JP4425776B2 - Resist material and pattern forming method using the same - Google Patents

Description

The present invention includes (1) an onium salt that generates a polymer type sulfonic acid as an acid generator, (2) and a high energy ray containing the onium salt, preferably having a wavelength of 300 nm or 200 nm or less, particularly an ArF excimer laser, F _{The present} invention relates to a resist material for ₂ excimer laser, EUV, X-ray, and EB, and (3) a pattern forming method using this resist material.

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

  In photolithography using ArF excimer laser light as a light source, there is a demand for a resist material with high sensitivity that can exhibit sufficient resolution with a small amount of exposure in order to prevent deterioration of a precise and expensive optical system material. As a method for realizing such a high-sensitivity resist material, it is most common to select a highly transparent material at a wavelength of 193 nm as each composition. For example, for the base resin, polyacrylic acid and its derivatives, norbornene-maleic anhydride alternating polymer, polynorbornene and metathesis ring-opening polymer, etc. have been proposed, and some results have been achieved in terms of increasing the transparency of the resin alone. Have gained.

ArF lithography began to be used in part from the device fabrication of the 130 nm node and became the main lithography technology from the 90 nm node device. As the next 45 nm node lithography technology, 157 nm lithography using an F ₂ laser was initially promising, but the quality of the CaF ₂ single crystal used for the projection lens and the optical system by using a hard pellicle must be used. Since development delays due to various problems such as design changes and a decrease in resist etching resistance have been pointed out, ArF immersion lithography has emerged rapidly (see, for example, Non-Patent Document 1).

  The resolution of the projection lens that projects the pattern image on the substrate increases as the numerical aperture (NA) increases. In the immersion lithography, by inserting a liquid having a refractive index higher than that of air between the projection lens and the wafer, the NA of the projection lens can be designed to be 1.0 or more, and high resolution can be achieved. As a liquid, water having a refractive index of 1.4366 has been studied.

  However, there has been a problem that the resist pattern after development collapses due to immersion exposure or becomes a T-top shape. Therefore, there is a need for a pattern forming method that can provide a resist pattern that is well developed in immersion lithography.

Journal of photopolymer Science and Technology Vol. 17, no. 4, p587 (2004)

The present invention has been made in view of such problems, and is a resist material having high sensitivity to high energy rays, particularly ArF excimer laser, F ₂ excimer laser, EUV, X-ray, EB, etc. High resolution resist material containing a polymer type acid generator suitable for immersion lithography because it has high resolution, low line edge roughness, and no dissolution in water, and a pattern forming method using the resist material The purpose is to provide.

The present invention has been made to solve the above problems, that provides at least, a resist material comprising a polymer obtained by polymerizing an onium salt of a sulfonic acid having a polymerizable unsaturated bond.

（式中、Ｒ^１は水素原子、メチル基、Ｒ^２は単結合、メチレン基、フェニレン基、−Ｃ（＝Ｏ）−Ｘ^１−Ｒ^３−である。Ｘ^１は酸素原子またはＮＨ、Ｒ^３は炭素数１〜１２の直鎖状、分岐状、環状のアルキレン基あるいはフェニレン基であり一部又は全ての水素原子がフッ素原子で置換されていても良く、エーテル基、エステル基の一方または両方を１以上有していてもよい。Ｒ^0１、Ｒ^0２、Ｒ^0３は同一又は異種の、炭素数１〜２０の直鎖状、分岐状又は環状のアルキル基でカルボニル基、エステル基、エーテル基、ラクトン環を含んでもよく、または、一部または全ての水素原子がハロゲン原子で置換されていてもよい炭素数６〜２０のアリール基で−S−を含んでもよく、または、一部または全ての水素原子がハロゲン原子で置換されていてもよい炭素数７〜２０のアラルキル基、チオフェニル基であり、Ｒ^0１とＲ^0２、Ｒ^0２とＲ^0３、Ｒ^0１とＲ^0３がそれぞれ結合して環を形成してもよい。Ｒ^0４とＲ^0５は同一又は異種の炭素数６〜２０のアリール基であり、一部または全ての水素原子がハロゲン原子で置換されていてもよく、Ｒ^0４とＲ^0５がそれぞれ結合して環を形成してもよい。） In this case, the polymer is at least, have the preferred of those having a repeating unit represented by the following general formula (1) and / or (2).

(Wherein R ¹ is a hydrogen atom, a methyl group, R ² is a single bond, a methylene group, a phenylene group, or —C (═O) —X ¹ —R ³ —. X ¹ is an oxygen atom or NH, R ³ is a linear, branched, or cyclic alkylene group or phenylene group having 1 to 12 carbon atoms, and some or all of the hydrogen atoms may be substituted with fluorine atoms, and one of an ether group and an ester group or Both of them may have at least 1. R ⁰¹ , R ⁰² and R ⁰³ are the same or different, linear, branched or cyclic alkyl groups having 1 to 20 carbon atoms, such as carbonyl group, ester group, ether Group, a lactone ring may be included, or an aryl group having 6 to 20 carbon atoms in which some or all of the hydrogen atoms may be substituted with halogen atoms may include -S- All hydrogen atoms are replaced by halogen atoms Which may be an aralkyl group having 7 to 20 carbon atoms, a thiophenyl group which may be R ⁰¹ and R ^02, R ⁰² and R ^03, R ⁰¹ and R ⁰³ are respectively bonded to form a ring .R ⁰⁴ and R ⁰⁵ are the same or different aryl groups having 6 to 20 carbon atoms, part or all of the hydrogen atoms may be substituted with halogen atoms, and R ⁰⁴ and R ⁰⁵ are bonded to form a ring. It may be formed.)

Such a resist material containing the polymer according to the present invention has high sensitivity, high resolution, and line edge roughness with respect to high energy rays, particularly ArF excimer laser, F ₂ excimer laser, EUV, X-ray, EB and the like. And a polymer-type acid generator having a sufficient thermal stability and storage stability without being dissolved in water. Therefore, it is suitable as a fine pattern forming material for the production of VLSI using high energy rays, and particularly suitable as a resist material used for ArF immersion lithography.

Further, the present invention, the polymer is further that provides the repeating unit having an acid leaving group, the resist material is one having a repeating unit having adhesive groups.

  With such a resist material, a high-accuracy pattern can be formed using a system in which an acid generated from a polymer-type acid generator at the time of exposure removes an acid leaving group. Since the adhesive group has good substrate adhesion, it can be suitably used as a fine pattern forming material for the production of VLSI.

In this case, the resist material of the present invention, have the preferred to the chemically amplified positive resist composition.

  As described above, the resist material containing the polymer having the repeating unit has a polymer-type acid generator, which removes the acid leaving group by the acid generated during exposure, so that the resist exposed portion is developed into a developing solution. The chemical amplification positive resist material that can obtain a very high-precision pattern can be obtained by converting it so as to be dissolved in the resin.

In this case, the resist material of the present invention, further, an organic solvent, a basic compound, Ru can contain any one or more dissolution inhibitors.

  Thus, by further blending an organic solvent, for example, the coating property of a resist material on a substrate can be improved, and by blending a basic compound, the diffusion rate of acid in the resist film By adding a dissolution inhibitor, the difference in dissolution rate between the exposed and unexposed areas can be further increased, and the resolution can be further improved. it can.

Such a resist material of the present invention includes at least a step of applying the resist material on the substrate, a step of exposing to high energy rays after the heat treatment, and a step of developing using a developer. , Ru can be used as a method for forming a pattern on a semiconductor substrate or a mask substrate.

  Needless to say, development may be performed after the post-exposure heat treatment, and various other processes such as an etching process, a resist removal process, and a cleaning process may be performed.

In this case, in the step of exposing with high energy rays, an ArF excimer laser with a wavelength of 193 nm is used as a light source, a liquid is inserted between the substrate coated with the resist material and the projection lens, and the substrate is exposed through the liquid. Ru can be carried out immersion exposure to.

  The resist material of the present invention has high sensitivity to ArF excimer laser light, high resolution, low line edge roughness, no dissolution in water, sufficient thermal stability, and storage stability. Has an agent. Therefore, if it is used as a pattern forming material in ArF immersion lithography, a highly accurate resist pattern can be obtained without deterioration of the pattern shape.

As described above, according to the present invention, the resist material has high sensitivity to high energy rays, particularly ArF excimer laser, F ₂ excimer laser, EUV, X-ray, EB, etc., and resolution. The pattern shape changes due to underwater exposure (immersion exposure) because it has excellent characteristics, the dimensional difference between isolated and dense patterns is small, the line edge roughness is small, and the generated acid is completely insoluble in water. It is possible to obtain a resist material that is extremely effective for precise microfabrication that is rare.

Hereinafter, although embodiment of this invention is described, this invention is not limited to these.
In recent years, along with higher integration and higher speed of LSIs, far-ultraviolet lithography and vacuum ultraviolet lithography are promising as next-generation microfabrication techniques, while miniaturization of pattern rules is required. Among them, photolithography using ArF excimer laser light as a light source is an indispensable technique for ultrafine processing of 0.13 μm or less.

  Among photolithography using ArF excimer laser light as a light source, ArF immersion lithography is attracting attention. In immersion lithography, high resolution is achieved by performing exposure by filling a liquid between a projection optical system and a substrate. However, this immersion exposure has caused problems that the resist pattern after development collapses or becomes a T-top shape.

  Accordingly, an analysis of immersion water confirmed that the acid generator and the anion produced by the photolysis of the acid generator were dissolved in water. On the other hand, it has been proposed to apply a resist protective film in order to prevent elution of an acid generator and an anion generated by photolysis of the acid generator into water. The development of a resist protective film that can be developed has made the protective film process realistic, but some device manufacturers do not like the increase in the number of process steps for applying a protective film, and there is a need for improvements from resists that do not use a protective film. It has been. Therefore, the development of an acid generator that does not dissolve in water and an anionic species has been desired.

  Therefore, as a result of intensive studies to achieve the above object, the present inventor has obtained a polymer obtained by polymerizing an onium salt of a sulfonic acid having a polymerizable unsaturated bond, particularly the following general formula (1) and / or ( The polymer having the repeating unit exemplified in 2) is highly sensitive to high energy rays, particularly ArF excimer laser light, and has no solubility in water, so that it can cope with ArF immersion exposure and is sufficient. It has thermal stability and storage stability, and furthermore, the resist material containing this polymer has high resolution, can improve line edge roughness and density dependence, and precise microfabrication It has been found that the present invention is extremely effective.

  That is, the resist material according to the present invention is a resist material comprising at least a polymer obtained by polymerizing an onium salt of a sulfonic acid having a polymerizable unsaturated bond.

