JP5148090B2 - Resist material and pattern forming method using the same - Google Patents

Description

  In the exposure with a high energy beam, the present invention has a significantly high alkali dissolution rate contrast before and after exposure, high sensitivity and high resolution, low line edge roughness, and excellent etching resistance. The present invention relates to a resist material suitable as a fine pattern forming material for LSI manufacturing or photomask pattern production, and more particularly to a chemically amplified positive resist material and a pattern forming method using the same.

  In recent years, along with higher integration and higher speed of LSI, pattern rule miniaturization is progressing rapidly. The background of rapid progress in miniaturization includes higher NA of projection lenses, improved performance of resist materials, and shorter wavelengths. In particular, the shortening of the wavelength from i-line (365 nm) to KrF (248 nm) has brought about a major change, and the mass production of 0.18 micron rule devices has become possible. Chemical amplification positive resist materials using acid as a catalyst (for example, refer to Patent Documents 1 and 2) have excellent characteristics for increasing the resolution and sensitivity of resist materials, and are particularly suitable for deep ultraviolet lithography. It became the mainstream resist material.

  Resist materials for KrF excimer lasers are generally used in 0.3 micron processes, passed through the 0.25 micron rule, and are now applied to mass production of the 0.18 micron rule. Has also begun, and the momentum of miniaturization is increasingly accelerated. The shortening of the wavelength from the KrF excimer laser to the ArF excimer laser (193 nm) is expected to reduce the design rule to 0.13 μm or less, but conventionally used novolak and polyvinylphenol resins Has a very strong absorption in the vicinity of a wavelength of 193 nm, so it was difficult to use as a base resin for resist. Therefore, acrylic resins and cycloolefin-based alicyclic resins have been studied in order to ensure transparency and necessary dry etching resistance (see, for example, Patent Documents 3 to 6).

  In particular, a resist material having a high resolution (meth) acrylic resin as a base resin has been studied. As a (meth) acrylic resin, a combination of a (meth) acrylic unit having a methyladamantane ester as an acid labile group unit and a (meth) acrylic unit having a lactone ring ester as an adhesive group unit has been proposed ( For example, see Patent Document 7). Furthermore, norbornyl lactone has been proposed as an adhesive group with enhanced etching resistance (see, for example, Patent Documents 8 to 10).

  One of the problems in ArF lithography is reduction of line edge roughness and reduction of residues after development. One factor of line edge roughness is swelling during development. Polyhydroxystyrene phenol used as a resist material for KrF lithography is a weakly acidic group, and it is difficult to swell due to moderate alkali solubility, but a polymer containing a highly hydrophobic alicyclic group is acidic. Therefore, swelling during development tends to occur.

  The naphthalene ring is an aromatic having a small absorption at a wavelength of 193 nm, and an ArF resist material based on a vinyl naphthalene copolymer has been proposed (see, for example, Non-Patent Document 1 and Patent Documents 11 and 12). A naphthalene ring having a hydroxy group is expected to be effective in preventing swelling during development because it exhibits weak acidity such as phenol. Furthermore, the naphthalene ring has an advantage of high etching resistance.

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 and 65 nm node devices. As lithography technology for the next 45nm node, although 157nm lithography using F ₂ laser initially is promising, the quality of the CaF ₂ single crystal used in projection lens, the optical system by not require the use of hard pellicles 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 2).

  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.

JP-B-2-27660 JP 63-27829 A JP-A-9-73173 Japanese Patent Laid-Open No. 10-10739 Japanese Patent Laid-Open No. 9-230595 International Publication No. 97/33198 Pamphlet JP-A-9-90637 JP 2000-26446 A JP 2000-159758 A JP 2002-371114 A JP 2004-163877 A JP 2002-107933 A J. et al. Photopolym. Sci. Technol. , Vol. 11, no. 3, p489 (1998) 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 that has high sensitivity and high resolution in exposure with a high energy beam, and can suppress swelling during development. Therefore, an object of the present invention is to provide a resist material having a small line edge roughness, a small amount of residue after development, excellent dry etching resistance, and suitable for immersion lithography, and a pattern forming method using the resist material And

（式中、Ｒ¹は同一又は異種の水素原子又はメチル基を示す。Ｒ^２は単結合、−Ｏ−、−Ｃ（＝Ｏ）−Ｏ−、−Ｃ（＝Ｏ）−ＮＨ−のいずれかである。Ｒ^３はヒドロキシ基、酸不安定基またはアセチル基で置換されたヒドロキシ基、カルボキシル基、酸不安定基で置換されたカルボキシル基のいずれかである。Ｒ^４はフェニレン基、−Ｏ−Ｒ^７−、−Ｃ（＝Ｏ）−Ｘ^１−Ｒ^７−、−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）−Ｘ^１−Ｒ^７−Ｚ^１−のいずれかである。Ｘ^１は酸素原子またはＮＨである。Ｒ^７は炭素数１〜６の直鎖状、分岐状または環状のアルキレン基、または炭素数６〜８のアリーレン基であり、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^５、Ｒ^６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^５、Ｒ^６は結合して環を形成してもよい。Ｋ^-は非求核性対向イオンを表す。ｍは１又は２であり、ａ、ｂは、０＜ａ＜１．０、０＜ｂ≦０．８の範囲である。） The present invention has been made to solve the above problems, and provides a resist material comprising at least a polymer compound having a repeating unit represented by the following general formulas (a) and (b). (Claim 1).

(In the formula, R ¹ represents the same or different hydrogen atom or methyl group. R ² represents a single bond, —O—, —C (═O) —O—, —C (═O) —NH—. R ³ is any one of a hydroxy group, an acid labile group, a hydroxy group substituted with an acetyl group, a carboxyl group, and a carboxyl group substituted with an acid labile group, R ⁴ is a phenylene group,- O—R ⁷ —, —C (═O) —X ¹ —R ⁷ —, —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) -X ¹ -R ⁷ -Z ^1- , X ¹ is an oxygen atom or NH, R ⁷ is a linear, branched or cyclic alkylene group having 1 to 6 carbon atoms, or carbon number An arylene group of 6 to 8, which may contain 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, and Z ¹ is a phenylene group. ⁵ , R ⁶ is the same or different 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 6 to 12 carbon atoms. Or an aryl group having 7 to 20 carbon atoms or a thiophenyl group, R ⁵ and R ⁶ may be bonded to form a ring, and K ⁻ represents a non-nucleophilic counter ion. Is 1 or 2, and a and b are in the range of 0 <a <1.0 and 0 <b ≦ 0.8.)

