JP2006215526A - Resist material and pattern forming method using it - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a high resolution resist material containing an acid forming agent of a polymer which is highly sensitive to high energy rays, especially ArF excimer laser beams, F<SB>2</SB>excimer laser beams, EUV rays, X rays, and EBs with less line edge roughness in high resolution without dissolving in water but has sufficient heat stability and shelf life stability. <P>SOLUTION: The resist material contains a high molecular compound obtained by copolymerizing (meta-)acrylate having at least sulfonium salt having polymerized unsaturated bonding, lactone or hydroxy group as an adhesion group, and (meta-)acrylate having an ester substituted by an acid-labile group. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

The present invention includes (1) a polymer-type sulfonium salt as an acid generator, (2) and a high energy ray containing the same, preferably having a wavelength of 300 nm or 200 nm or less, particularly ArF excimer laser, F ₂ excimer laser, EUV , X-ray, EB resist material, and (3) a pattern forming method using the 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. A 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-described problems, and is substituted with at least a sulfonium salt having a polymerizable unsaturated bond, a (lactone) having a lactone or a hydroxy group as an adhesive group, and an acid labile group. A resist material comprising a polymer compound obtained by copolymerizing a (meth) acrylate having an ester is provided.

（式中、Ｒ^１は水素原子、メチル基、Ｒ^２はフェニレン基、−Ｏ−Ｒ^６−、−Ｃ（＝Ｏ）−Ｘ^１−Ｒ^６−、−Ｃ（＝Ｏ）−Ｏ−Ｃ_２Ｈ_４−Ｏ−Ｙ^１−、−Ｃ（＝Ｏ）−Ｏ−Ｚ^１−Ｃ（＝Ｏ）−ＣＨ_２−、−Ｚ^１−Ｃ（＝Ｏ）−ＣＨ_２−、−Ｃ（＝Ｏ）−Ｏ−Ｚ^１−ＣＨ_２−、−Ｃ（＝Ｏ）−Ｏ−ＣＨ_２−Ｃ（＝Ｏ）−Ｏ−Ｚ^１−、−Ｃ（＝Ｏ）−Ｏ−Ｃ_２Ｈ_４−Ｃ（＝Ｏ）−Ｏ−Ｚ^１−のいずれかである。Ｘ^１は酸素原子またはＮＨ、Ｒ^６は炭素数１〜６の直鎖状、分岐状、環状のアルキレン基、フェニレン基であり、カルボニル基、エステル基又はエーテル基を含んでいてもよい。Ｙ^１はフェニレン基、ナフチレン基、アントリレン基のいずれかである。Ｚ^１はフェニレン基である。Ｒ^３、Ｒ^４は同一又は異種の炭素数１〜１２の直鎖状、分岐状又は環状のアルキル基であり、カルボニル基、エステル基又はエーテル基を含んでいてもよく、又は炭素数６〜１２のアリール基又は炭素数７〜２０のアラルキル基、チオフェニル基を表す。また、Ｒ^３、Ｒ^４は結合して環を形成してもよい。Ｒ^５は一部又は全ての水素原子がフッ素原子で置換された、炭素数４〜２０の直鎖状、分岐状、環状、あるいは環を含むアルキル基、アルケニル基であり、ベンゼン環、エーテル基を１以上有していてもよい、または一部又は全ての水素原子がフッ素原子で置換された炭素数４〜２０のアリール基である。） In this case, it is preferable that the repeating unit obtained by polymerizing the sulfonium salt having a polymerizable unsaturated bond is represented by the following general formula (1) (Claim 2).

(In the formula, R ¹ is a hydrogen atom, a methyl group, R ² is a phenylene group, —O—R ⁶ —, —C (═O) —X ¹ —R ⁶ —, —C (═O) —O—C ₂ H ₄ —O—Y ¹ —, —C (═O) —O—Z ¹ —C (═O) —CH ₂ —, —Z ¹ —C (═O) —CH ₂ —, —C (= O) —O—Z ¹ —CH ₂ —, —C (═O) —O—CH ₂ —C (═O) —O—Z ¹ —, —C (═O) —O—C ₂ H ₄ —. Any one of C (═O) —O—Z ¹ —, wherein X ¹ is an oxygen atom or NH, and R ⁶ is a linear, branched or cyclic alkylene group having 1 to ⁶ carbon atoms or a phenylene group. , A carbonyl group, an ester group or an ether group, Y ¹ is any ^one of a phenylene group, a naphthylene group and an anthrylene group, Z ¹ is a phenylene group, and R ³ and R ⁴ are the same or different. It is a linear, branched or cyclic alkyl group having 1 to 12 carbon atoms, and may contain a carbonyl group, an ester group or an ether group, or an aryl group having 6 to 12 carbon atoms or 7 carbon atoms. Represents an aralkyl group or a thiophenyl group of -20, R ³ and R ⁴ may be bonded to form a ring, and R ⁵ represents a carbon number in which some or all of the hydrogen atoms are substituted with fluorine atoms. 4-20 linear, branched, cyclic, or ring-containing alkyl or alkenyl groups, which may have one or more benzene rings or ether groups, or some or all of the hydrogen atoms are fluorine (It is an aryl group having 4 to 20 carbon atoms substituted with an atom.)

The resist material containing such a polymer compound according to the present invention is highly sensitive to high energy rays, particularly ArF excimer laser, F ₂ excimer laser, EUV, X-ray, EB, etc., and has a line edge with high resolution. It contains a polymer type acid generator having a small roughness, no dissolution in water, and sufficient thermal stability and storage stability. Furthermore, it has favorable board | substrate adhesiveness by having copolymerized (meth) acrylate which has a lactone or a hydroxy group as an adhesive group. Furthermore, by copolymerizing a (meth) acrylate having an ester substituted with an acid labile group, an acid generated from a polymer type acid generator at the time of exposure is used to release an acid leaving group. A high-precision pattern can be formed. 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.

