JP4386200B2 - Negative resist material and pattern forming method - Google Patents

Description

  In the present invention, an indene having a hexafluoroisopropyl alcohol group substituted with an acid labile group is blended with a negative resist material as a base resin, so that the alkali dissolution rate contrast before and after exposure is significantly high and high sensitivity. Negative resist material with high resolution, low line edge roughness, excellent etching resistance, especially suitable as a fine pattern forming material for VLSI manufacturing or photomask pattern production, especially chemically amplified negative resist The present invention relates to a material and a pattern forming method using the resist material.

  In recent years, with the high integration and high speed of LSI, there is a demand for finer pattern rules. The background of rapid progress in miniaturization includes higher NA of projection lenses, improved performance of resist materials, and shorter wavelengths. With regard to higher resolution and higher sensitivity of resist materials, chemically amplified negative resist materials catalyzed by the acid generated by light irradiation have excellent performance, and have become the mainstream resist materials especially in deep ultraviolet lithography. (Patent Documents 1 and 2: described in JP-B-2-27660, JP-A-63-27829, etc.). In addition, the shortening of the wavelength from i-line (365 nm) to KrF (248 nm) has brought about a major change. Resist materials for KrF excimer lasers started with the 0.30 micron process, passed the 0.25 micron rule, The micron rule is being applied to mass production. Furthermore, the study of the 0.15 micron rule has begun, and the momentum of miniaturization is increasingly accelerated.

  In ArF excimer laser (193 nm) lithography, processing with a design rule of 0.13 μm or less is expected. However, since resins that have been used conventionally such as novolac and polyvinylphenol have very strong absorption near 193 nm. It cannot be used as a base resin for resist. Therefore, acrylic resins and cycloolefin-based alicyclic resins have been studied in order to ensure transparency and necessary dry etching resistance (Patent Documents 3 to 6: JP-A-9-73173 and JP-A-10). No. -10739, JP-A-9-230595, pamphlet of International Publication No. 97/33198).

  Here, Non-Patent Document 1: J. Org. of Photopolymer Science and Technology Vol. 5, no. 1 (1992) p85-92, hexafluoroisopropanol pendant polystyrene has been proposed. Among them, hexafluoroisopropanol has the same acidity as phenol and a pattern is formed by adding a bisphenyl type dissolution inhibitor pendant with hexafluoroisopropanol substituted with an acid labile group. Yes. This is the first resist material using hexafluoroalcohol.

  By the way, the present inventors have disclosed in Patent Document 7: Indene and (meth) acrylic copolymer disclosed in JP-A-2002-202610, Patent Document 8: Hydroxystyrene and indene disclosed in JP-A-2004-115630. Copolymerization, Patent Document 9: Polyindene disclosed in Japanese Patent Application Laid-Open No. 2004-149756 has been found to have excellent etching resistance. By introducing indene, acid diffusion is suppressed, the dimensional difference in density is reduced, and resolution is improved. Indene has a cycloolefin structure, and it is considered that thermal diffusion in the molecule is suppressed and acid diffusion is suppressed by the main chain of the polymer being rigid. Further, a negative resist using a copolymer of hydroxystyrene and indene is proposed in Patent Document 10: JP-A-2006-201532.

  The present inventors have studied the synthesis of an indene derivative having a hexafluoroisopropanol pendant (Patent Document 11: Japanese Patent Laid-Open No. 2003-96007). Resist materials based on indene polymers containing hexafluoroisopropanol are more resistant to etching and resist acid diffusion and have higher resolution performance than styrene-based resist materials with hexafluoroisopropanol pendant. It can be done.

  In order to improve the etching resistance of resist materials based on polyhydroxystyrene, we investigated polymers in which indene was copolymerized with hydroxystyrene. However, increasing the introduction rate of indene, which does not dissolve in alkali, reduces the dissolution contrast and resolution. There was a problem that the performance decreased. A hydroxy group was introduced into indene to prevent a decrease in the alkali dissolution rate when indene was introduced, but further improvement was demanded.

JP-B-2-27660 JP 63-27829 A JP-A-9-73173 Japanese Patent Laid-Open No. 10-10739 Japanese Patent Laid-Open No. 9-230595 International Publication No. 97/33198 Pamphlet JP 2002-202610 A JP 2004-115630 A JP 2004-149756 A JP 2006-201532 A JP 2003-96007 A Non-Patent Document 1: J. Org. of Photopolymer Science and Technology Vol. 5, no. 1 (1992) p85-92

  The present invention has been made in view of the above circumstances, the alkali dissolution rate contrast before and after exposure is significantly high, high sensitivity and high resolution, low line edge roughness, particularly excellent etching resistance, It is an object of the present invention to provide a negative resist material suitable as a fine pattern forming material for VLSI manufacturing or photomask pattern production, particularly a chemically amplified negative resist material and a pattern forming method using the same.

  As a result of intensive studies to achieve the above object, the present inventors have found that a polymer compound having a repeating unit represented by the general formula (1) and having a weight average molecular weight of 1,000 to 500,000 is negative. Type resist material, especially as a base resin for chemically amplified negative resist material. This chemically amplified negative resist material containing polymer compound, acid generator, organic solvent and cross-linking agent makes resist film dissolution contrast and resolution High exposure, margin of exposure, excellent process adaptability, good pattern shape after exposure, better etching resistance, small density difference, especially low line edge roughness, Because of these, it is highly practical, and resist materials for VLSI, especially for KrF excimer laser, electron beam (EB), and vacuum ultraviolet (EUV) lithography. It was found that is very effective as a resist material.

（式中、Ｒ¹は水素原子、フッ素原子、又は炭素数１〜１０の直鎖状、分岐状もしくは環状のアルキル基又はフッ素化アルキル基であり、Ｘはメチレン基、酸素原子又は硫黄原子である。ｍは１〜３の整数、ｎは１又は２であり、ｍ＋ｎ＝４である。Ｒ²は水素原子又はメチル基、Ｒ³は水素原子、フッ素原子、又は炭素数１〜１０の直鎖状、分岐状もしくは環状のアルキル基又はフッ素化アルキル基であり、ｑは１〜３の整数、ｑ＋ｕ＝７、０＜（ａ−１）＜１．０、０＜（ｂ−２）＜１．０である。）
請求項２：
（Ａ）有機溶剤、
（Ｂ）ベース樹脂として請求項１記載の高分子化合物、
（Ｃ）酸発生剤、
（Ｄ）架橋剤
を含有してなることを特徴とする化学増幅ネガ型レジスト材料。
請求項３：
更に、（Ｅ）添加剤として塩基性化合物及び／又は界面活性剤を配合することを特徴とする請求項２記載の化学増幅ネガ型レジスト材料。
請求項４：
請求項２又は３に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ことを特徴とするパターン形成方法。 That is, the present invention provides the following negative resist material and pattern forming method.
Claim 1:
A negative resist material comprising a polymer compound comprising a repeating unit represented by the following general formula (1) and having a weight average molecular weight in the range of 1,000 to 500,000.

(Wherein R ¹ is a hydrogen atom, a fluorine atom, a linear, branched or cyclic alkyl group or a fluorinated alkyl group having 1 to 10 carbon atoms, and X is a methylene group, an oxygen atom or a sulfur atom. M is an integer of 1 to 3, n is 1 or 2, and m + n = 4, R ² is a hydrogen atom or a methyl group, R ³ is a hydrogen atom, a fluorine atom, or a straight chain having 1 to 10 carbon atoms. A chain, branched or cyclic alkyl group or a fluorinated alkyl group , q is an integer of 1 to 3 , q + u = 7 , 0 < (a-1) <1.0 , 0 < (b-2) < 1.0 .)
Claim 2:
(A) an organic solvent,
(B) The polymer compound according to claim 1 as a base resin,
(C) an acid generator,
(D) A chemically amplified negative resist material comprising a crosslinking agent.
Claim 3:
The chemical amplification negative resist composition according to claim 2, further comprising (E) a basic compound and / or a surfactant as an additive.
Claim 4:
A step of applying the resist material according to claim 2 or 3 onto a substrate, a step of exposing to high energy rays or an electron beam through a photomask after heat treatment, a heat treatment if necessary, and development And a step of developing using a liquid.

  The resist material of the present invention has a significantly high alkali dissolution rate contrast before and after exposure, high sensitivity and high resolution, good pattern shape after exposure, and in particular, suppresses acid diffusion rate and is excellent. High etching resistance. Accordingly, it is possible to provide a negative resist material, particularly a chemically amplified negative resist material, particularly suitable for VLSI manufacturing or as a photomask fine pattern forming material.

  The polymer compound used in the negative resist material of the present invention contains a repeating unit by copolymerization represented by the following general formula (1) and has a weight average molecular weight in the range of 1,000 to 500,000. is there.

（式中、Ｒ¹は水素原子、フッ素原子、又は炭素数１〜１０の直鎖状、分岐状もしくは環状のアルキル基又はフッ素化アルキル基であり、Ｘはメチレン基、酸素原子又は硫黄原子である。ｍは１〜３の整数、ｎは１又は２であり、ｍ＋ｎ＝４である。Ｒ²は水素原子又はメチル基、Ｒ³は水素原子、フッ素原子、又は炭素数１〜１０の直鎖状、分岐状もしくは環状のアルキル基又はフッ素化アルキル基であり、ｐ、ｑは１〜３の整数、ｐ＋ｔ＝５、ｑ＋ｕ＝７、０＜（ａ−１）＜１．０、０≦（ｂ−１）＜１．０、０＜（ｂ−２）＜１．０、０＜（ｂ−１）＋（ｂ−２）＜１．０である。）

(Wherein R ¹ is a hydrogen atom, a fluorine atom, a linear, branched or cyclic alkyl group or a fluorinated alkyl group having 1 to 10 carbon atoms, and X is a methylene group, an oxygen atom or a sulfur atom. M is an integer of 1 to 3, n is 1 or 2, and m + n = 4, R ² is a hydrogen atom or a methyl group, R ³ is a hydrogen atom, a fluorine atom, or a straight chain having 1 to 10 carbon atoms. A chain, branched or cyclic alkyl group or a fluorinated alkyl group, p and q are integers of 1 to 3, p + t = 5, q + u = 7, 0 <(a-1) <1.0, 0 ≦ (b-1) <1.0,0 < (b-2) <1.0,0 <(b-1) + (b-2) < 1.0.)

  Here, the repeating unit a-1 represented by the general formula (1) is obtained by polymerizing a hexafluoroisopropanol pendant indene derivative, and specifically, those represented by the following general formula (2) may be mentioned. it can.

  Here, R may be a hydrogen atom or an acetyl group, which may be hydrolyzed with alkaline water after polymerization to form a hydroxy group.