（式中、Ｒ^１は水素原子、メチル基、Ｒ^２は単結合、メチレン基、フェニレン基、−Ｃ（＝Ｏ）−Ｘ^１−Ｒ^３−である。Ｘ^１は酸素原子またはＮＨ、Ｒ^３は炭素数１〜１２の直鎖状、分岐状、環状のアルキレン基あるいはフェニレン基であり一部又は全ての水素原子がフッ素原子で置換されていても良く、エーテル基、エステル基の一方または両方を１以上有していてもよい。Ｒ^0１、Ｒ^0２、Ｒ^0３は同一又は異種の、炭素数１〜２０の直鎖状、分岐状又は環状のアルキル基でカルボニル基、エステル基、エーテル基、ラクトン環を含んでもよく、または、一部または全ての水素原子がハロゲン原子で置換されていてもよい炭素数６〜２０のアリール基で−S−を含んでもよく、または、一部または全ての水素原子がハロゲン原子で置換されていてもよい炭素数７〜２０のアラルキル基、チオフェニル基であり、Ｒ^0１とＲ^0２、Ｒ^0２とＲ^0３、Ｒ^0１とＲ^0３がそれぞれ結合して環を形成してもよい。Ｒ^0４とＲ^0５は同一又は異種の炭素数６〜２０のアリール基であり、一部または全ての水素原子がハロゲン原子で置換されていてもよく、Ｒ^0４とＲ^0５がそれぞれ結合して環を形成してもよい。） In this case, the polymer preferably has a repeating unit represented by the following general formula (1) and / or (2).

(Wherein R ¹ is a hydrogen atom, a methyl group, R ² is a single bond, a methylene group, a phenylene group, or —C (═O) —X ¹ —R ³ —. X ¹ is an oxygen atom or NH, R ³ is a linear, branched, or cyclic alkylene group or phenylene group having 1 to 12 carbon atoms, and some or all of the hydrogen atoms may be substituted with fluorine atoms, and one of an ether group and an ester group or Both of them may have at least 1. R ⁰¹ , R ⁰² and R ⁰³ are the same or different, linear, branched or cyclic alkyl groups having 1 to 20 carbon atoms, such as carbonyl group, ester group, ether Group, a lactone ring may be included, or an aryl group having 6 to 20 carbon atoms in which some or all of the hydrogen atoms may be substituted with halogen atoms may include -S- All hydrogen atoms are replaced by halogen atoms Which may be an aralkyl group having 7 to 20 carbon atoms, a thiophenyl group which may be R ⁰¹ and R ^02, R ⁰² and R ^03, R ⁰¹ and R ⁰³ are respectively bonded to form a ring .R ⁰⁴ and R ⁰⁵ are the same or different aryl groups having 6 to 20 carbon atoms, part or all of the hydrogen atoms may be substituted with halogen atoms, and R ⁰⁴ and R ⁰⁵ are bonded to form a ring. It may be formed.)

A polymer obtained by polymerizing such an onium salt of a sulfonic acid having a polymerizable unsaturated bond, particularly a polymer having a repeating unit represented by the above general formula (1) and / or (2), particularly has a wavelength of 300 nm. Alternatively, it is highly sensitive to high energy rays of 200 nm or less, particularly ArF excimer laser, F ₂ excimer laser, EUV, X-ray, EB, etc., and such a polymer type acid generator is soluble in water. Therefore, it can cope with immersion exposure (particularly immersion exposure using ArF excimer laser light) and has sufficient thermal stability and storage stability.

  Then, a polymer obtained by polymerizing such an onium salt of a sulfonic acid having a polymerizable unsaturated bond, particularly a polymer having a repeating unit represented by the above general formula (1) and / or (2) is blended. The resist material has high resolution, can improve line edge roughness and density dependence, and is extremely effective for precise microfabrication.

  That is, in the case of a resist material having such a polymer type acid generator, the anion of the acid generator does not dissolve in immersion water, and the resist pattern after development collapses or becomes a T-top shape. Without any fear, a high-accuracy pattern can be obtained by being suitably used for immersion lithography, particularly ArF immersion lithography.

（式中、Ｒ^１は水素原子、メチル基、Ｒ^２は単結合、メチレン基、フェニレン基、−Ｃ（＝Ｏ）−Ｘ^１−Ｒ^３−である。Ｘ^１は酸素原子またはＮＨ、Ｒ^３は炭素数１〜１２の直鎖状、分岐状、環状のアルキレン基あるいはフェニレン基であり一部又は全ての水素原子がフッ素原子で置換されていても良く、エーテル基、エステル基の一方または両方を１以上有していてもよい。Ｒ^0１、Ｒ^0２、Ｒ^0３は同一又は異種の、炭素数１〜２０の直鎖状、分岐状又は環状のアルキル基でカルボニル基、エステル基、エーテル基、ラクトン環を含んでもよく、または、一部または全ての水素原子がハロゲン原子で置換されていてもよい炭素数６〜２０のアリール基で−S−を含んでもよく、または、一部または全ての水素原子がハロゲン原子で置換されていてもよい炭素数７〜２０のアラルキル基、チオフェニル基であり、Ｒ^0１とＲ^0２、Ｒ^0２とＲ^0３、Ｒ^0１とＲ^0３がそれぞれ結合して環を形成してもよい。Ｒ^0４とＲ^0５は同一又は異種の炭素数６〜２０のアリール基であり、一部または全ての水素原子がハロゲン原子で置換されていてもよく、Ｒ^0４とＲ^0５がそれぞれ結合して環を形成してもよい。） Examples of the onium salt of sulfonic acid having a polymerizable double bond necessary for obtaining the polymer according to the present invention as described above include the following general formulas (3) and (4).

(Wherein R ¹ is a hydrogen atom, a methyl group, R ² is a single bond, a methylene group, a phenylene group, or —C (═O) —X ¹ —R ³ —. X ¹ is an oxygen atom or NH, R ³ is a linear, branched, or cyclic alkylene group or phenylene group having 1 to 12 carbon atoms, and some or all of the hydrogen atoms may be substituted with fluorine atoms, and one of an ether group and an ester group or Both of them may have at least 1. R ⁰¹ , R ⁰² and R ⁰³ are the same or different, linear, branched or cyclic alkyl groups having 1 to 20 carbon atoms, such as carbonyl group, ester group, ether Group, a lactone ring may be included, or an aryl group having 6 to 20 carbon atoms in which some or all of the hydrogen atoms may be substituted with halogen atoms may include -S- All hydrogen atoms are replaced by halogen atoms Which may be an aralkyl group having 7 to 20 carbon atoms, a thiophenyl group which may be R ⁰¹ and R ^02, R ⁰² and R ^03, R ⁰¹ and R ⁰³ are respectively bonded to form a ring .R ⁰⁴ and R ⁰⁵ are the same or different aryl groups having 6 to 20 carbon atoms, part or all of the hydrogen atoms may be substituted with halogen atoms, and R ⁰⁴ and R ⁰⁵ are bonded to form a ring. It may be formed.)

R ^{01 to} R ⁰³ are linear or branched alkyl groups having 1 to 20 carbon atoms, particularly 1 to 10 carbon atoms, which are the same or different, such as a carbonyl group (═C═O), an ester group (—COO). -) Or an ether group (-O-) or the like may be contained. R ^{01 to} R ⁰³ are 6 to 20 carbon atoms such as phenyl group, xylyl group, tolyl group and naphthyl group, particularly 6 to 10 carbon atoms such as aryl group, benzyl group, phenylethyl group and phenylpropyl group. The aralkyl group and thiophenyl group of -20, particularly 7-12 are thiophen-2-yl and thiophen-3-yl, and may be a 2-substituted-2-oxoethyl group.

R ⁰⁴ and R ⁰⁵ are the same or different aryl groups having 6 to 20 carbon atoms, particularly 6 to 10 carbon atoms, such as phenyl, xylyl, tolyl and naphthyl groups.

  Specific examples of the sulfonate anion in the general formulas (3) and (4) are as follows.

  The onium salt of the present invention limits the structure of the generated acid, that is, the anion side, but the cation side is not particularly limited.

  Specific examples of the cation side of the compound represented by the general formula (3) or (4) include those having the following structures.

In the above formula, R ^A11 , R ^A12 , R ^A13 , R ^A19 and R ^A20 are a hydrogen atom, a halogen atom, a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms, an alkoxy group, an aryl group, or It is a C1-C20 linear, branched or cyclic ester group, carbonyl group or alkyl group or perfluoroalkyl group containing a lactone ring. R ^A14 , R ^A15 and R ^A16 are linear, branched or cyclic alkyl groups having 1 to 10 carbon atoms and may contain a carbonyl group, an ester group or a lactone ring, and R ^A17 represents a methylene group, R ^A18 is a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms, and R ^A17 and R ^A18 may be bonded to form a ring. a, b, c, d, and e are integers of 0 to 5.

  As a method for synthesizing an onium salt of a sulfonic acid having a polymerizable unsaturated bond, which is necessary for obtaining a polymer according to the present invention, for example, a sulfonate anion having a polymerizable unsaturated bond and a known sulfonium salt are used. A method of synthesizing by exchanging anions such as halides, alkyl sulfonates, and aryl sulfonates.

  The synthesis of sulfonium salt (sulfonium cation) is known and is not particularly limited. However, a condensation reaction of sulfoxide and an aromatic compound with diphosphorus pentoxide / methanesulfonic acid, hydrogen fluoride, or sulfuric acid (JP-A-53). -44533 and 61-212554), a method of reacting a diaryl sulfoxide and an aryl Grignard reagent in the presence of a trialkylsilyl halide (JP 9-323970 A), in the presence of an excess of an aryl Grignard reagent. A method of reacting with thionyl chloride and then trialkylsilyl halide (JP-A-8-311018), a method of reacting phenacyl chloride or chloroacetone with a dialkyl sulfide or a cyclic alkylene sulfide (JP-A-2001-354669, JP-A-2003-321466), hydroxyl-containing aromatic compounds such as naphthol and phenol, and dialkyl sulfi And a method of reacting cyclic alkylene sulfide (Japanese Patent Laid-Open No. 2002-229192).

  Here, as the anion of the sulfonium salt, it is preferable to use an anion having an acid strength of the conjugate acid that is not too high. For example, as anions, chloride ions, bromide ions, halide ions such as iodide ions, methanesulfonate, ethanesulfonate, butanesulfonate, alkylsulfonate such as 10-camphorsulfonate, arylsulfonate such as benzenesulfonate, p-toluenesulfonate, etc. It is preferred to use a sulfonium salt. In this case, anion exchange between a sulfonium salt having a perfluoroalkyl sulfonate such as trifluoromethanesulfonate, nonafluoro-1-butanesulfonate or perfluoro-1-octanesulfonate as an anion and a sulfonate anion having a polymerizable double bond as described above The reaction often does not proceed quantitatively.

  Specifically, a sulfonium salt synthesized by an existing method as described above, in particular, a halide ion, an alkyl sulfonate, a sulfonium salt having an aryl sulfonate as an anion, and a sodium ion of a sulfonic acid having a polymerizable unsaturated bond, In the presence of water and an organic solvent capable of separating metal ion salts such as potassium ion and calcium ion or ammonium salts such as ammonium and triethylammonium salts from water such as dichloromethane, chloroform, ethyl acetate, methyl isobutyl ketone and tetrahydrofuran. And anion exchange reaction can be carried out.

  As described above, an onium salt of a sulfonic acid having a polymerizable unsaturated bond can be obtained. The resist material according to the present invention may contain a polymer obtained by polymerizing only an onium salt of a sulfonic acid having such a polymerizable unsaturated bond, and further, a sulfonic acid having such a polymerizable unsaturated bond. A polymer obtained by copolymerization of an onium salt with a copolymerizable monomer may be contained.