  In this case, the resist material of the present invention is preferably a chemically amplified positive resist material.

  Thus, the resist material containing the polymer compound has a polymer-type acid generator, which removes the acid leaving group by the acid generated during exposure and dissolves the resist exposure portion in the developer. By converting in this way, it is possible to obtain a chemically amplified positive resist material capable of obtaining a highly accurate pattern.

  In this case, the resist material of the present invention can further contain any one or more of an organic solvent, a basic compound, and a dissolution inhibitor (Claim 4).

  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. It can be used as a method for forming a pattern on a semiconductor substrate, a mask substrate or the like.

  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. Immersion exposure can be performed.

  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 the high integration and high speed of LSIs, far-ultraviolet lithography and vacuum ultraviolet lithography are promising as next-generation microfabrication technologies, 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.
In EB and EUV lithography, a resist with high sensitivity and high resolution is desired. For high-sensitivity resists, it is effective to add a large amount of an acid generator having a high acid generation efficiency. There arises a problem that the resolution increases and the resolution decreases. For this reason, there has been a demand for an acid generator that does not degrade resolution even when added to a high-sensitivity resist.
Here, Mat. Res. Soc. Symp. Proc. Vol. 636, D 6.5.1 (2001) proposes a silicone-containing bilayer resist copolymerized with a methacryl pendant sulfonium salt.
JP-A-4-230645 and JP-A-2005-084365 propose polymerizable onium salts.

  Therefore, the present inventor has conducted extensive studies to achieve the above object based on such knowledge, and as a result, an acid generator obtained by polymerizing a sulfonium salt having a polymerizable unsaturated bond, particularly the following general formula ( The polymer compound having a repeating unit obtained by polymerizing the sulfonium salt shown in 1) is highly sensitive to ArF excimer laser light and has no solubility in water so that it can be used for ArF immersion exposure. It has sufficient thermal stability and storage stability, and a resist material formulated with this has high resolution, can improve line edge roughness and density dependence, and is precise It has been found that it is extremely effective for microfabrication, and has led to the present invention.

  That is, the resist material according to the present invention has at least a sulfonium salt having a polymerizable unsaturated bond, (meth) acrylate having a lactone or hydroxy group as an adhesive group, and an ester substituted with an acid labile group (meta ) A resist material comprising a polymer compound obtained by copolymerizing an acrylate.

（式中、Ｒ^１は水素原子、メチル基、Ｒ^２はフェニレン基、−Ｏ−Ｒ^６−、−Ｃ（＝Ｏ）−Ｘ^１−Ｒ^６−、−Ｃ（＝Ｏ）−Ｏ−Ｃ_２Ｈ_４−Ｏ−Ｙ^１−、−Ｃ（＝Ｏ）−Ｏ−Ｚ^１−Ｃ（＝Ｏ）−ＣＨ_２−、−Ｚ^１−Ｃ（＝Ｏ）−ＣＨ_２−、−Ｃ（＝Ｏ）−Ｏ−Ｚ^１−ＣＨ_２−、−Ｃ（＝Ｏ）−Ｏ−ＣＨ_２−Ｃ（＝Ｏ）−Ｏ−Ｚ^１−、−Ｃ（＝Ｏ）−Ｏ−Ｃ_２Ｈ_４−Ｃ（＝Ｏ）−Ｏ−Ｚ^１−のいずれかである。Ｘ^１は酸素原子またはＮＨ、Ｒ^６は炭素数１〜６の直鎖状、分岐状、環状のアルキレン基、フェニレン基であり、カルボニル基、エステル基又はエーテル基を含んでいてもよい。Ｙ^１はフェニレン基、ナフチレン基、アントリレン基のいずれかである。Ｚ^１はフェニレン基である。Ｒ^３、Ｒ^４は同一又は異種の炭素数１〜１２の直鎖状、分岐状又は環状のアルキル基であり、カルボニル基、エステル基又はエーテル基を含んでいてもよく、又は炭素数６〜１２のアリール基又は炭素数７〜２０のアラルキル基、チオフェニル基を表す。また、Ｒ^３、Ｒ^４は結合して環を形成してもよい。Ｒ^５は一部又は全ての水素原子がフッ素原子で置換された、炭素数４〜２０の直鎖状、分岐状、環状、あるいは環を含むアルキル基、アルケニル基であり、ベンゼン環、エーテル基を１以上有していてもよい、または一部又は全ての水素原子がフッ素原子で置換された炭素数４〜２０のアリール基である。） In this case, it is preferable that a repeating unit obtained by polymerizing the sulfonium salt having a polymerizable unsaturated bond is represented by the following general formula (1).

(In the formula, R ¹ is a hydrogen atom, a methyl group, R ² is a phenylene group, —O—R ⁶ —, —C (═O) —X ¹ —R ⁶ —, —C (═O) —O—C ₂ H ₄ —O—Y ¹ —, —C (═O) —O—Z ¹ —C (═O) —CH ₂ —, —Z ¹ —C (═O) —CH ₂ —, —C (= O) —O—Z ¹ —CH ₂ —, —C (═O) —O—CH ₂ —C (═O) —O—Z ¹ —, —C (═O) —O—C ₂ H ₄ —. Any one of C (═O) —O—Z ¹ —, wherein X ¹ is an oxygen atom or NH, and R ⁶ is a linear, branched or cyclic alkylene group having 1 to ⁶ carbon atoms or a phenylene group. , A carbonyl group, an ester group or an ether group, Y ¹ is any ^one of a phenylene group, a naphthylene group and an anthrylene group, Z ¹ is a phenylene group, and R ³ and R ⁴ are the same or different. It is a linear, branched or cyclic alkyl group having 1 to 12 carbon atoms, and may contain a carbonyl group, an ester group or an ether group, or an aryl group having 6 to 12 carbon atoms or 7 carbon atoms. Represents an aralkyl group or a thiophenyl group of -20, R ³ and R ⁴ may be bonded to form a ring, and R ⁵ represents a carbon number in which some or all of the hydrogen atoms are substituted with fluorine atoms. 4-20 linear, branched, cyclic, or ring-containing alkyl or alkenyl groups, which may have one or more benzene rings or ether groups, or some or all of the hydrogen atoms are fluorine (It is an aryl group having 4 to 20 carbon atoms substituted with an atom.)