Hexafluoroisopropanol pendant indene derivatives are listed below.
In this case, formula (i) is 4-hexafluoroisopropanolindene, formula (ii) is 5-hexafluoroisopropanolindene, formula (iii) is 6-hexafluoroisopropanolindene, and formula (iv) is 7-hexafluoroisopropanolindene. It is. Among these, 7-hexafluoroisopropanolindene has a defect that the hexafluoroisopropanol indene is close to the polymerization position, and in the case of radical polymerization, it is difficult to polymerize due to large steric hindrance. Hexafluoroisopropanolindene and 6-hexafluoroisopropanolindene are preferred.

The method for synthesizing hexafluoroisopropanolindene can be performed, for example, in the following steps, but is not limited thereto.

In the above formula, Y represents a halogen atom such as chlorine, bromine or iodine. Although the reaction proceeds easily under known conditions, the starting halide is preferably used in a solvent such as tetrahydrofuran (for the synthesis method, see Journal of Organic Chemistry, Vol. 49, No. 22, 1984, p. 4226). And magnesium, and the resulting Grignard reagent and hexafluoroacetone gas are reacted at room temperature, followed by post-treatment with a saturated aqueous ammonium chloride solution, purification by silica gel column chromatography and distillation, and the target product ( R ⁴ = H) can be obtained. The acid labile group can be introduced from the obtained alcohol by a known method.

In addition to the repeating units (a-1) and (b-2) described above, the present invention can copolymerize the repeating unit (b-1 ) , and further comprises the following general formulas (3-1), (3- It is also possible to copolymerize the repeating units (c-1) and (c-2) having the sulfonium salt represented by 2).

（式中、Ｒ⁷は水素原子又はメチル基、Ｒ⁸はフェニレン基、フッ素で置換されたフェニレン基、−Ｏ−Ｒ¹¹−、又は−Ｃ（＝Ｏ）−Ｙ¹−Ｒ¹¹−である。Ｙ¹は酸素原子又はＮＨ、Ｒ¹¹は炭素数１〜６の直鎖状、分岐状又は環状のアルキレン基又はアルケニレン基、又はフェニレン基であり、カルボニル基（−ＣＯ−）、エステル基（−ＣＯＯ−）、エーテル基（−Ｏ−）又はヒドロキシ基を含んでいてもよい。Ｒ^8'はフェニレン基、−Ｏ−Ｒ¹⁵−、又は−Ｃ（＝Ｏ）−Ｙ²−Ｒ¹⁵−である。Ｙ²は酸素原子又はＮＨ、Ｒ¹⁵は炭素数１〜６の直鎖状、分岐状又は環状のアルキレン基又はアルケニレン基、又はフェニレン基であり、カルボニル基、エステル基、エーテル基又はヒドロキシ基を含んでいてもよく、フッ素で置換されていてもよい。Ｒ⁹、Ｒ¹⁰、Ｒ¹²、Ｒ¹³、Ｒ¹⁴は同一又は異種の炭素数１〜１２の直鎖状、分岐状又は環状のアルキル基であり、カルボニル基、エステル基又はエーテル基を含んでいてもよく、又は炭素数６〜１２のアリール基、炭素数７〜２０のアラルキル基又はチオフェニル基を表す。Ｋ^-は非求核性対向イオンを表す。）

Wherein R ⁷ is a hydrogen atom or a methyl group, R ⁸ is a phenylene group, a phenylene group substituted with fluorine, —O—R ¹¹ —, or —C (═O) —Y ¹ —R ¹¹ —. Y ¹ is an oxygen atom or NH, and R ¹¹ is a linear, branched or cyclic alkylene group, alkenylene group or phenylene group having 1 to 6 carbon atoms, a carbonyl group (—CO—), an ester group ( -COO-), which may contain an ether (-O-), or hydroxyl group .R ^{8 'is} a phenylene group, -O-R ¹⁵ -, or ^{-C (= O) -Y 2 -R} 15 - Y ² is an oxygen atom or NH, R ¹⁵ is a linear, branched or cyclic alkylene group, alkenylene group or phenylene group having 1 to 6 carbon atoms, and is a carbonyl group, ester group, ether group or It may contain hydroxy groups and may be substituted with fluorine ^{.R 9, R 10, R 12} , R 13, R 14 may be the same or different C 1 -C 12 linear carbon atoms in a branched or cyclic alkyl group, a carbonyl group, an ester group or an ether group Or an aryl group having 6 to 12 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, or a thiophenyl group, and K ⁻ represents a non-nucleophilic counter ion.)

The ratio of the repeating units (a-1), (b-1), (b-2), (c-1), and (c-2) is 0 <(a-1) <1.0, 0 ≦ (b-1) <1.0, 0 < (b-2) <1.0, 0 <(b-1) + (b-2) <1.0, 0 ≦ (c-1) ≦ 0 0.5, 0 ≦ (c−2) ≦ 0.5, preferably 0.05 ≦ (a−1) ≦ 0.95, 0 ≦ (b−1) ≦ 0.95, 0 < (b− 2) ≦ 0.95, 0.05 ≦ (b-1) + (b-2) ≦ 1.0, 0 ≦ (c-1) ≦ 0.4, 0 ≦ (c-2) ≦ 0.54 More preferably, 0.1 ≦ (a-1) ≦ 0.9, 0 ≦ (b-1) ≦ 0.9, 0 < (b-2) ≦ 0.9, 0.1 ≦ (b -1) + (b-2) ≤1.0, 0≤ (c-1) ≤0.3, 0≤ (c-2) ≤0.3.

  Here, (a-1) + (b-1) + (b-2) + (c-1) + (c-2) = 1. A total amount of these repeating units of 1 means that the total amount of these repeating units is 100 mol% with respect to the total amount of all repeating units.

As the polymer compound of the present invention, the repeating units (a-1) and (b-2) , and further (b-1 ) are copolymerized. If necessary, styrenes, vinylnaphthalenes, vinylanthracenes are copolymerized. , Indene, hydroxyindene, methyleneindane, acenaphthalene, norbornadiene, divinylbenzene, (meth) acrylic acid esters, (meth) acrylic acid, (meth) acrylonitrile, vinyl ethers throughout the polymer You may copolymerize in the ratio of 0-50 mol% with respect to.

  The polymer compound of the present invention has a polystyrene-reduced weight average molecular weight of 1,000 to 500,000, preferably 2,000 to 30,000, as determined by gel permeation chromatography (GPC). If the weight average molecular weight is too small, the resist material is inferior in heat resistance, and if it is too large, the alkali solubility is lowered, and the trailing phenomenon tends to occur after pattern formation.

  Furthermore, in the polymer compound of the present invention, when the molecular weight distribution (Mw / Mn) is wide, a low molecular weight or high molecular weight polymer exists, so that after exposure, foreign matter is seen on the pattern or the pattern shape is It gets worse. Therefore, since the influence of such molecular weight and molecular weight distribution tends to increase as the pattern rule becomes finer, in order to obtain a resist material suitably used for fine pattern dimensions, the multi-component copolymer to be used is obtained. The molecular weight distribution is preferably from 1.0 to 2.0, particularly preferably from 1.0 to 1.5 and narrow dispersion. It is also possible to blend two or more polymers having different composition ratios, molecular weight distributions, and molecular weights.

In order to synthesize these polymer compounds, one method is to add hydroxystyrene or hydroxyvinylnaphthalene copolymerized with hexafluoroisopropanolindene in an organic solvent, add a radical polymerization initiator or a cationic polymerization initiator, and heat polymerize. To obtain a polymer compound. Examples of the organic solvent used at the time of polymerization include toluene, benzene, tetrahydrofuran, diethyl ether, dioxane and the like. As radical polymerization initiators, 2,2′-azobisisobutyronitrile, 2,2′-azobis (2,4-dimethylvaleronitrile), dimethyl 2,2-azobis (2-methylpropionate), Examples include benzoyl peroxide, lauroyl peroxide, etc. Cationic polymerization initiators include sulfuric acid, phosphoric acid, hydrochloric acid, nitric acid, hypochlorous acid, trichloroacetic acid, trifluoroacetic acid, methanesulfonic acid, trifluoromethanesulfonic acid, camphorsulfone acid, acids such as _{tosylate, BF 3, AlCl 3, TiCl} 4, addition of Friedel-Crafts catalyst such as _{SnCl 4, I 2, (C} 6 H 5) 3 substance which easily generates a cation as CCl exemplified it can.

  As polymerization time, it can superpose | polymerize, preferably heating at 50-80 degreeC. The reaction time is 2 to 100 hours, preferably 5 to 20 hours. As the acid labile group, those introduced into the monomer may be used as they are, or the acid labile group may be once removed by an acid catalyst and then protected or partially protected.

  Alternatively, hexafluoroisopropanolindene substituted with an acetyl group, hydroxystyrene, hydroxyvinylnaphthalene may be added to a radical polymerization initiator in an organic solvent and subjected to heat polymerization, and then the acetyl group may be converted to a hydroxy group by alkali hydrolysis. . Ammonia water, triethylamine, etc. can be used as the base during the alkali hydrolysis. The reaction temperature is −20 to 100 ° C., preferably 0 to 60 ° C., and the reaction time is 0.2 to 100 hours, preferably 0.5 to 20 hours.

  The polymer compound is used as a base resin for a negative resist material. The negative resist material of the present invention is an organic solvent, a compound that generates an acid in response to high energy rays (acid generator), and a crosslinking agent. If necessary, a basic compound, a surfactant, and other components can be contained.

  The organic solvent used in the resist material of the present invention, particularly the chemically amplified negative resist material, 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-2-n-amyl ketone, 3-methoxybutanol, 3-methyl-3-methoxybutanol, 1-methoxy-2-propanol, 1-ethoxy- Alcohols such as 2-propanol, propylene glycol monomethyl ether, ethylene glycol monomethyl ether, propylene glycol monomethyl 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-ethoxy Examples thereof include esters such as ethyl propionate, tert-butyl acetate, tert-butyl propionate, propylene glycol mono tert-butyl ether acetate, and lactones such as γ-butyl lactone, one kind of these alone or two or more kinds. However, the present invention 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, and mixed solvents thereof, which have the highest solubility of the acid generator in the resist component, are preferably used. .

  The amount of the organic solvent used is preferably 200 to 1,000 parts, particularly 400 to 800 parts, with respect to 100 parts (parts by mass) of the base resin.

As the acid generator used in the present invention,
i. An onium salt of the following general formula (P1a-1), (P1a-2) or (P1b),
ii. A diazomethane derivative of the following general formula (P2):
iii. A glyoxime derivative of the following general formula (P3):
iv. A bissulfone derivative of the following general formula (P4):
v. A sulfonic acid ester of an N-hydroxyimide compound of the following general formula (P5),
vi. β-ketosulfonic acid derivatives,
vii. Disulfone derivatives,
viii. Nitrobenzyl sulfonate derivatives,
ix. Examples thereof include sulfonic acid ester derivatives.