  For example, in the resist material of the present invention, the base resin is a polymer obtained by polymerizing an onium salt of a sulfonic acid having a polymerizable unsaturated bond, and further includes a repeating unit having an acid leaving group and an adhesive group. A polymer having a repeating unit having is preferably used. As the repeating unit having an acid leaving group and the repeating unit having an adhesive group, for example, polyacrylic acid and polymethacrylic acid derivatives are preferably used. In the resist material of the present invention, in addition to these, conventional polymers in which an onium salt of a sulfonic acid having a polymerizable unsaturated bond is not copolymerized, specifically, polyacrylic acid and derivatives thereof, cycloolefin derivatives Selected from maleic anhydride alternating polymer and poly (acrylic acid) or a ternary or quaternary copolymer with polyacrylic acid or a derivative thereof, cycloolefin derivative-α trifluoromethyl acrylic copolymer, polynorbornene, and metathesis ring-opening polymer. One kind or two or more kinds of high molecular polymers may be blended.

  The method for synthesizing the polymer according to the present invention is not particularly limited. For example, in an organic solvent, the above-obtained onium salt of a sulfonic acid having a polymerizable unsaturated bond, or in addition, copolymerization with these is possible. It can be synthesized by adding a radical initiator to this monomer and subjecting it to heat polymerization. Examples of the organic solvent used in the polymerization include toluene, benzene, tetrahydrofuran, diethyl ether, dioxane and the like. Moreover, as a polymerization initiator, 2,2'-azobisisobutyronitrile, 2,2'-azobis (2,4-dimethylvaleronitrile), dimethyl 2,2-azobis (2-methylpropionate) Benzoyl peroxide, lauroyl peroxide, etc., and preferably polymerized by heating to 50 to 80 ° C. The reaction time is preferably 2 to 100 hours, more preferably 5 to 20 hours.

  In the polymer thus obtained, the repeating units of the onium salts of the above formulas (1) and (2) are 100 mol% or less, preferably 80 mol% or less, more preferably 60 mol% of all repeating units. It is as follows.

  In this case, when the resist material is prepared in a chemically amplified positive type, the base resin is insoluble or hardly soluble in a developer (usually an alkali developer) and is soluble in the developer by an acid. used. For this reason, as the base resin, one having an acid labile group (acid leaving group) that can be cleaved by an acid is used.

  Specifically, for example, those obtained by substituting the hydrogen atom of the carboxyl group of polyacrylic acid or polymethacrylic acid with an acid labile group are used. The acid labile group to be used is variously selected and is not particularly limited, but may be the same or different, and examples thereof include those represented by groups substituted by the following formulas (A-1) to (A-3).

In the formula (A-1), R ³⁰ is a tertiary alkyl group having 4 to 20 carbon atoms, preferably 4 to 15 carbon atoms, each alkyl group is a trialkylsilyl group having 1 to 6 carbon atoms, and 4 to 20 carbon atoms. An oxoalkyl group, a group represented by the above general formula (A-3), and the like. Specific examples of the tertiary alkyl group include a tert-butyl group, a tert-amyl group, a 1,1-diethylpropyl group, 1- Ethylcyclopentyl group, 1-butylcyclopentyl group, 1-ethylcyclohexyl group, 1-butylcyclohexyl group, 1-ethyl-2-cyclopentenyl group, 1-ethyl-2-cyclohexenyl group, 2-methyl-2-adamantyl group Specific examples of the trialkylsilyl group include trimethylsilyl group, triethylsilyl group, dimethyl-tert-butylsilyl group, and the like. , Specifically oxoalkyl group, 3-oxo-cyclohexyl group, 4-methyl-2-oxooxan-4-yl group, and 5-methyl-2-oxooxolan-5-yl group. a1 is an integer of 0-6.

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

  Furthermore, the substituent shown by following formula (A-1) -1-(A-1) -8 can also be mentioned.

Here, R ³⁷ is the same or different from each other, a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms, or an aryl group having 6 to 20 carbon atoms, R ³⁸ is a hydrogen atom, or 1 to 1 carbon atoms. 10 linear, branched or cyclic alkyl groups.

R ³⁹ is a linear, branched or cyclic alkyl group having 2 to 10 carbon atoms that is the same or different from each other, or an aryl group having 6 to 20 carbon atoms.
Moreover, a1 is an integer of 0-6.

In the above formula (A-2), R ³¹ and R ³² represent a hydrogen atom or a linear, branched or cyclic alkyl group having 1 to 18 carbon atoms, preferably 1 to 10 carbon atoms, specifically a methyl group. , Ethyl group, propyl group, isopropyl group, n-butyl group, sec-butyl group, tert-butyl group, cyclopentyl group, cyclohexyl group, 2-ethylhexyl group, n-octyl group and the like. R ³³ represents a monovalent hydrocarbon group which may have a hetero atom such as an oxygen atom having 1 to 18 carbon atoms, preferably 1 to 10 carbon atoms, a linear, branched or cyclic alkyl group, Examples include those in which a part of hydrogen atoms are substituted with a hydroxyl group, an alkoxy group, an oxo group, an amino group, an alkylamino group, and the like, and specific examples include the following substituted alkyl groups.

R ³¹ and R ³² , R ³¹ and R ³³ , and R ³² and R ³³ may combine to form a ring together with the carbon atoms to which they are bonded, and in the case of forming a ring, R ³¹ , R ³² , R ³³ represents a linear or branched alkylene group having 1 to 18 carbon atoms, preferably 1 to 10 carbon atoms, and preferably the ring has 3 to 10 carbon atoms, particularly 4 to 10 carbon atoms.

  Of the acid labile groups represented by the above formula (A-2), examples of the linear or branched groups include those of the following formulas (A-2) -1 to (A-2) -35. be able to.

  Among the acid labile groups represented by the above formula (A-2), the cyclic ones include tetrahydrofuran-2-yl group, 2-methyltetrahydrofuran-2-yl group, tetrahydropyran-2-yl group, 2- Examples thereof include a methyltetrahydropyran-2-yl group.

  Moreover, it may be intermolecularly or intramolecularly crosslinked by an acid labile group represented by the general formula (A-2a) or (A-2b).

In the formula, R ⁴⁰ and R ⁴¹ represent a hydrogen atom or a linear, branched or cyclic alkyl group having 1 to 8 carbon atoms. Alternatively, R ⁴⁰ and R ⁴¹ may be bonded to form a ring together with the carbon atom to which they are bonded. When forming a ring, R ⁴⁰ and R ⁴¹ are linear or branched having 1 to 8 carbon atoms. -Like alkylene group. R ⁴² is a straight-chain having 1 to 10 carbon atoms, branched or cyclic alkylene group, b1, d1 is 0 or 1 to 10, preferably 0 or an integer of 1 to 5, c1 is an integer of 1-7 . A represents a (c1 + 1) -valent aliphatic or alicyclic saturated hydrocarbon group having 1 to 50 carbon atoms, an aromatic hydrocarbon group or a heterocyclic group, and these groups may intervene a hetero atom, Alternatively, a part of hydrogen atoms bonded to the carbon atom may be substituted with a hydroxyl group, a carboxyl group, a carbonyl group, or a fluorine atom. B represents —CO—O—, —NHCO—O— or —NHCONH—.

  In this case, preferably, A is a divalent to tetravalent C1-20 linear, branched or cyclic alkylene group, an alkyltriyl group, an alkyltetrayl group, or an arylene group having 6 to 30 carbon atoms. In these groups, a hetero atom may be interposed, and a part of hydrogen atoms bonded to the carbon atom may be substituted with a hydroxyl group, a carboxyl group, an acyl group, or a halogen atom. C1 is preferably an integer of 1 to 3.

  Specific examples of the crosslinked acetal groups represented by the general formulas (A-2a) and (A-2b) include those represented by the following formulas (A-2) -36 to (A-2) -43.

Next, in the above formula (A-3), R ³⁴ , R ³⁵ and R ³⁶ are monovalent hydrocarbon groups such as linear, branched or cyclic alkyl groups having 1 to 20 carbon atoms, oxygen, sulfur May contain hetero atoms such as nitrogen, fluorine, etc., and R ³⁴ and R ³⁵ , R ³⁴ and R ³⁶ , R ³⁵ and R ³⁶ are bonded to each other, and together with the carbon atoms to which they are bonded, A ring may be formed.

  As the tertiary alkyl group represented by the above formula (A-3), a tert-butyl group, a triethylcarbyl group, a 1-ethylnorbornyl group, a 1-methylcyclohexyl group, a 1-ethylcyclopentyl group, 2- (2 -Methyl) adamantyl group, 2- (2-ethyl) adamantyl group, tert-amyl group and the like.

  Specific examples of the tertiary alkyl group include the following formulas (A-3) -1 to (A-3) -18.

In formulas (A-3) -1 to (A-3) -18, R ⁴³ is the same or different, linear, branched or cyclic alkyl group having 1 to 8 carbon atoms, or having 6 to 20 carbon atoms. An aryl group such as a phenyl group is shown. R ⁴⁴ and R ⁴⁶ represent a hydrogen atom or a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms. R ⁴⁵ represents an aryl group such as a phenyl group having 6 to 20 carbon atoms.

Furthermore, as shown in the following formulas (A-3) -19 and (A-3) -20, a divalent or higher valent alkylene group and an arylene group, R ^47, are contained, and the polymer molecule or between molecules is crosslinked. May be.

In formulas (A-3) -19 and (A-3) -20, R ⁴³ is the same as described above, and R ⁴⁷ is a linear, branched or cyclic alkylene group having 1 to 20 carbon atoms, a phenylene group, or the like. And may contain a hetero atom such as an oxygen atom, a sulfur atom or a nitrogen atom. e1 is an integer of 1 to 3.

  Here, the (A-3) -6 to (A-3) -9 have endo and exo stereoisomers, and the exo isomer has a high degree of stability in the intermediate of the elimination reaction, so that it can be eliminated. It is characterized by a high reaction rate and a low desorption activation energy. A fast desorption reaction rate means a high deprotection contrast and a high dissolution contrast, and a low activation energy means a dimensional change when the post-exposure bake (PEB) temperature is changed ( (PEB dependency) is small. The acid labile group of the exo form is exemplified below.

Moreover, R ^{< 30 >} , R ^{< 33>} , R ^<36 > in formula (A-1), (A-2), (A-3) is a phenyl group, p-methylphenyl group, p-ethylphenyl group, p-methoxy. An unsubstituted or substituted aryl group such as an alkoxy-substituted phenyl group such as a phenyl group, an aralkyl group such as a benzyl group or a phenethyl group, or a hydrogen atom having an oxygen atom in these groups or bonded to a carbon atom is substituted with a hydroxyl group Or an alkyl group represented by the following formula in which two hydrogen atoms are substituted with an oxygen atom to form a carbonyl group, or an oxoalkyl group.

  Furthermore, the acid labile group which has an oxygen atom as a tertiary alkyl group can be mentioned. Specifically, it can be exemplified below.

上記式中、Ｍｅはメチル基を、Ａｃはアセチル基を示す。

In the above formula, Me represents a methyl group, and Ac represents an acetyl group.