Such a copolymer of a sulfonium salt having a polymerizable unsaturated bond, a (meth) acrylate having a lactone or hydroxy group as an adhesive group, and a (meth) acrylate having an ester substituted with an acid labile group. A certain polymer compound, particularly a polymer compound having a repeating unit represented by the general formula (1) as a repeating unit obtained by polymerizing the sulfonium salt having a polymerizable unsaturated bond, particularly has a wavelength of 300 nm or 200 nm. It is highly sensitive to the following high energy rays, especially ArF excimer laser, F ₂ excimer laser, EUV, X-ray, EB, etc., and such a polymer type acid generator has absolutely no solubility in water. It can be used for immersion exposure (particularly immersion exposure using ArF excimer laser light), and has sufficient thermal stability and storage. It has a qualitative.

  Such a resist material blended with a sulfonium salt copolymer has high resolution, can improve line edge roughness and density dependency, 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 the immersion water, so that the resist pattern after development collapses or becomes a T-top shape. Without being feared, a highly accurate pattern can be obtained by being suitably used for immersion lithography, particularly ArF immersion lithography.
Moreover, even if it is added to a high-sensitivity resist in EB or EUV lithography, it is possible to efficiently suppress a decrease in resolution, and thus a highly accurate pattern can be obtained.

（式中、Ｒ^１は水素原子、メチル基、Ｒ^２はフェニレン基、−Ｏ−Ｒ^６−、−Ｃ（＝Ｏ）−Ｘ^１−Ｒ^６−、−Ｃ（＝Ｏ）−Ｏ−Ｃ_２Ｈ_４−Ｏ−Ｙ^１−、−Ｃ（＝Ｏ）−Ｏ−Ｚ^１−Ｃ（＝Ｏ）−ＣＨ_２−、−Ｚ^１−Ｃ（＝Ｏ）−ＣＨ_２−、−Ｃ（＝Ｏ）−Ｏ−Ｚ^１−ＣＨ_２−、−Ｃ（＝Ｏ）−Ｏ−ＣＨ_２−Ｃ（＝Ｏ）−Ｏ−Ｚ^１−、−Ｃ（＝Ｏ）−Ｏ−Ｃ_２Ｈ_４−Ｃ（＝Ｏ）−Ｏ−Ｚ^１−のいずれかである。Ｘ^１は酸素原子またはＮＨ、Ｒ^６は炭素数１〜６の直鎖状、分岐状、環状のアルキレン基、フェニレン基であり、カルボニル基、エステル基又はエーテル基を含んでいてもよい。Ｙ^１はフェニレン基、ナフチレン基、アントリレン基のいずれかである。Ｚ^１はフェニレン基である。Ｒ^３、Ｒ^４は同一又は異種の炭素数１〜１２の直鎖状、分岐状又は環状のアルキル基であり、カルボニル基、エステル基又はエーテル基を含んでいてもよく、又は炭素数６〜１２のアリール基又は炭素数７〜２０のアラルキル基、チオフェニル基を表す。また、Ｒ^３、Ｒ^４は結合して環を形成してもよい。Ｒ^５は一部又は全ての水素原子がフッ素原子で置換された、炭素数４〜２０の直鎖状、分岐状、環状、あるいは環を含むアルキル基、アルケニル基であり、ベンゼン環、エーテル基を１以上有していてもよい、または一部又は全ての水素原子がフッ素原子で置換された炭素数４〜２０のアリール基である。） As a sulfonium salt having a polymerizable double bond necessary for obtaining the polymer compound according to the present invention as described above, a sulfonium salt represented by the following general formula (2) is exemplified.

(In the formula, R ¹ is a hydrogen atom, a methyl group, R ² is a phenylene group, —O—R ⁶ —, —C (═O) —X ¹ —R ⁶ —, —C (═O) —O—C ₂ H ₄ —O—Y ¹ —, —C (═O) —O—Z ¹ —C (═O) —CH ₂ —, —Z ¹ —C (═O) —CH ₂ —, —C (= O) —O—Z ¹ —CH ₂ —, —C (═O) —O—CH ₂ —C (═O) —O—Z ¹ —, —C (═O) —O—C ₂ H ₄ —. Any one of C (═O) —O—Z ¹ —, wherein X ¹ is an oxygen atom or NH, and R ⁶ is a linear, branched or cyclic alkylene group having 1 to ⁶ carbon atoms or a phenylene group. , A carbonyl group, an ester group or an ether group, Y ¹ is any ^one of a phenylene group, a naphthylene group and an anthrylene group, Z ¹ is a phenylene group, and R ³ and R ⁴ are the same or different. It is a linear, branched or cyclic alkyl group having 1 to 12 carbon atoms, and may contain a carbonyl group, an ester group or an ether group, or an aryl group having 6 to 12 carbon atoms or 7 carbon atoms. Represents an aralkyl group or a thiophenyl group of -20, R ³ and R ⁴ may be bonded to form a ring, and R ⁵ represents a carbon number in which some or all of the hydrogen atoms are substituted with fluorine atoms. 4-20 linear, branched, cyclic, or ring-containing alkyl or alkenyl groups, which may have one or more benzene rings or ether groups, or some or all of the hydrogen atoms are fluorine (It is an aryl group having 4 to 20 carbon atoms substituted with an atom.)