（式中、Ｒ^101a、Ｒ^101b、Ｒ^101cはそれぞれ炭素数１〜１２の直鎖状、分岐状又は環状のアルキル基、アルケニル基、オキソアルキル基、オキソアルケニル基、炭素数６〜２０のアリール基、又は炭素数７〜１２のアラルキル基、アリールオキソアルキル基を示し、これらの基の水素原子の一部又は全部がアルコキシ基等によって置換されていてもよい。また、Ｒ^101bとＲ^101cとは環を形成してもよく、環を形成する場合には、Ｒ^101b、Ｒ^101cはそれぞれ炭素数１〜６のアルキレン基を示す。Ｋ^-は非求核性対向イオンを表す。）

Wherein R ^101a , R ^101b and R ^101c are each a linear, branched or cyclic alkyl group having 1 to 12 carbon atoms, an alkenyl group, an oxoalkyl group, an oxoalkenyl group or an aryl having 6 to 20 carbon atoms. Group, an aralkyl group having 7 to 12 carbon atoms, or an aryloxoalkyl group, and part or all of the hydrogen atoms of these groups may be substituted with an alkoxy group, etc. R ^101b and R ^{101c May} form a ring, and in the case of forming a ring, R ^101b and R ^101c each represent an alkylene group having 1 to 6 carbon atoms, and K ⁻ represents a non-nucleophilic counter ion.)

R ^101a , R ^101b and R ^101c may be the same as or different from each other. Specifically, as an 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, cyclohexyl group, cycloheptyl group, cyclopropylmethyl group, 4-methylcyclohexyl group, cyclohexylmethyl group, norbornyl group, adamantyl group, etc. Is mentioned. 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, and the like. 2-oxopropyl group, 2-cyclopentyl-2-oxoethyl group, 2-cyclohexyl-2-oxoethyl group, 2- (4 -Methylcyclohexyl) -2-oxoethyl group and the like can be mentioned. Examples of the oxoalkenyl group include 2-oxo-4-cyclohexenyl group and 2-oxo-4-propenyl group. Examples of the aryl group include a phenyl group, a naphthyl group, a p-methoxyphenyl group, an m-methoxyphenyl group, an o-methoxyphenyl group, an ethoxyphenyl group, a p-tert-butoxyphenyl group, and an m-tert-butoxyphenyl group. Alkylphenyl groups such as alkoxyphenyl groups, 2-methylphenyl groups, 3-methylphenyl groups, 4-methylphenyl groups, ethylphenyl groups, 4-tert-butylphenyl groups, 4-butylphenyl groups, dimethylphenyl groups, etc. Alkyl naphthyl groups such as methyl naphthyl group and ethyl naphthyl group, alkoxy naphthyl groups such as methoxy naphthyl group and ethoxy naphthyl group, dialkyl naphthyl groups such as dimethyl naphthyl group and diethyl naphthyl group, dimethoxy naphthyl group and diethoxy naphthyl group Dialkoxynaphthyl group And the like. Examples of the aralkyl group include a benzyl group, a phenylethyl group, and a phenethyl 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. 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. Arylsulfonates such as 4-fluorobenzenesulfonate, 1,2,3,4,5-pentafluorobenzenesulfonate, alkylsulfonates such as mesylate and butanesulfonate, bis (trifluoromethylsulfonyl) imide, bis (perfluoroethylsulfonyl) ) Imido acids such as imide and bis (perfluorobutylsulfonyl) imide, methide acids such as tris (trifluoromethylsulfonyl) methide and tris (perfluoroethylsulfonyl) methide, and Sulfonate position alpha of the formula (K-1) is fluoro substituted, the following formula (K-1), α represented by (K-2), β-position include sulfonates fluorine substituted.

（上記式（Ｋ−１）中のＲ¹⁰²は水素原子、炭素数１〜３０の直鎖状、分岐状又は環状のアルキル基又はアシル基、炭素数２〜２０のアルケニル基、炭素数６〜２０のアリール基又はアリーロキシ基であり、エーテル基、エステル基、カルボニル基、ラクトン環を有していてもよく、フッ素で置換されていてもよい。式（Ｋ−２）中のＲ¹⁰³は水素原子、炭素数１〜２０の直鎖状、分岐状又は環状のアルキル基、炭素数２〜２０のアルケニル基、炭素数６〜２０のアリール基であり、エーテル基、エステル基、カルボニル基、ラクトン環を有していてもよく、フッ素で置換されていてもよい。）

(The formula (K-1) R ¹⁰² in a hydrogen atom, 1-30 straight, branched or cyclic alkyl group or an acyl group, an alkenyl group having 2 to 20 carbon atoms, 6 carbon atoms 20 aryl group or aryloxy group, which may have an ether group, an ester group, a carbonyl group or a lactone ring, and may be substituted with fluorine, R ¹⁰³ in formula (K-2) is hydrogen An atom, a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, and an aryl group having 6 to 20 carbon atoms, ether group, ester group, carbonyl group, lactone (It may have a ring and may be substituted with fluorine.)

（式中、Ｒ^102a、Ｒ^102bはそれぞれ炭素数１〜８の直鎖状、分岐状又は環状のアルキル基を示す。Ｒ¹⁰³は炭素数１〜１０の直鎖状、分岐状又は環状のアルキレン基を示す。Ｒ^104a、Ｒ^104bはそれぞれ炭素数３〜７の２−オキソアルキル基を示す。Ｋ^-は非求核性対向イオンを表す。）

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

Specific examples of R ^102a and R ^102b include a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, a tert-butyl group, a pentyl group, a hexyl group, a heptyl group, and an octyl group. , Cyclopentyl group, cyclohexyl group, cyclopropylmethyl group, 4-methylcyclohexyl group, cyclohexylmethyl group and the like. R ¹⁰³ is methylene group, ethylene group, propylene group, butylene group, pentylene group, hexylene group, heptylene group, octylene group, nonylene group, 1,4-cyclohexylene group, 1,2-cyclohexylene. Group, 1,3-cyclopentylene group, 1,4-cyclooctylene group, 1,4-cyclohexanedimethylene group and the like. ^{Examples of} R ^104a and R ^104b include a 2-oxopropyl group, a 2-oxocyclopentyl group, a 2-oxocyclohexyl group, and a 2-oxocycloheptyl group. K ^- is can be exemplified the same ones as described in the formulas (P1a-1) and (P1a-2).

（式中、Ｒ¹⁰⁵、Ｒ¹⁰⁶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６〜２０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のアラルキル基を示す。）

(In the formula, R ¹⁰⁵ and R ¹⁰⁶ 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 20 carbon atoms, or carbon atoms. 7 to 12 aralkyl groups are shown.)

^Examples of the alkyl group of R ¹⁰⁵ and R ¹⁰⁶ include 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, amyl Group, cyclopentyl group, cyclohexyl group, cycloheptyl group, norbornyl group, adamantyl group and the like. Examples of the halogenated alkyl group for R ¹⁰⁵ and R ¹⁰⁶ include a trifluoromethyl group, a 1,1,1-trifluoroethyl group, a 1,1,1-trichloroethyl group, a nonafluorobutyl group, and the like. As the aryl group for R ¹⁰⁵ and R ^106, a phenyl group, a p-methoxyphenyl group, an m-methoxyphenyl group, an o-methoxyphenyl group, an ethoxyphenyl group, a p-tert-butoxyphenyl group, and an m-tert-butoxyphenyl group Alkylphenyl groups such as alkoxyphenyl groups, 2-methylphenyl groups, 3-methylphenyl groups, 4-methylphenyl groups, ethylphenyl groups, 4-tert-butylphenyl groups, 4-butylphenyl groups, dimethylphenyl groups, etc. Is mentioned. Examples of the halogenated aryl group for R ¹⁰⁵ and R ¹⁰⁶ include a fluorophenyl group, a chlorophenyl group, and 1,2,3,4,5-pentafluorophenyl group. ^Examples of the aralkyl group for R ¹⁰⁵ and R ¹⁰⁶ include a benzyl group and a phenethyl group.

（式中、Ｒ¹⁰⁷、Ｒ¹⁰⁸、Ｒ¹⁰⁹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６〜２０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のアラルキル基を示す。Ｒ¹⁰⁸、Ｒ¹⁰⁹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、Ｒ¹⁰⁸、Ｒ¹⁰⁹はそれぞれ炭素数１〜６の直鎖状、分岐状のアルキレン基を示す。Ｒ¹⁰⁵は式（Ｐ２）のものと同様である。）

(Wherein R ¹⁰⁷ , R ¹⁰⁸ and R ¹⁰⁹ are each a linear, branched or cyclic alkyl group or halogenated alkyl group having 1 to 12 carbon atoms, an aryl group or halogenated aryl group having 6 to 20 carbon atoms, Or an aralkyl group having 7 to 12 carbon atoms, R ¹⁰⁸ and R ¹⁰⁹ may be bonded to each other to form a cyclic structure, and in the case of forming a cyclic structure, R ¹⁰⁸ and R ¹⁰⁹ each have 1 to 6 carbon atoms. And R ¹⁰⁵ is the same as that in formula (P2).

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

（式中、Ｒ^101a、Ｒ^101bは前記と同様である。）

(In the formula, R ^101a and R ^101b are the same as described above.)

（式中、Ｒ¹¹⁰は炭素数６〜１０のアリーレン基、炭素数１〜６のアルキレン基又は炭素数２〜６のアルケニレン基を示し、これらの基の水素原子の一部又は全部は更に炭素数１〜４の直鎖状又は分岐状のアルキル基又はアルコキシ基、ニトロ基、アセチル基、又はフェニル基で置換されていてもよい。Ｒ¹¹¹は炭素数１〜８の直鎖状、分岐状又は置換のアルキル基、アルケニル基又はアルコキシアルキル基、フェニル基、又はナフチル基を示し、これらの基の水素原子の一部又は全部は更に炭素数１〜４のアルキル基又はアルコキシ基；炭素数１〜４のアルキル基、アルコキシ基、ニトロ基又はアセチル基で置換されていてもよいフェニル基；炭素数３〜５のヘテロ芳香族基；又は塩素原子、フッ素原子で置換されていてもよい。）

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

Here, as the arylene group of R ¹¹⁰ , 1,2-phenylene group, 1,8-naphthylene group, etc., and as the alkylene group, methylene group, ethylene group, trimethylene group, tetramethylene group, phenylethylene group, norbornane Examples of the alkenylene group such as -2,3-diyl group include 1,2-vinylene group, 1-phenyl-1,2-vinylene group, 5-norbornene-2,3-diyl group and the like. The alkyl group for R ¹¹¹ is the same as R ^{101a to} R ^101c, and the alkenyl group is a vinyl group, 1-propenyl group, allyl group, 1-butenyl group, 3-butenyl group, isoprenyl group, 1- Pentenyl group, 3-pentenyl group, 4-pentenyl group, dimethylallyl group, 1-hexenyl group, 3-hexenyl group, 5-hexenyl group, 1-heptenyl group, 3-heptenyl group, 6-heptenyl group, 7-octenyl Groups such as alkoxyalkyl groups include methoxymethyl, ethoxymethyl, propoxymethyl, butoxymethyl, pentyloxymethyl, hexyloxymethyl, heptyloxymethyl, methoxyethyl, ethoxyethyl, Propoxyethyl, butoxyethyl, pentyloxyethyl, hexyloxyethyl, methoxypro Group, ethoxypropyl group, propoxypropyl group, butoxy propyl group, methoxybutyl group, ethoxybutyl group, propoxybutyl group, a methoxy pentyl group, an ethoxy pentyl group, a methoxy hexyl group, a methoxy heptyl group.

