preferably 1 to 5 parts.

In order to form a pattern using the chemically amplified resist material of the present invention, a known lithography technique can be employed. For example, a substrate for manufacturing an integrated circuit (Si, SiO ₂ , SiN, SiON, TiN, WSi, BPSG, SOG, organic antireflection coating, etc.) The coating thickness is 0.1-2.0 μm by an appropriate coating method such as spin coating, roll coating, flow coating, dip coating, spray coating, doctor coating, etc. Then, it is pre-baked on a hot plate at 60 to 150 ° C. for 1 to 10 minutes, preferably at 80 to 140 ° C. for 1 to 5 minutes. Next, a target pattern is exposed through a predetermined mask at a light source selected from ultraviolet rays, far ultraviolet rays, electron beams, X-rays, excimer lasers, γ rays, synchrotron radiation, and the like, preferably at an exposure wavelength of 300 nm or less.

Among these, more preferable light sources include excimer lasers, particularly KrF excimer lasers, deep ultraviolet rays of 245 to 255 nm, and ArF excimer lasers. It is preferable to expose so that the exposure amount is about 1 to 200 mJ / cm ² , preferably about 10 to 100 mJ / cm ² . Post exposure baking (PEB) is performed on a hot plate at 60 to 150 ° C. for 1 to 5 minutes, preferably at 80 to 140 ° C. for 1 to 3 minutes.

  Further, 0.1 to 5% by weight, preferably 2 to 3% by weight, using an aqueous developer such as tetramethylammonium hydroxide (TMAH) for 0.1 to 3 minutes, preferably 0.5 to 2 minutes. The target pattern is formed on the substrate by development by a conventional method such as a dip method, a paddle method, or a spray method.

The chemically amplified resist material of the present invention is particularly suitable for fine patterning using 254 to 193 nm far ultraviolet rays, 157 nm vacuum ultraviolet rays, electron beams, X-rays, excimer lasers, γ rays and synchrotron radiation among high energy rays. It is. In addition, when deviating from the upper limit and the lower limit of the above range, the target pattern may not be obtained.
In the present invention, an immersion lithography method in which an ArF excimer laser having a wavelength of 193 nm is used and a liquid such as water, glycerin, or ethylene glycol is inserted between the wafer and the projection lens is preferably employed.

  EXAMPLES Hereinafter, although a synthesis example, an Example, and a comparative example are shown and this invention is demonstrated concretely, this invention is not restrict | limited to the following Example.

[Synthesis Example 1] Synthesis of triphenylsulfonium chloride 40 g (0.2 mol) of diphenylsulfoxide was dissolved in 400 g of dichloromethane and stirred under ice cooling. Trimethylsilyl chloride (65 g, 0.6 mol) was added dropwise at a temperature not exceeding 20 ° C., and aging was further performed at this temperature for 30 minutes. Subsequently, Grignard reagent separately prepared from 14.6 g (0.6 mol) of metal magnesium, 67.5 g (0.6 mol) of chlorobenzene, and 168 g of tetrahydrofuran (THF) was added dropwise at a temperature not exceeding 20 ° C. After aging the reaction for 1 hour, 50 g of water was added at a temperature not exceeding 20 ° C. to stop the reaction, and 150 g of water, 10 g of 12N hydrochloric acid and 200 g of diethyl ether were further added.
The aqueous layer was separated and washed with 100 g of diethyl ether to obtain an aqueous triphenylsulfonium chloride solution. This was used in the next reaction as an aqueous solution without further isolation.

[Synthesis Example 2] Synthesis of 4-tert-butylphenyldiphenylsulfonium bromide Same as Synthesis Example 1 except that 4-tert-butylbromobenzene was used instead of chlorobenzene of Synthesis Example 1 and the amount of water was increased during extraction. The desired product was obtained.

[Synthesis Example 3] Synthesis of 4-tert-butoxyphenyldiphenylsulfonium chloride 4-tert-butoxychlorobenzene was used in place of chlorobenzene of Synthesis Example 1 and a dichloromethane solvent containing 5% by mass of triethylamine was used as a solvent. The target product was obtained in the same manner as in Synthesis Example 1 except that the amount of was increased.