R ³ and R ⁴ are the same or different linear, branched or cyclic alkyl groups having 1 to 12 carbon atoms, such as a carbonyl group (═C═O), an ester group (—COO—) or an ether group ( -O-) and the like may be contained. R ³ and R ⁴ are the same or different phenyl group, xylyl group, tolyl group, naphthyl group and the like having 6 to 12 carbon atoms, particularly 6 to 10 aryl groups, benzyl group, phenylethyl group, phenylpropyl group, etc. The aralkyl group and thiophenyl group having 7 to 20 carbon atoms, particularly 7 to 12 carbon atoms are thiophen-2-yl and thiophen-3-yl, and may be a 2-substituted-2-oxoethyl group.

  Specific examples of the sulfonium salt in the general formula (2) include the following.

上記式中、Ｒ^５は前記と同様である。

In the above formula, R ⁵ is the same as described above.

  The anion side of the sulfonium salt in the above general formulas (1) and (2) may have one or more benzene rings and ether groups, and some or all of the hydrogen atoms are substituted with fluorine atoms. 4-20 linear, branched, cyclic, or alkyl group containing a ring, sulfonic acid of alkenyl group, or aryl group having 4-20 carbon atoms, wherein some or all of the hydrogen atoms are substituted with fluorine atoms Examples of the sulfonic acid are as follows.

上記式中、Ｒ^５は前記と同様である。
以上のようにして、重合性不飽和結合を有するスルホニウム塩を得ることができる。 The method for synthesizing the methacrylic pendant sulfonium salt shown in the above specific examples is not particularly limited. For example, Mat. Res. Soc. Symp. Proc. Vol. As shown in 636, D6.5. 1 (2001), there is a method of reacting a sulfonium salt having a phenol group shown below and methacryl chloride.

In the above formula, R ⁵ is the same as described above.
As described above, a sulfonium salt having a polymerizable unsaturated bond can be obtained.

  The resist material according to the present invention has at least a sulfonium salt having such a polymerizable unsaturated bond, a (meth) acrylate having an lactone or hydroxy group as an adhesive group, and an ester substituted with an acid labile group ( It includes a polymer compound obtained by copolymerization of (meth) acrylate, and such a polymer compound can be suitably used as a base resin.

  The method for synthesizing such a polymer compound according to the present invention is not particularly limited. For example, in an organic solvent, the sulfonium salt having a polymerizable unsaturated bond obtained above, and having a lactone or hydroxy group as an adhesive group It can be synthesized by (meth) acrylate, (meth) acrylate having an ester substituted with an acid labile group, or in addition, a monomer copolymerizable therewith, and adding a radical initiator to this to perform 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 compound thus obtained, the repeating unit of the sulfonium salt of the above formula (1) is preferably 90 mol% or less of the total repeating units, more preferably 80 mol% or less, still more preferably 60 mol% or less.

  In addition to the polymer compound according to the present invention, a conventional polymer in which an onium salt of a sulfonic acid having a polymerizable unsaturated bond is not copolymerized, specifically, polyacrylic acid and its derivatives, cycloolefin From derivative-maleic anhydride alternating polymer and polyacrylic acid or a copolymer of three or more with polyacrylic acid or a derivative thereof, cycloolefin derivative-α-trifluoromethylacrylic copolymer, polynorbornene, and metathesis ring-opening polymer You may blend the 1 type (s) or 2 or more types of high molecular polymer selected.

  When the resist material is prepared in a chemically amplified positive type, a base resin that is insoluble or hardly soluble in a developer (usually an alkali developer) and is soluble in an acid developer can be used. Is done. 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.

Polyacrylic acid and polymethacrylic acid can be made insoluble or hardly soluble in an alkali developer by replacing the hydrogen atom of the carboxyl group with an acid labile group. Since the polymer compound according to the present invention has (meth) acrylate having an ester substituted with an acid labile group as a repeating unit, a chemically amplified positive type can be used as long as it is a resist material using this polymer compound as a base resin. It can be suitably used as a resist material.
The acid labile group used in this case is variously selected and is not particularly limited, but may be the same or different, particularly those represented by the groups substituted by the following formulas (A-1) to (A-3). Can be mentioned.

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 or a group represented by the above general formula (A-3) is shown. Specific examples of the tertiary alkyl group include a tert-butyl group, a tert-amyl group, a 1,1-diethylpropyl group, and 1-ethyl. Cyclopentyl 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, etc. Specific examples of the trialkylsilyl group include a trimethylsilyl group, a triethylsilyl group, a 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, specific examples of the repeating unit of (meth) acrylate having a lactone as the adhesive group contained in the polymer compound according to the present invention are shown below.

上記式中、Ｒ¹⁵は水素原子、メチル基である。

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

  Next, the repeating unit of the (meth) acrylate which has a hydroxyl group as an adhesive group which the high molecular compound which concerns on this invention contains is specifically illustrated below.

上記式中、Ｒ¹⁵は水素原子、メチル基である。

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

  The polymer compound according to the present invention has at least a sulfonium salt having a polymerizable unsaturated bond, (meth) acrylate having a lactone or hydroxy group as an adhesive group, and an ester substituted with an acid labile group (meth). Although it is a copolymer obtained by copolymerizing acrylate, it may further contain a repeating unit of (meth) acrylate having an adhesive group shown below.

上記式中、Ｒ¹⁵は水素原子、メチル基である。

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

  Furthermore, the polymer compound according to the present invention may include the following styrene-based repeating units.

上記式中、Ｒ¹⁵は水素原子、メチル基であり、ｐは０〜２の整数である。

In the above formula, R ¹⁵ is a hydrogen atom or a methyl group, and p is an integer of 0-2.