  In addition, examples of the optionally substituted alkyl group having 1 to 4 carbon atoms include a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, an isobutyl group, and a tert-butyl group. As the alkoxy group of ˜4, a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, an n-butoxy group, an isobutoxy group, a tert-butoxy group and the like are an alkyl group having 1 to 4 carbon atoms, an alkoxy group, and a nitro group. As the phenyl group which may be substituted with an acetyl group, a phenyl group, a tolyl group, a p-tert-butoxyphenyl group, a p-acetylphenyl group, a p-nitrophenyl group, etc. are heterocycles having 3 to 5 carbon atoms. Examples of the aromatic group include a pyridyl group and a furyl group.

Specific examples of the acid generator exemplified above include the following.
Examples of the onium salt include diphenyliodonium trifluoromethanesulfonate, trifluoromethanesulfonic acid (p-tert-butoxyphenyl) phenyliodonium, p-toluenesulfonic acid diphenyliodonium, p-toluenesulfonic acid (p-tert-butoxyphenyl) phenyl. Iodonium, triphenylsulfonium trifluoromethanesulfonate, trifluoromethanesulfonate (p-tert-butoxyphenyl) diphenylsulfonium, bis (p-tert-butoxyphenyl) phenylsulfonium trifluoromethanesulfonate, tris (p-tert) trifluoromethanesulfonate -Butoxyphenyl) sulfonium, p-toluenesulfonic acid triphenylsulfonium, p-toluenesulfonic acid p-tert-butoxyphenyl) diphenylsulfonium, bis (p-tert-butoxyphenyl) phenylsulfonium p-toluenesulfonate, tris (p-tert-butoxyphenyl) sulfonium p-toluenesulfonate, triphenyl nonafluorobutanesulfonate Sulfonium, triphenylsulfonium butanesulfonate, trimethylsulfonium trifluoromethanesulfonate, trimethylsulfonium p-toluenesulfonate, cyclohexylmethyl trifluoromethanesulfonate (2-oxocyclohexyl) sulfonium, cyclohexylmethyl p-toluenesulfonate (2-oxocyclohexyl) ) Sulfonium, dimethylphenylsulfonium trifluoromethanesulfonate, di-p-toluenesulfonic acid Tylphenylsulfonium, dicyclohexylphenylsulfonium trifluoromethanesulfonate, dicyclohexylphenylsulfonium p-toluenesulfonate, trinaphthylsulfonium trifluoromethanesulfonate, (2-norbornyl) methyl (2-oxocyclohexyl) sulfonium trifluoromethanesulfonate, ethylenebis [ And onium salts such as methyl (2-oxocyclopentyl) sulfonium trifluoromethanesulfonate] and 1,2′-naphthylcarbonylmethyltetrahydrothiophenium triflate.

  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 And the like.

  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, and bis -O- (camphorsulfonyl)-.alpha.-glyoxime derivatives such as dimethylglyoxime.

  Examples of bissulfone derivatives include bisnaphthylsulfonylmethane, bistrifluoromethylsulfonylmethane, bismethylsulfonylmethane, bisethylsulfonylmethane, bispropylsulfonylmethane, bisisopropylsulfonylmethane, bis-p-toluenesulfonylmethane, and bisbenzenesulfonylmethane. Bissulfone derivatives can be mentioned.

  Examples of β-ketosulfonic acid derivatives include β-ketosulfonic acid derivatives such as 2-cyclohexylcarbonyl-2- (p-toluenesulfonyl) propane and 2-isopropylcarbonyl-2- (p-toluenesulfonyl) propane.

  Examples of the disulfone derivative include disulfone derivatives such as diphenyldisulfone and dicyclohexyldisulfone.

  Examples of the nitrobenzyl sulfonate derivative include nitrobenzyl sulfonate derivatives such as 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). Mention may be made of sulfonic acid ester derivatives such as benzene.

  Examples of sulfonic acid ester derivatives of N-hydroxyimide compounds include N-hydroxysuccinimide methanesulfonic acid ester, N-hydroxysuccinimide trifluoromethanesulfonic acid ester, N-hydroxysuccinimide ethanesulfonic acid ester, N-hydroxysuccinimide 1-propanesulfonic acid. Ester, N-hydroxysuccinimide 2-propanesulfonic acid ester, N-hydroxysuccinimide 1-pentanesulfonic acid ester, N-hydroxysuccinimide 1-octanesulfonic acid ester, N-hydroxysuccinimide p-toluenesulfonic acid ester, N-hydroxysuccinimide p-methoxybenzenesulfonic acid ester, N-hydroxysuccinimide 2-chloroethanesulfonic acid ester N-hydroxysuccinimide benzenesulfonic acid ester, N-hydroxysuccinimide-2,4,6-trimethylbenzenesulfonic acid ester, N-hydroxysuccinimide 1-naphthalenesulfonic acid ester, N-hydroxysuccinimide 2-naphthalenesulfonic acid ester, N- Hydroxy-2-phenylsuccinimide methanesulfonate, N-hydroxymaleimide methanesulfonate, N-hydroxymaleimide ethanesulfonate, N-hydroxy-2-phenylmaleimide methanesulfonate, N-hydroxyglutarimide methanesulfonate Ester, N-hydroxyglutarimide benzenesulfonic acid ester, N-hydroxyphthalimide methanesulfonic acid ester, N-hydro Siphthalimidobenzenesulfonic acid ester, N-hydroxyphthalimide trifluoromethanesulfonic acid ester, N-hydroxyphthalimide p-toluenesulfonic acid ester, N-hydroxynaphthalimide methanesulfonic acid ester, N-hydroxynaphthalimide benzenesulfonic acid ester, N- Hydroxy-5-norbornene-2,3-dicarboximide methanesulfonate, N-hydroxy-5-norbornene-2,3-dicarboximide trifluoromethanesulfonate, N-hydroxy-5-norbornene-2,3 -Sulphonic acid ester derivatives of N-hydroxyimide compounds such as dicarboximide p-toluenesulfonic acid ester.

  In particular, triphenylsulfonium trifluoromethanesulfonate, triphenylsulfonium trifluoromethanesulfonate (p-tert-butoxyphenyl) diphenylsulfonium, tris (p-tert-butoxyphenyl) sulfonium trifluoromethanesulfonate, triphenylsulfonium p-toluenesulfonate, p -Toluenesulfonic acid (p-tert-butoxyphenyl) diphenylsulfonium, p-toluenesulfonic acid tris (p-tert-butoxyphenyl) sulfonium, trifluoromethanesulfonic acid trinaphthylsulfonium, trifluoromethanesulfonic acid cyclohexylmethyl (2-oxocyclohexyl) ) Sulfonium, (2-norbornyl) methyl (2-oxocyclohexyl) sulfonyl trifluoromethanesulfonate Onium salts such as 1,2′-naphthylcarbonylmethyltetrahydrothiophenium triflate, bis (benzenesulfonyl) diazomethane, bis (p-toluenesulfonyl) diazomethane, bis (cyclohexylsulfonyl) diazomethane, bis (n-butylsulfonyl) Diazomethane derivatives such as diazomethane, bis (isobutylsulfonyl) diazomethane, bis (sec-butylsulfonyl) diazomethane, bis (n-propylsulfonyl) diazomethane, bis (isopropylsulfonyl) diazomethane, bis (tert-butylsulfonyl) diazomethane, bis-O Glyoxime derivatives such as-(p-toluenesulfonyl) -α-dimethylglyoxime and bis-O- (n-butanesulfonyl) -α-dimethylglyoxime, bisnaphthy Bissulfone derivatives such as sulfonylmethane, N-hydroxysuccinimide methanesulfonate, N-hydroxysuccinimide trifluoromethanesulfonate, N-hydroxysuccinimide 1-propanesulfonate, N-hydroxysuccinimide 2-propanesulfonate, N- Hydroxysuccinimide 1-pentanesulfonic acid ester, N-hydroxysuccinimide p-toluenesulfonic acid ester, N-hydroxynaphthalimide methanesulfonic acid ester, N-hydroxynaphthalimide benzenesulfonic acid ester, etc. Derivatives are preferably used.

  Furthermore, an oxime type acid generator represented by WO2004 / 074242 A2 may be added.

  In addition, the said acid generator can be used individually by 1 type or in combination of 2 or more types. Since onium salts are excellent in rectangularity improving effect and diazomethane derivatives and glyoxime derivatives are excellent in standing wave reducing effect, it is possible to finely adjust the profile by combining both.

  The addition amount of the acid generator is preferably 0.1 to 50 parts, more preferably 0.5 to 40 parts with respect to 100 parts of the base resin. If the amount is less than 0.1 part, the amount of acid generated during exposure is small and the sensitivity and resolution may be inferior. If the amount exceeds 50 parts, the transmittance of the resist may be lowered and the resolution may be inferior.

  Next, as a cross-linking agent blended in the negative resist material of the present invention, particularly a chemically amplified negative resist material, specific examples of cross-linking agents that can be used in the present invention are listed as methylol group, alkoxymethyl group, A compound containing a double bond such as a melamine compound, a guanamine compound, a glycoluril compound or a urea compound, an epoxy compound, an isocyanate compound, an azide compound, an alkenyl ether group substituted with at least one group selected from an acyloxymethyl group Can be mentioned. These may be used as additives, but may be introduced as pendant groups in the polymer side chain. A compound containing a hydroxy group can also be used as a crosslinking agent.