Such a resist material according to the present invention has a significantly high alkali dissolution rate contrast before and after exposure, high sensitivity and high resolution in exposure with a high energy beam, and swelling during development is suppressed. The line edge roughness is small, the etching residue is small, and the etching resistance is excellent. Therefore, since it has these characteristics, it is extremely practical and suitable as a fine pattern forming material for VLSI manufacturing or photomask pattern production.
In addition, even when the resist material according to the present invention is applied to immersion lithography, the problem that water soaks into the resist and the resist swells hardly occurs, and the pattern shape hardly changes even under water exposure (immersion exposure). Absent. Therefore, the resist material of the present invention can be suitably used for immersion lithography.

（式中、Ｒ¹は水素原子又はメチル基を示す。Ｒ^８はラクトンを有する密着性基、Ｒ^９は酸不安定基である。Ｒ^１０は、水素原子、メチル基、−ＣＨ_２−Ｃ（＝Ｏ）−Ｏ−ＣＨ_３のいずれかである。ｃ、ｄは、０≦ｃ≦０．８、０≦ｄ≦０．８、０＜ｃ＋ｄ≦０．８の範囲である。） In this case, it is preferable that the polymer compound further includes a repeating unit represented by the following general formula (c) and / or (d) (Claim 2).

(In the formula, R ¹ represents a hydrogen atom or a methyl group. R ⁸ is an adhesive group having a lactone, R ⁹ is an acid labile group. R ¹⁰ is a hydrogen atom, a methyl group, —CH ₂ —C. (= O) -O-CH _3. c and d are in a range of 0 ≦ c ≦ 0.8, 0 ≦ d ≦ 0.8, and 0 <c + d ≦ 0.8.)

  Thus, it can be set as the resist material which has desired hydrophilicity, alkali solubility, and adhesiveness by containing repeating unit (c) and / or (d) further.

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

  As described above, the resist material containing the polymer compound has a polymer type acid generator as the repeating unit (b), and this removes the acid leaving group by the acid generated during exposure, so that a resist exposed portion is obtained. Can be made to be a chemically amplified positive resist material capable of obtaining a highly accurate pattern.

  In this case, the resist material of the present invention may further contain any one or more of an organic solvent, a basic compound, a dissolution inhibitor, and a surfactant (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. In addition, the coating property of the resist material can be further improved or controlled by adding a surfactant.

  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, it is preferable that the high energy ray has a wavelength of 200 nm or less.

  The resist material according to the present invention can be suitably used particularly in exposure with a high energy ray having a wavelength of 200 nm or less, and has excellent sensitivity at an exposure wavelength in this range.

  Further, 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. 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, and it is difficult for water to penetrate into the resist to swell the resist. Underwater exposure (immersion exposure) There is almost no change in the pattern shape. 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. It has excellent characteristics, has small dimensional difference between isolated pattern and dense pattern, small line edge roughness, excellent dry etching resistance, and lack of solubility of generated acid in water. ) Can provide a resist material that is very effective for precise microfabrication with almost no change in pattern shape.

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

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

  Therefore, an analysis of immersion water confirmed that the acid generator and the anion generated by 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 with high acid generation efficiency, but adding a large amount of the monomer component acid generator reduces the rigidity of the film, so that the acid diffusion distance is long. 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-described object based on such knowledge, and as a result, an acid generator formed by polymerizing a sulfonium salt having a polymerizable unsaturated bond, particularly the following general formula: Since the polymer compound having a repeating unit (b) obtained by polymerizing the sulfonium salt shown is highly sensitive to ArF excimer laser light and has no solubility in water, it can cope with ArF immersion exposure, It has sufficient thermal stability and storage stability, and a resist material containing this has high resolution, can improve line edge roughness and density dependence, It was found that it is extremely effective for processing.

  Furthermore, the inventors of the present invention have high sensitivity and high resolution in exposure with high energy rays, and since the swelling at the time of development is suppressed, the line edge roughness is small, and the residue after development is small. In order to obtain a type resist material, intensive studies were conducted.

  The polyhydroxystyrene used in KrF excimer laser lithography has a characteristic of less swelling in an alkaline developer because it has a phenol group having moderate acidity. Since the benzene ring has very strong absorption at a wavelength of 193 nm, it cannot be used, and it has been proposed to use vinylnaphthalene whose absorption maximum value is shifted to the long wavelength side. However, although vinyl naphthalene has a smaller absorption than styrene, it has a considerable absorption for use in a resist material, so that the introduction rate is limited and the resist film has to be thinned.

In addition, the problem of falling after development of the resist pattern has become serious, and the resist film is becoming thinner. In the 45 nm generation, a film thickness of 150 nm or less has been studied, and at the same time, a decrease in etching resistance has become serious. Further, the problem that the line edge roughness increases with the thinning of the film is also surfaced. As the resist film becomes thinner, the larger the absorption of the resist material, the more advantageous is that the reverse taper shape does not occur.
In addition, since the resist material for implants becomes a highly reflective substrate, it is necessary to actively reduce the transmittance in order to suppress substrate reflection. Conventionally, a method of increasing the amount of acid generator (PAG) added has been effective in reducing the transmittance. However, an increase in the amount of PAG added more than necessary leads to a decrease in characteristics such as a decrease in etching resistance, a decrease in resolution due to an increase in acid diffusion, and an increase in proximity bias.

  Accordingly, as a result of various studies, the present inventors have considered the introduction of a phenolic hydroxyl group, and accordingly, hydroxynaphthalene having a polymerizable unsaturated bond such as vinyl, vinyl ether, (meth) acrylate such as the repeating unit (a). And a sulfonium salt having a polymerizable unsaturated bond such as the repeating unit (b) were studied. Furthermore, it was also found that hydrophilicity, alkali solubility, and adhesion can be balanced by copolymerizing with a repeating unit (c) having a lactone as an adhesion group. In particular, adhesion having (meth) acrylate having a bridged cyclic lactone group, (meth) acrylate having an acid leaving group such as repeating unit (d), and (meth) acrylate having a hydroxynaphthyl group pendant By using as a base resin a polymer compound obtained by combining a sulfonium salt having a polymerizable group and a polymerizable unsaturated bond, it has high sensitivity and high resolution, and less line edge roughness due to swelling during development. The inventors have conceived that a positive resist material having little residue after development and excellent in dry etching resistance can be provided, and the present invention has been completed.