  Next, examples of the monomer having an adhesive group that can be copolymerized with the onium salt of a sulfonic acid having a polymerizable unsaturated bond include a hydroxy group, a carboxyl group, an ether group, a lactone ring, and a sulfonamide. Specific examples of methacrylic acid or acrylic acid derivatives are given below.

In the formula, R ¹⁵ is a hydrogen atom or a methyl group.

  Furthermore, the resist material according to the present invention may have a repeating unit having an adhesive group obtained by polymerizing a norbornene derivative and maleic anhydride. Adhesive groups obtained by polymerizing norbornene derivatives are exemplified below.

  In the above formula, n is 0 or 1.

  Examples of maleic anhydride or maleimides copolymerized with norbornenes include the following.

  Moreover, the base resin of the resist material according to the present invention may be a polymer structure containing silicon atoms. In this case, examples of the repeating unit containing a silicon atom include those represented by the following formulas (9) -1 to (9) -6. The mass average molecular weight is preferably in the range of 3,000 to 100,000.

In the above formula, R ²⁰ is a hydrogen atom, a methyl group, a fluorine atom, or a trifluoromethyl group, R ²¹ is a single bond or a divalent hydrocarbon group such as an alkylene group having 1 to 10 carbon atoms, R ²² R ²³ and R ²⁴ are the same or different hydrogen atoms, alkyl groups having 1 to 10 carbon atoms, aryl groups, alkyl groups containing fluorine atoms, hydrocarbon groups containing silicon atoms, or groups containing siloxane bonds. , R ²² and R ²³ , R ²³ and R ^24, or R ²² and R ²⁴ may be bonded to each other to form a ring. r is 0 or 1;

Furthermore, when the formula (9) -5 is illustrated more specifically, those represented by the following formulas (10) -1 to (10) -20 are exemplified, and in the formulas (9) -1 to (9) -4: -R ²¹ -SiR ²² R ²³ R ²⁴ can be exemplified by the same as those in formula (10) -1 to (10) -20.

  Furthermore, a repeating structure containing fluorine atoms can be used as the base resin of the resist material according to the present invention. Fluorine atom-containing repeating units can be represented by, for example, the following formulas (11) -1 to (11) -8.

Among the above general formula (11) -1~ (11) -8 , R 30, R 31, R 32 may be the same or different hydrogen atom, a fluorine atom, a methyl group, or trifluoromethyl group, R ³⁰ ~ R ³² contains at least one fluorine atom. R ³³ , R ³⁷ , R ³⁹ , R ⁴² and R ⁴⁴ are the same or different hydrogen atoms, acid labile groups, or adhesive groups. R ³⁴ , R ³⁵ , and R ³⁶ are the same or different hydrogen atom, fluorine atom, methyl group, or trifluoromethyl group, and contain at least one fluorine atom among R ^{34 to} R ³⁶ . R ³⁸ and R ⁴³ are each a hydrogen atom, a fluorine atom, a methyl group, or a trifluoromethyl group, and R ⁴⁰ and R ⁴¹ are a hydrogen atom, a fluorine atom, an alkyl group having 1 to 4 carbon atoms, or fluorinated. It is an alkyl group, and R ⁴⁰ and R ⁴¹ contain at least one fluorine atom. R ⁴⁵ , R ⁴⁶ , R ⁴⁷ and R ⁴⁸ are a hydrogen atom, a fluorine atom, an alkyl group having 1 to 4 carbon atoms, or a fluorinated alkyl group, and R ⁴⁵ , R ⁴⁶ , R ⁴⁷ and R ⁴⁸ are It contains at least one fluorine atom. R ⁴⁹ , R ⁵⁰ , R ⁵¹ , and R ⁵² are a hydrogen atom, a fluorine atom, a methyl group, or a trifluoromethyl group, and contain at least one fluorine atom from R ^{49 to} R ⁵² . In the formula, R ⁵³ and R ⁵⁴ are a hydrogen atom or an acid labile group, and 0 <l <1, 0 <m <1. r is 0 or 1;

  Although the resist material of the present invention proposes a polymer type acid generator, a conventional acid generator may be further added.

As an acid generator used in the resist material of 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、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、又は炭素数６〜２０のアリール基、炭素数７〜１２のアラルキル基又は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^-は前記一般式（１）〜（４）中のもの以外の非求核性対向イオンを表す。）

(In the formula, R ^101a , R ^101b and R ^101c are each a linear, branched or cyclic alkyl group, alkenyl group, oxoalkyl group, oxoalkenyl group having 6 to 20 carbon atoms, or 6 to 20 carbon atoms. An aryl group, an aralkyl group having 7 to 12 carbon atoms, or an aryloxoalkyl group, and a part or all of hydrogen atoms of these groups may be substituted by 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, K ⁻ in the general formulas (1) to (4). Represents non-nucleophilic counter ions other than those of

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 ions and bromide ions, triflate, fluoroalkyl sulfonates such as 1,1,1-trifluoroethanesulfonate, nonafluorobutanesulfonate, tosylate, and benzenesulfonate. And aryl sulfonates such as 4-fluorobenzene sulfonate and 1,2,3,4,5-pentafluorobenzene sulfonate, and alkyl sulfonates such as mesylate and butane sulfonate.

（式中、Ｒ^102a、Ｒ^102bはそれぞれ炭素数１〜８の直鎖状、分岐状、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、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。）

(Wherein 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. Examples of K ⁻ are the same as those 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、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。）

(Wherein 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 numbers 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 include a trifluoromethyl group, a 1,1,1-trifluoroethyl group, a 1,1,1-trichloroethyl group, and a nonafluorobutyl group. As the aryl group, an alkoxyphenyl group such as a phenyl group, p-methoxyphenyl group, m-methoxyphenyl group, o-methoxyphenyl group, ethoxyphenyl group, p-tert-butoxyphenyl group, m-tert-butoxyphenyl group, Examples thereof include alkylphenyl groups such as 2-methylphenyl group, 3-methylphenyl group, 4-methylphenyl group, ethylphenyl group, 4-tert-butylphenyl group, 4-butylphenyl group, and dimethylphenyl group. Examples of the halogenated aryl group include a fluorophenyl group, a chlorophenyl group, and 1,2,3,4,5-pentafluorophenyl group. Examples of the aralkyl group 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、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の直鎖状又は分岐状のアルキレン基を示す。）

(Wherein R ¹⁰⁷ , R ¹⁰⁸ , and R ¹⁰⁹ 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 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. Represents a linear or branched alkylene group.)

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 and the like are exemplified, and as the alkylene group, methylene group, 1,2-ethylene group, 1,3-propylene group, 1 1,4-butylene group, 1-phenyl-1,2-ethylene group, norbornane-2,3-diyl group, etc., as alkenylene group, 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 include onium salts such as diphenyliodonium trifluoromethanesulfonate, trifluoromethanesulfonate (p-tert-butoxyphenyl) phenyliodonium, diphenyliodonium p-toluenesulfonate, and p-toluenesulfone. Acid (p-tert-butoxyphenyl) phenyliodonium, triphenylsulfonium trifluoromethanesulfonate, trifluoromethanesulfonic acid (p-tert-butoxyphenyl) diphenylsulfonium, bis (p-tert-butoxyphenyl) phenylsulfonium trifluoromethanesulfonate , Tris (p-tert-butoxyphenyl) sulfonium trifluoromethanesulfonate, triphenylsulfonium p-toluenesulfonate p-toluenesulfonic acid (p-tert-butoxyphenyl) diphenylsulfonium, p-toluenesulfonic acid bis (p-tert-butoxyphenyl) phenylsulfonium, p-toluenesulfonic acid tris (p-tert-butoxyphenyl) sulfonium, nona Triphenylsulfonium fluorobutanesulfonate, triphenylsulfonium butanesulfonate, trimethylsulfonium trifluoromethanesulfonate, trimethylsulfonium p-toluenesulfonate, cyclohexylmethyl (2-oxocyclohexyl) sulfonium trifluoromethanesulfonate, cyclohexyl p-toluenesulfonate Methyl (2-oxocyclohexyl) sulfonium, dimethylphenylsulfonium trifluoromethanesulfonate, -Toluenesulfonic acid dimethylphenylsulfonium, trifluoromethanesulfonic acid dicyclohexylphenylsulfonium, p-toluenesulfonic acid dicyclohexylphenylsulfonium, trifluoromethanesulfonic acid trinaphthylsulfonium, trifluoromethanesulfonic acid (2-norbornyl) methyl (2-oxocyclohexyl) sulfonium And onium salts such as ethylenebis [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-ketosulfone derivatives include β-ketosulfone 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, 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 , 1,2'-naphthyl carbonyl methyl tetrahydrothiophenium triflate onium salts such as,
Bis (benzenesulfonyl) diazomethane, bis (p-toluenesulfonyl) diazomethane, bis (cyclohexylsulfonyl) diazomethane, bis (n-butylsulfonyl) diazomethane, bis (isobutylsulfonyl) diazomethane, bis (sec-butylsulfonyl) diazomethane, bis ( diazomethane derivatives such as n-propylsulfonyl) diazomethane, bis (isopropylsulfonyl) diazomethane, bis (tert-butylsulfonyl) diazomethane,
Glyoxime derivatives such as bis-O- (p-toluenesulfonyl) -α-dimethylglyoxime, bis-O- (n-butanesulfonyl) -α-dimethylglyoxime,
Bissulfone derivatives such as bisnaphthylsulfonylmethane,
N-hydroxysuccinimide methanesulfonic acid ester, N-hydroxysuccinimide trifluoromethanesulfonic acid ester, N-hydroxysuccinimide 1-propanesulfonic acid ester, N-hydroxysuccinimide 2-propanesulfonic acid ester, N-hydroxysuccinimide 1-pentanesulfonic acid Preferred examples include sulfonate derivatives of N-hydroxyimide compounds such as esters, N-hydroxysuccinimide p-toluenesulfonate, N-hydroxynaphthalimide methanesulfonate, and N-hydroxynaphthalimide benzenesulfonate.

  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 amount of the acid generator added is such that the total amount of the acid generator that generates a polymer type acid, particularly the onium salt of the above formula (1) and / or (2), is the polymer type acid generator. The amount is preferably 0 to 15 parts, more preferably 0 to 8 parts, relative to 100 parts of base resin (parts by mass, the same applies hereinafter). If it is 15 parts or less, there is a low possibility that the transparency is lowered, the resolution performance of the resist material is lowered, and the amount of elution of the acid generator into water is increased in immersion exposure.

  The organic solvent that can be used in the resist material according to the present invention is not particularly limited as long as it can dissolve a base resin, an acid generator, and other additives. Examples of such an organic solvent include ketones such as cyclohexanone and methyl-2-amyl ketone; 3-methoxybutanol, 3-methyl-3-methoxybutanol, 1-methoxy-2-propanol, 1-ethoxy-2- Alcohols such as propanol; ethers such as propylene glycol monomethyl ether, ethylene glycol monomethyl ether, propylene glycol monoethyl ether, ethylene glycol monoethyl ether, propylene glycol dimethyl ether, diethylene glycol dimethyl ether; propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether Acetate, ethyl lactate, ethyl pyruvate, butyl acetate, methyl 3-methoxypropionate, 3-ethoxypropyl Examples include esters such as ethyl pionate, tert-butyl acetate, tert-butyl propionate, propylene glycol mono tert-butyl ether acetate, and the like. It is not a thing.