  Among specific examples of the crosslinking agent, when an epoxy compound is further exemplified, tris (2,3-epoxypropyl) isocyanurate, trimethylolmethane triglycidyl ether, trimethylolpropane triglycidyl ether, triethylolethane triglycidyl ether and the like Illustrated. Specific examples of the melamine compound include hexamethylol melamine, hexamethoxymethyl melamine, a compound in which 1 to 6 methylol groups of hexamethylol melamine are methoxymethylated, or a mixture thereof, hexamethoxyethyl melamine, hexaacyloxymethyl melamine, Examples thereof include compounds in which 1 to 6 methylol groups of hexamethylolmelamine are acyloxymethylated, or a mixture thereof. Examples of the guanamine compound include tetramethylolguanamine, tetramethoxymethylguanamine, a compound in which 1 to 4 methylol groups of tetramethylolguanamine are methoxymethylated, or a mixture thereof, tetramethoxyethylguanamine, tetraacyloxyguanamine, and tetramethylolguanamine. A compound in which ˜4 methylol groups are acyloxymethylated or a mixture thereof may be mentioned. Examples of the glycoluril compound include tetramethylol glycoluril, tetramethoxyglycoluril, tetramethoxymethylglycoluril, a compound in which 1 to 4 methylol groups of tetramethylolglycoluril are methoxymethylated, or a mixture thereof, and tetramethylolglycoluril methylol. Examples thereof include compounds in which 1 to 4 of the groups are acyloxymethylated or a mixture thereof. Examples of the urea compound include tetramethylol urea, tetramethoxymethyl urea, a compound in which 1 to 4 methylol groups of tetramethylol urea are methoxymethylated, a mixture thereof, tetramethoxyethyl urea, and the like.

  Examples of the isocyanate compound include tolylene diisocyanate, diphenylmethane diisocyanate, hexamethylene diisocyanate, and cyclohexane diisocyanate. Examples of the azide compound include 1,1′-biphenyl-4,4′-bisazide and 4,4′-methylidenebis. Examples include azide and 4,4′-oxybisazide.

  Examples of the compound containing an alkenyl ether group include ethylene glycol divinyl ether, triethylene glycol divinyl ether, 1,2-propanediol divinyl ether, 1,4-butanediol divinyl ether, tetramethylene glycol divinyl ether, neopentyl glycol divinyl ether, Examples include trimethylolpropane trivinyl ether, hexanediol divinyl ether, 1,4-cyclohexanediol divinyl ether, pentaerythritol trivinyl ether, pentaerythritol tetravinyl ether, sorbitol tetravinyl ether, sorbitol pentavinyl ether, and trimethylolpropane trivinyl ether.

  The amount of the crosslinking agent is preferably 5 to 50 parts, particularly preferably 10 to 40 parts, relative to 100 parts of the base resin. If it is less than 5 parts, the exposed portion may be dissolved in alkali due to insufficient crosslinking density, and if it exceeds 50 parts, the film after crosslinking may crack or the pattern after development may be reverse tapered. There is.

  Furthermore, a basic compound can be blended in the negative resist material of the present invention, particularly in the chemically amplified negative resist material.

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

  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 (eg, nicotinic acid, alanine, arginine, aspartic acid, glutamic acid, glycine, histidine, isoleucine, glycylleucine, leucine, methionine , Phenylalanine, threonine, lysine, 3-aminopyrazine-2-carboxylic acid, methoxyalanine) and the like, 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 (B) -1 can also be added.
N (X) _n (Y) _3-n (B) -1
(In the above formula, n = 1, 2, or 3. The side chain X may be the same or different, and can be represented by the following general formulas (X) -1 to (X) -3. 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, and X may be bonded to form a ring. May be.)

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. Or a cyclic alkyl group, which may contain one or a plurality of hydroxy groups, ether groups, ester groups and lactone rings.
R ³⁰³ is a single bond or 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 more ether groups, ester groups and lactone rings may be contained.

Specific examples of the compound represented by the general formula (B) -1 include the following.
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-acetoxyethyl) amine, tris (2-propionyloxyethyl) amine, Tris (2-butyryloxyethyl) amine, tris (2-isobutyryloxyethyl) amine, tris (2-valeryloxyethyl) amine, tris (2-pivaloyloxyethyl) 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] amino , Tris [2- (tert-butoxycarbonylmethyloxy) ethyl] amine, tris [2- (cyclohexyloxycarbonylmethyloxy) ethyl] amine, tris (2-methoxycarbonylethyl) amine, tris (2-ethoxycarbonylethyl) Amine, N, N-bis (2-hydroxyethyl) 2- (methoxycarbonyl) ethylamine, N, N-bis (2-acetoxyethyl) 2- (methoxycarbonyl) ethylamine, N, N-bis (2-hydroxyethyl) ) 2- (ethoxycarbonyl) ethylamine, N, N-bis (2-acetoxyethyl) 2- (ethoxycarbonyl) ethylamine, N, N-bis (2-hydroxyethyl) 2- (2-methoxyethoxycarbonyl) ethylamine, N, N-bis (2-acetoxyethyl ) 2- (2-methoxyethoxycarbonyl) ethylamine, N, N-bis (2-hydroxyethyl) 2- (2-hydroxyethoxycarbonyl) ethylamine, N, N-bis (2-acetoxyethyl) 2- (2- Acetoxyethoxycarbonyl) ethylamine, N, N-bis (2-hydroxyethyl) 2-[(methoxycarbonyl) methoxycarbonyl] ethylamine, N, N-bis (2-acetoxyethyl) 2-[(methoxycarbonyl) methoxycarbonyl] Ethylamine, N, N-bis (2-hydroxyethyl) 2- (2-oxopropoxycarbonyl) ethylamine, N, N-bis (2-acetoxyethyl) 2- (2-oxopropoxycarbonyl) ethylamine, N, N- Bis (2-hydroxyethyl) 2- (tetrahydrofurf Ruoxycarbonyl) ethylamine, N, N-bis (2-acetoxyethyl) 2- (tetrahydrofurfuryloxycarbonyl) ethylamine, N, N-bis (2-hydroxyethyl) 2-[(2-oxotetrahydrofuran-3- Yl) oxycarbonyl] ethylamine, N, N-bis (2-acetoxyethyl) 2-[(2-oxotetrahydrofuran-3-yl) oxycarbonyl] ethylamine, N, N-bis (2-hydroxyethyl) 2- ( 4-hydroxybutoxycarbonyl) ethylamine, N, N-bis (2-formyloxyethyl) 2- (4-formyloxybutoxycarbonyl) ethylamine, N, N-bis (2-formyloxyethyl) 2- (2-formyl) Oxyethoxycarbonyl) ethylamine, N, N-bis (2 Methoxyethyl) 2- (methoxycarbonyl) ethylamine, N- (2-hydroxyethyl) bis [2- (methoxycarbonyl) ethyl] amine, N- (2-acetoxyethyl) bis [2- (methoxycarbonyl) ethyl] amine N- (2-hydroxyethyl) bis [2- (ethoxycarbonyl) ethyl] amine, N- (2-acetoxyethyl) bis [2- (ethoxycarbonyl) ethyl] amine, N- (3-hydroxy-1- Propyl) bis [2- (methoxycarbonyl) ethyl] amine, N- (3-acetoxy-1-propyl) bis [2- (methoxycarbonyl) ethyl] amine, N- (2-methoxyethyl) bis [2- ( Methoxycarbonyl) ethyl] amine, N-butylbis [2- (methoxycarbonyl) ethyl] amine, N-butyl Tylbis [2- (2-methoxyethoxycarbonyl) ethyl] amine, N-methylbis (2-acetoxyethyl) amine, N-ethylbis (2-acetoxyethyl) amine, N-methylbis (2-pivaloyloxyethyl) amine N-ethylbis [2- (methoxycarbonyloxy) ethyl] amine, N-ethylbis [2- (tert-butoxycarbonyloxy) ethyl] amine, tris (methoxycarbonylmethyl) amine, tris (ethoxycarbonylmethyl) amine, N -Butylbis (methoxycarbonylmethyl) amine, N-hexylbis (methoxycarbonylmethyl) amine, and β- (diethylamino) -δ-valerolactone can be exemplified, but are not limited thereto.

（上記式中、Ｘは前述の通り、Ｒ³⁰⁷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、スルフィドを１個あるいは複数個含んでいてもよい。） Furthermore, 1 type, or 2 or more types of the basic compound which has a 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.)

  Specific examples of the formula (B) -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] Ruphorin, 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 Propionate tetrahydrofurf 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, Examples thereof include methyl thiomorpholinoacetate, ethyl 1-pyrrolidinyl acetate, 2-methoxyethyl morpholinoacetate and the like.

（上記式中、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 (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 or branched alkylene groups having 1 to 4 carbon atoms.)

  Specific examples of the basic compound 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-aminopropi Ononitrile, methyl 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-cyanoe ) Methyl 3-aminopropionate, N- (2-cyanoethyl) -N-ethyl-3-aminopropiononitrile, N- (2-cyanoethyl) -N- (2-hydroxyethyl) -3-aminopropi Ononitrile, N- (2-acetoxyethyl) -N- (2-cyanoethyl) -3-aminopropiononitrile, N- (2-cyanoethyl) -N- (2-formyloxyethyl) -3-aminopropiono Nitrile, N- (2-cyanoethyl) -N- (2-methoxyethyl) -3-aminopropiononitrile, N- (2-cyanoethyl) -N- [2- (methoxymethoxy) ethyl] -3-aminopropi Ononitrile, 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) amino Acetonitrile, 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) -3-aminopropionic acid methyl, N-cyanomethyl-N- (2-hydroxyethyl) -3-aminopropionic acid methyl, N- (2-acetoxyethyl) -N-cyanomethyl-3- Methyl aminopropionate, N-cyanomethyl-N- (2-hydroxyethyl) aminoacetonitrile, N- (2-acetoxyethyl) -N- (cyanomethyl) aminoacetonitrile, N-cyanomethyl-N- (2-formyloxyethyl) Aminoacetonitrile, N-cyanomethyl-N- (2-methoxyethyl) aminoacetonitrile, N-cyanomethyl-N- [2- (methoxymethoxy) ethyl] aminoacetonitrile, N- (cyanomethyl) -N- (3-hydroxy-1 -Propyl) aminoacetonitrile, N- (3-acetoxy -1-propyl) -N- (cyanomethyl) aminoacetonitrile, N-cyanomethyl-N- (3-formyloxy-1-propyl) aminoacetonitrile, N, N-bis (cyanomethyl) aminoacetonitrile, 1-pyrrolidinepropiononitrile 1-piperidinepropiononitrile, 4-morpholinepropiononitrile, 1-pyrrolidineacetonitrile, 1-piperidineacetonitrile, 4-morpholineacetonitrile, cyanomethyl 3-diethylaminopropionate, N, N-bis (2-hydroxyethyl) -3 -Cyanomethyl aminopropionate, N, N-bis (2-acetoxyethyl) -3-aminopropionic acid cyanomethyl, N, N-bis (2-formyloxyethyl) -3-aminopropionic acid cyanomethyl, N, N-bis 2-methoxyethyl) -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-piperi Examples thereof include cyanomethyl dinpropionate, cyanomethyl 4-morpholinepropionate, 1-pyrrolidinepropionic acid (2-cyanoethyl), 1-piperidinepropionic acid (2-cyanoethyl), 4-morpholinepropionic acid (2-cyanoethyl) and the like.

