JP4659770B2 - Resist material and pattern forming method - Google Patents

Description

  The present invention relates to a novel basic compound useful for a resist material suitable for microfabrication technology, a resist material containing the same, particularly a novel chemically amplified resist material, and a pattern forming method using the same.

  Along with the high integration and high speed of LSI, there is a demand for miniaturization of pattern rules, and far-ultraviolet lithography is promising as a next-generation fine processing technology. Far-ultraviolet lithography can process 0.2 μm or less, and when a resist material with low light absorption is used, it is possible to form a pattern having sidewalls that are nearly perpendicular to the substrate. In recent years, a technique using a high-brightness KrF excimer laser and further an ArF excimer laser as a deep ultraviolet light source has attracted attention. Since this is used as a mass-production technique, it has low light absorption and high sensitivity. Resist materials are desired.

  From this point of view, recently developed acid-amplified chemically amplified positive resist materials (described in Patent Documents 1 and 2) have high sensitivity, resolution, dry etching resistance, and have excellent characteristics. It is a particularly promising resist material for deep ultraviolet lithography.

  As a disadvantage of the chemically amplified resist, if the standing time from exposure to PEB (Post Exposure Bake) becomes long, the line pattern becomes T-top shape when the pattern is formed, that is, the pattern upper part becomes thick (PED ( There is a problem of so-called tailing phenomenon in which a pattern near a substrate on a basic substrate, particularly a silicon nitride or titanium nitride substrate becomes thick. The T-top phenomenon is considered to be due to a decrease in solubility on the resist film surface, and the tailing on the substrate surface is considered to be due to a decrease in solubility near the substrate. In addition, the dark reaction of elimination of the acid labile group proceeds from exposure to PEB, resulting in a problem that the remaining line size is reduced. These are major drawbacks when the chemically amplified resist is put to practical use. Due to this drawback, the conventional chemically amplified positive resist material has a problem that it is difficult to control the dimensions in the lithography process, and the control of the dimensions is impaired even during substrate processing using dry etching (reference: Non-Patent Documents 1 to 3). 2).

  In the chemically amplified positive resist material, it is considered that the basic compound on the surface of the substrate or the substrate surface is largely involved in the cause of the problem of the PED or the bottom of the substrate surface. The acid on the resist film surface generated by exposure reacts and deactivates with basic compounds in the air, and the amount of deactivated acid increases as the standing time until PEB increases. Is less likely to occur. Therefore, a hardly soluble layer is formed on the surface, and the pattern has a T-top shape.

  Here, since the influence of the basic compound in the air can be suppressed by adding the basic compound, it is well known that PED is also effective (described in Patent Documents 3 to 8). .

As the basic compound, a nitrogen-containing compound is well known, and examples thereof include an amine compound or an amide compound having a boiling point of 150 ° C. or higher.
Specifically, pyridine, polyvinylpyridine, aniline, N-methylaniline, N, N-dimethylaniline, o-toluidine, m-toluidine, p-toluidine, 2,4-lutidine, quinoline, isoquinoline, formamide, N- Methylformamide, N, N-dimethylformamide, acetamide, N-methylacetamide, N, N-dimethylacetamide, 2-pyrrolidone, N-methylpyrrolidone, imidazole, α-picoline, β-picoline, γ-picoline, o-amino Benzoic acid, m-aminobenzoic acid, p-aminobenzoic acid, 1,2-phenylenediamine, 1,3-phenylenediamine, 1,4-phenylenediamine, 2-quinolinecarboxylic acid, 2-amino-4-nitrophenol 2- (p-chlorophenyl) -4,6-trichlorome Triazine compounds such as Le -s- triazine. Among these, pyrrolidone, N-methylpyrrolidone, o-aminobenzoic acid, m-aminobenzoic acid, p-aminobenzoic acid, and 1,2-phenylenediamine are particularly mentioned.

  However, these nitrogen-containing compounds are weak bases and can alleviate the T-Top problem, but control of the reaction when using a highly reactive acid labile group, for example an acetal group such as 1-ethoxyethyl, ie acid The diffusion cannot be controlled. The addition of a weak base caused a dark reaction particularly in PED to proceed in the unexposed area, causing reduction in line size (slimming) in the acetal acid leaving group and reduction in film thickness on the line surface. In order to solve the above problem, it was effective to add a strong base. However, the higher the basicity, the better, and the addition of quaternary amines such as DBU, DBN, proton sponge or tetramethylammonium hydrooxide, which is said to be a super strong base, could not provide a sufficient effect.

  The effect of adding the basic compound to the resist composition includes not only improvement of environmental stability but also improvement of resolution. Although the sensitivity is reduced by adding a base, the acid generation contrast is improved. In exposed areas where the number of moles of acid generated is less than the number of moles of base added, the acid can be lost by neutralizing with the base and not cause a catalytic reaction. Acid is generated, causing a catalytic reaction.

  The rapid acid generation phenomenon in the vicinity of the neutralization point due to the addition of the base was called a proton jump in NPL 3 by Kashiyama et al. Furthermore, Kashiyama et al. Conducted a detailed study on the mechanism of proton jump, and in Non-Patent Document 4, proposed a competitive reaction theory in which a neutralization reaction between an acid and a base generated by exposure and an acid-catalyzed reaction occur simultaneously. Here, the neutralization reaction between the photogenerated acid and the added base was solved kinetically, and it was suggested that the resist added with a base having a larger reaction rate constant of the neutralization reaction had higher contrast.

  When the inventors conducted experiments by adding various bases, it was found that the reaction rate constant with the acid and pKa were not particularly closely related. For example, DBU (1,8-Diazabicyclo [5.4.0] -7-undecene) or DBN (1,5-Diazabicyclo [4.3.0] -5-nonene) or proton sponge, which is called a super strong base, A higher reaction rate constant was obtained with quaternary amine such as tetramethylammonium hydroxide or triethanolamine, which is less basic than sodium hydroxide or potassium hydroxide. Furthermore, tris {2- (methoxymethoxy) ethyl} amine and tris [2-{(2-methoxyethoxy) methoxy} ethyl] amine are more preferable than triethanolamine than triethanolamine. Acetoxy) ethyl} amine and N, N-bis (2-acetoxyethyl) -3-aminopropiononitrile had a higher reaction rate, and a high contrast could be obtained. By the way, the pKa of these bases is estimated to be around 7, and is much weaker than about 13 DBU or DBN, quaternary ammonium hydroxide or proton sponge.

JP-B-2-27660 JP 63-27829 A USP5609989 WO98 / 37458 JP-A 63-149640 JP-A-5-113666 JP-A-5-232706 Japanese Patent Laid-Open No. 5-249662 W. Hinsberg, et. al. , J .; Photopolym. Sci. Technol. , 6 (4), 535-546 (1993) T.A. Kumada, et. al. , J .; Photopolym. Sci. Technol. , 6 (4), 571-574 (1993) SPIE symp.Proc., 3333, 62, (1998) J. Potopoly. Sci. Technol., Vol13, (4), p519 (2000)

  As a result, the base added to the resist does not need to be a particularly strong base, and is a hydratable group such as a hydroxy group, an ether group, particularly an ester group, a carbonyl group, a carbonate group, a cyano group, or a lactone ring. It has been clarified that amines having the above are effective, but further improvement in contrast is required. The present invention has been made in view of the above circumstances, and an object thereof is to provide a resist material having a higher contrast, that is, a wider focus margin, and a pattern forming method using the same.