[Synthesis Example 4] Synthesis of tris (4-methylphenyl) sulfonium chloride Bis (4-methylphenyl) sulfoxide was used instead of diphenyl sulfoxide in Synthesis Example 1, and 4-chlorotoluene was used instead of chlorobenzene. The target product was obtained in the same manner as in Synthesis Example 1 except that the amount of water was increased.

[Synthesis Example 5] Synthesis of tris (4-tert-butylphenyl) sulfonium bromide Bis (4-tert-butylphenyl) sulfoxide was used instead of diphenyl sulfoxide of Synthesis Example 1, and 4-tert-butylbromobenzene was used instead of chlorobenzene. Was used in the same manner as in Synthesis Example 1 except that the amount of water during extraction was increased.

Synthesis Example 6 Synthesis of bis (4-tert-butylphenyl) iodonium hydrogen sulfate A mixture of 84 g (0.5 mol) of tert-butylbenzene, 53 g (0.25 mol) of potassium iodate, and 50 g of acetic anhydride was added to ice. The mixture was stirred under cooling, and a mixture of 35 g of acetic anhydride and 95 g of concentrated sulfuric acid was added dropwise at a temperature not exceeding 30 ° C. Next, aging was carried out at room temperature for 3 hours, ice-cooled again, and 250 g of water was added dropwise to stop the reaction. This reaction solution was extracted with 400 g of dichloromethane, and 6 g of sodium bisulfite was added to the organic layer for decolorization. Further, washing this organic layer with 250 g of water was repeated three times. The washed organic layer was concentrated under reduced pressure to obtain the desired crude product. It was used for the next reaction without further purification.

Synthesis Example 7 Synthesis of phenacyltetrahydrothiophenium bromide 88.2 g (0.44 mol) of phenacyl bromide and 39.1 g (0.44 mol) of tetrahydrothiophene were dissolved in 220 g of nitromethane and stirred at room temperature for 4 hours. Went. 800 g of water and 400 g of diethyl ether were added to the reaction solution, and the separated aqueous layer was separated to obtain a target aqueous solution of phenacyltetrahydrothiophenium bromide.

[Synthesis Example 8] Synthesis of dimethylphenylsulfonium sulfate 6.2 g (0.05 mol) of thioanisole and 6.9 g (0.055 mol) of dimethylsulfuric acid were stirred at room temperature for 12 hours. 100 g of water and 50 ml of diethyl ether were added to the reaction solution, and the aqueous layer was separated to obtain the desired aqueous dimethylphenylsulfonium sulfate solution.

Synthesis Example 9 Synthesis of sodium 2-benzoyloxy-1,1,3,3,3-pentafluoropropane-1-sulfonate 1,1,3,3,3-pentafluoro-2 synthesized by a conventional method -Propan-2-ylbenzoate 10.0g was disperse | distributed to water 72g, sodium hydrogen sulfite 12.0g and benzoyl peroxide 1.24g were added, and it reacted at 85 degreeC for 65 hours. The reaction solution was allowed to cool, and toluene was added to carry out a liquid separation operation. A saturated aqueous sodium chloride solution was added to the collected aqueous layer, and the precipitated white crystals were separated by filtration. The crystals were washed with a small amount of saturated sodium chloride solution and then dried under reduced pressure to obtain the target sodium 2-benzoyloxy-1,1,3,3,3-pentafluoropropane-1-sulfonate [white 5.85 g of crystals (43% yield)].

[Synthesis Example 10] Synthesis of triphenylsulfonium-2-benzoyloxy-1,1,3,3,3-pentafluoropropane-1-sulfonate An aqueous solution equivalent to 0.011 mol of the triphenylsulfonium chloride aqueous solution of Synthesis Example 1 3.6 g (0.01 mol) of sodium 2-benzoyloxy-1,1,3,3,3-pentafluoropropane-1-sulfonate synthesized in Synthesis Example 9 was stirred in 50 g of dichloromethane. The organic layer was separated, and the organic layer was washed 3 times with 50 g of water. The organic layer was concentrated, and 25 g of diethyl ether was added to the residue for crystallization. The target product was obtained by filtering and drying the crystals [4.5 g of white crystals (yield 75%)].