  In addition, the compounding quantity of a basic compound is 0.001-2 parts with respect to 100 parts of base resins, and 0.01-1 part is especially suitable. If the blending amount is less than 0.001 part, the blending effect is small, and if it exceeds 2 parts, the sensitivity may be too low.

  Examples of the compound having a group represented by ≡C—COOH in the molecule that can be added to the negative resist material of the present invention include one or more selected from the following [Group I] and [Group II]. However, it is not limited to these. By blending this component, the PED (Post Exposure Delay) stability of the resist is improved, and the edge roughness on the nitride film substrate is improved.

[Group I]
A part or all of the hydrogen atoms of the phenolic hydroxyl groups of the compounds represented by the following general formulas (A1) to (A10) are converted to —R ⁴⁰¹ —COOH (where R ⁴⁰¹ is a linear or branched alkylene having 1 to 10 carbon atoms). The molar ratio of the phenolic hydroxyl group (C) in the molecule to the group (D) represented by ≡C—COOH is C / (C + D) = 0.1 to 1.0. Compound.

（式中、Ｒ⁴⁰⁸は水素原子又はメチル基を示す。Ｒ⁴⁰²、Ｒ⁴⁰³はそれぞれ水素原子又は炭素数１〜８の直鎖状又は分岐状のアルキル基又はアルケニル基を示す。Ｒ⁴⁰⁴は水素原子又は炭素数１〜８の直鎖状又は分岐状のアルキル基又はアルケニル基、あるいは−（Ｒ⁴⁰⁹）_h−ＣＯＯＲ’基（Ｒ’は水素原子又は−Ｒ⁴⁰⁹−ＣＯＯＨ）を示す。Ｒ⁴⁰⁵は−（ＣＨ₂）_i−（ｉ＝２〜１０）、炭素数６〜１０のアリーレン基、カルボニル基、スルホニル基、酸素原子又は硫黄原子を示す、Ｒ⁴⁰⁶は炭素数１〜１０のアルキレン基、炭素数６〜１０のアリーレン基、カルボニル基、スルホニル基、酸素原子又は硫黄原子を示す。Ｒ⁴⁰⁷は水素原子又は炭素数１〜８の直鎖状又は分岐状のアルキル基、アルケニル基、それぞれ水酸基で置換されたフェニル基又はナフチル基を示す。Ｒ⁴⁰⁹は炭素数１〜１０の直鎖状又は分岐状のアルキル基又はアルケニル基又は−Ｒ⁴¹¹−ＣＯＯＨ基を示す。Ｒ⁴¹⁰は水素原子、炭素数１〜８の直鎖状又は分岐状のアルキル基又はアルケニル基又は−Ｒ⁴¹¹−ＣＯＯＨ基を示す。Ｒ⁴¹¹は炭素数１〜１０の直鎖状又は分岐状のアルキレン基を示す。ｈは１〜４の整数である。ｊは０〜３、ｓ１〜ｓ４、ｔ１〜ｔ４はそれぞれｓ１＋ｔ１＝８、ｓ２＋ｔ２＝５、ｓ３＋ｔ３＝４、ｓ４＋ｔ４＝６を満足し、かつ各フェニル骨格中に少なくとも１つの水酸基を有するような数である。ｕは１〜４の整数である。κは式（Ａ６）の化合物を重量平均分子量１，０００〜５，０００とする数である。λは式（Ａ７）の化合物を重量平均分子量１，０００〜１０，０００とする数である。）

(In the formula, R ⁴⁰⁸ represents a hydrogen atom or a methyl group. R ⁴⁰² and R ⁴⁰³ each represents a hydrogen atom or a linear or branched alkyl group or alkenyl group having 1 to 8 carbon atoms. R ⁴⁰⁴ represents hydrogen. atom or a linear or branched alkyl or alkenyl group having 1 to 8 carbon atoms _{^{or, - (R 409) h -COOR}} ' group (R' is a hydrogen atom or -R ⁴⁰⁹ -COOH) shows a .R ⁴⁰⁵ Is — (CH ₂ ) _i — (i = 2 to 10), an arylene group having 6 to 10 carbon atoms, a carbonyl group, a sulfonyl group, an oxygen atom or a sulfur atom, R ⁴⁰⁶ is an alkylene group having 1 to 10 carbon atoms. Represents an arylene group having 6 to 10 carbon atoms, a carbonyl group, a sulfonyl group, an oxygen atom or a sulfur atom, and R ⁴⁰⁷ represents a hydrogen atom or a linear or branched alkyl group or alkenyl group having 1 to 8 carbon atoms, A phenyl group substituted by a hydroxyl group or .R ⁴⁰⁹ showing a naphthyl group is a straight or branched alkyl or alkenyl group or a -R ⁴¹¹ -COOH group having 1 to 10 carbon atoms .R ⁴¹⁰ represents a hydrogen atom, a straight-chain having 1 to 8 carbon atoms Represents a linear or branched alkyl group or alkenyl group or —R ⁴¹¹ —COOH group, R ⁴¹¹ represents a linear or branched alkylene group having 1 to 10 carbon atoms, and h is an integer of 1 to 4. J is 0 to 3, s1 to s4, and t1 to t4 are numbers satisfying s1 + t1 = 8, s2 + t2 = 5, s3 + t3 = 4, s4 + t4 = 6, and having at least one hydroxyl group in each phenyl skeleton U is an integer of 1 to 4. κ is a number that makes the compound of formula (A6) a weight average molecular weight of 1,000 to 5,000, and λ is a weight average molecular weight of the compound of formula (A7). 1,000 to 10,000 )

（式中、Ｒ⁴⁰²、Ｒ⁴⁰³、Ｒ⁴¹¹は上記と同様の意味を示す。Ｒ⁴¹²は水素原子又は水酸基を示す。ｓ５、ｔ５は、ｓ５≧０、ｔ５≧０で、ｓ５＋ｔ５＝５を満足する数である。ｈ’は０又は１である。） [Group II]
Compounds represented by the following general formulas (A11) to (A15).

(Wherein R ⁴⁰² , R ⁴⁰³ , and R ⁴¹¹ have the same meanings as described above. R ⁴¹² represents a hydrogen atom or a hydroxyl group. S5 and t5 satisfy s5 + t5 = 5 with s5 ≧ 0 and t5 ≧ 0. H 'is 0 or 1.)

  Specific examples of this component include, but are not limited to, compounds represented by the following general formulas (AI-1) to (AI-14) and (AII-1) to (AII-10). It is not a thing.

（式中、Ｒ’’は水素原子又は−ＣＨ₂ＣＯＯＨ基を示し、各化合物においてＲ’’の１０〜１００モル％は−ＣＨ₂ＣＯＯＨ基である。κ、λは上記と同様の意味を示す。）

(In the formula, R ″ represents a hydrogen atom or a —CH ₂ COOH group, and in each compound, 10 to 100 mol% of R ″ is a —CH ₂ COOH group. Κ and λ have the same meanings as described above. Show.)

なお、上記分子内に≡Ｃ−ＣＯＯＨで示される基を有する化合物の添加量は、ベース樹脂１００部に対して０〜５部、好ましくは０．１〜５部、より好ましくは０．１〜３部、更に好ましくは０．１〜２部である。５部より多いとレジスト材料の解像度が低下する場合がある。

The amount of the compound having a group represented by ≡C—COOH in the molecule is 0 to 5 parts, preferably 0.1 to 5 parts, more preferably 0.1 to 100 parts of the base resin. 3 parts, more preferably 0.1 to 2 parts. If it exceeds 5 parts, the resolution of the resist material may be lowered.

  In the negative resist material of the present invention, particularly a chemically amplified negative resist material, a surfactant for improving the coating property can be further added.

  Examples of the surfactant include, but are not limited to, polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether, polyethylene stearyl ether, polyoxyethylene cetyl ether, polyoxyethylene olein ether, and polyoxyethylene Polyoxyethylene alkyl allyl ethers such as octylphenol ether and polyoxyethylene nonylphenol, polyoxyethylene polyoxypropylene block copolymers, sorbitan fatty acid esters such as sorbitan monolaurate, sorbitan monovalmitate, sorbitan monostearate, poly Oxyethylene sorbitan monolaurate, polyoxyethylene sorbitan monovalmitate, polyoxyethylene sorbitan monostearate Non-ionic surfactants of polyoxyethylene sorbitan fatty acid esters such as polyoxyethylene sorbitan trioleate and polyoxyethylene sorbitan tristearate, F-top EF301, EF303, EF352 (Tokemuputtokutsu), Megafuck F171, F172, F173 (Dainippon Ink Chemical Co., Ltd.), Florard FC-430, FC-431 (Sumitomo 3M), Asahi Guard AG710, Surflon S-381, S-382, SC101, SC102, SC103, SC104, SC105, SC106, Surfinol E1004, Fluorosurfactants such as KH-10, KH-20, KH-30, KH-40 (Asahi Glass), organosiloxane polymers KP-341, X-70-092, X-70-093 (Shin-Etsu) Manabu Industry), acrylic acid or methacrylic acid Polyflow No. 75, no. 95 (Kyoeisha Yushi Chemical Industry Co., Ltd.), etc., among which FC-430, FC-4430, Surflon S-381, Surfynol E1004, KH-20, KH-30 are preferred. These can be used alone or in combination of two or more.

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

  Negative resist material of the present invention, in particular, an organic solvent, a polymer compound having a repeating unit represented by the following general formula (a-1), (b-1) or (b-2), and acid generation When a chemically amplified negative resist material containing an agent or the like is used for manufacturing various integrated circuits, a known lithography technique can be used, although not particularly limited.

For example, the negative resist material of the present invention is applied to an integrated circuit manufacturing substrate (Si, SiO ₂ , SiN, SiON, TiN, WSi, BPSG, SOG, organic antireflection film, Cr, CrO, CrON, MoSi, etc.) The film is applied to a coating film thickness of 0.01 to 2.0 μm by a suitable coating method such as spin coating, roll coating, flow coating, dip coating, spray coating, doctor coating, etc., and 60 to 150 on a hot plate. Prebaking at 1 ° C. for 1 to 10 minutes, preferably 80 to 120 ° C. for 1 to 5 minutes.