（上式中、Ｒは、同一又は異種のヒドロキシ基、又はホルミルオキシ基、又はラクトン環、又はカーボネート基を含んでいてもよい炭素数１〜２０の直鎖状、分岐状若しくは環状のアルコキシ基、アルコキシカルボニル基、アシロキシ基、又はシアノ基である。）
一般式（１）−Ａで表される塩基性化合物の製造方法は、（ＲＣＨ₂ＣＨ₂）₂ＮＨで表される第二級アミン化合物をメチルビニルスルホンにマイケル付加させることを含む。
本発明は、スルホンを含む塩基性化合物を添加してなるレジスト材料、好ましくは、下記一般式（１）と（２）とからなる一群から選ばれる塩基性化合物の１種又は２種以上を含有するレジスト材料を提供する。

（上式中、Ｒ¹とＲ^1'は同一又は異種の炭素数１〜４の直鎖状若しくは分岐状のアルキレン基、Ｒ²は同一又は異種の水素原子、又は炭素数１〜２０の直鎖状、分岐状若しくは環状のアルキル基、アリール基又はアラルキル基であって、ヒドロキシ基、エーテル基、カルボニル基、エステル基、ラクトン環、カーボネート基又はシアノ基を含んでいても良く、Ｒ³は同一又は異種の炭素数１〜２０の直鎖状若しくは分岐状のアルキレン基であり、ヒドロキシ基、エーテル基、カルボニル基、エステル基、又はカーボネート基を含んでいても良く、Ｒ⁴は同一又は異種の炭素数１〜４のアルキル基である。ａは同一又は異なる１〜３の整数であり、ｂは同一又は異なる０〜２の整数であるが、各化合物ではａ＋ｂ＝３である。）
また、好ましくは、（Ａ）これらの塩基性化合物と、（Ｂ）有機溶剤と、（Ｃ１）酸不安定基で保護された酸性官能基を有するアルカリ不溶性又は難溶性の樹脂であって、該酸不安定基が脱離したときにアルカリ可溶性となるベース樹脂と、（Ｄ）酸発生剤とを含有するポジ型レジスト材料、及びさらに（Ｅ）溶解阻止剤を含有するポジ型レジスト材料を提供する。さらに、好ましくは、（Ａ）これらの塩基性化合物と、（Ｂ）有機溶剤と、（Ｃ２）アルカリ可溶性樹脂であって、架橋剤による架橋によってアルカリ難溶性となるベース樹脂と、（Ｄ）酸発生剤と、（Ｆ）酸によって架橋する架橋剤とを含有するネガ型レジスト材料を提供する。なお、アルカリ不溶性又はアルカリ難溶性とは、１０〜３０℃において、２．３８重量％ＴＭＡＨ（テトラメチルアンモニウムヒドロキシド）水溶液に対する溶解度が０〜２０Å／sec未満であり、アルカリ可溶性とは、２０〜３０，０００Å／secである。
また、これらのレジスト材料を基板上に塗布する工程と、次いで加熱処理後、フォトマスクを介して波長３００ｎｍ以下の高エネルギー線もしくは電子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パターン形成方法を提案するものである。 As a result of intensive studies to achieve the above object, the present inventors have found that a basic compound containing a sulfone is extremely effective in increasing the contrast of a resist, and have led to the present invention. .
First, a basic compound represented by the following general formula (1) -A is provided as a basic compound.

(In the above formula, R is the same or different hydroxy group, formyloxy group, lactone ring, or linear, branched or cyclic alkoxy group having 1 to 20 carbon atoms which may contain a carbonate group. , An alkoxycarbonyl group, an acyloxy group, or a cyano group.)
The production method of the basic compound represented by the general formula (1) -A includes Michael addition of a secondary amine compound represented by (RCH ₂ CH ₂ ) ₂ NH to methyl vinyl sulfone.
The present invention contains a resist material to which a basic compound containing sulfone is added, preferably one or more basic compounds selected from the group consisting of the following general formulas (1) and (2) A resist material is provided.

(In the above formula, R ¹ and R ^{1 ′} are the same or different linear or branched alkylene group having 1 to 4 carbon atoms, R ² is the same or different hydrogen atom, or a straight chain having 1 to 20 carbon atoms. chain, branched or cyclic alkyl group, an aryl group or an aralkyl group, hydroxy group, an ether group, a carbonyl group, an ester group, lactone ring, also contain carbonate group or a cyano group may, R ³ is It is the same or different linear or branched alkylene group having 1 to 20 carbon atoms and may contain a hydroxy group, an ether group, a carbonyl group, an ester group or a carbonate group, and R ⁴ is the same or different. A is an identical or different integer of 1 to 3, and b is an identical or different integer of 0 to 2, but in each compound, a + b = 3.)
Preferably, (A) these basic compounds, (B) an organic solvent, and (C1) an alkali-insoluble or hardly soluble resin having an acidic functional group protected with an acid labile group, Provided are a positive resist material containing a base resin that becomes alkali-soluble when an acid labile group is eliminated, (D) an acid generator, and (E) a positive resist material containing a dissolution inhibitor. To do. Further preferably, (A) these basic compounds, (B) an organic solvent, (C2) an alkali-soluble resin, and a base resin that becomes hardly soluble in alkali by crosslinking with a crosslinking agent, and (D) an acid. Provided is a negative resist material containing a generator and (F) a crosslinking agent that is crosslinked by an acid. In addition, alkali-insoluble or alkali-insoluble is that the solubility in a 2.38 wt% TMAH (tetramethylammonium hydroxide) aqueous solution at 10 to 30 ° C. is less than 0 to 20% / sec. 30,000 Å / sec.
In addition, the step of applying these resist materials on the substrate, the subsequent heat treatment, the step of exposing with a high energy ray or an electron beam having a wavelength of 300 nm or less through a photomask, and the heat treatment as necessary, The present invention proposes a pattern forming method including a step of developing using a developer.

  As shown in Tables 1 to 3 described later, it can be seen that the resist material of the present invention is a resist material having a wide focus margin, that is, a high contrast.

ここで、Ｒ⁵、Ｒ⁷、Ｒ¹⁰、Ｒ¹²は同一又は異種の炭素数１〜４の直鎖状若しくは分岐状のアルキレン基であり、Ｒ⁶、Ｒ⁹は同一又は異種の水素原子、又は炭素数１〜２０の直鎖状、分岐状若しくは環状のアルキル基であり、ヒドロキシ基、エーテル基、エステル基、又はラクトン環を含んでいても良い。また、Ｒ⁵とＲ⁶は、互いに結合して環を形成してもよい。
Ｒ⁸は同一又は異種の単結合、又は炭素数１〜４の直鎖状若しくは分岐状のアルキレン基であり、Ｒ¹¹は同一又は異種の炭素数１〜２０の直鎖状、分岐状若しくは環状のアルキル基であり、ヒドロキシ基、エーテル基、エステル基、カルボニル基、シアノ基又はラクトン環を含んでいても良い。 Hereinafter, the present invention will be described in more detail.
In the basic compound used in the present invention, R ² in the general formula (1) is preferably selected from the group consisting of the following general formulas (3) to (6).

Here, R ⁵ , R ⁷ , R ¹⁰ and R ¹² are the same or different linear or branched alkylene groups having 1 to 4 carbon atoms, R ⁶ and R ⁹ are the same or different hydrogen atoms, Or it is a C1-C20 linear, branched or cyclic alkyl group, and may contain a hydroxy group, an ether group, an ester group, or a lactone ring. R ⁵ and R ⁶ may combine with each other to form a ring.
R ⁸ is the same or different single bond, or a linear or branched alkylene group having 1 to 4 carbon atoms, and R ¹¹ is the same or different linear, branched or cyclic group having 1 to 20 carbon atoms. And may contain a hydroxy group, an ether group, an ester group, a carbonyl group, a cyano group, or a lactone ring.

Here, the general formulas (3) to (6) represented by R ² in the general formula (1) are specifically the following (3) -1 to (3) -4, (4) -1 to (4). -10, (5) -1 to (5) -17, (6) -1.

In the general formula (1), when R ² is an aryl group or aralkyl group having 6 to 20 carbon atoms, it can be represented by the following general formulas (7) -1 to (7) -2.

In the Formula (7) -1 and (7) -2, R ¹³ is a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an aryl group, an aralkyl group, an alkoxy group, a hydroxyl group, a halogen atom, a nitro group, a cyano group , An ester group and an acetoxy group, and x and y are integers satisfying 0 ≦ x ≦ 5 and 0 ≦ y ≦ 7. R ¹⁴ is a single bond or a linear, branched or cyclic alkylene group having 1 to 10 carbon atoms.

Bases having a phenyl group are mainly used for KrF excimer laser, and bases having a naphthyl group are preferably used because of high transparency in ArF excimer laser light.
A basic compound containing an aryl group is considered to have a large diffusion distance, so that the dimensional difference between the group line pattern and the isolated line pattern is reduced, the line edge roughness is reduced, or the pattern side wall due to the generation of low standing waves is reduced. It has the effect of reducing the unevenness.