[Synthesis Example 11] Synthesis of triphenylsulfonium-2-hydroxy-1,1,3,3,3-pentafluoropropane-1-sulfonate (PAG1)
34.4 g of triphenylsulfonium-2-benzoyloxy-1,1,3,3,3-pentafluoropropane-1-sulfonate of Synthesis Example 10 was dissolved in 72 g of methanol and stirred under ice cooling. Thereto, 54.0 g of 5% aqueous sodium hydroxide solution was added dropwise at a temperature not exceeding 10 ° C. After aging at this temperature for 4 hours, 6.8 g of 12N hydrochloric acid was added at a temperature not exceeding 10 ° C. to stop the reaction, and methanol was removed under reduced pressure. After adding 270 g of dichloromethane and washing the organic layer 3 times with 40 g of water, the organic layer was concentrated, and 60 g of diethyl ether was added to the residue for crystallization. The target product was obtained by filtering and drying the crystals [24.3 g (85% yield) of white crystals].

The spectrum data of the obtained target object are shown. 1 and 2 show nuclear magnetic resonance spectra ( ¹ H-NMR (300 MHz DMSO-d ₆ ), ¹⁹ F-NMR (282 MHz DMSO-d ₆ (shift standard CF ₃ CO ₂ D))).
Infrared absorption spectrum (IR (KBr); cm ⁻¹ )
3278, 3064, 1722, 1479, 1448, 1367, 1261, 1234, 1211, 1172, 1124, 1106, 1070, 987, 823, 755, 746, 684, 644, 503
Time-of-flight mass spectrometry (TOFMS; MALDI)
POSITIVE M ⁺ 263 (equivalent to (C ₆ H ₅ ) ₃ S ⁺ )
NEGATIVE M ^- 229 (CF ₃ CH (OH) CF ₂ SO ₃ ^- equivalent)

[Synthesis Examples 12 to 18]
The target product was synthesized in the same manner as in Synthesis Examples 10 and 11 except that the sulfonium salts prepared in Synthesis Examples 2 to 8 were used. These onium salts (PAG2 to PAG8) are shown below.
3 and 4 show nuclear magnetic resonance spectra of PAG2 ( ¹ H-NMR (300 MHz DMSO-d ₆ ), ¹⁹ F-NMR (282 MHz DMSO-d ₆ (shift standard CF ₃ CO ₂ D))). .

[Synthesis Example 19] Synthesis of sodium 2-hydroxy-1,1,3,3,3-pentafluoropropane-1-sulfonate (Anion 1)
14.6 g of sodium 2-benzoyloxy-1,1,3,3,3-pentafluoropropane-1-sulfonate of Synthesis Example 9 was dissolved in 43 g of water and stirred under ice cooling. There, 7.4 g of 26% aqueous sodium hydroxide solution was added dropwise at a temperature not exceeding 10 ° C. After aging at this temperature for 1 hour and at room temperature for 1 hour, it was washed with toluene and the aqueous layer was separated to obtain the desired sodium 2-hydroxy-1,1,3,3,3-pentafluoropropane-1-sulfonate. Was obtained as an aqueous solution. The production of the target product was confirmed by nuclear magnetic resonance spectrum and time-of-flight mass spectrometry without further isolation.

The spectrum data of the obtained target object are shown. A nuclear magnetic resonance spectrum ( ¹⁹ F-NMR (282 MHz D ₂ O (shift standard CF ₃ CO ₂ D))) is shown in FIG.
Time-of-flight mass spectrometry (TOFMS; MALDI)
NEGATIVE M ^- 229 (CF ₃ CH (OH) CF ₂ SO ₃ ^- equivalent)

[Reference Example 1] Synthesis of triphenylsulfonium-2-acetoxy-1,1,3,3,3-pentafluoropropane-1-sulfonate (PAG9)
3.0 g of triphenylsulfonium-2-hydroxy-1,1,3,3,3-pentafluoropropane-1-sulfonate of Synthesis Example 11 and 0.7 g of pyridine were dissolved in 28 g of methylene chloride and stirred under ice cooling. . Acetic anhydride 0.8g was added there, triethylamine 0.7g and 4- (N, N-dimethylamino) pyridine 0.04g were added after that, and it stirred for 4 hours, and stopped reaction with 20g of water. The organic layer was separated and washed three times with 20 g of water, then the organic layer was concentrated and triphenylsulfonium-2-acetoxy-1,1,3,3,3-pentafluoropropane-1-sulfonate [Colourless oily substance 2.2 g (yield 70%)].