  As the resist thickness becomes thinner, the processing becomes stricter due to the etching selectivity of the substrate to be processed. The silicon-containing intermediate film is formed under the resist, the underlying carbon film has a high carbon density and high etching resistance, and the processed film is formed thereunder. A three-layer process for laminating substrates has been studied. The etching selectivity between the silicon-containing intermediate film using oxygen gas, hydrogen gas, ammonia gas, or the like and the lower layer film is high, and the silicon-containing intermediate film can be thinned. The etching selectivity between the single layer resist and the silicon-containing intermediate layer is also relatively high, and the single layer resist can be thinned. In this case, examples of the method for forming the lower layer film include a method using coating and baking, and a method using CVD. In the case of the coating type, a novolak resin or a resin obtained by polymerizing an olefin having a condensed ring is used, and a gas such as butane, ethane, propane, ethylene, acetylene, or the like is used for producing a CVD film. In the case of the silicon-containing intermediate layer, there are a coating type and a CVD type. Examples of the coating type include silsesquioxane and POSS (registered trademark). Various types of silane gases are used as a raw material for CVD. The silicon-containing intermediate layer may have an antireflection function having light absorption, and may be a light-absorbing group such as a phenyl group or a SiON film. An organic film may be formed between the silicon-containing intermediate film and the photoresist, and the organic film in this case may be an organic antireflection film.

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. 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 . Next, post exposure baking (PEB) is performed on a hot plate at 60 to 150 ° C. for 1 to 5 minutes, preferably 80 to 120 ° 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. Note that the negative resist material of the present invention is a high-energy ray, particularly far ultraviolet rays having a wavelength of 254 to 193 nm, vacuum ultraviolet rays having a wavelength of 157 nm, electron beams, soft X-rays, X-rays, excimer lasers, γ rays, and synchrotron radiation. It is most suitable for fine patterning with high energy rays.

  Furthermore, the negative resist material of the present invention can also be used for EB and EUV lithography. In particular, the polymer of the present invention having an indene, styrene, and naphthalene ring having a high carbon ratio is expected to have high transmittance in EUV light having a wavelength of 13.5 nm.

  EXAMPLES Hereinafter, although a synthesis example, a comparative 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 5- (2-hydroxy-1,1,1,3,3,3-hexafluoroisopropyl) indene 6.5 g of magnesium and a small amount of tetrahydrofuran were placed in a 1 L four-necked flask. It was. After adding a small amount of 6-bromoindene in tetrahydrofuran and confirming the start of the Grignard reaction, the flask was added dropwise little by little so that the internal temperature of the flask was maintained at 55 ° C., and a total of 50.0 g of 6-bromoindene solution was added dropwise. . The reaction mixture was reacted for 2 hours under heated reflux, then cooled to room temperature, and hexafluoroacetone gas was blown into the solution. After completion of the blowing, the reaction was allowed to proceed at room temperature for 2 hours, and then a saturated aqueous ammonium chloride solution was added while the flask was immersed in a water bath. The usual reaction post-treatment was performed, and the resulting oily substance was purified by silica gel chromatography and distillation to obtain 25.3 g of 5- (2-hydroxy-1,1,1,3,3,3-hexafluoroisopropyl). Inden was obtained. The yield was 30.0%.

¹ H-NMR (CDCl ₃ , 270 MHz):
δ 7.85 (m, 1H), 7.49 (m, 1H), 7.28-7.25 (m, 2H), 6.97 (s, 1H), 3.52 (t, 2H), 3 .48 (s, 1H)
FT-IR (NaCl):
3597, 3516, 3072, 1622, 1459, 1385, 1339, 1272, 1217, 1171, 1128, 1099, 1063, 1028, 991, 962, 926, 864, 785, 766, 737, 715 cm ^-1

[Synthesis Example 2]
To a 100 mL flask, 8.5 g of 5- (2-hydroxy-1,1,1,3,3,3-hexafluoroisopropyl) indene, 11.3 g of 4-acetoxystyrene, and 30 g of tetrahydrofuran as a solvent were added. The reaction vessel was cooled to −70 ° C. in a nitrogen atmosphere, and vacuum degassing and nitrogen flow were repeated three times. After raising the temperature to room temperature, 0.8 g of AIBN (azobisisobutyronitrile) was added as a polymerization initiator, and the temperature was raised to 60 ° C., followed by reaction for 15 hours. This reaction solution was precipitated in a 500 mL solution of hexane, and the resulting white solid was filtered and dried under reduced pressure at 60 ° C. to obtain a white polymer.

  This polymer was dissolved again in 0.5 L of methanol and 1.0 L of tetrahydrofuran, 70 g of triethylamine and 15 g of water were added, the acetyl group was deprotected, and neutralized with acetic acid. The reaction solution was concentrated and then dissolved in 0.5 L of acetone, and precipitation, filtration and drying were performed in the same manner as above to obtain a white polymer.

When the obtained polymer was measured by ¹³ C, ¹ H-NMR and GPC, the following analysis results were obtained.
Copolymerization composition ratio 5- (2-hydroxy-1,1,1,3,3,3-hexafluoroisopropyl) indene: 4-hydroxystyrene = 0.3: 0.7 (molar ratio)
Weight average molecular weight (Mw) = 6,900
Molecular weight distribution (Mw / Mn) = 1.77
This is designated as (Polymer 1).

[Synthesis Example 3]
In a 100 mL flask, 8.5 g of 5- (2-hydroxy-1,1,1,3,3,3-hexafluoroisopropyl) indene, 8.1 g of 4-acetoxystyrene, 2.1 g of styrene, and 30 g of tetrahydrofuran as a solvent. Added. The reaction vessel was cooled to −70 ° C. in a nitrogen atmosphere, and vacuum degassing and nitrogen flow were repeated three times. After raising the temperature to room temperature, 0.8 g of AIBN was added as a polymerization initiator, and the temperature was raised to 60 ° C., followed by reaction for 15 hours. This reaction solution was precipitated in a 500 mL solution of hexane, and the resulting white solid was filtered and dried under reduced pressure at 60 ° C. to obtain a white polymer.

  This polymer was dissolved again in 0.5 L of methanol and 1.0 L of tetrahydrofuran, 70 g of triethylamine and 15 g of water were added, the acetyl group was deprotected, and neutralized with acetic acid. The reaction solution was concentrated and then dissolved in 0.5 L of acetone, and precipitation, filtration and drying were performed in the same manner as above to obtain a white polymer.

When the obtained polymer was measured by ¹³ C, ¹ H-NMR and GPC, the following analysis results were obtained.
Copolymerization composition ratio 5- (2-hydroxy-1,1,1,3,3,3-hexafluoroisopropyl) indene: 4-hydroxystyrene: styrene = 0.3: 0.5: 0.2 (molar ratio) )
Weight average molecular weight (Mw) = 7,600
Molecular weight distribution (Mw / Mn) = 1.78
This is designated as (Polymer 2).

[Synthesis Example 4]
In a 100 mL flask, 8.5 g of 5- (2-hydroxy-1,1,1,3,3,3-hexafluoroisopropyl) indene, 8.1 g of 4-acetoxystyrene, 2.3 g of indene, and 30 g of tetrahydrofuran as a solvent. Added. The reaction vessel was cooled to −70 ° C. in a nitrogen atmosphere, and vacuum degassing and nitrogen flow were repeated three times. After raising the temperature to room temperature, 0.8 g of AIBN was added as a polymerization initiator, and the temperature was raised to 60 ° C., followed by reaction for 15 hours. This reaction solution was precipitated in a 500 mL solution of hexane, and the resulting white solid was filtered and dried under reduced pressure at 60 ° C. to obtain a white polymer.

  This polymer was dissolved again in 0.5 L of methanol and 1.0 L of tetrahydrofuran, 70 g of triethylamine and 15 g of water were added, the acetyl group was deprotected, and neutralized with acetic acid. The reaction solution was concentrated and then dissolved in 0.5 L of acetone, and precipitation, filtration and drying were performed in the same manner as above to obtain a white polymer.

When the obtained polymer was measured by ¹³ C, ¹ H-NMR and GPC, the following analysis results were obtained.
Copolymerization composition ratio 5- (2-hydroxy-1,1,1,3,3,3-hexafluoroisopropyl) indene: 4-hydroxystyrene: indene = 0.3: 0.5: 0.2 (molar ratio) )
Weight average molecular weight (Mw) = 4,500
Molecular weight distribution (Mw / Mn) = 1.54
This is designated as (Polymer 3).

[Synthesis Example 5]
11.2 g of 5- (2-hydroxy-1,1,1,3,3,3-hexafluoroisopropyl) indene, 12.7 g of 2-vinyl-6-acetoxynaphthalene and 30 g of tetrahydrofuran as a solvent are added to a 100 mL flask. did. The reaction vessel was cooled to −70 ° C. in a nitrogen atmosphere, and vacuum degassing and nitrogen flow were repeated three times. After raising the temperature to room temperature, 0.8 g of AIBN was added as a polymerization initiator, and the temperature was raised to 60 ° C., followed by reaction for 15 hours. This reaction solution was precipitated in a 500 mL solution of hexane, and the resulting white solid was filtered and dried under reduced pressure at 60 ° C. to obtain a white polymer.

  This polymer was dissolved again in 0.5 L of methanol and 1.0 L of tetrahydrofuran, 70 g of triethylamine and 15 g of water were added, the acetyl group was deprotected, and neutralized with acetic acid. The reaction solution was concentrated and then dissolved in 0.5 L of acetone, and precipitation, filtration and drying were performed in the same manner as above to obtain a white polymer.

When the obtained polymer was measured by ¹³ C, ¹ H-NMR and GPC, the following analysis results were obtained.
Copolymerization composition ratio 5- (2-hydroxy-1,1,1,3,3,3-hexafluoroisopropyl) indene: 2-vinyl-6-hydroxynaphthalene = 0.4: 0.6 (molar ratio)
Weight average molecular weight (Mw) = 6,300
Molecular weight distribution (Mw / Mn) = 1.66
This is designated as (Polymer 4).

[Synthesis Example 6]
In a 100 mL flask, 9.7 g of 5- (2-acetoxy-1,1,1,3,3,3-hexafluoroisopropyl) indene, 8.1 g of 4-acetoxystyrene, 1.8 g of 2,5-norbornadiene, solvent As a result, 20 g of 1,2-dichloroethane was added. In a nitrogen atmosphere, 0.1 g of trifluoroboron as a polymerization initiator was added to the reaction vessel, and the temperature was raised to 60 ° C., followed by reaction for 15 hours. This reaction solution was concentrated to 1/2, precipitated in a mixed solution of 1.5 L of methanol and 0.2 L of water, and the resulting white solid was filtered and dried under reduced pressure at 60 ° C. to obtain a white polymer. . This polymer was dissolved again in 0.5 L of methanol and 1.0 L of tetrahydrofuran, 70 g of triethylamine and 15 g of water were added, the acetyl group was deprotected, and neutralized with acetic acid. The reaction solution was concentrated and then dissolved in 0.5 L of acetone, and precipitation, filtration and drying were performed in the same manner as above to obtain a white polymer.