とした場合、［ ］で囲まれた置換基は具体的には（８）−１〜（８）−１２に例示される。

In the general formula (2), R ³ is a linear or branched alkylene group having 1 to 20 carbon atoms, and may contain a hydroxy group, an ether group, a carbonyl group, an ester group, or a carbonate group.

In this case, the substituents surrounded by [] are specifically exemplified by (8) -1 to (8) -12.

In the general formula (2), R ⁴ is an alkyl group having 1 to ⁴ carbon atoms. Specific examples include a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, and a t-butyl group. Groups.

  The basic compound of the present invention can be synthesized according to a general method for synthesizing amine compounds. For example, it can be synthesized using a Michael addition reaction of a secondary amine to an α, β-unsaturated sulfone compound or an N-alkylation reaction of a secondary amine with a haloalkyl sulfone compound. In particular, the basic compound of the present invention represented by the general formula (1) -A can be easily produced in a high yield by, for example, the following method, but is not limited thereto. This will be described in detail below.

（上式中、Ｒは前記と同様である。） The basic compound of the present invention represented by the general formula (1) -A can be efficiently synthesized using a Michael addition reaction of a secondary amine to methyl vinyl sulfone.

(In the above formula, R is as defined above.)

  The amount of methyl vinyl sulfone (S2) used is desirably 0.5 to 5.0 mol, particularly 0.8 to 1.2 mol, per 1 mol of the amine compound (S1). The reaction is carried out without solvent or in a solvent. Solvents include alcohols such as methanol, ethanol, isopropyl alcohol, t-butyl alcohol, ethylene glycol, hydrocarbons such as hexane, heptane, benzene, toluene, xylene, diethyl ether, dibutyl ether, tetrahydrofuran, 1, 4 -Ethers such as dioxane and diglyme, chlorinated solvents such as methylene chloride, chloroform and 1,2-dichloroethylene, N, N-dimethylformamide, N, N-dimethylacetamide, dimethyl sulfoxide, N-methylpyrrolidone and the like Proton polar solvents, carboxylic acids such as formic acid and acetic acid, esters such as ethyl acetate and butyl acetate, ketones such as acetone and 2-butanone, nitriles such as acetonitrile, pyridine and triethylamine Emissions such, and to select the reaction conditions out of the water can be used alone or as a mixture. The reaction time is selected in the range from 0 ° C. to the reflux temperature of the solvent depending on the reaction rate. In the reaction, as a catalyst for improving the reaction rate, an inorganic acid such as hydrochloric acid, sulfuric acid, nitric acid or a salt thereof, an organic acid such as p-toluenesulfonic acid, formic acid, acetic acid, oxalic acid, trifluoroacetic acid or the like The salt may be added. In order to prevent the polymerization of methyl vinyl sulfone, a polymerization inhibitor such as hydroquinone, p-methoxyphenol, benzoquinone, phenylenediamine may be added. The reaction time is preferably about 2 to 200 hours in terms of yield, although it is desirable to complete the reaction by following the reaction by gas chromatography (GC) or thin layer chromatography (TLC). The target basic compound (1) is obtained by concentrating the reaction mixture under reduced pressure directly or after a normal aqueous work-up. The obtained basic compound (1) can be purified by conventional methods such as distillation, chromatography, recrystallization and the like, if necessary.

  The organic solvent of the component (B) used in the resist material of the present invention may be any organic solvent that can dissolve acid generators, base resins, dissolution inhibitors, and the like. Examples of such an organic solvent include ketones such as cyclohexanone and methyl-2-n-amyl ketone, 3-methoxybutanol, 3-methyl-3-methoxybutanol, 1-methoxy-2-propanol, and 1-ethoxy-2. Alcohols such as propanol, propylene glycol monomethyl ether, ethylene glycol monomethyl ether, propylene glycol monoethyl ether, ethyl lactate, ethyl pyruvate, butyl acetate, methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, tert-acetate And esters such as butyl, tert-butyl propionate, propylene glycol mono-tert-butyl ether acetate, etc., one of these alone or two or more of ethylene glycol monoethyl ether Propylene glycol dimethyl ether, and diethylene glycol dimethyl ether, propylene glycol monomethyl ether acetate, can be used as a mixture of propylene glycol monoethyl ether acetate, but is not limited thereto. In the present invention, among these organic solvents, diethylene glycol dimethyl ether, 1-ethoxy-2-propanol, and ethyl lactate, which are most excellent in solubility of the acid generator in the resist component, as well as propylene glycol monomethyl ether acetate, which is a safety solvent, are used. And mixed solvents thereof are preferably used.

The base polymer mentioned as the component (C) is a polyhydroxystyrene (PHS), and a copolymer of PHS and styrene, (meth) acrylic acid ester, maleimide N carboxylic acid ester for resists for KrF excimer laser. As resists for ArF excimer laser, (meth) acrylic acid ester system, alternating copolymer system of norbornene and maleic anhydride, alternating copolymer system of tetracyclododecene and maleic anhydride, polynorbornene system, ring opening For the metathesis polymerization system by polymerization and for the F ₂ excimer laser, the above-mentioned KrF, ArF polymer fluorine-substituted products, and copolymerization with tetrafluoroethylene can be mentioned, but it is not limited to these polymerization polymers. (Meth) acrylic acid is an abbreviation for methacrylic acid or acrylic acid. In the case of a positive resist, the dissolution rate of the unexposed area is generally lowered by substituting the hydroxyl group of the phenol, carboxyl group or fluorinated alkyl alcohol with an acid labile group.

The acid labile group is variously selected, and is particularly a group represented by the following formulas (AL10) and (AL11), a tertiary alkyl group having 4 to 40 carbon atoms represented by the following formula (AL12), and 1 carbon atom. A trialkylsilyl group having 6 to 6 carbon atoms, an oxoalkyl group having 4 to 20 carbon atoms, and the like are preferable.

In the formulas (AL10) and (AL11), R ¹⁵ and R ¹⁸ are linear, branched and cyclic alkyl groups having 1 to 20 carbon atoms and may contain heteroatoms such as oxygen, sulfur, nitrogen and fluorine. .
R ¹⁶ and R ¹⁷ are a hydrogen atom, a linear, branched, or cyclic alkyl group having 1 to 20 carbon atoms, and may include heteroatoms such as oxygen, sulfur, nitrogen, fluorine, and c is 0 to 10 Is an integer. R ¹⁶ and R ¹⁷ , R ¹⁶ and R ¹⁸ , and R ¹⁷ and R ¹⁸ may be bonded to form a ring.
In the formula (AL12), R ¹⁹ , R ²⁰ and R ²¹ are monovalent hydrocarbon groups such as linear, branched or cyclic alkyl groups having 1 to 20 carbon atoms, such as oxygen, sulfur, nitrogen, fluorine, etc. And R ¹⁹ and R ²⁰ , R ¹⁹ and R ²¹ , and R ²⁰ and R ²¹ may be bonded to each other to form a ring.

  Specific examples of the acid labile group represented by the formula (AL10) include tert-butoxycarbonyl group, tert-butoxycarbonylmethyl group, tert-amyloxycarbonyl group, tert-amyloxycarbonylmethyl group, 1-ethoxyethoxy. Examples include carbonylmethyl group, 2-tetrahydropyranyloxycarbonylmethyl group, 2-tetrahydrofuranyloxycarbonylmethyl group and the like, and substituents represented by the following general formulas (AL10) -1 to (AL10) -9.

In the formulas (AL10) -1 to (AL10) -9, R ²² is the same or non-identical linear, branched or cyclic alkyl group having 1 to 8 carbon atoms, aryl group having 6 to 20 carbon atoms, An aralkyl group is shown. R ²³ does not exist or represents a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms. R ²⁴ represents an aryl group or aralkyl group having 6 to 20 carbon atoms.

Examples of the acid labile group represented by the formula (AL11) are (AL11) -1 to (AL11) -23.

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 (AL11a) or (AL11b).

In the above formula, R ²⁵ and R ²⁶ represent a hydrogen atom or a linear, branched or cyclic alkyl group having 1 to 8 carbon atoms. Alternatively, R ²⁵ and R ²⁶ may combine to form a ring, and when forming a ring, R ²⁵ and R ²⁶ represent a linear or branched alkylene group having 1 to 8 carbon atoms. . R ²⁷ is a linear, branched or cyclic alkylene group having 1 to 10 carbon atoms, and e is 0 or an integer of 1 to 10. A represents a d + 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 hetero atom, 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-. d is an integer of 1-7.