（式中、Ｒ¹は同一又は異種の水素原子又はメチル基を示す。Ｒ^２は単結合、−Ｏ−、−Ｃ（＝Ｏ）−Ｏ−、−Ｃ（＝Ｏ）−ＮＨ−のいずれかである。Ｒ^３はヒドロキシ基、酸不安定基またはアセチル基で置換されたヒドロキシ基、カルボキシル基、酸不安定基で置換されたカルボキシル基のいずれかである。Ｒ^４はフェニレン基、−Ｏ−Ｒ^７−、−Ｃ（＝Ｏ）−Ｘ^１−Ｒ^７−、−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）−Ｘ^１−Ｒ^７−Ｚ^１−のいずれかである。Ｘ^１は酸素原子またはＮＨである。Ｒ^７は炭素数１〜６の直鎖状、分岐状または環状のアルキレン基、またはフェニレン基等を含む炭素数６〜８のアリーレン基であり、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^５、Ｒ^６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^５、Ｒ^６は結合して環を形成してもよい。Ｋ^-は非求核性対向イオンを表す。ｍは１又は２であり、ａ、ｂは、０＜ａ＜１．０、０＜ｂ≦０．８の範囲である。） That is, the resist material according to the present invention includes at least a polymer compound having a repeating unit represented by the following general formulas (a) and (b).

(In the formula, R ¹ represents the same or different hydrogen atom or methyl group. R ² represents a single bond, —O—, —C (═O) —O—, —C (═O) —NH—. R ³ is any one of a hydroxy group, an acid labile group, a hydroxy group substituted with an acetyl group, a carboxyl group, and a carboxyl group substituted with an acid labile group, R ⁴ is a phenylene group,- O—R ⁷ —, —C (═O) —X ¹ —R ⁷ —, —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) -X ¹ -R ⁷ -Z ^1- , X ¹ is an oxygen atom or NH, R ⁷ is a linear, branched or cyclic alkylene group having 1 to 6 carbon atoms, or phenyl An arylene group having 6 to 8 carbon atoms including alkylene group, a carbonyl group, optionally .Y ¹ also contain ester or ether groups are phenylene group, a naphthylene group, any of anthrylene group .Z ¹ R ⁵ and R ⁶ are the same or different linear, branched or cyclic alkyl groups having 1 to 12 carbon atoms and may contain a carbonyl group, an ester group or an ether group. or an aralkyl group, thiophenyl group aryl group or C 7-20 having 6 to 12 carbon atoms ^also, R 5, ^{R 6} mAY form a ring .K ^-. the non-nucleophilic M represents 1 or 2, and a and b are in the range of 0 <a <1.0 and 0 <b ≦ 0.8.)

  Such a resist material according to the present invention has a significantly high alkali dissolution rate contrast before and after exposure, high sensitivity and high resolution in exposure with a high energy beam, and swelling during development is suppressed. The line edge roughness is small, the residue after development is small, and the etching resistance is excellent. Therefore, since it has these characteristics, it is extremely practical and suitable as a fine pattern forming material for VLSI manufacturing or photomask pattern production.

  Further, since the repeating unit (a) is not dissolved in water, even if the resist material of the present invention is applied in immersion lithography, the problem that water soaks into the resist and the resist swells hardly occurs. Further, since the acid generated from the polymer type acid generator shown in the repeating unit (b) is not soluble in water, there is almost no change in pattern shape even under water exposure (immersion exposure). Therefore, the resist material of the present invention can be suitably used for immersion lithography.

（式中、Ｒ¹は水素原子又はメチル基を示す。Ｒ^８はラクトンを有する密着性基、Ｒ^９は酸不安定基である。Ｒ^１０は、水素原子、メチル基、−ＣＨ_２−Ｃ（＝Ｏ）−Ｏ−ＣＨ_３のいずれかである。ｃ、ｄは、０≦ｃ≦０．８、０≦ｄ≦０．８、０＜ｃ＋ｄ≦０．８の範囲である。） In this case, it is preferable that the polymer compound further includes a repeating unit represented by the following general formula (c) and / or (d).

(In the formula, R ¹ represents a hydrogen atom or a methyl group. R ⁸ is an adhesive group having a lactone, R ⁹ is an acid labile group. R ¹⁰ is a hydrogen atom, a methyl group, —CH ₂ —C. (= O) -O-CH _3. c and d are in a range of 0 ≦ c ≦ 0.8, 0 ≦ d ≦ 0.8, and 0 <c + d ≦ 0.8.)

  Thus, it can be set as the resist material which has desired hydrophilic property, alkali solubility, and adhesiveness by containing the said repeating unit (c) and / or (d) further.

  Next, examples of the monomer a for obtaining the repeating unit represented by the general formula (a) include those shown below.

  In the above formula, R is a hydrogen atom or an acid labile group. When the hydroxy group is substituted with an acetyl group, the acetyl group can be deprotected by alkali hydrolysis after polymerization to form a hydroxy group, and the hydroxy group is substituted with an acid labile group such as acetal Further, it can be deprotected by hydrolysis with an acid catalyst to form a hydroxy group, or deprotection after polymerization may not be performed.

  The polymer compound of the present invention copolymerizes a polymerizable unsaturated compound having a naphthyl group corresponding to the general formula (a) and a sulfonium salt having a polymerizable unsaturated bond corresponding to the general formula (b). It is essential.

  Here, examples of the monomer b for obtaining the repeating unit represented by the general formula (b) include those shown below.

In the above formula, K ⁻ represents a non-nucleophilic counter ion. K ^- a non-nucleophilic counter chloride ions as the ion, halide ions such as bromide ion, triflate, 1,1,1-trifluoroethane sulfonate, fluoroalkyl sulfonate such as nonafluorobutanesulfonate, tosylate, benzenesulfonate , Xylene sulfonate, mesitylene sulfonate, t-butylbenzene sulfonate, 2,4,6-triisopropylbenzene sulfonate, aryl sulfonate such as naphthalene sulfonate, alkyl sulfonate such as mesylate, butane sulfonate, camphor sulfonate, bisalkylsulfonylimide, trisalkylsulfonyl Methide and the like. In particular, fluoroalkyl sulfonates, sulfonimides and sulfonemethides shown below are preferably used.

  Although the synthesis method of the methacryl pendant sulfonium salt shown in the specific example of the monomer b 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.

上記式中、Ｋ^-は前記と同様である。

In the above formula, K ⁻ is the same as described above.

  Here, examples of the monomer c ((meth) acrylate having a lactone adhesive group) for obtaining the repeating unit represented by the general formula (c) include those shown below.