The spectrum data of the obtained target object are shown. Further, nuclear magnetic resonance spectra ( ¹ H-NMR 300 MHz DMSO-d ₆ , ¹⁹ F-NMR (282 MHz DMSO-d ₆ (shift standard CF ₃ CO ₂ D)) are shown in FIG. 6 and FIG.
Infrared absorption spectrum (IR (KBr); cm ⁻¹ )
3089, 3064, 2971, 1779, 1581, 1477, 1448, 1373, 1322, 1253, 1213, 1186, 1164, 1116, 1091, 1072, 995, 919, 750, 684, 642

[Examples 1 to 16 and Comparative Examples 1 to 3]
Evaluation of resist resolution Using the photoacid generator shown in the above synthesis example and the polymer represented by the following formula (Polymers 1 to 8) as a base resin, a dissolution accelerator DRR1 represented by the following formula, a dissolution inhibitor DRI1 and a basic compound having the composition shown in Tables 1 and 2 were dissolved in a solvent containing 0.01% by mass of FC-430 (manufactured by Sumitomo 3M Co., Ltd.) to prepare a resist material. Each resist solution was prepared by filtering through a 2 μm Teflon (registered trademark) filter.

  An antireflection film solution (Nissan Chemical Industry Co., Ltd., ARC-29A) is applied on a silicon substrate and baked at 200 ° C. for 60 seconds. Coating was performed and baking was performed at 120 ° C. for 60 seconds using a hot plate to prepare a resist film having a thickness of 200 nm. This is exposed using an ArF excimer laser microstepper (Nikon Corporation, S305B, NA = 0.68, 2/3 annular illumination, Cr mask), and baked at 110 ° C. for 90 seconds (PEB), Development was performed for 60 seconds with an aqueous solution of 2.38% by mass of tetramethylammonium hydroxide.

The evaluation of the resist is performed by taking the exposure amount for resolving the 0.12 μm group line and space at 1: 1 as the optimum exposure amount (Eop, mJ / cm ² ), and separating the line and space at this exposure amount. The minimum line width (μm) was taken as the resolution of the evaluation resist. Moreover, the resist cross section was observed for the shape of the resolved resist pattern using a scanning electron microscope. The compositions and evaluation results of each resist are shown in Tables 1 and 2.

In Tables 1 and 2, the solvents, basic compounds, and photoacid generators used in Comparative Examples are as follows.
Solvent A: Propylene glycol monomethyl ether acetate Solvent B: Cyclohexanone basic compound A: Tri-n-octylamine basic compound B: Triethanolamine basic compound C: Trismethoxymethoxyethylamine basic compound D: Tris (2-acetoxy Ethyl) amine TPS-NfO: triphenylsulfonium perfluoro-1-butanesulfonate TPS-PFOS: triphenylsulfonium perfluoro-1-octanesulfonate

Next, pseudo immersion exposure was performed using the resists of Examples 1, 4, 9 and Comparative Example 1. Specifically, a 125 nm resist film was formed by the same process as described above, and exposed using an ArF excimer laser microstepper (manufactured by Nikon Corporation, S307E, NA = 0.85, dipole). Immediately after the exposure, pure water was added to the entire surface of the wafer, and the resist exposure surface was immersed in pure water for 60 seconds (paddle). After pure water was shaken off by wafer spinning, the PEB process as usual was followed by development. The number of defects in the pattern formed after development was inspected by a defect inspection apparatus WINWIN 50-1200L (manufactured by Tokyo Seimitsu Co., Ltd.), and the defect density was determined according to the following formula.
Defect density (pieces / cm ² ) = total number of detected defects / inspection area pattern formed: repeated pattern of 80 nm / pitch 160 nm line and space Defect inspection conditions: light source UV, inspection pixel size 0.125 μm, cell to cell mode Moreover, the shape of the resist cross-section pattern was observed using a scanning electron microscope. The results are shown in Table 3.