Specific examples of the cross-linked acetal represented by the general formulas (AL11a) and (AL11b) include the following (AL11) -24 to (AL11) -31.

The tertiary alkyl group represented by the formula (AL12) includes a tert-butyl group, a triethylcarbyl group, a 1-ethylnorbornyl group, a 1-methylcyclohexyl group, a 1-ethylcyclopentyl group, and 2- (2-methyl). Examples thereof include an adamantyl group, a 2- (2-ethyl) adamantyl group, a tert-amyl group, and the following general formulas (AL12) -1 to (AL12) -18.

In the formula, R ²⁸ represents the same or non-identical linear, branched or cyclic alkyl group having 1 to 8 carbon atoms, aryl group having 6 to 20 carbon atoms, and aralkyl group. R ²⁹ and R ³¹ are not present or represent a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms. R ³⁰ represents an aryl group or aralkyl group having 6 to 20 carbon atoms.

Furthermore, as shown in the following formulas (AL12) -19 and (AL12) -20, even if R ³² which is a divalent or higher valent alkylene group or an arylene group is included, the polymer molecule or between the molecules may be crosslinked. good. In the formula (12) -19, R ²⁸ is the same as described above, and R ³² represents a linear, branched, or cyclic alkylene group or arylene group having 1 to 20 carbon atoms, such as an oxygen atom, a sulfur atom, or a nitrogen atom. Hetero atoms may be included. f is an integer of 1 to 3.

Further, R ²⁸ , R ²⁹ , R ³⁰ and R ³¹ may have heteroatoms such as oxygen, nitrogen and sulfur, and specifically, the following (13) -1 to (13) -7 Can do.

As the acid labile group, a trialkylsilyl group having 1 to 6 carbon atoms can be used. Examples of the trialkylsilyl group having 1 to 6 carbon atoms include trimethylsilyl group, triethylsilyl group, dimethyl-tert-butylsilyl group and the like. Can be mentioned.
Although an oxoalkyl group having 4 to 20 carbon atoms can be used as the acid labile group, examples of the oxoalkyl group having 4 to 20 carbon atoms include a 3-oxocyclohexyl group and a group represented by the following formula.

  The weight average molecular weight of the base polymer is preferably set to 5,000 to 100,000 when measured using polystyrene-performed gel permeation chromatography (GPC). The resolution may be inferior, and if it exceeds 100,000, the resolution may be inferior.

（但し、Ｒ³³は炭素数１〜１２の直鎖状、分岐状又は環状のアルキル基、炭素数６〜１２のアリール基、又は炭素数７〜１２のアラルキル基を表し、Ｍ⁺はヨードニウム、スルホニウムを表し、Ｋ^-は非求核性対向イオンを表し、ｇは２又は３である。） As the acid generator of the component (D), an onium salt of the following general formula (AG1), a diazomethane derivative of the formula (AG2), a glyoxime derivative of the formula (AG3), a β-ketosulfone derivative, a disulfone derivative, a nitrobenzyl sulfonate derivative, Examples thereof include sulfonic acid ester derivatives and imido-yl sulfonate derivatives.

(Wherein R ³³ represents a linear, branched or cyclic alkyl group having 1 to 12 carbon atoms, an aryl group having 6 to 12 carbon atoms, or an aralkyl group having 7 to 12 carbon atoms, and M ⁺ represents iodonium, Represents sulfonium, K ⁻ represents a non-nucleophilic counter ion, and g is 2 or 3.)

^Examples of the alkyl group for R ³³ include a methyl group, an ethyl group, a propyl group, a butyl group, a cyclohexyl group, a 2-oxocyclohexyl group, a norbornyl group, and an adamantyl group. As the aryl group, an alkoxyphenyl group such as a phenyl group, p-methoxyphenyl group, m-methoxyphenyl group, o-methoxyphenyl group, ethoxyphenyl group, p-tert-butoxyphenyl group, m-tert-butoxyphenyl group, Examples thereof include alkylphenyl groups such as 2-methylphenyl group, 3-methylphenyl group, 4-methylphenyl group, ethylphenyl group, 4-tert-butylphenyl group, 4-butylphenyl group, and dimethylphenyl group. Examples of the aralkyl group include a benzyl group and a phenethyl group. Non-nucleophilic counter ions of K ⁻ include halide ions such as chloride ion and bromide ion, fluoroalkyl sulfonates such as triflate, 1,1,1-trifluoroethane sulfonate, and nonafluorobutane sulfonate, tosylate, and benzene sulfonate. And aryl sulfonates such as 4-fluorobenzene sulfonate and 1,2,3,4,5-pentafluorobenzene sulfonate, and alkyl sulfonates such as mesylate and butane sulfonate.

（但し、Ｒ³⁴、Ｒ³⁵は炭素数１〜１２の直鎖状、分岐状又は環状のアルキル基又はハロゲン化アルキル基、炭素数６〜１２のアリール基又はハロゲン化アリール基又は炭素数７〜１２のアラルキル基を表す。）

(However, R ³⁴ and R ³⁵ are linear, branched or cyclic alkyl groups or halogenated alkyl groups having 1 to 12 carbon atoms, aryl groups or halogenated aryl groups having 6 to 12 carbon atoms, or 7 to 7 carbon atoms. Represents 12 aralkyl groups.)

^Examples of the alkyl group for R ³⁴ and R ³⁵ include a methyl group, an ethyl group, a propyl group, a butyl group, an amyl group, a cyclopentyl group, a cyclohexyl group, a norbornyl group, and an adamantyl group. Examples of the halogenated alkyl group include a trifluoromethyl group, a 1,1,1-trifluoroethyl group, a 1,1,1-trichloroethyl group, and a nonafluorobutyl group. As the aryl group, an alkoxyphenyl group such as a phenyl group, p-methoxyphenyl group, m-methoxyphenyl group, o-methoxyphenyl group, ethoxyphenyl group, p-tert-butoxyphenyl group, m-tert-butoxyphenyl group, Examples thereof include alkylphenyl groups such as 2-methylphenyl group, 3-methylphenyl group, 4-methylphenyl group, ethylphenyl group, 4-tert-butylphenyl group, 4-butylphenyl group, and dimethylphenyl group. Examples of the halogenated aryl group include a fluorobenzene group, a chlorobenzene group, and 1,2,3,4,5-pentafluorobenzene group. Examples of the aralkyl group include a benzyl group and a phenethyl group.

（但し、Ｒ³⁶、Ｒ³⁷、Ｒ³⁸は炭素数１〜１２の直鎖状、分岐状又は環状のアルキル基又はハロゲン化アルキル基、炭素数６〜１２のアリール基又はハロゲン化アリール基又は炭素数７〜１２のアラルキル基を表す。また、Ｒ³⁷、Ｒ³⁸は互いに結合して環状構造を形成してもよく、環状構造を形成する場合、Ｒ³⁷、Ｒ³⁸はそれぞれ炭素数１〜６の直鎖状又は分岐状のアルキレン基を表す。）

(However, R ³⁶ , R ³⁷ , and R ³⁸ are linear, branched or cyclic alkyl groups or halogenated alkyl groups having 1 to 12 carbon atoms, aryl groups or halogenated aryl groups having 6 to 12 carbon atoms, or carbon atoms. Represents an aralkyl group having a number of 7 to 12. R ³⁷ and R ³⁸ may be bonded to each other to form a cyclic structure, and when forming a cyclic structure, R ³⁷ and R ³⁸ each have 1 to 6 carbon atoms. Represents a linear or branched alkylene group.)

Examples of the alkyl group, halogenated alkyl group, aryl group, halogenated aryl group, and aralkyl group for R ³⁶ , R ³⁷ , and R ³⁸ include the same groups as those described for R ³⁴ and R ³⁵ . ^Examples of the alkylene group for R ³⁷ and R ³⁸ include a methylene group, an ethylene group, a propylene group, a butylene group, and a hexylene group.