  Here, examples of the monomer d ((meth) acrylate having an acid labile group) for obtaining the repeating unit represented by the general formula (d) include those shown below.

（ここで、Ｒ¹は前述の通り、Ｒ^９は酸不安定基である。）

(Wherein, R ¹ is as defined above, ^{R 9} is an acid labile group.)

In the above formula, the acid labile groups represented by R and R ⁹ are variously selected and may be the same or different, and the hydrogen atom of the hydroxyl group or the hydroxyl group of the carboxyl group is particularly represented by the following formula (AL-10) , A group represented by (AL-11), a tertiary alkyl group having 4 to 40 carbon atoms represented by the following formula (AL-12), an oxoalkyl group having 4 to 20 carbon atoms, or the like Is mentioned.

In the formulas (AL-10) and (AL-11), R ⁵¹ and R ⁵⁴ are monovalent hydrocarbon groups such as linear, branched or cyclic alkyl groups having 1 to 40 carbon atoms, particularly 1 to 20 carbon atoms. And may contain heteroatoms such as oxygen, sulfur, nitrogen and fluorine. R ⁵² and R ⁵³ are each a monovalent hydrocarbon group such as a hydrogen atom, a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms, and may contain heteroatoms such as oxygen, sulfur, nitrogen and fluorine. Well, a5 is an integer of 0-10. R ⁵² and R ⁵³ , R ⁵² and R ⁵⁴ , R ⁵³ and R ⁵⁴ are bonded to each other to form a ring having 3 to 20 carbon atoms, particularly 4 to 16 carbon atoms together with the carbon atom or carbon atom and oxygen atom to which they are bonded. May be.
R ⁵⁵ , R ⁵⁶ , and R ⁵⁷ are each a monovalent hydrocarbon group such as a linear, branched, or cyclic alkyl group having 1 to 20 carbon atoms, and include heteroatoms such as oxygen, sulfur, nitrogen, and fluorine. But you can. Alternatively, R ⁵⁵ and R ⁵⁶ , R ⁵⁵ and R ⁵⁷ , R ⁵⁶ and R ⁵⁷ may be bonded to form a ring having 3 to 20 carbon atoms, particularly 4 to 16 carbon atoms, together with the carbon atom to which they are bonded.

  Specific examples of the compound represented by the formula (AL-10) include tert-butoxycarbonyl group, tert-butoxycarbonylmethyl group, tert-amyloxycarbonyl group, tert-amyloxycarbonylmethyl group, 1-ethoxyethoxycarbonyl. Examples include a methyl group, 2-tetrahydropyranyloxycarbonylmethyl group, 2-tetrahydrofuranyloxycarbonylmethyl group and the like, and substituents represented by the following general formulas (AL-10) -1 to (AL-10) -10. .

In the above formulas (AL-10) -1 to (AL-10) -10, R ⁵⁸ is the same or different linear, branched or cyclic alkyl group having 1 to 8 carbon atoms, having 6 to 20 carbon atoms. An aryl group or an aralkyl group having 7 to 20 carbon atoms is shown. R ⁵⁹ represents a hydrogen atom or a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms. R ⁶⁰ represents an aryl group having 6 to 20 carbon atoms or an aralkyl group having 7 to 20 carbon atoms. a5 is the same as described above.

  Examples of the acetal compound represented by the formula (AL-11) are (AL-11) -1 to (AL-11) -34.

  In addition, the base resin may be intermolecularly or intramolecularly crosslinked by an acid labile group represented by the following general formula (AL-11a) or (AL-11b).

In the above formula, R ⁶¹ and R ⁶² represent a hydrogen atom or a linear, branched or cyclic alkyl group having 1 to 8 carbon atoms. Alternatively, R ⁶¹ and R ⁶² may be bonded to form a ring together with the carbon atom to which they are bonded, and when forming a ring, R ⁶¹ and R ⁶² are linear or branched having 1 to 8 carbon atoms. -Like alkylene group. R ⁶³ is a linear, branched or cyclic alkylene group having 1 to 10 carbon atoms, b5 and d5 are 0 or 1 to 10, preferably 0 or an integer of 1 to 5, and c5 is an integer of 1 to 7. . A represents a (c5 + 1) -valent aliphatic or alicyclic saturated hydrocarbon group, aromatic hydrocarbon group or heterocyclic group having 1 to 50 carbon atoms, and these groups are heteroatoms such as O, S, and N. Or a part of hydrogen atoms bonded to the carbon atom may be substituted with a hydroxyl group, a carboxyl group, a carbonyl group or a fluorine atom. B represents —CO—O—, —NHCO—O— or —NHCONH—.

  In this case, A is preferably 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. These groups may have intervening heteroatoms such as O, S, N, etc., and a part of the hydrogen atoms bonded to the carbon atoms are substituted by a hydroxyl group, a carboxyl group, an acyl group or a halogen atom. Also good. C5 is preferably an integer of 1 to 3.

  Specific examples of the crosslinked acetal groups represented by the general formulas (AL-11a) and (AL-11b) include those represented by the following formulas (AL-11) -35 to (AL-11) -42.

  Next, examples of the tertiary alkyl group represented by the formula (AL-12) include tert-butyl group, triethylcarbyl group, 1-ethylnorbornyl group, 1-methylcyclohexyl group, 1-ethylcyclopentyl group, tert -An amyl group etc. or the following general formula (AL-12) -1-(AL-12) -16 can be mentioned.

In the above formula, R ⁶⁴ represents the same or different linear, branched or cyclic alkyl group having 1 to 8 carbon atoms, an aryl group having 6 to 20 carbon atoms, or an aralkyl group having 7 to 20 carbon atoms. R ⁶⁵ and R ^{67 each} represent a hydrogen atom or a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms. R ⁶⁶ represents an aryl group having 6 to 20 carbon atoms or an aralkyl group having 7 to 20 carbon atoms.

Furthermore, as shown in the following formulas (AL-12) -17 and (AL-12) -18, a divalent or higher valent alkylene group or an arylene group R ⁶⁸ is included, and the polymer within or between the molecules is It may be cross-linked. In the formulas (AL-12) -17 and (AL-12) -18, R ⁶⁴ represents the same as described above, and R ⁶⁸ represents a linear, branched or cyclic alkylene group having 1 to 20 carbon atoms, or an arylene group. And may contain a hetero atom such as an oxygen atom, a sulfur atom or a nitrogen atom. b6 is an integer of 1 to 3.