  From the results of Tables 1 to 3, the resist material of the present invention has high sensitivity and high resolution, and there is no change in shape or the appearance of defects even when rinsing with water for a long time compared to conventional products, and immersion exposure. It was confirmed that it can fully cope with. Further, as shown in Reference Example 1, the photoacid generator for chemically amplified resist material, which generates the sulfonic acid represented by the general formula (1) of the present invention, is a hydroxyl group held in the molecule. Can be converted into a bulky functional group and is also very useful as a synthetic intermediate.

₆ is a diagram showing ¹ H-NMR / DMSO-d ₆ of PAG1 of Synthesis Example 11. FIG. 14 is a diagram showing ¹⁹ F-NMR / DMSO-d ₆ of PAG1 of Synthesis Example 11. FIG. ₆ is a diagram showing ¹ H-NMR / DMSO-d ₆ of PAG2 in Synthesis Example 12. FIG. 14 is a diagram showing ¹⁹ F-NMR / DMSO-d ₆ of PAG2 in Synthesis Example 12. FIG. 19 is a diagram showing ¹⁹ F-NMR / D ₂ O of Anion 1 of Synthesis Example 19. FIG. 2 is a diagram showing ¹ H-NMR / DMSO-d ₆ of PAG9 in Reference Example 1. FIG. ₄ is a diagram showing ¹⁹ F-NMR / DMSO-d ₆ of PAG9 in Reference Example 1. FIG.

Claims (22)

A sulfonate represented by the following general formula (1a).
_{CF 3 -CH (OH) -CF 2} SO 3 - M + (1a)
(In the formula, M ⁺ represents lithium ion, sodium ion, potassium ion, ammonium ion, or tetramethylammonium ion.) Sulfonic acid represented by the following following general formula (1).
CF ₃ —CH (OH) —CF ₂ SO ₃ ⁻ H ⁺ (1) A sulfonium salt represented by the following general formula (2).
R ¹ R ² R ³ S ⁺ CF ₃ —CH (OH) —CF ₂ SO ₃ ⁻ (2)
Wherein R ¹ , R ² and R ³ are each independently substituted or unsubstituted linear or branched alkyl group, alkenyl group or oxoalkyl group having 1 to 10 carbon atoms, or substituted or unsubstituted. An aryl group having 6 to 18 carbon atoms, an aralkyl group or an aryloxoalkyl group, or any two or more of R ¹ , R ² and R ³ are bonded to each other together with the sulfur atom in the formula A ring may be formed.) A sulfonium salt represented by the following general formula (2a).

(In the formula, R ⁴ represents a substituted or unsubstituted linear, branched or cyclic alkyl group or alkenyl group having 1 to 20 carbon atoms, or a substituted or unsubstituted aryl group having 6 to 14 carbon atoms . m represents 1 to 5, and n represents 0 or 1.) An iodonium salt represented by the following general formula (2b).

(In the formula, R ⁴ represents a substituted or unsubstituted linear, branched or cyclic alkyl group or alkenyl group having 1 to 20 carbon atoms, or a substituted or unsubstituted aryl group having 6 to 14 carbon atoms . n represents 0 or 1.) An N-sulfonyloxyimide compound represented by the following general formula (3a).

(In the formula, X and Y each independently represent a hydrogen atom or a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms, or X and Y are bonded to each other and bonded to each other) And may form a saturated or unsaturated ring having 6 to 12 carbon atoms, Z represents a single bond, a double bond, a methylene group, or an oxygen atom.) An oxime sulfonate compound represented by the following general formula (3b).

(In the formula, q represents 0 or 1, but when q is 0, p is a single bond, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, or a substituted or unsubstituted carbon group having 6 to 15 carbon atoms. Represents an aryl group, and when q is 1, p represents a substituted or unsubstituted alkylene group having 1 to 20 carbon atoms, or a substituted or unsubstituted arylene group having 6 to 15 carbon atoms, EWG represents a cyano group, A trifluoromethyl group, a perfluoroethyl group, a perfluoropropyl group, a 5H-perfluoropentyl group, a 6H-perfluorohexyl group, a nitro group or a methyl group. When q is 1, the EWGs are bonded to each other. And may form a ring of 6 carbon atoms together with the carbon atom to which they are bonded.) A chemistry characterized by generating sulfonic acid represented by the following general formula (1) in response to ultraviolet rays, far ultraviolet rays, electron beams, X-rays, excimer lasers, γ rays, or high energy rays of synchrotron radiation irradiation Photoacid generator for amplified resist material.
CF _Three -CH (OH) -CF ₂ SO _Three ^- H ⁺ (1) The photoacid generator according to claim 8, comprising a sulfonium salt represented by the following general formula (2).
R ¹ R ² R ^Three S ⁺   CF _Three -CH (OH) -CF ₂ SO _Three ^- (2)
(Wherein R ¹ , R ² And R ^Three Are each independently a substituted or unsubstituted C1-C10 linear or branched alkyl group, alkenyl group or oxoalkyl group, or a substituted or unsubstituted C6-C18 aryl group or aralkyl group. Or an aryloxoalkyl group, or R ¹ , R ² And R ^Three Any two or more of these may be bonded to each other to form a ring together with the sulfur atom in the formula. ) The photoacid generator according to claim 8, comprising a sulfonium salt represented by the following general formula (2a).