  Specifically, examples of onium salts include diphenyliodonium trifluoromethanesulfonate, trifluoromethanesulfonate (p-tert-butoxyphenyl) phenyliodonium, p-toluenesulfonate diphenyliodonium, p-toluenesulfonate (p-tert -Butoxyphenyl) phenyliodonium, triphenylsulfonium trifluoromethanesulfonate, trifluoromethanesulfonic acid (p-tert-butoxyphenyl) diphenylsulfonium, bis (p-tert-butoxyphenyl) phenylsulfonium trifluoromethanesulfonate, trifluoromethanesulfonic acid Tris (p-tert-butoxyphenyl) sulfonium, p-toluenesulfonic acid triphenylsulfonium, p-tolue Sulfonic acid (p-tert-butoxyphenyl) diphenylsulfonium, p-toluenesulfonic acid bis (p-tert-butoxyphenyl) phenylsulfonium, p-toluenesulfonic acid tris (p-tert-butoxyphenyl) sulfonium, nonafluorobutanesulfone Triphenylsulfonium acid, triphenylsulfonium butanesulfonate, trimethylsulfonium trifluoromethanesulfonate, trimethylsulfonium p-toluenesulfonate, cyclohexylmethyl trifluoromethanesulfonate (2-oxocyclohexyl) sulfonium, cyclohexylmethyl p-toluenesulfonate (2 -Oxocyclohexyl) sulfonium, dimethylphenylsulfonium trifluoromethanesulfonate, p-toluene Sulfonic acid dimethylphenyl trifluoromethanesulfonate, dicyclohexyl phenyl sulfonium, p- toluenesulfonic acid dicyclohexyl phenyl sulfonium and the like.

  Diazomethane derivatives include bis (benzenesulfonyl) diazomethane, bis (p-toluenesulfonyl) diazomethane, bis (xylenesulfonyl) diazomethane, bis (cyclohexylsulfonyl) diazomethane, bis (cyclopentylsulfonyl) diazomethane, bis (n-butylsulfonyl) diazomethane Bis (isobutylsulfonyl) diazomethane, bis (sec-butylsulfonyl) diazomethane, bis (n-propylsulfonyl) diazomethane, bis (isopropylsulfonyl) diazomethane, bis (tert-butylsulfonyl) diazomethane, bis (n-amylsulfonyl) diazomethane Bis (isoamylsulfonyl) diazomethane, bis (sec-amylsulfonyl) diazomethane, bis (tert-amylsulfur) Nyl) diazomethane, 1-cyclohexylsulfonyl-1- (tert-butylsulfonyl) diazomethane, 1-cyclohexylsulfonyl-1- (tert-amylsulfonyl) diazomethane, 1-tert-amylsulfonyl-1- (tert-butylsulfonyl) diazomethane Etc.

  Examples of glyoxime derivatives include bis-o- (p-toluenesulfonyl) -α-dimethylglyoxime, bis-o- (p-toluenesulfonyl) -α-diphenylglyoxime, bis-o- (p-toluenesulfonyl)- α-dicyclohexylglyoxime, bis-o- (p-toluenesulfonyl) -2,3-pentanedione glyoxime, bis-o- (p-toluenesulfonyl) -2-methyl-3,4-pentanedione glyoxime, Bis-o- (n-butanesulfonyl) -α-dimethylglyoxime, bis-o- (n-butanesulfonyl) -α-diphenylglyoxime, bis-o- (n-butanesulfonyl) -α-dicyclohexylglyoxime Bis-o- (n-butanesulfonyl) -2,3-pentanedione glyoxime, bis-o- ( -Butanesulfonyl) -2-methyl-3,4-pentanedione glyoxime, bis-o- (methanesulfonyl) -α-dimethylglyoxime, bis-o- (trifluoromethanesulfonyl) -α-dimethylglyoxime, bis -O- (1,1,1-trifluoroethanesulfonyl) -α-dimethylglyoxime, bis-o- (tert-butanesulfonyl) -α-dimethylglyoxime, bis-o- (perfluorooctanesulfonyl)- α-dimethylglyoxime, bis-o- (cyclohexanesulfonyl) -α-dimethylglyoxime, bis-o- (benzenesulfonyl) -α-dimethylglyoxime, bis-o- (p-fluorobenzenesulfonyl) -α- Dimethylglyoxime, bis-o- (p-tert-butylbenzenesulfonyl) α- dimethylglyoxime, bis-o-(xylene sulfonyl)-.alpha.-dimethylglyoxime, bis-o-(camphorsulfonyl)-.alpha.-dimethylglyoxime, and the like.

  Examples of the β-ketosulfone derivative include 2-cyclohexylcarbonyl-2- (p-toluenesulfonyl) propane and 2-isopropylcarbonyl-2- (p-toluenesulfonyl) propane.

  Examples of the disulfone derivative include diphenyl disulfone and dicyclohexyl disulfone.

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

  Examples of sulfonic acid ester derivatives include 1,2,3-tris (methanesulfonyloxy) benzene, 1,2,3-tris (trifluoromethanesulfonyloxy) benzene, 1,2,3-tris (p-toluenesulfonyloxy). Examples include benzene.

  Imido-yl-sulfonate derivatives include phthalimido-yl-triflate, phthalimido-yl-tosylate, 5-norbornene-2,3-dicarboximido-yl-triflate, 5-norbornene-2,3-dicarboximide -Yl-tosylate, 5-norbornene-2,3-dicarboximido-yl-n-butylsulfonate and the like.

  Preferably, triphenylsulfonium trifluoromethanesulfonate, trifluoromethanesulfonic acid (p-tert-butoxyphenyl) diphenylsulfonium, trifluoromethanesulfonic acid tris (p-tert-butoxyphenyl) sulfonium, p-toluenesulfonic acid triphenylsulfonium, Onium salts such as p-toluenesulfonic acid (p-tert-butoxyphenyl) diphenylsulfonium, p-toluenesulfonic acid tris (p-tert-butoxyphenyl) sulfonium, bis (benzenesulfonyl) diazomethane, bis (p-toluenesulfonyl) Diazomethane, bis (cyclohexylsulfonyl) diazomethane, bis (n-butylsulfonyl) diazomethane, bis (isobutylsulfonyl) diazomethane, Diazomethane derivatives such as bis (tert-butylsulfonyl) diazomethane, bis (n-propylsulfonyl) diazomethane, bis (isopropylsulfonyl) diazomethane, bis (tert-butylsulfonyl) diazomethane, bis-o- (p-toluenesulfonyl) -α Glyoxime derivatives such as dimethylglyoxime and bis-o- (n-butanesulfonyl) -α-dimethylglyoxime, and naphthoquinone diazide sulfonic acid ester derivatives are used.

  In addition, the said acid generator can be used individually by 1 type or in combination of 2 or more types. An onium salt is excellent in the effect of improving rectangularity, and a diazomethane derivative and a glyoxime derivative are excellent in a standing wave reducing effect. However, by combining both, the profile can be finely adjusted.

  The blending amount of the acid generator is preferably 0.2 to 50 parts by weight, particularly preferably 0.5 to 40 parts by weight with respect to 100 parts by weight of the total base resin. The amount of acid generated is small and the sensitivity and resolving power may be inferior, and if it exceeds 50 parts by weight, the transmittance of the resist may be lowered and the resolving power may be inferior.

  (E) Component dissolution inhibitors include compounds having a molecular weight of 3,000 or less, particularly low molecular weight phenols having a molecular weight of 2,500 or less or part of carboxylic acid derivatives or the like, whose solubility in an alkaline developer is changed by the action of an acid. Examples thereof include compounds in which all are substituted with an acid-labile substituent.

  The phenol or carboxylic acid derivative having a 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, etc. And the same as the base polymer.

  Examples of suitable dissolution inhibitors include bis (4- (2′tetrahydropyranyloxy) phenyl) methane, bis (4- (2′tetrahydrofuranyloxy) phenyl) methane, bis (4-tert-butoxy Phenyl) 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′-ter) -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, tert-butyl 4,4-bis (4'-(2''tetrahydropyranyloxy) phenyl) valerate, 4,4-bis (4 ′-(2 ″ tetrahydrofuranyloxy) phenyl) tert-butyl valerate, 4,4-bis (4′-tert-butoxyphenyl) valerate tert-butyl, 4,4-bis (4-tert- Tert-butyl butoxycarbonyloxyphenyl) valerate, 4,4-bis (4′-tert-butoxycarbonylmethyloxyphenyl) valerate te rt-butyl, 4,4-bis (4 ′-(1 ″ -ethoxyethoxy) phenyl) tert-butyl valerate, 4,4-bis (4 ′-(1 ″ -ethoxypropyloxy) phenyl) yoshi Tert-butyl herbate, 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-butoxycarbonylmethyloxyphenyl) ethane, 1,1,2-tris (4 ′-(1′-ethoxy) Ethoxy) phenyl) ethane, 1,1,2-tris (4 ′-(1′-ethoxypropyloxy) phenyl) ethane and the like.