Further, R ⁶⁴ , R ⁶⁵ , R ⁶⁶ and R ⁶⁷ may have a heteroatom such as oxygen, nitrogen and sulfur, specifically, the following formulas (AL-13) -1 to (AL-13) It can be shown in -7.

  In particular, as the acid labile group of the above formula (AL-12), those having an exo structure represented by the following formula (AL-12) -19 are preferable.

（式中、Ｒ⁶⁹は炭素数１〜８の直鎖状、分岐状又は環状のアルキル基又は炭素数６〜２０の置換されていてもよいアリール基を示す。Ｒ⁷⁰〜Ｒ⁷⁵及びＲ⁷⁸、Ｒ⁷⁹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し、Ｒ⁷⁶は水素原子を示す。あるいは、Ｒ⁷⁰とＲ⁷¹、Ｒ⁷²とＲ⁷⁴、Ｒ⁷²とＲ⁷⁵、Ｒ⁷³とＲ⁷⁵、Ｒ⁷³とＲ⁷⁹、Ｒ⁷⁴とＲ⁷⁸、Ｒ⁷⁶とＲ⁷⁷又はＲ⁷⁷とＲ⁷⁸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Ｒ⁷⁰とＲ⁷⁹、Ｒ⁷⁶とＲ⁷⁹又はＲ⁷²とＲ⁷⁴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。Ｒ⁷⁷は水素原子、ヘテロ原子を含んでもよい炭素数１〜１５の直鎖状、分岐状又は環状のアルキル基を示す。また、本式により、鏡像体も表す。）

(In the formula, R ⁶⁹ represents a linear, branched or cyclic alkyl group having 1 to 8 carbon atoms or an optionally substituted aryl group having 6 to 20 carbon atoms. R ^{70 to} R ⁷⁵ and R ^78. , R ⁷⁹ each independently represents a hydrogen atom or a monovalent hydrocarbon group that may contain a C 1-15 hetero atom, R ⁷⁶ represents a hydrogen atom, or R ⁷⁰ and R ⁷¹ , R ⁷² and R ⁷⁴ , R ⁷² and R ⁷⁵ , R ⁷³ and R ⁷⁵ , R ⁷³ and R ⁷⁹ , R ⁷⁴ and R ⁷⁸ , R ⁷⁶ and R ⁷⁷ or R ⁷⁷ and R ⁷⁸ may form a ring, In this case, it represents a divalent hydrocarbon group which may contain a hetero atom having 1 to 15 carbon atoms, and R ⁷⁰ and R ⁷⁹ , R ⁷⁶ and R ⁷⁹ or R ⁷² and R ⁷⁴ are bonded to adjacent carbon atoms. nothing binds not through with each other, may form a double bond .R ⁷⁷ is hydrogen atom, of which may 1 to 15 carbon atoms include a hetero atom linear, branched Or an cyclic alkyl group. The formula also represents enantiomer.)

上記式中、Ｒ^１、Ｒ⁶⁹〜Ｒ⁷⁹は上記と同様である。また、本式により、鏡像体も表す。 Here, the repeating unit having the exo structure represented by the general formula (AL-12) -19 is shown below.

In said formula, R < ¹ >, R < ⁶⁹ > -R < ⁷⁹ > is the same as the above. In addition, this formula also represents a mirror image body.

JP-A 2000-327633 discloses an ester monomer for obtaining a repeating unit having such an exo structure. Specific examples include the following, but are not limited thereto.

（式中、Ｒ⁸⁰、Ｒ⁸¹はそれぞれ独立に炭素数１〜１０の直鎖状、分岐状又は環状の１価炭化水素基を示す。又は、Ｒ⁸⁰、Ｒ⁸¹は互いに結合してこれらが結合する炭素原子と共に炭素数３〜２０の脂肪族炭化水素環を形成してもよい。Ｒ⁸²はフランジイル、テトラヒドロフランジイル又はオキサノルボルナンジイルから選ばれる２価の基を示す。Ｒ⁸³は水素原子又はヘテロ原子、ヒドロキシ基を含んでもよい炭素数１〜１０の直鎖状、分岐状又は環状の１価炭化水素基を示す。） Furthermore, examples of the acid labile group of the above formula (AL-12) include an acid labile group having frangiyl, tetrahydrofurandiyl or oxanorbornanediyl represented by the following formula (AL-12) -20.

(In the formula, R ⁸⁰ and R ⁸¹ each independently represents a linear, branched or cyclic monovalent hydrocarbon group having 1 to 10 carbon atoms. Or, R ⁸⁰ and R ⁸¹ are bonded to each other to form a monovalent hydrocarbon group. An aliphatic hydrocarbon ring having 3 to 20 carbon atoms may be formed together with the carbon atom to be bonded, R ⁸² represents a divalent group selected from flangedyl, tetrahydrofurandiyl or oxanorbornanediyl, and R ⁸³ represents a hydrogen atom. Or a C1-C10 linear, branched or cyclic monovalent hydrocarbon group which may contain a hetero atom or a hydroxy group.

（式中、Ｒ¹、Ｒ⁸⁰、Ｒ⁸¹、Ｒ⁸²、Ｒ⁸³は上記と同じ。） The repeating unit substituted with an acid labile group having frangiyl, tetrahydrofurandiyl or oxanorbornanediyl is shown below.

(In the formula, R ¹ , R ⁸⁰ , R ⁸¹ , R ⁸² and R ⁸³ are the same as above.)

Examples of the monomer for obtaining the repeating unit are exemplified below. In the following formulae, Me represents a methyl group, and Ac represents an acetyl group.

  The polymer compound of the present invention essentially includes the repeating units represented by the above general formulas (a) and (b), and may further include the repeating units represented by the above general formulas (c) and / or (d). A repeating unit having an adhesive group other than those represented by formulas (a), (b), (c), and (d) may be copolymerized. Specifically, a repeating unit obtained by polymerizing monomers exemplified below ( e) can be included.

  In the above repeating units (a), (b), (c), (d), (e), the ratio of a, b, c, d, e is 0 <a <1.0, 0 <b ≦ 0. 8, 0 ≦ c ≦ 0.8, 0 ≦ d ≦ 0.8, 0 ≦ e ≦ 0.8 are preferable, more preferably 0.01 ≦ a ≦ 0.9, 0.01 ≦ b ≦ 0.7 0.05 ≦ c + d ≦ 0.7 and 0 ≦ e ≦ 0.7.

  The polymer compound of the present invention preferably has a polystyrene-reduced mass average molecular weight of 1,000 to 500,000, particularly 2,000 to 30,000, as determined by gel permeation chromatography (GPC). If the mass average molecular weight is 1,000 or more, the resist material has sufficient heat resistance, and if it is 500,000 or less, the alkali solubility is reduced, and there is little possibility that a trailing phenomenon occurs after pattern formation.