When the obtained polymer was measured by ¹³ C, ¹ H-NMR and GPC, the following analysis results were obtained.
Copolymerization composition ratio 5- (2-hydroxy-1,1,1,3,3,3-hexafluoroisopropyl) indene: 4-hydroxystyrene: 5-norbornadiene = 0.3: 0.5: 0.2 ( Molar ratio)
Weight average molecular weight (Mw) = 8,700
Molecular weight distribution (Mw / Mn) = 1.64
This is designated as (Polymer 5).

[Synthesis Example 7]
In a 100 mL flask, 9.7 g of 5- (2-acetoxy-1,1,1,3,3,3-hexafluoroisopropyl) indene, 8.1 g of 4-acetoxystyrene, 3.2 g of acenaphthylene, and 1,2 as a solvent. -20 g of dichloroethane was added. In a nitrogen atmosphere, 0.1 g of trifluoroboron as a polymerization initiator was added to the reaction vessel, and the temperature was raised to 60 ° C., followed by reaction for 15 hours. This reaction solution was concentrated to 1/2, precipitated in a mixed solution of 1.5 L of methanol and 0.2 L of water, and the resulting white solid was filtered and dried under reduced pressure at 60 ° C. to obtain a white polymer. . This polymer was dissolved again in 0.5 L of methanol and 1.0 L of tetrahydrofuran, 70 g of triethylamine and 15 g of water were added, the acetyl group was deprotected, and neutralized with acetic acid. The reaction solution was concentrated and then dissolved in 0.5 L of acetone, and precipitation, filtration and drying were performed in the same manner as above to obtain a white polymer.

When the obtained polymer was measured by ¹³ C, ¹ H-NMR and GPC, the following analysis results were obtained.
Copolymerization composition ratio 5- (2-hydroxy-1,1,1,3,3,3-hexafluoroisopropyl) indene: 4-hydroxystyrene: acenaphthylene = 0.3: 0.5: 0.2 (molar ratio) )
Weight average molecular weight (Mw) = 4,900
Molecular weight distribution (Mw / Mn) = 1.53
This is designated as (Polymer 6).

[Synthesis Example 8]
In a 100 mL flask, 8.5 g of 5- (2-hydroxy-1,1,1,3,3,3-hexafluoroisopropyl) indene, 9.7 g of 4-acetoxystyrene, 5.6 g of the following monomer 1, solvent As a result, 30 g of tetrahydrofuran was added. The reaction vessel was cooled to −70 ° C. in a nitrogen atmosphere, and vacuum degassing and nitrogen flow were repeated three times. After raising the temperature to room temperature, 0.8 g of AIBN was added as a polymerization initiator, and the temperature was raised to 60 ° C., followed by reaction for 15 hours. This reaction solution was precipitated in a 500 mL solution of hexane, and the resulting white solid was filtered and dried under reduced pressure at 60 ° C. to obtain a white polymer.

  This polymer was dissolved again in 0.5 L of methanol and 1.0 L of tetrahydrofuran, 70 g of triethylamine and 15 g of water were added, the acetyl group was deprotected, and neutralized with acetic acid. The reaction solution was concentrated and then dissolved in 0.5 L of acetone, and precipitation, filtration and drying were performed in the same manner as above to obtain a white polymer.

When the obtained polymer was measured by ¹³ C, ¹ H-NMR and GPC, the following analysis results were obtained.
Copolymerization composition ratio 5- (2-hydroxy-1,1,1,3,3,3-hexafluoroisopropyl) indene: 4-hydroxystyrene: monomer 1 = 0.3: 0.6: 0.1 (mol) ratio)
Weight average molecular weight (Mw) = 5,500
Molecular weight distribution (Mw / Mn) = 1.58
This is designated as (Polymer 7).

[Synthesis Example 9]
In a 100 mL flask, 8.5 g of 5- (2-hydroxy-1,1,1,3,3,3-hexafluoroisopropyl) indene, 9.7 g of 4-acetoxystyrene, 7.3 g of monomer 2 below, solvent As a result, 30 g of tetrahydrofuran was added. The reaction vessel was cooled to −70 ° C. in a nitrogen atmosphere, and vacuum degassing and nitrogen flow were repeated three times. After raising the temperature to room temperature, 0.8 g of AIBN was added as a polymerization initiator, and the temperature was raised to 60 ° C., followed by reaction for 15 hours. This reaction solution was precipitated in a 500 mL solution of hexane, and the resulting white solid was filtered and dried under reduced pressure at 60 ° C. to obtain a white polymer.

  This polymer was dissolved again in 0.5 L of methanol and 1.0 L of tetrahydrofuran, 70 g of triethylamine and 15 g of water were added, the acetyl group was deprotected, and neutralized with acetic acid. The reaction solution was concentrated and then dissolved in 0.5 L of acetone, and precipitation, filtration and drying were performed in the same manner as above to obtain a white polymer.

When the obtained polymer was measured by ¹³ C, ¹ H-NMR and GPC, the following analysis results were obtained.
Copolymer composition ratio 5- (2-hydroxy-1,1,1,3,3,3-hexafluoroisopropyl) indene: 4-hydroxystyrene: monomer 2 = 0.3: 0.6: 0.1 (mol) ratio)
Weight average molecular weight (Mw) = 5,900
Molecular weight distribution (Mw / Mn) = 1.67
This is designated as (Polymer 8).

[Comparative Synthesis Example 1]
To a 100 mL flask, 3.1 g of styrene, 11.3 g of 4-acetoxystyrene, and 30 g of tetrahydrofuran as a solvent were added. The reaction vessel was cooled to −70 ° C. in a nitrogen atmosphere, and vacuum degassing and nitrogen flow were repeated three times. After raising the temperature to room temperature, 0.8 g of AIBN was added as a polymerization initiator, and the temperature was raised to 60 ° C., followed by reaction for 15 hours. This reaction solution was precipitated in a 500 mL solution of hexane, and the resulting white solid was filtered and dried under reduced pressure at 60 ° C. to obtain a white polymer.

This polymer was dissolved again in 0.5 L of methanol and 1.0 L of tetrahydrofuran, 70 g of triethylamine and 15 g of water were added, the acetyl group was deprotected, and neutralized with acetic acid. The reaction solution was concentrated and then dissolved in 0.5 L of acetone, and precipitation, filtration and drying were performed in the same manner as above to obtain a white polymer.
When the obtained polymer was measured by ¹³ C, ¹ H-NMR and GPC, the following analysis results were obtained.
Copolymer composition ratio Styrene: 4-Hydroxystyrene = 0.7: 0.3 (molar ratio)
Weight average molecular weight (Mw) = 12,000
Molecular weight distribution (Mw / Mn) = 1.92
This polymer compound is referred to as (Comparative Polymer 1).

[Examples and Comparative Examples]
Using the polymer compound synthesized above, a solution dissolved in the composition shown in Table 1 was filtered through a 0.2 μm size filter to prepare a negative resist material.
Each composition in Table 1 is as follows.
Polymers 2 to 8: Polymers obtained in Synthesis Examples 3 to 9 Comparative polymer 1: Polymer obtained in Comparative Synthesis Example 1 Organic solvent: PGMEA (propylene glycol monomethyl ether acetate)
EL (ethyl lactate)
Acid generator: PAG1, PAG2, PAG3 (see structural formula below)
Basic compounds: Quencher1, Quencher2, Quencher3 (see the structural formula below)
Crosslinker: Crosslinker (see the structural formula below)

Electron Beam Drawing Evaluation In the drawing evaluation, a negative resist material was prepared by filtering a solution dissolved in the composition shown in Table 1 using a polymer compound synthesized above with a 0.2 μm size filter.
The obtained negative resist material was spin-coated on a 6-inch diameter Si substrate using a clean track Mark 5 (manufactured by Tokyo Electron Ltd.) and pre-baked on a hot plate at 110 ° C. for 90 seconds. A 100 nm resist film was prepared. To this, drawing in a vacuum chamber was performed with an HV voltage of 50 keV using L-800D manufactured by Hitachi, Ltd.
Immediately after drawing, a post-exposure bake (PEB) was performed for 90 seconds at 100 ° C. on a hot plate using a clean track Mark 5 (manufactured by Tokyo Electron Co., Ltd.) and paddled with a 2.38 mass% TMAH aqueous solution for 30 seconds. Development was performed to obtain a negative pattern.

The obtained resist pattern was evaluated as follows.
The minimum dimension at the exposure amount for resolving 0.12 μm line and space at 1: 1 was taken as the resolution, and the edge roughness of 120 nm LS was measured by SEM.
Table 1 shows the results of resist composition, sensitivity and resolution in EB exposure.

Evaluation of dry etching resistance In the dry etching resistance test, 10 g of PGMEA was dissolved in 2 g of each of the above polymers, and a polymer solution filtered through a 0.2 μm size filter was formed on a Si substrate by spin coating. Films were evaluated under the following conditions.
(1) Etching test with CHF ₃ / CF ₄ -based gas Using a dry etching apparatus TE-8500P manufactured by Tokyo Electron Co., Ltd., the difference in thickness of the polymer film before and after etching was determined.
Etching conditions are as shown below.
Chamber pressure 40.0Pa
RF power 1,000W
Gap 9mm
CHF ₃ gas flow rate 30ml / min
CF ₄ gas flow rate 30ml / min
Ar gas flow rate 100ml / min
60 sec
The results of dry etching resistance are shown in Table 2.

  From the results in Tables 1 and 2, the negative resist material using the polymer compound of the present invention has a sufficient resolution and sensitivity, and has excellent dry etching resistance due to a small film thickness difference after etching. I found out.

Claims (4)

A negative resist material comprising a polymer compound comprising a repeating unit represented by the following general formula (1) and having a weight average molecular weight in the range of 1,000 to 500,000.

(Wherein R ¹ is a hydrogen atom, a fluorine atom, a linear, branched or cyclic alkyl group or a fluorinated alkyl group having 1 to 10 carbon atoms, and X is a methylene group, an oxygen atom or a sulfur atom. M is an integer of 1 to 3, n is 1 or 2, and m + n = 4, R ² is a hydrogen atom or a methyl group, R ³ is a hydrogen atom, a fluorine atom, or a straight chain having 1 to 10 carbon atoms. A chain, branched or cyclic alkyl group or a fluorinated alkyl group , q is an integer of 1 to 3 , q + u = 7 , 0 < (a-1) <1.0 , 0 < (b-2) < 1.0 .) (A) an organic solvent,
(B) The polymer compound according to claim 1 as a base resin,
(C) an acid generator,
(D) A chemically amplified negative resist material comprising a crosslinking agent.   The chemical amplification negative resist composition according to claim 2, further comprising (E) a basic compound and / or a surfactant as an additive.   A step of applying the resist material according to claim 2 or 3 onto a substrate, a step of exposing to high energy rays or an electron beam through a photomask after heat treatment, a heat treatment if necessary, and development And a step of developing using a liquid.