  In the resist material of the present invention, among these organic solvents, diethylene glycol dimethyl ether and 1-ethoxy-2-propanol, which have the highest solubility of the base polymer and acid generator in the resist component, as well as propylene glycol, which is a safety solvent, are used. Monomethyl ether acetate and mixed solvents thereof are preferably used.

  The blending amount of the organic solvent is preferably 200 to 1,000 parts, particularly preferably 400 to 800 parts, with respect to 100 parts of the base resin.

  A dissolution inhibitor can be further added to the resist material of the present invention. As a dissolution inhibitor, an average molecular weight of 100 to 1,000, preferably 150 to 800, and a compound having two or more phenolic hydroxyl groups in the molecule, all of the hydrogen atoms of the phenolic hydroxyl groups are formed by acid labile groups. As a compound substituted at an average rate of 0 to 100 mol% or a compound having an average of 80 to 100 mol% of hydrogen atoms of the carboxyl group in the molecule having a carboxy group in the molecule by an acid labile group as a whole preferable.

  The substitution rate of the hydrogen atom of the phenolic hydroxyl group or carboxy group by an acid labile group is on average 0 mol% or more, preferably 30 mol% or more of the entire phenolic hydroxyl group or carboxy group, and the upper limit is 100 mol. %, More preferably 80 mol%.

  In this case, as the compound having two or more phenolic hydroxyl groups or the compound having a carboxy group, those represented by the following formulas (D1) to (D14) are preferable.

（但し、上記式中Ｒ^２０１、Ｒ^２０２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。Ｒ^２０３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−(Ｒ^２０７)_ｈＣＯＯＨを示す。Ｒ^２０４は−（ＣＨ_２）_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。Ｒ^２０５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。Ｒ^２０６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、アルケニル基又は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。Ｒ^２０７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。Ｒ^２０８は水素原子又は水酸基を示す。ｊは０〜５の整数である。ｕ、ｈは０又は１である。ｓ、ｔ、ｓ´、ｔ´、ｓ´´、ｔ´´はそれぞれｓ＋ｔ＝８、ｓ´＋ｔ´＝５、ｓ´´＋ｔ´´＝４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。αは式（Ｄ８）、（Ｄ９）の化合物の分子量を１００〜１，０００とする数である。）

(In the above formulae, R ²⁰¹ and R ²⁰² each represent a hydrogen atom, or a linear or branched alkyl group or alkenyl group having 1 to 8 carbon atoms. R ²⁰³ represents a hydrogen atom or 1 to 8 carbon atoms. A linear or branched alkyl group or alkenyl group, or — (R ²⁰⁷ ) _h COOH, wherein R ²⁰⁴ is — (CH ₂ ) _i — (i = 2 to 10), arylene having 6 to 10 carbon atoms; A group, a carbonyl group, a sulfonyl group, an oxygen atom or a sulfur atom, and R ²⁰⁵ represents an alkylene group having 1 to 10 carbon atoms, an arylene group having 6 to 10 carbon atoms, a carbonyl group, a sulfonyl group, an oxygen atom or a sulfur atom. .R ²⁰⁶ is hydrogen, a straight or branched alkyl group having 1 to 8 carbon atoms, .R ²⁰⁷ carbon number of an alkenyl group or is a hydroxyl-substituted phenyl or naphthyl group ^{.R 208} to a straight or branched alkylene group of 10 is .j represents a hydrogen atom or a hydroxyl group is an integer of 0 to 5 .u, h is 0 or 1 .s, t, s ′, T ′, s ″, t ″ satisfy s + t = 8, s ′ + t ′ = 5, s ″ + t ″ = 4, respectively, and each phenyl skeleton has at least one hydroxyl group. (Alpha is a number which makes the molecular weight of the compound of Formula (D8) and (D9) 100-1,000.).

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

  The acid labile group of the dissolution inhibitor can be variously used. Specifically, the groups represented by the following general formulas (L1) to (L5), a tertiary alkyl group having 4 to 20 carbon atoms, and each alkyl Examples thereof include a trialkylsilyl group having 1 to 6 carbon atoms and an oxoalkyl group having 4 to 20 carbon atoms.

（上記式中、Ｒ^L01、Ｒ^L02は水素原子又は炭素数１〜１８の直鎖状、分岐状又は環状のアルキル基を示す。Ｒ^L03は炭素数１〜１８の酸素原子等のヘテロ原子を有してもよい１価の炭化水素基を示す。Ｒ^L01とＲ^L02、Ｒ^L01とＲ^L03、Ｒ^L02とＲ^L03とは環を形成してもよく、環を形成する場合にはＲ^L01、Ｒ^L02、Ｒ^L03はそれぞれ炭素数１〜１８の直鎖状又は分岐状のアルキレン基を示す。Ｒ^L04は炭素数４〜２０の三級アルキル基、各アルキル基がそれぞれ炭素数１〜６のトリアルキルシリル基、炭素数４〜２０のオキソアルキル基又は上記一般式（Ｌ１）で示される基を示す。Ｒ^L05は炭素数１〜８のヘテロ原子を含んでもよい１価の炭化水素基又は炭素数６〜２０の置換されていてもよいアリール基を示す。Ｒ^L06は炭素数１〜８のヘテロ原子を含んでもよい１価の炭化水素基又は炭素数６〜２０の置換されていてもよいアリール基を示す。Ｒ^L07〜Ｒ^L16はそれぞれ独立に水素原子又は炭素数１〜１５のヘテロ原子を含んでもよい１価の炭化水素基を示す。Ｒ^L07〜Ｒ^L16は互いに環を形成していてもよく、その場合には炭素数１〜１５のヘテロ原子を含んでもよい２価の炭化水素基を示す。また、Ｒ^L07〜Ｒ^L16は隣接する炭素に結合するもの同士で何も介さずに結合し、二重結合を形成してもよい。ａは０〜６の整数である。ｍは０又は１、ｎは０、１、２、３のいずれかであり、２ｍ＋ｎ＝２又は３を満足する数である。）

(In the above formula, R ^L01 and R ^L02 represent a hydrogen atom or a linear, branched or cyclic alkyl group having 1 to 18 carbon atoms. R ^L03 represents a hetero atom such as an oxygen atom having 1 to 18 carbon atoms. .R ^L01 showing a monovalent hydrocarbon group which may have and R ^L02, R ^L01 and R ^L03, R ^L02 and R ^L03 may form a ring, when they form a ring R ^L01 , R ^L02 and R ^L03 each represent a linear or branched alkylene group having 1 to 18 carbon atoms, R ^L04 is a tertiary alkyl group having 4 to 20 carbon atoms, and each alkyl group has 1 to 6 carbon atoms. A trialkylsilyl group, a oxoalkyl group having 4 to 20 carbon atoms or a group represented by the above general formula (L1), wherein R ^L05 is a monovalent hydrocarbon group which may contain a heteroatom having 1 to 8 carbon atoms. or an optionally substituted aryl group having 6 to 20 carbon atoms .R ^L06 hetero atoms having 1 to 8 carbon atoms Also include which may contain 1 be monovalent hydrocarbon radicals or substituted .R represents an aryl group optionally ^L07 to R ^L16 are each independently a hydrogen atom or a hetero atom number of 1 to 15 carbon atoms of 6 to 20 carbon atoms R ^{L07 to} R ^L16 each represents a divalent hydrocarbon group that may form a ring with each other and may contain a hetero atom having 1 to 15 carbon atoms. R ^{L07 to} R ^L16 may be bonded to each other adjacent to each other to form a double bond, where a is an integer of 0 to 6. m is 0 or 1 and n are any one of 0, 1, 2, and 3, and 2m + n = 2 or 3 is satisfied.)

  The amount of the dissolution inhibitor is 0 to 50 parts, preferably 5 to 50 parts, and more preferably 10 to 30 parts, based on 100 parts of the base resin, and can be used alone or in combination of two or more.

  If the blending amount is 5 parts or more, the resolution is further improved, and if it is 50 parts or less, there is little fear that the film thickness of the pattern is reduced or the resolution is lowered.

  The dissolution inhibitor as described above is synthesized by introducing an acid labile group into a compound having a phenolic hydroxyl group or a carboxy group using an organic chemical formulation.

Further, the resist material of the present invention can be blended with a basic compound for improving storage stability.
As the basic compound, a compound capable of suppressing the diffusion rate when the acid generated from the acid generator diffuses into the resist film is suitable. By adding a basic compound, the acid diffusion rate in the resist film is suppressed and resolution is improved, sensitivity change after exposure is suppressed, and 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 (for example, nicotinic acid, alanine, arginine, aspartic acid, glutamic acid, glycine, histidine, isoleucine, glycylleucine, leucine, methionine. , Phenylalanine, threonine, lysine, 3-aminopyrazine-2-carboxylic acid, methoxyalanine) and the like, and examples of the nitrogen-containing compound having a sulfonyl group include 3-pyridinesulfonic acid, pyridinium p-toluenesulfonate, and the like. Nitrogen-containing compounds having a hydroxyl group, nitrogen-containing compounds having a hydroxyphenyl group, and alcoholic nitrogen-containing compounds include 2-hydroxypyridine, aminocresol, 2,4-quinolinediol, and 3-indolemethanol. Drate, monoethanolamine, diethanolamine, triethanolamine, N-ethyldiethanolamine, N, N-diethylethanolamine, triisopropanolamine, 2,2'-iminodiethanol, 2-aminoethanol, 3-amino-1-propanol 4-amino-1-butanol, 4- (2-hydroxyethyl) morpholine, 2- (2-hydroxyethyl) pyridine, 1- (2-hydroxyethyl) piperazine, 1- [2- (2-hydroxyethoxy) Ethyl] piperazine, piperidineethanol, 1- (2-hydroxyethyl) pyrrolidine, 1- (2-hydroxyethyl) -2-pyrrolidinone, 3-piperidino-1,2-propanediol, 3-pyrrolidino-1,2-propane Diol, 8-hydroxyuroli , 3-cuincridinol, 3-tropanol, 1-methyl-2-pyrrolidineethanol, 1-aziridineethanol, N- (2-hydroxyethyl) phthalimide, N- (2-hydroxyethyl) isonicotinamide, etc. Illustrated.

  Examples of amide derivatives include formamide, N-methylformamide, N, N-dimethylformamide, acetamide, N-methylacetamide, N, N-dimethylacetamide, propionamide, benzamide and the like.

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

Furthermore, 1 type, or 2 or more types chosen from the basic compound shown by the following general formula (B) -1 can also be added.
N (X) _n (Y) _3-n (B) -1
(In the above formula, n = 1, 2, 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 Xs are bonded to form a ring. You may do it.)

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 or branched structures having 1 to 20 carbon atoms. And 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, a linear or branched alkylene group having 1 to 4 carbon atoms, R ³⁰⁶ is a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms, a hydroxy group, One or a plurality of ether, ester groups and lactone rings may be contained.