  Furthermore, in the polymer compound of the present invention, when the molecular weight distribution (Mw / Mn) is narrow, foreign substances are seen on the pattern after exposure due to the presence of a low molecular weight or high molecular weight polymer, or the pattern shape deteriorates. Is less likely to occur. Therefore, since the influence of such molecular weight and molecular weight distribution tends to increase as the pattern rule becomes finer, in order to obtain a resist material suitably used for fine pattern dimensions, the multi-component copolymer to be used is obtained. The molecular weight distribution is preferably from 1.0 to 2.0, particularly preferably from 1.0 to 1.5 and narrow dispersion.

  As described above, the base resin in the resist material of the present invention includes a repeating unit having a naphthylene group, a repeating unit of a sulfonium salt, a repeating unit having an acid leaving group, and / or a repeating unit having lactone adhesion. A high molecular compound which is a copolymer having the following is preferably used. As a monomer for obtaining a repeating unit having an acid leaving group and a repeating unit having lactone adhesion, polyacrylic acid or polymethacrylic acid derivatives are preferably used.

  In addition to the above base resins, conventional polymers in which an onium salt of a sulfonic acid having a polymerizable unsaturated bond is not copolymerized, specifically, polyacrylic acid and its derivatives, cycloolefin derivatives-maleic anhydride One or two selected from a copolymer and a ternary or quaternary copolymer with polyacrylic acid or a derivative thereof, cycloolefin derivative-α-trifluoromethylacrylic copolymer, polynorbornene, and metathesis ring-opening polymer More than one type of polymer may be blended.

  In order to synthesize the polymer compound according to the present invention, as one method, a monomer having an unsaturated bond for obtaining the repeating units (a), (b), (c), (d), and (e) is used. Is present in an organic solvent, a radical initiator is added, and heat polymerization is performed, whereby a polymer compound can be obtained. Examples of the organic solvent used at the time of polymerization include toluene, benzene, tetrahydrofuran, diethyl ether, dioxane and the like. As polymerization initiators, 2,2'-azobisisobutyronitrile (AIBN), 2,2'-azobis (2,4-dimethylvaleronitrile), dimethyl-2,2-azobis (2-methylpropio) Nate), benzoyl peroxide, lauroyl peroxide, and the like, preferably polymerized by heating to 50 to 80 ° C. The reaction time is 2 to 100 hours, preferably 5 to 20 hours. As the acid labile group, those introduced into the monomer may be used as they are, or the acid labile group may be once removed by an acid catalyst and then protected or partially protected.

  The resist material containing the polymer compound according to the present invention can be a chemically amplified positive resist material. The polymer compound according to the present invention has a polymer-type acid generator as the repeating unit (b), and this removes the acid leaving group by the acid generated during exposure to dissolve the resist exposed 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.

The resist material of the present invention may contain an organic solvent and, if necessary, a dissolution inhibitor, a basic compound, a surfactant, and other components in addition to the above polymer compound as a base resin.
The polymer compound contained in the resist material of the present invention has a polymer type acid generator as the repeating unit (b), but an acid generator may be added separately.

  The organic solvent used in the resist material of the present invention, particularly the chemically amplified positive resist material, may be any organic solvent that can dissolve the base resin, acid generator, other additives, and the like. Examples of such organic solvents include ketones such as cyclohexanone and methyl-2-n-amyl ketone, 3-methoxybutanol, 3-methyl-3-methoxybutanol, 1-methoxy-2-propanol, 1-ethoxy- Alcohols such as 2-propanol, propylene glycol monomethyl ether, ethylene glycol monomethyl ether, propylene glycol monomethyl ether, ethylene glycol monoethyl ether, propylene glycol dimethyl ether, diethylene glycol dimethyl ether, and other ethers, propylene glycol monomethyl ether acetate, propylene glycol monoethyl Ether acetate, ethyl lactate, ethyl pyruvate, butyl acetate, methyl 3-methoxypropionate, 3-ethoxy Examples thereof include esters such as ethyl propionate, tert-butyl acetate, tert-butyl propionate, propylene glycol mono tert-butyl ether acetate, and lactones such as γ-butyl lactone, one kind of these alone or two or more kinds. However, the present invention is not limited to these. In the present invention, among these organic solvents, diethylene glycol dimethyl ether, 1-ethoxy-2-propanol, propylene glycol monomethyl ether acetate, cyclohexanone, ethyl lactate, γ-butyrolactone, which have the highest solubility of the acid generator in the resist component, and The mixed solvent is preferably used.

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

The acid generator added separately is one that has been proposed in the past,
i. An onium salt of the following general formula (P1a-1), (P1a-2) or (P1b),
ii. A diazomethane derivative of the following general formula (P2):
iii. A glyoxime derivative of the following general formula (P3):
iv. A bissulfone derivative of the following general formula (P4):
v. A sulfonic acid ester of an N-hydroxyimide compound of the following general formula (P5),
vi. β-ketosulfonic acid derivatives,
vii. Disulfone derivatives,
viii. Nitrobenzyl sulfonate derivatives,
ix. Examples thereof include sulfonic acid ester derivatives.