  Although the addition amount of the dissolution inhibitor in the resist material of the present invention is arbitrary, it is preferably 20 parts by weight or less, more preferably 15 parts by weight or less with respect to 100 parts by weight of the base resin in the resist material. If the amount is more than 20 parts by weight, the heat resistance of the resist material may decrease.

  Examples of the crosslinking agent as the component (F) include compounds having two or more hydroxymethyl groups, alkoxymethyl groups, epoxy groups or vinyl ether groups in the molecule, substituted glycouril derivatives, urea derivatives, hexa (methoxymethyl) melamine. Etc. are preferably used.

  For example, tetraalkoxymethyl substituted glycolurils such as N, N, N ′, N′-tetramethoxymethylurea and hexamethylmelamine, tetrahydroxymethyl substituted glycolurils and tetramethoxymethylglycolurils, substituted and interstitial bis- Examples include phenolic compounds such as hydroxymethylphenols and bisphenol A and condensates such as epichlorohydrin.

  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′-tetrahydroxymethylbisphenol A, and 1,4-bis- [2- (2-hydroxypropyl) ] -Benzene, N, N, N ′, N′-tetramethoxymethylurea, hexamethoxymethylmelamine and the like. Although the addition amount is arbitrary, it is preferably 1 to 25 parts by weight, more preferably 5 to 20 parts by weight with respect to the base resin in the resist material. These may be added alone or in combination of two or more.

  In addition to the base of the present invention, one or two or more bases other than the conventionally used base of the present invention can be used in combination. Conventionally used bases include primary, secondary and tertiary aliphatic amines, hybrid amines, aromatic amines, heterocyclic amines, nitrogen-containing compounds having a carboxy group, sulfonyl A nitrogen-containing compound having a group, a nitrogen-containing compound having a hydroxy group, a nitrogen-containing compound having a hydroxyphenyl group, an alcoholic nitrogen-containing compound, an amide derivative, and an imide derivative.

  Primary aliphatic amines include ammonia, methylamine, ethylamine, n-propylamine, isopropylamine, n-butylamine, isobutylamine, sec-butylamine, tert-butylamine, pentylamine, tert-amylamine, cyclopentylamine, Examples include hexylamine, cyclohexylamine, heptylamine, octylamine, nonylamine, decylamine, dodecylamine, cetylamine, methylenediamine, ethylenediamine, tetraethylenepentamine and the like.

  Secondary aliphatic amines include dimethylamine, diethylamine, di-n-propylamine, diisopropylamine, di-n-butylamine, diisobutylamine, di-sec-butylamine, dipentylamine, dicyclopentylamine, dihexylamine, Examples include dicyclohexylamine, diheptylamine, dioctylamine, dinonylamine, didecylamine, didodecylamine, dicetylamine, N, N-dimethylmethylenediamine, N, N-dimethylethylenediamine, N, N-dimethyltetraethylenepentamine and the like.

  Tertiary aliphatic amines include trimethylamine, triethylamine, tri-n-propylamine, triisopropylamine, tri-n-butylamine, triisobutylamine, tri-sec-butylamine, tripentylamine, tricyclopentylamine, tri Hexylamine, tricyclohexylamine, triheptylamine, trioctylamine, trinonylamine, tridecylamine, tridodecylamine, tricetylamine, N, N, N ′, N′-tetramethylmethylenediamine, N, N, Examples thereof include N ′, N′-tetramethylethylenediamine, N, N, N ′, N′-tetramethyltetraethylenepentamine and the like.

  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.

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

  Nitrogen-containing compounds having a hydroxy group, nitrogen-containing compounds having a hydroxyphenyl group, and alcoholic nitrogen-containing compounds include 2-hydroxypyridine, aminocresol, 2,4-quinolinediol, 3-indolemethanol hydrate, 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, piperidine Eta 1- (2-hydroxyethyl) pyrrolidine, 1- (2-hydroxyethyl) -2-pyrrolidinone, 3-piperidino-1,2-propanediol, 3-pyrrolidino-1,2-propanediol, 8-hydroxy Yurolidine, 3-cuincridinol, 3-tropanol, 1-methyl-2-pyrrolidine ethanol, 1-aziridine ethanol, N- (2-hydroxyethyl) phthalimide, N- (2-hydroxyethyl) isonicotinamide, etc. Is exemplified.

  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 (B) -1 can also be added.

In the formula, n = 1, 2, and 3. The side chains X may be the same or different, and can be represented by the following general formulas (X) -1 to (X) -3.

  The side chain Y represents the same or different hydrogen atom or a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms, and may contain an ether group or a hydroxyl group. Xs may be bonded to form a ring.

Here, R ³⁰⁰ , R ³⁰² and R ³⁰⁵ are linear or branched alkylene groups having 1 to 4 carbon atoms, and R ³⁰¹ and R ³⁰⁴ are hydrogen atoms, linear and branched chains having 1 to 20 carbon atoms. And cyclic alkyl groups, which may contain one or more hydroxy groups, ether groups, ester groups, and lactone rings.
R ³⁰³ is a single bond, a linear or branched alkylene group having 1 to 4 carbon atoms, R ³⁰⁶ is a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms, a hydroxy group, One or a plurality of ether, ester groups and lactone rings may be contained.

Specific examples of the compound represented by formula (B) -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.

（上式中、Ｘは前述の通り、Ｒ³⁰⁷は炭素数２〜２０の直鎖状、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、スルフィドを１個あるいは複数個含んでいても良い。） Furthermore, 1 type, or 2 or more types of the basic compound which has the cyclic structure shown by the following general formula (B) -2 can also be added.

(In the above formula, X is as described above, and R ³⁰⁷ is a linear or branched alkylene group having 2 to 20 carbon atoms, including one or more carbonyl groups, ether groups, ester groups, and sulfides. May be.)

  B-2 specifically includes 1- [2- (methoxymethoxy) ethyl] pyrrolidine, 1- [2- (methoxymethoxy) ethyl] piperidine, 4- [2- (methoxymethoxy) ethyl] morpholine, [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-methoxyacetate (1-pyrrolidinyl) ethyl, 4- [2- (methoxycarbonyloxy) ethyl] morpholine, 1 [2- (t-Butoxycarbonyloxy) ethyl] piperidine, 4- [2- (2-methoxyethoxycarbonyloxy) ethyl] morpholine, methyl 3- (1-pyrrolidinyl) propionate, methyl 3-piperidinopropionate Methyl 3-morpholinopropionate, methyl 3- (thiomorpholino) propionate, methyl 2-methyl-3- (1-pyrrolidinyl) propionate, ethyl 3-morpholinopropionate, methoxycarbonylmethyl 3-piperidinopropionate 2-hydroxyethyl 3- (1-pyrrolidinyl) propionate, 2-acetoxyethyl 3-morpholinopropionate, 2-oxotetrahydrofuran-3-yl 3- (1-pyrrolidinyl) propionate, tetrahydrofuro 3-morpholinopropionate Frill, 3-pipe Glycidyl dinopropionate, 2-methoxyethyl 3-morpholinopropionate, 2- (2-methoxyethoxy) ethyl 3- (1-pyrrolidinyl) propionate, butyl 3-morpholinopropionate, cyclohexyl 3-piperidinopropionate, α- (1-pyrrolidinyl) methyl-γ-butyrolactone, β-piperidino-γ-butyrolactone, β-morpholino-δ-valerolactone, methyl 1-pyrrolidinyl acetate, methyl piperidinoacetate, methyl morpholinoacetate, methyl thiomorpholinoacetate, 1 -Ethyl pyrrolidinyl acetate, 2-methoxyethyl morpholinoacetate.