Specific examples of the compound represented by formula (B) -1 are given below.
Tris (2-methoxymethoxyethyl) amine, tris {2- (2-methoxyethoxy) ethyl} amine, tris {2- (2-methoxyethoxymethoxy) ethyl} amine, tris {2- (1-methoxyethoxy) ethyl } Amine, Tris {2- (1-ethoxyethoxy) ethyl} amine, Tris {2- (1-ethoxypropoxy) ethyl} amine, Tris [2- {2- (2-hydroxyethoxy) ethoxy} ethyl] amine, 4,7,13,16,21,24-hexaoxa-1,10-diazabicyclo [8.8.8] hexacosane, 4,7,13,18-tetraoxa-1,10-diazabicyclo [8.5.5] Eicosane, 1,4,10,13-tetraoxa-7,16-diazabicyclooctadecane, 1-aza-12-crown-4 1-aza-15-crown-5, 1-aza-18-crown-6, tris (2-formyloxyethyl) amine, tris (2-formyloxyethyl) amine, tris (2-acetoxyethyl) amine, Tris (2-propionyloxyethyl) amine, tris (2-butyryloxyethyl) amine, tris (2-isobutyryloxyethyl) amine, tris (2-valeryloxyethyl) amine, tris (2-pivalo) Yloxyethyl) 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- (mes Xycarbonylmethyl) oxyethyl] amine, tris [2- (tert-butoxycarbonylmethyloxy) ethyl] amine, tris [2- (cyclohexyloxycarbonylmethyloxy) ethyl] amine, tris (2-methoxycarbonylethyl) amine, tris (2-ethoxycarbonylethyl) amine, N, N-bis (2-hydroxyethyl) 2- (methoxycarbonyl) ethylamine, N, N-bis (2-acetoxyethyl) 2- (methoxycarbonyl) ethylamine, N, N -Bis (2-hydroxyethyl) 2- (ethoxycarbonyl) ethylamine, N, N-bis (2-acetoxyethyl) 2- (ethoxycarbonyl) ethylamine, N, N-bis (2-hydroxyethyl) 2- (2 -Methoxyethoxycarbonyl) ethyl Amine, N, N-bis (2-acetoxyethyl) 2- (2-methoxyethoxycarbonyl) ethylamine, N, N-bis (2-hydroxyethyl) 2- (2-hydroxyethoxycarbonyl) ethylamine, N, N- Bis (2-acetoxyethyl) 2- (2-acetoxyethoxycarbonyl) ethylamine, N, N-bis (2-hydroxyethyl) 2-[(methoxycarbonyl) methoxycarbonyl] ethylamine, N, N-bis (2-acetoxy) Ethyl) 2-[(methoxycarbonyl) methoxycarbonyl] ethylamine, N, N-bis (2-hydroxyethyl) 2- (2-oxopropoxycarbonyl) ethylamine, N, N-bis (2-acetoxyethyl) 2- ( 2-oxopropoxycarbonyl) ethylamine, N, N-bis (2- Droxyethyl) 2- (tetrahydrofurfuryloxycarbonyl) ethylamine, N, N-bis (2-acetoxyethyl) 2- (tetrahydrofurfuryloxycarbonyl) ethylamine, N, N-bis (2-hydroxyethyl) 2-[( 2-oxotetrahydrofuran-3-yl) oxycarbonyl] ethylamine, N, N-bis (2-acetoxyethyl) 2-[(2-oxotetrahydrofuran-3-yl) oxycarbonyl] ethylamine, N, N-bis (2 -Hydroxyethyl) 2- (4-hydroxybutoxycarbonyl) ethylamine, N, N-bis (2-formyloxyethyl) 2- (4-formyloxybutoxycarbonyl) ethylamine, N, N-bis (2-formyloxyethyl) ) 2- (2-Formyloxyethoxy) Rubonyl) 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 ], N- (3-hydroxy-1-propyl) bis [2- (methoxycarbonyl) ethyl] amine, N- (3-acetoxy-1-propyl) bis [2- (methoxycarbonyl) ethyl] amine, N -(2-methoxyethyl) bis [2- (methoxycarbonyl) ethyl] amine, N-butylbis [2- ( Methoxycarbonyl) ethyl] amine, N-butylbis [2- (2-methoxyethoxycarbonyl) ethyl] amine, N-methylbis (2-acetoxyethyl) amine, N-ethylbis (2-acetoxyethyl) amine, N-methylbis ( 2-pivaloyloxyethyl) amine, N-ethylbis [2- (methoxycarbonyloxy) ethyl] amine, N-ethylbis [2- (tert-butoxycarbonyloxy) ethyl] amine, tris (methoxycarbonylmethyl) amine, Examples include, but are not limited to, tris (ethoxycarbonylmethyl) amine, N-butylbis (methoxycarbonylmethyl) amine, N-hexylbis (methoxycarbonylmethyl) amine, β- (diethylamino) -δ-valerolactone, and the like.

  Furthermore, 1 type, or 2 or more types of the basic compound which has the cyclic structure shown by the following general formula (B) -2 can also be added.

（式中、Ｘは前述の通り、Ｒ^３０７は炭素数２〜２０の直鎖状、分岐状のアルキレン基であり、カルボニル基、エーテル基、エステル基、スルフィドを１個あるいは複数個含んでいても良い。）

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

  (B) -2 is specifically 1- [2- (methoxymethoxy) ethyl] pyrrolidine, 1- [2- (methoxymethoxy) ethyl] piperidine, 4- [2- (methoxymethoxy) ethyl] morpholine, 1- [2-[(2-methoxyethoxy) methoxy] ethyl] pyrrolidine, 1- [2-[(2-methoxyethoxy) methoxy] ethyl] piperidine, 4- [2-[(2-methoxyethoxy) methoxy] Ethyl] morpholine, 2- (1-pyrrolidinyl) ethyl acetate, 2-piperidinoethyl acetate, 2-morpholinoethyl acetate, 2- (1-pyrrolidinyl) ethyl formate, 2-piperidinoethyl propionate, 2-morpholinoethyl acetoxyacetate, methoxyacetic acid 2- (1-pyrrolidinyl) ethyl, 4- [2- (methoxycarbonyloxy) ethyl] morpholine 1- [2- (t-butoxycarbonyloxy) ethyl] piperidine, 4- [2- (2-methoxyethoxycarbonyloxy) ethyl] morpholine, methyl 3- (1-pyrrolidinyl) propionate, 3-piperidinopropion Acid methyl, methyl 3-morpholinopropionate, methyl 3- (thiomorpholino) propionate, methyl 2-methyl-3- (1-pyrrolidinyl) propionate, ethyl 3-morpholinopropionate, methoxy 3-piperidinopropionate Carbonylmethyl, 2-hydroxyethyl 3- (1-pyrrolidinyl) propionate, 2-acetoxyethyl 3-morpholinopropionate, 2-oxotetrahydrofuran-3-yl 3- (1-pyrrolidinyl) propionate, 3-morpholinopropionic acid Tetrahydrofurfuryl, 3- Glycidyl peridinopropionate, 2-methoxyethyl 3-morpholinopropionate, 2- (2-methoxyethoxy) ethyl 3- (1-pyrrolidinyl) propionate, butyl 3-morpholinopropionate, cyclohexyl 3-piperidinopropionate , Α- (1-pyrrolidinyl) methyl-γ-butyrolactone, β-piperidino-γ-butyrolactone, β-morpholino-δ-valerolactone, methyl 1-pyrrolidinyl acetate, methyl piperidinoacetate, methyl morpholinoacetate, methyl thiomorpholinoacetate, Examples include ethyl 1-pyrrolidinyl acetate and 2-methoxyethyl morpholinoacetate.

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

（式中、Ｘ、Ｒ^３０７、ｎは前述の通り、Ｒ^３０８、Ｒ^３０９は同一又は異種の炭素数１〜４の直鎖状、分岐状のアルキレン基である。）

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

  In addition, the compounding quantity of a basic compound is 0.001-10 parts with respect to 1 part of acid generators, and 0.01-1 part is especially suitable. If the blending amount is 0.001 part or more, a sufficient blending effect is obtained, and if it is 10 parts or less, there is little fear that the resolution and sensitivity are lowered.

As the resist composition of the present invention, a dissolution accelerator can be further added. As the dissolution accelerator, a compound having a fluoroalcohol group such as hexafluoroalcohol is preferably used. Specifically, the following can be mentioned.
Moreover, a dissolution inhibitor can be further added to the resist composition of the present invention. As the dissolution inhibitor, a compound in which the hydroxy group of the alcohol of the following dissolution accelerator is substituted with an acid labile group is preferably used. As the acid labile group, those described above can be used.

Furthermore, the resist material of the present invention can contain an acetylene alcohol derivative as an additive, thereby improving storage stability.
As the acetylene alcohol derivative, those represented by the following general formulas (S1) and (S2) can be preferably used.

（式中、Ｒ⁵⁰¹、Ｒ⁵⁰²、Ｒ⁵⁰³、Ｒ⁵⁰⁴、Ｒ⁵⁰⁵はそれぞれ水素原子、又は炭素数１〜８の直鎖状、分岐状又は環状のアルキル基であり、Ｘ、Ｙは０又は正数を示し、下記値を満足する。０≦Ｘ≦３０、０≦Ｙ≦３０、０≦Ｘ＋Ｙ≦４０である。）

Wherein R ⁵⁰¹ , R ⁵⁰² , R ⁵⁰³ , R ⁵⁰⁴ and R ⁵⁰⁵ are each a hydrogen atom or a linear, branched or cyclic alkyl group having 1 to 8 carbon atoms, and X and Y are 0 or Indicates a positive number and satisfies the following values: 0 ≦ X ≦ 30, 0 ≦ Y ≦ 30, 0 ≦ X + Y ≦ 40.)

  The acetylene alcohol derivative is preferably Surfinol 61, Surfinol 82, Surfinol 104, Surfinol 104E, Surfinol 104H, Surfinol 104A, Surfinol TG, Surfinol PC, Surfinol 440, Surfinol 465, Surfinol 485 (Air Products and Chemicals Inc.), Surfynol E1004 (manufactured by Nissin Chemical Industry Co., Ltd.) and the like.

  The addition amount of the acetylene alcohol derivative is 0.01 to 2% by weight, more preferably 0.02 to 1% by weight in 100% by weight of the resist composition. When the amount is less than 0.01% by weight, the effect of improving the coating property and storage stability may not be sufficiently obtained. When the amount is more than 2% by weight, the resolution of the resist material may be lowered.

  In addition to the above components, a surfactant conventionally used for improving the coating property can be added to the resist material of the present invention. In addition, the addition amount of an arbitrary component can be made into a normal amount in the range which does not inhibit the effect of this invention.

  Here, the surfactant is preferably nonionic, such as perfluoroalkyl polyoxyethylene ethanol, fluorinated alkyl ester, perfluoroalkylamine oxide, perfluoroalkyl EO adduct, fluorine-containing organosiloxane compound, and the like. Can be mentioned. For example, Florard “FC-430”, “FC-431”, “FC-4430” (all manufactured by Sumitomo 3M), Surflon “S-141”, “S-145” (all manufactured by Asahi Glass Co., Ltd.) ), Unidyne “DS-401”, “DS-403”, “DS-451” (all manufactured by Daikin Industries, Ltd.), MegaFuck “F-8151” (manufactured by Dainippon Ink Industries, Ltd.), “ X-70-092 "and" X-70-093 "(both manufactured by Shin-Etsu Chemical Co., Ltd.). Preferably, Florard “FC-430”, “FC-4430” (manufactured by Sumitomo 3M Co., Ltd.), “KH-20”, “KH-30” (both manufactured by Asahi Glass Co., Ltd.), “X-70- 093 "(manufactured by Shin-Etsu Chemical Co., Ltd.).