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

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

R ^101a , R ^101b and R ^101c may be the same as or different from each other. Specifically, as an alkyl group, methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, sec-butyl Group, tert-butyl group, pentyl group, hexyl group, heptyl group, octyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclopropylmethyl group, 4-methylcyclohexyl group, cyclohexylmethyl group, norbornyl group, adamantyl group, etc. Is mentioned. Examples of the alkenyl group include a vinyl group, an allyl group, a propenyl group, a butenyl group, a hexenyl group, and a cyclohexenyl group. Examples of the oxoalkyl group include 2-oxocyclopentyl group, 2-oxocyclohexyl group, and the like. 2-oxopropyl group, 2-cyclopentyl-2-oxoethyl group, 2-cyclohexyl-2-oxoethyl group, 2- (4 -Methylcyclohexyl) -2-oxoethyl group and the like can be mentioned. Examples of the oxoalkenyl group include 2-oxo-4-cyclohexenyl group and 2-oxo-4-propenyl group. Examples of the aryl group include a phenyl group, a naphthyl group, a p-methoxyphenyl group, an m-methoxyphenyl group, an o-methoxyphenyl group, an ethoxyphenyl group, a p-tert-butoxyphenyl group, and an m-tert-butoxyphenyl group. Alkylphenyl groups such as alkoxyphenyl groups, 2-methylphenyl groups, 3-methylphenyl groups, 4-methylphenyl groups, ethylphenyl groups, 4-tert-butylphenyl groups, 4-butylphenyl groups, dimethylphenyl groups, etc. Alkyl naphthyl groups such as methyl naphthyl group and ethyl naphthyl group, alkoxy naphthyl groups such as methoxy naphthyl group and ethoxy naphthyl group, dialkyl naphthyl groups such as dimethyl naphthyl group and diethyl naphthyl group, dimethoxy naphthyl group and diethoxy naphthyl group Dialkoxynaphthyl group And the like. Examples of the aralkyl group include a benzyl group, a phenylethyl group, and a phenethyl group. As the aryloxoalkyl group, 2-aryl-2-oxoethyl group such as 2-phenyl-2-oxoethyl group, 2- (1-naphthyl) -2-oxoethyl group, 2- (2-naphthyl) -2-oxoethyl group and the like Groups and the like. K ^- a non-nucleophilic counter chloride ions as the ion, halide ions such as bromide ion, triflate, 1,1,1-trifluoroethane sulfonate, fluoroalkyl sulfonate such as nonafluorobutanesulfonate, tosylate, benzenesulfonate And aryl sulfonates such as 4-fluorobenzene sulfonate and 1,2,3,4,5-pentafluorobenzene sulfonate, and alkyl sulfonates such as mesylate and butane sulfonate.

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

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

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

（式中、Ｒ¹⁰⁵、Ｒ¹⁰⁶は炭素数１〜１２の直鎖状、分岐状又は環状のアルキル基又はハロゲン化アルキル基、炭素数６〜２０のアリール基又はハロゲン化アリール基、又は炭素数７〜１２のアラルキル基を示す。）

(In the formula, R ¹⁰⁵ and R ¹⁰⁶ are linear, branched or cyclic alkyl groups or halogenated alkyl groups having 1 to 12 carbon atoms, aryl groups or halogenated aryl groups having 6 to 20 carbon atoms, or carbon atoms. 7 to 12 aralkyl groups are shown.)

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

（式中、Ｒ¹⁰⁷、Ｒ¹⁰⁸、Ｒ¹⁰⁹は炭素数１〜１２の直鎖状、分岐状又は環状のアルキル基又はハロゲン化アルキル基、炭素数６〜２０のアリール基又はハロゲン化アリール基、又は炭素数７〜１２のアラルキル基を示す。Ｒ¹⁰⁸、Ｒ¹⁰⁹は互いに結合して環状構造を形成してもよく、環状構造を形成する場合、Ｒ¹⁰⁸、Ｒ¹⁰⁹はそれぞれ炭素数１〜６の直鎖状、分岐状のアルキレン基を示す。Ｒ¹⁰⁵は式（Ｐ２）のものと同様である。）

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

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

（式中、Ｒ^101a、Ｒ^101bは前記と同様である。）

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

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

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

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

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

  Specific examples of the acid generator include onium salts such as diphenyliodonium trifluoromethanesulfonate, trifluoromethanesulfonate (p-tert-butoxyphenyl) phenyliodonium, diphenyliodonium p-toluenesulfonate, and p-toluenesulfone. Acid (p-tert-butoxyphenyl) phenyliodonium, triphenylsulfonium trifluoromethanesulfonate, trifluoromethanesulfonic acid (p-tert-butoxyphenyl) diphenylsulfonium, bis (p-tert-butoxyphenyl) phenylsulfonium trifluoromethanesulfonate , Tris (p-tert-butoxyphenyl) sulfonium trifluoromethanesulfonate, triphenylsulfonium p-toluenesulfonate p-toluenesulfonic acid (p-tert-butoxyphenyl) diphenylsulfonium, p-toluenesulfonic acid bis (p-tert-butoxyphenyl) phenylsulfonium, p-toluenesulfonic acid tris (p-tert-butoxyphenyl) sulfonium, nona Triphenylsulfonium fluorobutanesulfonate, triphenylsulfonium butanesulfonate, trimethylsulfonium trifluoromethanesulfonate, trimethylsulfonium p-toluenesulfonate, cyclohexylmethyl 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 diphenyl disulfone derivatives and dicyclohexyl disulfone derivatives.

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

  Examples of sulfonic acid ester derivatives include 1,2,3-tris (methanesulfonyloxy) benzene, 1,2,3-tris (trifluoromethanesulfonyloxy) benzene, 1,2,3-tris (p-toluenesulfonyloxy). Mention may be made of sulfonic acid ester derivatives such as benzene.

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

In particular, triphenylsulfonium trifluoromethanesulfonate, trifluoromethanesulfonate (p-tert-butoxyphenyl) diphenylsulfonium, tris (p-tert-butoxyphenyl) sulfonium trifluoromethanesulfonate, triphenylsulfonium p-toluenesulfonate, p -Toluenesulfonic acid (p-tert-butoxyphenyl) diphenylsulfonium, p-toluenesulfonic acid tris (p-tert-butoxyphenyl) sulfonium, trifluoromethanesulfonic acid trinaphthylsulfonium, trifluoromethanesulfonic acid cyclohexylmethyl (2-oxocyclohexyl) ) Sulfonium, (2-norbornyl) methyl (2-oxocyclohexyl) sulfonyl trifluoromethanesulfonate Onium salts such as 1,2′-naphthylcarbonylmethyltetrahydrothiophenium triflate, bis (benzenesulfonyl) diazomethane, bis (p-toluenesulfonyl) diazomethane, bis (cyclohexylsulfonyl) diazomethane, bis (n-butylsulfonyl) Diazomethane derivatives such as diazomethane, bis (isobutylsulfonyl) diazomethane, bis (sec-butylsulfonyl) diazomethane, bis (n-propylsulfonyl) diazomethane, bis (isopropylsulfonyl) diazomethane, bis (tert-butylsulfonyl) diazomethane, bis-O -Glyoxime derivatives such as-(p-toluenesulfonyl) -α-dimethylglyoxime and bis-O- (n-butanesulfonyl) -α-dimethylglyoxime, bisnaphthyl Bissulfone derivatives such as sulfonylmethane, N-hydroxysuccinimide methanesulfonate, N-hydroxysuccinimide trifluoromethanesulfonate, N-hydroxysuccinimide 1-propanesulfonate, N-hydroxysuccinimide 2-propanesulfonate, N- Hydroxysuccinimide 1-pentanesulfonic acid ester, N-hydroxysuccinimide p-toluenesulfonic acid ester, N-hydroxynaphthalimide methanesulfonic acid ester, N-hydroxynaphthalimide benzenesulfonic acid ester, etc. Derivatives are preferably used.
Furthermore, an oxime type acid generator represented by WO2004 / 074242 A2 may be added.