(Wherein R ^Four Represents a substituted or unsubstituted linear, branched or cyclic alkyl group or alkenyl group having 1 to 20 carbon atoms, or a substituted or unsubstituted aryl group having 6 to 14 carbon atoms. m represents 1 to 5, and n represents 0 or 1. ) The photoacid generator according to claim 8, comprising an iodonium salt represented by the following general formula (2b).

(Wherein R ^Four Represents a substituted or unsubstituted linear, branched or cyclic alkyl group or alkenyl group having 1 to 20 carbon atoms, or a substituted or unsubstituted aryl group having 6 to 14 carbon atoms. n represents 0 or 1. ) The photoacid generator according to claim 8, comprising an N-sulfonyloxyimide compound represented by the following general formula (3a).

(In the formula, X and Y each independently represent a hydrogen atom or a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms, or X and Y are bonded to each other and bonded to each other) And may form a saturated or unsaturated ring having 6 to 12 carbon atoms, Z represents a single bond, a double bond, a methylene group, or an oxygen atom.) The photo-acid generator of Claim 8 which consists of an oxime sulfonate compound shown by the following general formula (3b).

(In the formula, q represents 0 or 1, but when q is 0, p is a single bond, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, or a substituted or unsubstituted carbon group having 6 to 15 carbon atoms. Represents an aryl group, and when q is 1, p represents a substituted or unsubstituted alkylene group having 1 to 20 carbon atoms, or a substituted or unsubstituted arylene group having 6 to 15 carbon atoms, EWG represents a cyano group, A trifluoromethyl group, a perfluoroethyl group, a perfluoropropyl group, a 5H-perfluoropentyl group, a 6H-perfluorohexyl group, a nitro group, or a methyl group. And may form a ring of 6 carbon atoms together with the carbon atom to which they are bonded.) Base resin in the resist composition comprising an acid generator and a solvent, the resist material, wherein the acid generator is a photoacid generator of any one of claims 8 to 13. Base resin is poly (meth) acrylic acid and derivatives thereof, cycloolefin derivative-maleic anhydride alternating polymer, copolymer of cycloolefin derivative, maleic anhydride and polyacrylic acid or derivative thereof. , Cycloolefin derivative-α-trifluoromethylacrylic acid derivative copolymer, polynorbornene, ring-opening metathesis polymer, and one or more polymer polymers selected from hydrogenated ring-opening metathesis polymers The resist material according to claim 14 , wherein: The resist material according to claim 14 , wherein the base resin is a polymer structure containing a silicon atom. The resist material according to claim 14 , wherein the base resin is a polymer structure containing a fluorine atom. 15., 16 or 17, wherein the base resin contains a photoacid generator and a solvent according to any one of claims 8 to 13, wherein said base resin is insoluble or poorly soluble in the developing solution, acid A chemically amplified positive resist material that becomes soluble in the developer by the above. The chemically amplified positive resist material according to claim 18 , further comprising a basic compound. Furthermore, chemically amplified positive resist composition according to claim 18 or 19, wherein it contains a dissolution inhibitor. A step of applying the resist material according to any one of claims 14 to 20 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 as necessary. And a step of developing using a developing solution. The pattern forming method according to claim 21, wherein the wavelength using an ArF excimer laser of 193 nm, an immersion lithography technique to insert the liquid body between the resist material is applied the substrate and the projection lens.

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