  Furthermore, the polymer compound 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.

上記式中、ｎは０または１である。

In the above formula, n is 0 or 1.

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

  The resist material of the present invention proposes a polymer-type sulfonium salt acid generator obtained by polymerizing a sulfonium salt having a polymerizable unsaturated bond, but 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 And may form a ring, and in the case of forming a ring, R ^101b and R ^101c each represent an alkylene group having 1 to 6 carbon atoms, and K ⁻ represents a non-nucleophilic counter ion.)

R ^101a , R ^101b and R ^101c may be the same as or different from each other. Specifically, as an alkyl group, methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, sec-butyl Group, tert-butyl group, pentyl group, hexyl group, heptyl group, octyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclopropylmethyl group, 4-methylcyclohexyl group, cyclohexylmethyl group, norbornyl group, adamantyl group, etc. Is mentioned. Examples of the alkenyl group include a vinyl group, an allyl group, a propenyl group, a butenyl group, a hexenyl group, and a cyclohexenyl group. Examples of the oxoalkyl group include 2-oxocyclopentyl group, 2-oxocyclohexyl group, and the like. 2-oxopropyl group, 2-cyclopentyl-2-oxoethyl group, 2-cyclohexyl-2-oxoethyl group, 2- (4 -Methylcyclohexyl) -2-oxoethyl group and the like can be mentioned. Examples of the oxoalkenyl group include 2-oxo-4-cyclohexenyl group and 2-oxo-4-propenyl group. Examples of the aryl group include a phenyl group, a naphthyl group, a p-methoxyphenyl group, an m-methoxyphenyl group, an o-methoxyphenyl group, an ethoxyphenyl group, a p-tert-butoxyphenyl group, and an m-tert-butoxyphenyl group. Alkylphenyl groups such as alkoxyphenyl groups, 2-methylphenyl groups, 3-methylphenyl groups, 4-methylphenyl groups, ethylphenyl groups, 4-tert-butylphenyl groups, 4-butylphenyl groups, dimethylphenyl groups, etc. Alkyl naphthyl groups such as methyl naphthyl group and ethyl naphthyl group, alkoxy naphthyl groups such as methoxy naphthyl group and ethoxy naphthyl group, dialkyl naphthyl groups such as dimethyl naphthyl group and diethyl naphthyl group, dimethoxy naphthyl group and diethoxy naphthyl group Dialkoxynaphthyl group And the like. Examples of the aralkyl group include a benzyl group, a phenylethyl group, and a phenethyl group. As the aryloxoalkyl group, 2-aryl-2-oxoethyl group such as 2-phenyl-2-oxoethyl group, 2- (1-naphthyl) -2-oxoethyl group, 2- (2-naphthyl) -2-oxoethyl group and the like Groups and the like. Non-nucleophilic counter ions of K ⁻ include halide ions such as chloride ion and bromide ion, fluoroalkyl sulfonates such as triflate, 1,1,1-trifluoroethane sulfonate, and nonafluorobutane sulfonate, tosylate, and benzene sulfonate. 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, phenyliodonium trifluoromethanesulfonate (p-tert-butoxyphenyl), 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 trifluoromethanesulfonate (2-oxocyclohexyl) sulfonium, 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. Moreover, the oxime type acid generator of WO2004 / 074242 A2 can also be mentioned.

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 such an acid generator added is 100 parts of base resin having a polymer type acid generator as a total amount with an acid generator that generates a polymer type acid, particularly the sulfonium salt of the above formula (1) ( The amount is preferably 0 to 15 parts, more preferably 0 to 8 parts relative to parts by mass. 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, but one or more of these may be used in combination, but are not limited thereto. 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. , A cyclic alkyl group or an aryl group having 6 to 20 carbon atoms, and 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 be blended with 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 mass, more preferably 0.02 to 1% by mass in 100% by mass of the resist composition. If it is 0.01% by mass or more, the effect of improving coating properties and storage stability is sufficiently obtained, and if it is 2% by mass or less, the resolution of the resist material is less likely to deteriorate.

  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 Limited), Surflon “S-141”, “S-145”, “KH-20”, “ KH-40 "(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”, “X-70-093” (all manufactured by Shin-Etsu Chemical Co., Ltd.), and the like. Preferably, Florard “FC-430”, “FC-4430” (manufactured by Sumitomo 3M), “X-70-093” (manufactured by Shin-Etsu Chemical Co., Ltd.), “KH-20” (Asahi Glass 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, and the substrate is exposed through this liquid. 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 based on the polymer-type sulfonium salt according to the present invention has no solubility of the acid generator in water, so that a good resist pattern can be obtained and is particularly preferably used for immersion lithography. it can.

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

[Synthesis Example 1] Synthesis of 4-tert-butoxyphenyldiphenylsulfonium perfluoro-4-ethylcyclohexylsulfonate
2-tert-butoxyphenyldiphenylsulfonium p-toluenesulfonate 20.1g (0.040mol) and potassium perfluoro-4-ethylcyclohexanesulfonate 19.8g (0.040mol) were added to 200g of dichloromethane and 200g of water and stirred at room temperature for 2 hours. . Insoluble matter was filtered, and the organic layer was separated. The organic layer was then washed 5 times with 200 g of water. Dichloromethane was distilled off under reduced pressure with a rotary evaporator, and recrystallization was performed by adding diethyl ether to 36 g of the resulting residue. Filtration under reduced pressure and drying under reduced pressure yielded 22.5 g of the desired product as white crystals (yield 71.2%).
The results of time-of-flight mass spectrometry (TOFMS) and nuclear magnetic resonance spectrum (1H-NMR) of the obtained compound are shown.
TOFMS (MALDI)
POSITIVE M + 335 (4-tert-BuOPhS + (Ph) 2 equivalent)
M + 279 (4-HOPhS + (Ph) 2 equivalent; progress of cleavage of tert-butoxy group during analysis)
NEGATIVE M-461 (4-C2F5-C6F10-SO3- equivalent)
1H-NMR (CDCl3: ppm)
1.48 (9H, single wire, Ha), 7.22-7.25 (2H, double wire, Hb), 7.65-7.76 (12H, multiple wire, Hc)