（上式中、Ｘ、Ｒ³⁰⁷、ｎは前述の通り、Ｒ³⁰⁸、Ｒ³⁰⁹は同一又は異種の炭素数１〜４の直鎖状、分岐状のアルキレン基である。） Furthermore, a basic compound containing a cyano group represented by general formulas (B) -3 to (B) -6 can be added.

(In the above formula, X, R ³⁰⁷ and n are as described above, and R ³⁰⁸ and R ³⁰⁹ are the same or different linear and branched alkylene groups having 1 to 4 carbon atoms.)

  Specific examples of the base containing a cyano group include 3- (diethylamino) propiononitrile, N, N-bis (2-hydroxyethyl) -3-aminopropiononitrile, and N, N-bis (2-acetoxyethyl). -3-aminopropiononitrile, N, N-bis (2-formyloxyethyl) -3-aminopropiononitrile, N, N-bis (2-methoxyethyl) -3-aminopropiononitrile, N, N -Bis [2- (methoxymethoxy) ethyl] -3-aminopropiononitrile, 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-aminopro Methyl onate, 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-tetrahydrofur Furyl-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-methoxyethyl) ) Methyl 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) -N (Cyanomethyl) aminoacetonitrile, N-cyanomethyl-N- (3-formyloxy-1-propyl) aminoacetonitrile, N, N-bis (cyanomethyl) aminoacetonitrile, 1-pyrrolidinepropiononitrile, 1-piperidinepropiononitrile, 4-morpholinepropiononitrile, 1-pyrrolidineacetonitrile, 1-piperidineacetonitrile, 4-morpholineacetonitrile, cyanomethyl 3-diethylaminopropionate, cyanomethyl N, N-bis (2-hydroxyethyl) -3-aminopropionate, N, Cyanomethyl N-bis (2-acetoxyethyl) -3-aminopropionate, cyanomethyl N, N-bis (2-formyloxyethyl) -3-aminopropionate, N, N-bis (2-methoxyethyl) Cyanomethyl 3-aminopropionate, N, N-bis [2- (methoxymethoxy) ethyl] -3-aminopropionate cyanomethyl, 3-diethylaminopropionic acid (2-cyanoethyl), N, N-bis (2-hydroxyethyl) ) -3-Aminopropionic acid (2-cyanoethyl), N, N-bis (2-acetoxyethyl) -3-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), 1-pyrrolidinepropionate cyanomethyl, 1-piperidinepropionate cyano Examples include methyl, cyanomethyl 4-morpholine propionate, 1-pyrrolidinepropionic acid (2-cyanoethyl), 1-piperidinepropionic acid (2-cyanoethyl), 4-morpholine propionic acid (2-cyanoethyl).

  In addition, the compounding quantity of this invention basic compound becomes like this. Preferably it is 0.001-2 weight part with respect to 100 weight part of all base resins, Most preferably, it is 0.01-1 weight part. If the blending amount is less than 0.001 part by weight, the blending effect may not be obtained.

  The pattern forming method of the present invention comprises a step of applying the resist material of the present invention on a substrate, and then a heat treatment at 50 to 200 ° C. for evaporating the solvent and solidifying the film, and then through a photomask. It includes a step of exposing with a high energy beam or an electron beam having a wavelength of 300 nm or less, preferably 3 to 300 nm, and a step of developing using a developer after heat treatment as necessary. The heat treatment as necessary is, for example, heat treatment for promoting the acid catalyst reaction, and preferably heating at 50 to 180 ° C.

ジエタノールアミン４８．５ｇに２０℃でメチルビニルスルホン４９．０ｇを加え２００時間攪拌することによりＮ−［２−（メチルスルホニル）エチル］ジエタノールアミン９７．５ｇを得た（定量的収率）。 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]
The basic compound of the present invention was synthesized by the method shown below.
[Synthesis Example 1] Synthesis of N- [2- (methylsulfonyl) ethyl] diethanolamine.

By adding 49.0 g of methylvinylsulfone to 48.5 g of diethanolamine at 20 ° C. and stirring for 200 hours, 97.5 g of N- [2- (methylsulfonyl) ethyl] diethanolamine was obtained (quantitative yield).

Ｎ−［２−（メチルスルホニル）エチル］ジエタノールアミン９７．５ｇ、トリエチルアミン１２２ｇ、テトラヒドロフラン１５０ｇの混合物に２０℃で無水酢酸１０８ｇを滴下した。２時間攪拌後、水を加えて反応を停止、酢酸エチルで抽出、有機層を水洗、減圧濃縮した。減圧蒸留により精製を行ないＮ−［２−（メチルスルホニル）エチル］ビス（２−アセトキシエチル）アミン１１０ｇを得た（収率８１％）。
ＩＲ (薄膜): ν ＝３０１２，２９６２，２８３７，１７３６，１４５６，１３７３，１２９６，１２３８，１１４２，１１２０，１０４５，９６６ｃｍ^-11Ｈ−ＮＭＲ（３００ＭＨｚ ｉｎ ＣＤＣｌ₃） : δ＝２．０３（６Ｈ，ｓ），２．７９（４Ｈ，ｔ，Ｊ＝５．６Ｈｚ），３．００（３Ｈ，ｓ），３．１０（４Ｈ，ｍ），４．１３（４Ｈ，ｔ，Ｊ＝５．６Ｈｚ）． [Synthesis Example 2] Synthesis of N- [2- (methylsulfonyl) ethyl] bis (2-acetoxyethyl) amine.

108 g of acetic anhydride was added dropwise at 20 ° C. to a mixture of 97.5 g of N- [2- (methylsulfonyl) ethyl] diethanolamine, 122 g of triethylamine, and 150 g of tetrahydrofuran. After stirring for 2 hours, the reaction was stopped by adding water, extracted with ethyl acetate, the organic layer was washed with water, and concentrated under reduced pressure. Purification by vacuum distillation yielded 110 g of N- [2- (methylsulfonyl) ethyl] bis (2-acetoxyethyl) amine (yield 81%).
IR (thin film): ν = 3012, 2962, 2837, 1736, 1456, 1373, 1296, 1238, 1142, 1120, 1045, 966 cm ⁻¹¹ H-NMR (300 MHz in CDCl ₃ ): δ = 2.03 (6H, s), 2.79 (4H, t, J = 5.6 Hz), 3.00 (3H, s), 3.10 (4H, m), 4.13 (4H, t, J = 5.6 Hz) .

Ｎ−［２−（メチルスルホニル）エチル］ジエタノールアミン９７．５ｇ、ギ酸５００ｇの混合物を８０℃で２０時間攪拌した。過剰のギ酸を留去後、酢酸エチルで希釈、重曹水、水で洗浄した。減圧濃縮後、減圧蒸留により精製を行ないＮ−［２−（メチルスルホニル）エチル］ビス（２−ホルミルオキシエチル）アミン８６．４ｇを得た（収率７０％）。 Synthesis Example 3 Synthesis of N- [2- (methylsulfonyl) ethyl] bis (2-formyloxyethyl) amine.

A mixture of 97.5 g of N- [2- (methylsulfonyl) ethyl] diethanolamine and 500 g of formic acid was stirred at 80 ° C. for 20 hours. Excess formic acid was distilled off, diluted with ethyl acetate, and washed with aqueous sodium bicarbonate and water. After concentration under reduced pressure, purification was performed by distillation under reduced pressure to obtain 86.4 g of N- [2- (methylsulfonyl) ethyl] bis (2-formyloxyethyl) amine (yield 70%).

ジエタノールアミンの替わりにビス（２−メトキシエチル）アミンを用いた以外は合成例１と同様の方法によりＮ−［２−（メチルスルホニル）エチル］ビス（２−メトキシエチル）アミンを合成した（定量的収率）。 Synthesis Example 4 Synthesis of N- [2- (methylsulfonyl) ethyl] bis (2-methoxyethyl) amine.

N- [2- (methylsulfonyl) ethyl] bis (2-methoxyethyl) amine was synthesized in the same manner as in Synthesis Example 1 except that bis (2-methoxyethyl) amine was used instead of diethanolamine (quantitative). yield).

ジエタノールアミンの替わりに３、３'−イミノジプロピオン酸ジメチルを用いた以外は合成例１と同様の方法により３、３'−［２−（メチルスルホニル）エチル］イミノジプロピオン酸ジメチルを合成した（定量的収率）。 Synthesis Example 5 Synthesis of dimethyl 3,3 ′-[2- (methylsulfonyl) ethyl] iminodipropionate.