An acid multiplication agent can be further added to the resist material of the present invention. Since the acid diffusion of the polymer type acid generator is very limited, there is a drawback that the deprotection contrast tends to be lowered in the positive resist. Therefore, it is effective to improve contrast by adding an acid proliferating agent as disclosed in JP-A Nos. 2000-34272 and 2002-6481.
The addition amount of such an acid proliferating agent is preferably 0 to 20 parts by weight, more preferably 0 to 15 parts by weight with respect to 100 parts by weight of the addition amount of the polymer type acid generator. If the addition amount is 20 parts or less, there is little possibility that the transparency is lowered or the acid diffusion is increased and the resolution is lowered.

  In order to form a pattern using the resist material of the present invention, a known lithography technique can be employed.

For example, a resist material is applied onto a substrate such as a silicon wafer by spin coating or the like so that the film thickness becomes 0.03 to 1.0 μm, and this is applied on a hot plate at 60 to 180 ° C. for 20 seconds to Pre-baking is performed for 10 minutes, preferably 80 to 150 ° C. for 30 seconds to 5 minutes, to form a resist film. Next, a mask for forming a target pattern is placed over the resist film, and high energy rays such as ArF excimer laser, deep ultraviolet rays, X-rays, and electron beams are exposed to about 1 to 100 mJ / cm ² , preferably 5 After irradiation so as to be about ˜80 mJ / cm ^2, post exposure baking (PEB) is performed on a hot plate at 60 to 150 ° C. for 20 seconds to 5 minutes, preferably 80 to 130 ° C. for 30 seconds to 3 minutes.

  Further, a developer of an alkaline aqueous solution such as 0.1 to 5%, preferably 2-3% tetramethylammonium hydroxide (TMAH) is used for 10 seconds to 3 minutes, preferably 15 seconds to 2 minutes. ) Method, paddle method, spray method and the like, and a desired pattern is formed on the substrate. The material of the present invention is particularly suitable for fine patterning with an 193 nm ArF excimer laser among high energy rays.

  The resist material of the present invention can be applied to immersion lithography. In immersion lithography, a liquid having a high refractive index is inserted between a projection lens and a wafer. In immersion lithography using ArF excimer laser light, water is being studied as a liquid. Further, alcohols such as ethylene glycol, phosphoric acid, and alumina-dispersed water are being studied as high refractive index liquids. The resist material having a polymer containing a polymer type acid generator according to the present invention as a base polymer has no solubility in water of the acid generator or the generated acid, so that a good resist pattern can be obtained. It can be particularly suitably used for lithography.

  EXAMPLES Hereinafter, although a synthesis example, a polymer synthesis example, an Example, and a comparative example are shown and this invention is demonstrated concretely, this invention is not limited by these description.

[Synthesis Example 1] Synthesis of triphenylsulfonium chloride 40 g (0.2 mol) of phenylsulfoxide was dissolved in 400 g of an organic solvent dichloromethane and stirred under ice cooling. 65 g (0.6 mol) of trimethylsilyl chloride was added dropwise at a temperature not exceeding 20 ° C., and aging was further performed at this temperature for 30 minutes. Subsequently, a Grignard reagent separately prepared from 14.6 g (0.6 mol) of metallic magnesium, 67.5 g (0.6 mol) of chlorobenzene, and 168 g of THF was added dropwise at a temperature not exceeding 20 ° C. After aging the reaction for 1 hour, the reaction was stopped by adding 50 g of water at a temperature not exceeding 20 ° C., and 150 g of water, 10 g of 12 N hydrochloric acid and 200 g of diethyl ether were added for extraction.
The aqueous layer was separated and washed with 100 g of diethyl ether to obtain an aqueous triphenylsulfonium chloride solution. This was used for the synthesis of Synthesis Example 9 in the form of an aqueous solution without further isolation.

Synthesis Example 2 Synthesis of 4-tert-butylphenyldiphenylsulfonium chloride Synthesis Example 1 except that 4-tert-butylchlorobenzene was used in place of the chlorobenzene of Synthesis Example 1 and the amount of water during extraction was increased by 50 g. The target product was obtained in the same manner.

[Synthesis Example 3] Synthesis of 4-tert-butoxyphenyldiphenylsulfonium chloride In the extraction, 4-tert-butoxychlorobenzene was used in place of the chlorobenzene of Synthesis Example 1, and a dichloromethane solvent containing 5% by weight of triethylamine as an organic solvent was used. The target product was obtained in the same manner as in Synthesis Example 1 except that the amount of water was increased by 50 g.

[Synthesis Example 4] Synthesis of tris (4-methylphenyl) sulfonium chloride Using bis (4-methylphenyl) sulfoxide instead of phenyl sulfoxide in Synthesis Example 1, and using 4-chlorotoluene instead of chlorobenzene, The target product was obtained in the same manner as in Synthesis Example 1 except that the amount of water at the time was increased by 50 g.

[Synthesis Example 5] Synthesis of tris (4-tert-butylphenyl) sulfonium chloride Bis (4-tert-butylphenyl) sulfoxide was used instead of phenylsulfoxide of Synthesis Example 1, and 4-tert-butylchlorobenzene was used instead of chlorobenzene. Was used in the same manner as in Synthesis Example 1 except that the amount of water during extraction was increased by 50 g.

[Synthesis Example 6] Synthesis of bis (4-tert-butylphenyl) iodonium hydrogen sulfate A mixture of 84 g (0.5 mol) of tert-butylbenzene, 53 g (0.25 mol) of potassium iodate, and 50 g of acetic anhydride was stirred under ice cooling. Then, a mixture of 35 g of acetic anhydride and 95 g of concentrated sulfuric acid was added dropwise at a temperature not exceeding 30 ° C. Next, the mixture was aged at room temperature for 3 hours, cooled on ice again, and 250 g of water was added dropwise to stop the reaction. This reaction solution was extracted with 400 g of dichloromethane, and 6 g of sodium bisulfite was added to the organic layer for decolorization. Further, washing the organic layer with 250 g of water was repeated three times. The washed organic layer was concentrated under reduced pressure to obtain the desired crude product. The product was used in Synthesis Example 17 as it was without further purification.

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

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

Using the sulfonium salt halides, aryl sulfonates, and the like obtained in Synthesis Examples 1 to 8 above, onium salts of sulfonic acid having a polymerizable unsaturated bond were synthesized in Synthesis Examples 9 to 19 below.
[Synthesis Example 9] Synthesis of triphenylsulfonium 4-styrenesulfonate To the aqueous triphenylsulfonium chloride solution obtained in Synthesis Example 1, ammonium p-styrenesulfonate and dichloromethane were added, and the target product was extracted into an organic layer. Water was added to the organic layer to remove excess acid in the aqueous layer, and the organic solvent in the washed organic layer was removed with a rotary evaporator. The residue was purified by silica gel column chromatography (eluent; dichloromethane-methanol 95: 5% by volume) to obtain the desired product.

[Synthesis Example 10] Synthesis of triphenylsulfonium 4-methacryloxy-1-butanesulfonate In place of p-styrenesulfonic acid ammonium salt used in Synthesis Example 9, sodium 4-methacryloxy-1-butanesulfonate was used. Were synthesized in the same manner as in Synthesis Example 9.

[Synthesis Example 11] Synthesis of triphenylsulfonium vinyl sulfonate The target product was synthesized in the same manner as in Synthesis Example 9 except that vinyl sulfonic acid was used instead of the p-styrenesulfonic acid ammonium salt used in Synthesis Example 9.

[Synthesis Example 12] Synthesis of triphenylsulfonium 4-allyloxybenzenesulfonate Same as Synthesis Example 9 except that sodium 4-allyloxybenzenesulfonate was used instead of the ammonium p-styrenesulfonate used in Synthesis Example 9. Thus, the target product was synthesized.

[Synthesis Example 13] Synthesis of 4-tert-butylphenyldiphenylsulfonium 4-styrenesulfonate 4-tert-butylphenyldiphenylsulfonium chloride obtained in Synthesis Example 2 instead of the aqueous triphenylsulfonium chloride solution used in Synthesis Example 9 The target product was synthesized in the same manner as in Synthesis Example 9 except that was used.

[Synthesis Example 14] Synthesis of 4-tert-butoxyphenyldiphenylsulfonium 4-styrenesulfonate 4-tert-butoxyphenyldiphenylsulfonium chloride obtained in Synthesis Example 3 instead of the triphenylsulfonium chloride aqueous solution used in Synthesis Example 9 The target product was synthesized in the same manner as in Synthesis Example 9 except that was used.

[Synthesis Example 15] Synthesis of tris (4-methylphenyl) sulfonium 4-styrenesulfonate Tris (4-methylphenyl) sulfonium chloride obtained in Synthesis Example 4 instead of the triphenylsulfonium chloride aqueous solution used in Synthesis Example 9 The target product was synthesized in the same manner as in Synthesis Example 9 except that was used.

[Synthesis Example 16] Synthesis of tris (4-tert-butylphenyl) sulfonium 4-styrenesulfonate Tris (4-tert-butylphenyl) obtained in Synthesis Example 5 instead of the aqueous triphenylsulfonium chloride solution used in Synthesis Example 9 ) The target product was synthesized in the same manner as in Synthesis Example 9 except that sulfonium chloride was used.

Synthesis Example 17 Synthesis of bis (4-tert-butylphenyl) iodonium 4-styrenesulfonate Instead of the aqueous triphenylsulfonium chloride solution used in Synthesis Example 9, the bis (4-tert-butylphenyl) obtained in Synthesis Example 6 was used. ) The desired product was synthesized in the same manner as in Synthesis Example 9 except that iodonium hydrogen sulfate was used.

[Synthesis Example 18] Synthesis of Phenacyltetrahydrothiophenium 4-Styrenesulfonate Except for using the aqueous solution of phenacyltetrahydrothiophenium bromide obtained in Synthesis Example 7 in place of the triphenylsulfonium chloride aqueous solution used in Synthesis Example 9. The target product was synthesized in the same manner as in Synthesis Example 9.

[Synthesis Example 19] Synthesis of dimethylphenylsulfonium 4-styrenesulfonate Same as Synthesis Example 9 except that instead of the triphenylsulfonium chloride aqueous solution used in Synthesis Example 9, the dimethylphenylsulfonium sulfate aqueous solution obtained in Synthesis Example 8 was used. Thus, the target product was synthesized.

  As described above, an onium salt of a sulfonic acid having a polymerizable unsaturated bond was obtained. The polymer according to the present invention can be obtained by copolymerizing the onium salt of sulfonic acid having a polymerizable unsaturated bond thus obtained and a monomer copolymerizable therewith.