[Synthesis Example 2] Synthesis of 4-oxyphenyldiphenylsulfonium 4-methacrylate methacrylate and perfluoro-4-ethylcyclohexylsulfonate 20 g (0.025 mol) of 4-tert-butoxyphenyldiphenylsulfonium perfluoro-4-ethylcyclohexylsulfonate obtained in Synthesis Example 1 ) Was dissolved in 200 g of dichloromethane, 0.6 g (0.0025 mol) of 10-camphorsulfonic acid was added, and the mixture was heated and stirred at 40 ° C. for 4 hours. The reaction mixture was ice-cooled, 2.7 g (0.026 mol) of methacryloyl chloride was added, and 2.8 g (0.028 mol) of triethylamine was added at a temperature not exceeding 10 ° C. To the reaction solution, 2.0 g of 10-camphorsulfonic acid and 100 g of water were added to separate the organic layer. The organic layer was then washed 5 times with 200 g of water. Dichloromethane was distilled off under reduced pressure using a rotary evaporator, and diethyl ether was added to the resulting residue for recrystallization. Filtration under reduced pressure and drying under reduced pressure gave 9.6 g of the desired product as white crystals (yield 47%).
The results of time-of-flight mass spectrometry (TOFMS) and nuclear magnetic resonance spectrum (1H-NMR) of the obtained object are shown.
TOFMS (MALDI)
POSITIVE M + 347 (4- (CH2 = C (CH3) -CO-O PhS + (Ph) 2 equivalent)
NEGATIVE M-461 (4-C2F5-C6F10-SO3- equivalent)
1H-NMR (CDCl3: ppm)
2.046 to 2.050 (3H, triple line, Ha), 5.840 to 5.859 (1H, multiple line, Hb), 6.373 to 6.387 (1H, multiple line, Hc), 7.482 to 7.512 (2H, double line, Hd), 7.65 ~ 7.86 (12H, multi-line, He)

  Using the sulfonium salt having a polymerizable unsaturated bond obtained in Synthesis Example 2, a polymer compound according to the present invention is synthesized below.

[Polymer synthesis example 1]
In a 100 mL flask, 4-methacrylic acid oxyphenyldiphenylsulfonium obtained in Synthesis Example 2, 4.0 g perfluoro-4-ethylcyclohexyl sulfonate, 7.4 g methacrylate-2-adamantylethyl, 5-oxo-4-methacrylic acid 9.7 g of oxatricyclo [4.2.1.0 ^3,7 ] nonan-2-yl, 4.2 g of 3-hydroxy-1-adamantyl methacrylate, and 30 g of tetrahydrofuran as a solvent were added. The reaction vessel was cooled to −70 ° C. in a nitrogen atmosphere, and vacuum degassing and nitrogen flow were repeated three times. After raising the temperature to room temperature, 0.2 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 18.1 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: d11 = 0.05: 0.30: 0.45: 0.20
Mass average molecular weight (Mw) = 9,200
This polymer is referred to as polymer 1.

[Polymer synthesis example 2]
In a 100 mL flask, 4-methacrylic acid oxyphenyldiphenylsulfonium obtained in Synthesis Example 2, 4.0 g perfluoro-4-ethylcyclohexyl sulfonate, 7.4 g methacrylate-2-adamantylethyl, 5-oxo-4-methacrylic acid Oxatricyclo [4.2.1.0 ^3,7 ] nonan-2-yl 7.6 g, methacrylate-3-hydroxy-1-adamantyl 4.2 g, methacrylate 3,5-bis [3,3 3-trifluoro-2-hydroxy-2-trifluoroethylpropyl] cyclohexyl (5.0 g) and 30 g of tetrahydrofuran as a solvent were added. The reaction vessel was cooled to −70 ° C. in a nitrogen atmosphere, and vacuum degassing and nitrogen flow were repeated three times. After raising the temperature to room temperature, 0.2 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 19.9 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: d11: d12 = 0.050: 0.30: 0.35: 0.20: 0.10
Mass average molecular weight (Mw) = 8,700
This polymer is designated as Polymer 2.

[Polymer synthesis example 3]
In a 100 mL flask, 4-methacrylic acid oxyphenyldiphenylsulfonium, perfluoro-4-ethylcyclohexyl sulfonate 4.0 g, methacrylic acid-2-adamantylethyl 7.4 g, methacrylic acid 5-oxo-4-oxatricyclo [4. 2.1.0 ^3,7 ] nonan-2-yl 6.5 g, methacrylic acid-3-hydroxy-1-adamantyl 4.2 g, methacrylic acid 5,6- [3,3,3-trifluoro-2- 5.4 g of hydroxy-2-trifluoromethylpropyl] bicyclo [2.2.1] hept-2-yl and 30 g of tetrahydrofuran as a solvent were added. The reaction vessel was cooled to −70 ° C. in a nitrogen atmosphere, and vacuum degassing and nitrogen flow were repeated three times. After raising the temperature to room temperature, 0.2 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 17.5 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: d11: d13 = 0.05: 0.30: 0.30: 0.20: 0.15
Mass average molecular weight (Mw) = 9,800
This polymer is designated as Polymer 3.