Dimethyl 3,3 ′-[2- (methylsulfonyl) ethyl] iminodipropionate was synthesized in the same manner as in Synthesis Example 1 except that dimethyl 3,3′-iminodipropionate was used instead of diethanolamine ( Quantitative yield).

エタノールアミン１４．１ｇに２０℃でメチルビニルスルホン４９．０ｇを加え２００時間攪拌した。つづいて、テトラヒドロフラン１５０ｇ、トリエチルアミン６１．０ｇ、無水酢酸５４．０ｇを順次加えさらに１０時間攪拌した。水を加えて反応を停止、酢酸エチルで抽出、有機層を水洗、減圧濃縮した。減圧蒸留により精製を行ないＮ−（２−アセトキシエチル）ビス［２−（メチルスルホニル）エチル］アミン５８．３ｇを得た（収率８０％）。 Synthesis Example 6 Synthesis of N- (2-acetoxyethyl) bis [2- (methylsulfonyl) ethyl] amine.

Methyl vinyl sulfone (49.0 g) was added to ethanolamine (14.1 g) at 20 ° C. and stirred for 200 hours. Subsequently, 150 g of tetrahydrofuran, 61.0 g of triethylamine, and 54.0 g of acetic anhydride were sequentially added, and the mixture was further stirred for 10 hours. The reaction was stopped by adding water, extracted with ethyl acetate, the organic layer was washed with water and concentrated under reduced pressure. Purification was performed by distillation under reduced pressure to obtain 58.3 g of N- (2-acetoxyethyl) bis [2- (methylsulfonyl) ethyl] amine (yield 80%).

テトラヒドロフルフリルアミン１０１ｇに２０℃でメチルビニルスルホン２１２ｇを加え２００時間攪拌することによりＮ−（テトラヒドロフルフリル）ビス［２−（メチルスルホニル）エチル］アミン３１３ｇを得た（定量的収率）。 Synthesis Example 7 Synthesis of N- (tetrahydrofurfuryl) bis [2- (methylsulfonyl) ethyl] amine.

To 101 g of tetrahydrofurfurylamine, 212 g of methyl vinyl sulfone was added at 20 ° C. and stirred for 200 hours to obtain 313 g of N- (tetrahydrofurfuryl) bis [2- (methylsulfonyl) ethyl] amine (quantitative yield).

アンモニア１７．０ｇ、メタノール２００ｇの混合物に０℃でメチルビニルスルホン３１８ｇを加え、その後２０℃で１０時間、７０℃で１００時間攪拌した。減圧濃縮を行ないトリス［２−（メチルスルホニル）エチル］アミン３３５ｇを得た（定量的収率）。 [Synthesis Example 8] Synthesis of tris [2- (methylsulfonyl) ethyl] amine.

318 g of methyl vinyl sulfone was added to a mixture of 17.0 g of ammonia and 200 g of methanol at 0 ° C., and then stirred at 20 ° C. for 10 hours and at 70 ° C. for 100 hours. Concentration under reduced pressure gave 335 g of tris [2- (methylsulfonyl) ethyl] amine (quantitative yield).

ジエタノールアミンの替わりにモルホリンを用いた以外は合成例１と同様の方法により４−［２−（メチルスルホニル）エチル］モルホリンを合成した（定量的収率）。 [Synthesis Example 9] Synthesis of 4- [2- (methylsulfonyl) ethyl] morpholine.

4- [2- (methylsulfonyl) ethyl] morpholine was synthesized in the same manner as in Synthesis Example 1 except that morpholine was used instead of diethanolamine (quantitative yield).

メチルビニルスルホンの替わりにエチルビニルスルホンを用いた以外は合成例９と同様の方法により４−［２−（エチルスルホニル）エチル］モルホリンを合成した（定量的収率）。 [Synthesis Example 10] Synthesis of 4- [2- (ethylsulfonyl) ethyl] morpholine.

4- [2- (Ethylsulfonyl) ethyl] morpholine was synthesized in the same manner as in Synthesis Example 9 except that ethyl vinyl sulfone was used instead of methyl vinyl sulfone (quantitative yield).

[Examples and Comparative Examples]
Resist evaluation example A polymer, an acid generator, a base, a dissolution inhibitor, and a cross-linking agent in a mixed solvent of propylene glycol monomethyl ether acetate (PGMEA) and ethyl lactate (EL) in a weight ratio of 70:30 are shown in Tables 1 to 3. A resist solution was prepared by dissolving and filtering through a 0.1 μm sized Teflon (registered trademark) filter.
Next, the obtained resist solution is formed on a silicon wafer by depositing DUV-30 (manufactured by Nissan Chemical Co., Ltd.) with a film thickness of 55 nm, and with KrF light (248 nm), the reflectance is suppressed to 1% or less. And then baked at 100 ° C. for 90 seconds using a hot plate to make the resist thickness 550 nm.
This was exposed using an excimer laser stepper (Nikon Corporation, NSR-S202A, NA-0.6, σ0.75, 2/3 annular illumination) while changing the exposure amount and focus, and immediately after exposure at 110 ° C. The pattern was obtained by baking for 90 seconds and developing with an aqueous solution of 2.38% tetramethylammonium hydroxide for 60 seconds.

The obtained resist pattern was evaluated as follows. The results are shown in Tables 1-3.
Evaluation methods:
The focus margin at this time was obtained by using the exposure amount for resolving 0.16 μm line and space at 1: 1 as sensitivity. The definition of the focus margin is that there is no film loss of the pattern and that the dimension is within a dimension of 0.16 μm ± 10%.

  As shown in Tables 1 to 3, it can be seen that the resist material of the present invention is a resist material having a wide focus margin, that is, a high contrast.

Claims (6)

A resist material to which a basic compound containing sulfone is added, wherein the basic compound is represented by the following general formulas (1) and (2):

(In the above formula, R ¹ and R ^{1 ′} are the same or different linear or branched alkylene group having 1 to 4 carbon atoms, R ² is the same or different hydrogen atom, or a straight chain having 1 to 20 carbon atoms. chain, branched or cyclic alkyl group, an aryl group or an aralkyl group, hydroxy group, an ether group, a carbonyl group, an ester group, lactone ring, also contain carbonate group or a cyano group may, R ³ is It is the same or different linear or branched alkylene group having 1 to 20 carbon atoms and may contain a hydroxy group, an ether group, a carbonyl group, an ester group or a carbonate group, and R ⁴ is the same or different. A is an identical or different integer of 1 to 3, and b is an identical or different integer of 0 to 2, but in each compound, a + b = 3.)
One or more der Relais resist material selected from the group consisting of. R ² in the general formula (1) is represented by the following general formulas (3) to (6).

(In the above formula, R ⁵ , R ⁷ , R ¹⁰ and R ¹² are the same or different linear or branched alkylene groups having 1 to 4 carbon atoms, and R ⁶ and R ⁹ are the same or different hydrogen. It is an atom or a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms and may contain a hydroxy group, an ether group, an ester group or a lactone ring, and R ⁵ and R ⁶ are R ⁸ is a single bond or a linear or branched alkylene group having 1 to 4 carbon atoms, and R ¹¹ is the same or different and having 1 to 20 carbon atoms. (It is a linear, branched or cyclic alkyl group and may contain a hydroxy group, an ether group, an ester group, a carbonyl group, a cyano group, or a lactone ring.)
The resist material according to claim 1, which is selected from the group consisting of: Further, an organic solvent, an alkali-insoluble or hardly soluble resin having an acidic functional group protected with an acid labile group, and a base resin that becomes alkali-soluble when the acid labile group is eliminated, and an acid The resist material according to claim 1, which contains a generator and is a positive type. The resist material according to claim 3 , further comprising a dissolution inhibitor. Further, an organic solvent, an alkali-soluble resin, and a base resin as a alkali-soluble by crosslinking with a crosslinking agent, and an acid generator, and a crosslinking agent capable of crosslinking by an acid, according to claim 1 or a negative type The resist material according to claim 2 . A step of applying the resist material according to any one of claims 3 to 5 on a substrate, a step of exposing to a high energy beam having a wavelength of 300 nm or less or an electron beam through a photomask after the heat treatment, and a necessity The pattern formation method including the process of developing using a developing solution after heat-processing according to it.