[Polymer synthesis example 1]
In a 100-mL flask, 6.2 g of 2-adamantyloxymethyl methacrylate, 6.2 g of 3-hydroxy-1-adamantyl methacrylate, 5-oxo-4-oxatricyclo methacrylate [4.2.1.0 ^[3,7 ] 10.1 g of nonan-2-yl, 3.0 g of triphenylsulfonium methacrylate-4-butanesulfonate, and 20 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, 0.2 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 500 mL of isopropyl alcohol, and the resulting white solid was filtered and dried under reduced pressure at 60 ° C. to obtain 22.1 g of 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 a11: b11: c11: s1 = 0.25: 0.25: 0.45: 0.05
Mass average molecular weight (Mw) = 9,200
This polymer is referred to as polymer 1.

[Polymer synthesis example 2]
In a 100-mL flask, 6.2 g of 2-adamantyloxymethyl methacrylate, 6.2 g of 3-hydroxy-1-adamantyl methacrylate, 3-oxo-2,7-dioxatricyclomethacrylate [4.2. ^1.04,8 ] -9-nonyl 10.1 g, 2.5 g of triphenylsulfonium 4-styrenesulfonate, and 20 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, 0.2 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 isopropyl alcohol, and the obtained white solid was filtered and dried under reduced pressure at 60 ° C. to obtain 22.8 g of 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 a11: b11: c12: s2 = 0.25: 0.25: 0.45: 0.05
Mass average molecular weight (Mw) = 9,100
This polymer is designated as Polymer 2.

[Polymer Synthesis Example 3]
In a 100 mL flask, 5.1 g of cyclohexyloxymethyl methacrylate, 4.7 g of 3-hydroxy-1-adamantyl methacrylate, 5-oxo-4-oxatricyclomethacrylate [4.2.1.0 ^3,7 ] 11.1 g of nonan-2-yl, 2.5 g of triphenylsulfonium 4-styrenesulfonate, and 20 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, 0.2 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 isopropyl alcohol, and the obtained white solid was filtered and dried under reduced pressure at 60 ° C. to obtain 19.8 g of 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 a12: b11: c11: s2 = 0.25: 0.20: 0.50: 0.05
Mass average molecular weight (Mw) = 8,300
This polymer is designated as Polymer 3.

[Polymer Synthesis Example 4]
In a 100 mL flask, 6.2 g of methacrylic acid-cyclohexyloxymethyl, 9.4 g of methacrylic acid-3-hydroxy-1-adamantyl, methacrylic acid-bis-3,5- (2-hydroxy-1,1,1,3,3) , 3-hexafluoro-2-propyl) cyclohexyl 12.2 g, methacrylic acid-4-butanesulfonate 2.6 g triphenylsulfonium, and 20 g 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, 0.2 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 isopropyl alcohol, and the resulting white solid was filtered and dried under reduced pressure at 60 ° C. to obtain 24.8 g of 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 a12: b11: c13: s1 = 0.30: 0.40: 0.25: 0.05
Mass average molecular weight (Mw) = 8,200
This polymer is designated as polymer 4.

[Polymer synthesis example 5]
In a 100 mL flask, 5.9 g methacrylic acid-cyclohexyloxymethyl, 7.1 g methacrylic acid-3-hydroxy-1-adamantyl, methacrylic acid-bis 3,5- (2-hydroxy-1,1,1,3,3) , 3-hexafluoro-2-propyl) cyclohexyl 10.1 g, methacrylic acid-4-butanesulfonate triphenylsulfonium 9.8 g, and 20 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, 0.2 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 isopropyl alcohol, and the obtained white solid was filtered and dried under reduced pressure at 60 ° C. to obtain 26.3 g of 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 a12: b11: c13: s1 = 0.30: 0.30: 0.20: 0.20
Mass average molecular weight (Mw) = 9,800
This polymer is designated as polymer 5.

[Polymer synthesis example 6]
In a 100 mL flask, 5.9 g of 2-adamantyloxymethyl methacrylate, 7.1 g of 3-hydroxy-1-adamantyl methacrylate, 3-oxo-2,7-dioxatricyclomethacrylate [4.2. ^1.04,8 ] -9-nonyl 10.1 g and 20 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, 0.2 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 isopropyl alcohol, and the obtained white solid was filtered and dried under reduced pressure at 60 ° C. to obtain 19.6 g of 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 a11: b11: c12 = 0.25: 0.30: 0.45
Mass average molecular weight (Mw) = 8,300
This polymer is designated as polymer 6.

[Polymer 7]
A metathesis polymer (ROMP-E) manufactured by Mitsui Chemicals is referred to as Polymer 7.
Copolymer composition ratio g1: h1: i1 = 0.35: 0.15: 0.50
Mass average molecular weight (Mw) = 8,100

[Polymer Synthesis Example 8]
In a 100-mL flask, 6.2 g of methacrylic acid-cyclohexyloxymethyl, 9.3 g of methacrylic acid-3-propyl-heptaisopropylPOSS ^™ , 3-oxo-2,7-dioxatricyclomethacrylate [4.2.1. 0 ^4,8 ] -9-nonyl 8.5 g, methacrylic acid-4-butanesulfonate 2.5 g triphenylsulfonium, and 20 g 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, 0.2 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 isopropyl alcohol, and the resulting white solid was filtered and dried under reduced pressure at 60 ° C. to obtain 22.3 g of 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 a12: d11: c12: s1 = 0.30: 0.10: 0.40: 0.05
Mass average molecular weight (Mw) = 7,600
This polymer is designated as polymer 8.

(Examples and comparative examples)
[Preparation of resist material]
Polymers shown in the above polymer synthesis examples 1 to 8, acid generators (PAG1, PAG2), acid growth agents (PAAG1), dissolution inhibitors (DRI-1), dissolution accelerators (DRR-) represented by the following formulas 1) The basic compound (TOA) was dissolved in a solvent containing 0.01% by weight of FC-430 (manufactured by Sumitomo 3M) with the composition shown in Table 1, and a resist material was prepared. Each resist solution was prepared by filtering through a 2 μm Teflon (registered trademark) filter.

酸増殖剤： ＰＡＡＧ１（下記構造式参照）

溶解阻止剤： ＤＲI−１（下記構造式参照）

溶解促進剤： ＤＲＲ−１（下記構造式参照）

塩基性化合物： ＴＯＡ（トリ-n-オクチルアミン）
有機溶剤： ＰＧＭＥＡ（プロピレングリコールモノメチルエーテルアセテート）、ＣｙＨＯ（シクロヘキサノン） Each composition in Table 1 is as follows.
Polymers 1 to 8: From polymer synthesis examples 1 to 8 Acid generator: PAG1, PAG2 (see the following structural formula)

Acid proliferator: PAAG1 (see the following structural formula)

Dissolution inhibitor: DRI-1 (see structural formula below)

Dissolution promoter: DRR-1 (see the structural formula below)

Basic compound: TOA (tri-n-octylamine)
Organic solvent: PGMEA (propylene glycol monomethyl ether acetate), CyHO (cyclohexanone)

[Exposure patterning evaluation]
The resist material solution thus prepared (Examples 1 to 11 and Comparative Example 1) was coated with an antireflection film solution (ARC-29A manufactured by Nissan Chemical Industries, Ltd.) on a silicon substrate and baked at 200 ° C. for 60 seconds. The antireflection film (78 nm film thickness) thus prepared was spin-coated on the substrate and baked (prebaked) at 120 ° C. for 60 seconds using a hot plate to form a 200 nm film thickness resist film.
This is exposed using an ArF excimer laser microstepper (Nikon S305B, NA = 0.68, σ0.85, 2/3 annular illumination, Cr mask) and baked (PEB) at 130 ° C. for 90 seconds. Development was carried out with an aqueous solution of 2.38% tetramethylammonium hydroxide for 60 seconds to obtain positive patterns (Examples 1 to 11 and Comparative Example 1).

The obtained resist pattern was evaluated as follows, and the results are shown in Table 1.
The exposure amount for resolving the 0.12 μm group line and space at 1: 1 is the optimum exposure amount (Eop, mJ / cm ² ), and the minimum line width of the separated line and space at this exposure amount (μm ) As the resolution of the evaluation resist.

[Observation of resist pattern shape by simulated immersion exposure]
Next, using the resist material solutions prepared above (Examples 1 to 11 and Comparative Example 1), a 300-second pure water rinse is performed between pre-baking and exposure or between exposure and PEB. Liquid immersion exposure was performed, and the shape of a 110 nm line and space pattern after development was observed. The results are summarized in Table 2.

  From the results of Tables 1 and 2, the resist materials (Examples 1 to 11) of the present invention have high sensitivity and high resolution, and there is no change in shape even when rinsing with water for a long time as compared with Comparative Example 1. It was confirmed that it can sufficiently cope with immersion exposure.

The present invention is not limited to the above embodiment. The above-described embodiment is an exemplification, and the present invention has substantially the same configuration as the technical idea described in the claims of the present invention, and any device that exhibits the same function and effect is the present invention. It is included in the technical scope of the invention.

Claims (5)

At least, seen containing a polymer obtained by polymerizing an onium salt of a sulfonic acid having a polymerizable unsaturated bond, the polymer comprises a repeating unit represented by at least the following general formula (1) and / or (2)

(Wherein R ¹ is a hydrogen atom, a methyl group, R ² is a single bond, a methylene group, a phenylene group, or —C (═O) —X ¹ —R ³ —. X ¹ is an oxygen atom or NH, R ³ is a linear, branched, or cyclic alkylene group or phenylene group having 1 to 12 carbon atoms, and some or all of the hydrogen atoms may be substituted with fluorine atoms, and one of an ether group and an ester group or Both of them may have at least 1. R ⁰¹ , R ⁰² and R ⁰³ are the same or different, linear, branched or cyclic alkyl groups having 1 to 20 carbon atoms, such as carbonyl group, ester group, ether Group, a lactone ring may be included, or an aryl group having 6 to 20 carbon atoms in which some or all of the hydrogen atoms may be substituted with halogen atoms may include -S- All hydrogen atoms are replaced by halogen atoms Which may be an aralkyl group having 7 to 20 carbon atoms, a thiophenyl group which may be R ⁰¹ and R ^02, R ⁰² and R ^03, R ⁰¹ and R ⁰³ are respectively bonded to form a ring .R ⁰⁴ and R ⁰⁵ are the same or different aryl groups having 6 to 20 carbon atoms, part or all of the hydrogen atoms may be substituted with halogen atoms, and R ⁰⁴ and R ⁰⁵ are bonded to form a ring. May be formed),
Furthermore, it has a repeating unit having an acid leaving group and a repeating unit having an adhesive group, and the repeating unit having the adhesive group is any one or more represented by the following general formula Resist material.

(In the formula, R ¹⁵ is a hydrogen atom or a methyl group.) The resist material according to claim 1 , wherein the resist material is a chemically amplified positive resist material. The resist material according to claim 1 or 2 , wherein the resist material further contains one or more of an organic solvent, a basic compound, and a dissolution inhibitor. At least a step of applying the resist material according to any one of claims 1 to 3 on a substrate, a step of exposing to high energy rays after heat treatment, and a step of developing using a developer. A pattern forming method comprising: In the step of exposing with the high energy beam, an ArF excimer laser having a wavelength of 193 nm is used as a light source, a liquid is inserted between the substrate coated with the resist material and the projection lens, and the substrate is exposed through the liquid The pattern forming method according to claim 4 , wherein immersion exposure is performed.