[Polymer Synthesis Example 4]
In a 100 mL flask, 4.0 g of oxyphenyldiphenylsulfonium methacrylate, 4.0 g of perfluoro-4-ethylcyclohexylsulfonate, -3-ethyl-3-exotetracyclomethacrylate [4.4.0.1 ^2,5 . 1 ^7,10 ] dodecanyl 8.2 g, methacrylic acid 3-oxo-2,7-dioxatricyclo [4.2.1.0 ^4,8 ] -9-nonyl 8.9 g, methacrylic acid-3-hydroxy 5.9 g of -1-adamantyl and 30 g of tetrahydrofuran as a solvent were added. The reaction vessel was cooled to −70 ° C. in a nitrogen atmosphere, and vacuum degassing and nitrogen flow were repeated three times. After raising the temperature to room temperature, 0.2 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 19.4 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: b12: c12: d11 = 0.05: 0.30: 0.40: 0.25
Mass average molecular weight (Mw) = 7,600
This polymer is designated as polymer 4.

[Polymer synthesis example 5]
In a 100 mL flask, 8.0 g of 4-methacrylic acid oxyphenyldiphenylsulfonium, perfluoro-4-ethylcyclohexyl sulfonate, methacrylic acid-3-ethyl-3-exotetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodecanyl 8.2 g, methacrylic acid 3-oxo-2,7-dioxatricyclo [4.2.1.0 ^4,8 ] -9-nonyl 7.8 g, methacrylic acid-3-hydroxy 5.1 g of -1-adamantyl and 30 g of tetrahydrofuran as a solvent were added. The reaction vessel was cooled to −70 ° C. in a nitrogen atmosphere, and vacuum degassing and nitrogen flow were repeated three times. After raising the temperature to room temperature, 0.2 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 20.9 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: b12: c12: d11 = 0.10: 0.30: 0.40: 0.20
Mass average molecular weight (Mw) = 8,400
This polymer is designated as polymer 5.

[Polymer Synthesis Example 6]
In a 100 mL flask, methacrylic acid-3-ethyl-3-exotetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodecanyl 8.2 g, methacrylic acid 3-oxo-2,7-dioxatricyclo [4.2.1.0 ^4,8 ] -9-nonyl 7.8 g, methacrylic acid-3-hydroxy 5.9 g of -1-adamantyl, 5.0 g of 3,5-bis [3,3,3-trifluoro-2-hydroxy-2-trifluoroethylpropyl] cyclohexyl methacrylate, and 30 g of tetrahydrofuran as a solvent were added. The reaction vessel was cooled to −70 ° C. in a nitrogen atmosphere, and vacuum degassing and nitrogen flow were repeated three times. After raising the temperature to room temperature, 0.2 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 19.3 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.
Copolymerization ratio b12: c12: d11: d12 = 0.30: 0.35: 0.25: 0.10
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.
Copolymerization composition ratio h1: i1: j1 = 0.35: 0.15: 0.50
Mass average molecular weight (Mw) = 8,100

[Polymer Synthesis Example 8]
In a 100 mL flask, 4-methacrylic acid oxyphenyl diphenylsulfonium, perfluoro-4-ethylcyclohexyl sulfonate 8.0 g, methacrylic acid-2-adamantylethyl 7.4 g, methacrylic acid-3-hydroxy-1-adamantyl 9.2 g,
11.0 g of 3,5-bis [3,3,3-trifluoro-2-hydroxy-2-trifluoroethylpropyl] cyclohexyl methacrylate and 30 g of tetrahydrofuran as a solvent were added. The reaction vessel was cooled to −70 ° C. in a nitrogen atmosphere, and vacuum degassing and nitrogen flow were repeated three times. After raising the temperature to room temperature, 0.2 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 39.8 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 a11: b11: d11: d12 = 0.10: 0.30: 0.40: 0.20
Mass average molecular weight (Mw) = 8,500
This polymer is designated as polymer 8.

[Polymer synthesis example 9]
In a 100 mL flask, 4-methyloxyphenyldiphenylsulfonium methacrylate, 12.0 g of perfluorobutanesulfonate, 7.4 g of 2-adamantylethyl methacrylate, 3-oxo-2,7-dioxatricyclomethacrylate [4.2 .1.0 ^4,8] -9-nonyl 9.8 g, 4-hydroxy styrene 15.0 g, of tetrahydrofuran as a solvent 30g. 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 39.8 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 a12: b11: c12: d14 = 0.15: 0.25: 0.20: 0.40
Mass average molecular weight (Mw) = 7,900
This polymer is designated as polymer 9.

[Polymer Synthesis Example 10]
In a 100 mL flask, 7.4 g of 2-adamantylethyl methacrylate, 3-oxo-2,7-dioxatricyclomethacrylate [4.2.1.0 ^4,8 ] -9-nonyl 9.8 g, 4 -19.0 g of hydroxystyrene and 30 g of tetrahydrofuran as a solvent were added. The reaction vessel was cooled to −70 ° C. in a nitrogen atmosphere, and vacuum degassing and nitrogen flow were repeated three times. After raising the temperature to room temperature, 0.2 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 39.8 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 b11: c12: d14 = 0.25: 0.30: 0.45
Mass average molecular weight (Mw) = 7,800
This polymer is designated as polymer 10.

(Examples and comparative examples)
[Preparation of resist material]
Polymers shown in the above polymer synthesis examples 1 to 8, acid generators (PAG1, PAG2, and PAG3) represented by the following formulas, acid growth agents (PAAG1), dissolution inhibitors (DRI-1), dissolution accelerators ( DRR-1) and a basic compound (2NapMp, AdMp) were dissolved in a solvent containing 0.01% by mass of FC-430 (manufactured by Sumitomo 3M) with the composition shown in Table 1, and a resist material was prepared. Resist solutions were prepared by filtering the composition through a 0.2 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： ２ＮａｐＭｐ、ＡｄＭｐ（下記構造式参照）

有機溶剤： ＰＧＭＥＡ（プロピレングリコール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, and PAG3 (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 compounds: 2NapMp, AdMp (see structural formula below)

Organic solvent: PGMEA (propylene glycol methyl ether acetate), CyHO (cyclohexanone)

[Exposure patterning evaluation]
The resist material solution thus prepared (Examples 1 to 13 and Comparative Examples 1 to 3) was coated on a silicon substrate with an antireflection film solution (ARC-29A manufactured by Nissan Chemical Industries, Ltd.) at 200 ° C. for 60 seconds. An antireflective film (78 nm film thickness) substrate prepared by baking was spin-coated and baked (prebaked) at 120 ° C. for 60 seconds using a hot plate to form a resist film having a film thickness of 200 nm.
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 120 ° 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 13 and Comparative Examples 1 to 3).

The obtained resist pattern was evaluated as follows, and the results are shown in Table 1.
The exposure amount for resolving the line and space of the 0.12 μm group 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 (Examples 1 to 13 and Comparative Examples 1 to 3) prepared above, a resist film was prepared, exposed, and developed in the same manner as described above. The shape of the space pattern was observed.
Further, except for performing pseudo immersion exposure by performing a 300-second pure water rinse between pre-bake and exposure (before exposure) and / or between exposure and PEB (after exposure). Similarly, the resist film was produced, exposed and developed, and the shape of the 110 nm line and space pattern after development was observed.
The results obtained are summarized in Table 2.

[Electron beam drawing evaluation]
In drawing evaluation, a positive resist material was prepared by filtering a solution obtained by dissolving the polymers shown in the polymer synthesis examples 9 and 10 with the composition shown in Table 3 through a 0.2 μm size filter.

  The obtained positive resist material is spin-coated on a Si substrate having a diameter of 6 inches using a clean track Mark 5 (manufactured by Tokyo Electron), prebaked on a hot plate at 110 ° C. for 90 seconds, and a 100 nm resist film Was made. For this, drawing in a vacuum chamber was performed at an HV voltage of 50 keV using a Hitachi HL-800D.

Immediately after drawing, post-exposure baking (PEB) was performed at 110 ° C. for 90 seconds on a hot plate using a clean track Mark 5 (manufactured by Tokyo Electron), and paddle development was performed for 30 seconds with a 2.38 mass% TMAH aqueous solution. A positive pattern was obtained.
The obtained resist pattern was evaluated as follows.
The exposure amount for resolving 0.12 μm line and space at 1: 1 was defined as resist sensitivity, and the minimum dimension resolved at this time was defined as resolution.
Table 3 shows the results of resist composition, sensitivity and resolution in EB exposure.

表３中の酸発生剤ＰＡＧ３および有機溶剤ＰＧＭＥＡについては、上記表１と同様である。

The acid generator PAG3 and the organic solvent PGMEA in Table 3 are the same as in Table 1 above.

From the results of Tables 1 and 2, the resist material of the present invention (Examples 1 to 13) has high sensitivity and high resolution, and changes in shape even with long-term rinsing with water compared to Comparative Examples 1 to 3. It was confirmed that the film can be sufficiently applied to immersion exposure.
From the results of Table 3, the resist material of the present invention (Example 14) has high sensitivity and high resolution in EB exposure, and is superior to the case where only the monomer type acid generator is added (Comparative Example 4). Was confirmed.

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 (6)

  At least a sulfonium salt having a polymerizable unsaturated bond, a (meth) acrylate having a lactone or hydroxy group as an adhesive group, and a (meth) acrylate having an ester substituted with an acid labile group are copolymerized. A resist material comprising a molecular compound. The resist material according to claim 1, wherein a repeating unit obtained by polymerizing the sulfonium salt having a polymerizable unsaturated bond is represented by the following general formula (1).

(In the formula, R ¹ is a hydrogen atom, a methyl group, R ² is a phenylene group, —O—R ⁶ —, —C (═O) —X ¹ —R ⁶ —, —C (═O) —O—C ₂ H ₄ —O—Y ¹ —, —C (═O) —O—Z ¹ —C (═O) —CH ₂ —, —Z ¹ —C (═O) —CH ₂ —, —C (= O) —O—Z ¹ —CH ₂ —, —C (═O) —O—CH ₂ —C (═O) —O—Z ¹ —, —C (═O) —O—C ₂ H ₄ —. Any one of C (═O) —O—Z ¹ —, wherein X ¹ is an oxygen atom or NH, and R ⁶ is a linear, branched or cyclic alkylene group having 1 to ⁶ carbon atoms or a phenylene group. , A carbonyl group, an ester group or an ether group, Y ¹ is any ^one of a phenylene group, a naphthylene group and an anthrylene group, Z ¹ is a phenylene group, and R ³ and R ⁴ are the same or different. It is a linear, branched or cyclic alkyl group having 1 to 12 carbon atoms, and may contain a carbonyl group, an ester group or an ether group, or an aryl group having 6 to 12 carbon atoms or 7 carbon atoms. Represents an aralkyl group or a thiophenyl group of -20, R ³ and R ⁴ may be bonded to form a ring, and R ⁵ represents a carbon number in which some or all of the hydrogen atoms are substituted with fluorine atoms. 4-20 linear, branched, cyclic, or ring-containing alkyl or alkenyl groups, which may have one or more benzene rings or ether groups, or some or all of the hydrogen atoms are fluorine (It is an aryl group having 4 to 20 carbon atoms substituted with an atom.)   The resist material according to claim 1, wherein the resist material is a chemically amplified positive resist material.   The resist according to any one of claims 1 to 3, wherein the resist material further contains one or more of an organic solvent, a basic compound, and a dissolution inhibitor. material.   At least a step of applying the resist material according to any one of claims 1 to 4 on a substrate, a step of exposing to high energy rays after heat treatment, and a step of developing using a developer. The pattern formation method characterized by including.   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 5, wherein immersion exposure is performed.