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

  The addition amount of the acid generator is preferably 0.1 to 50 parts, more preferably 0.5 to 40 parts, relative to 100 parts of the base resin. If the amount is 0.1 part or more, the amount of acid generated during exposure is sufficient, and sufficient sensitivity and resolution can be obtained. If the amount is 50 parts or less, there is little possibility that the transmittance of the resist is lowered or the resolution is inferior.

  Next, as a dissolution inhibitor (dissolution control agent) blended in the resist material of the present invention, particularly a chemically amplified positive resist material, the mass average molecular weight is 100 to 1,000, preferably 150 to 800, and Of a compound having two or more phenolic hydroxyl groups in the molecule, wherein the hydrogen atom of the phenolic hydroxyl group is substituted with an acid labile group in an average of 0 to 100 mol% as a whole, or a compound having a carboxy group in the molecule A compound in which the hydrogen atoms of the carboxy group are substituted with an acid labile group as a whole in an average ratio of 50 to 100 mol% is blended.

The substitution rate of the hydrogen atom of the phenolic hydroxyl group by an acid labile group is on average 0 mol% or more, preferably 30 mol% or more of the entire phenolic hydroxyl group, and the upper limit is 100 mol%, more preferably 80 mol%. Mol%. The substitution rate of the hydrogen atom of the carboxy group with an acid labile group is 50 mol% or more, preferably 70 mol% or more of the entire carboxy group on average, and the upper limit is 100 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、式中Ｒ²⁰¹、Ｒ²⁰²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。Ｒ²⁰³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−（Ｒ²⁰⁷）_hＣＯＯＨを示す。Ｒ²⁰⁴は−（ＣＨ₂）_i−（ｉ＝２〜１０）、炭素数６〜１０のアリーレン基、カルボニル基、スルホニル基、酸素原子又は硫黄原子を示す。Ｒ²⁰⁵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。Ｒ²⁰⁶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。Ｒ²⁰⁷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。Ｒ²⁰⁸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。

However, in the formula, 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, a linear or branched alkyl group or alkenyl group having 1 to 8 carbon atoms, or — (R ²⁰⁷ ) _h COOH. R ²⁰⁴ is _{- (CH 2) i - (} i = 2~10), shows an arylene group having 6 to 10 carbon atoms, a carbonyl group, a sulfonyl group, an oxygen atom or a sulfur atom. 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 represents a hydrogen atom, a linear or branched alkyl group having 1 to 8 carbon atoms, an alkenyl group, or a phenyl group or naphthyl group each substituted with a hydroxyl group. R ²⁰⁷ represents a linear or branched alkylene group having 1 to 10 carbon atoms. R ²⁰⁸ represents a hydrogen atom or a hydroxyl group. j is an integer of 0-5. u and h are 0 or 1. s, t, s ′, t ′, s ″, t ″ satisfy s + t = 8, s ′ + t ′ = 5, s ″ + t ″ = 4, respectively, and at least 1 in each phenyl skeleton The number has two hydroxyl groups. α is a number that makes the molecular weight of the compounds of formulas (D8) and (D9) 100 to 1,000.

  The compounding quantity of a dissolution inhibitor is 0-50 parts with respect to 100 parts of base resins, Preferably it is 5-50 parts, More preferably, it is 10-30 parts, It can use individually or in mixture of 2 or more types. By adding a dissolution inhibitor, the resolution is improved, and if the blending amount is 50 parts or less, there is little risk of film loss of the pattern or a decrease in resolution.

Furthermore, a basic compound can be blended in the resist material of the present invention, particularly in the chemically amplified positive resist material.
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, or 3. The side chain X may be the same or different, and can be represented by the following general formulas (X) -1 to (X) -3. Side chain Y Represents the same or different hydrogen atom or a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms, and may contain an ether group or a hydroxyl group, and X may be bonded to form a ring. May be.)

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

Specific examples of the compound represented by the general formula (B) -1 include the following.
Tris (2-methoxymethoxyethyl) amine, tris {2- (2-methoxyethoxy) ethyl} amine, tris {2- (2-methoxyethoxymethoxy) ethyl} amine, tris {2- (1-methoxyethoxy) ethyl } Amine, Tris {2- (1-ethoxyethoxy) ethyl} amine, Tris {2- (1-ethoxypropoxy) ethyl} amine, Tris [2- {2- (2-hydroxyethoxy) ethoxy} ethyl] amine, 4,7,13,16,21,24-hexaoxa-1,10-diazabicyclo [8.8.8] hexacosane, 4,7,13,18-tetraoxa-1,10-diazabicyclo [8.5.5] Eicosane, 1,4,10,13-tetraoxa-7,16-diazabicyclooctadecane, 1-aza-12-crown-4 1-aza-15-crown-5, 1-aza-18-crown-6, tris (2-formyloxyethyl) amine, tris (2-acetoxyethyl) amine, tris (2-propionyloxyethyl) amine, Tris (2-butyryloxyethyl) amine, tris (2-isobutyryloxyethyl) amine, tris (2-valeryloxyethyl) amine, tris (2-pivaloyloxyethyl) amine, N, N- Bis (2-acetoxyethyl) 2- (acetoxyacetoxy) ethylamine, tris (2-methoxycarbonyloxyethyl) amine, tris (2-tert-butoxycarbonyloxyethyl) amine, tris [2- (2-oxopropoxy) ethyl Amine, tris [2- (methoxycarbonylmethyl) oxyethyl] amino , Tris [2- (tert-butoxycarbonylmethyloxy) ethyl] amine, tris [2- (cyclohexyloxycarbonylmethyloxy) ethyl] amine, tris (2-methoxycarbonylethyl) amine, tris (2-ethoxycarbonylethyl) Amine, N, N-bis (2-hydroxyethyl) 2- (methoxycarbonyl) ethylamine, N, N-bis (2-acetoxyethyl) 2- (methoxycarbonyl) ethylamine, N, N-bis (2-hydroxyethyl) ) 2- (ethoxycarbonyl) ethylamine, N, N-bis (2-acetoxyethyl) 2- (ethoxycarbonyl) ethylamine, N, N-bis (2-hydroxyethyl) 2- (2-methoxyethoxycarbonyl) ethylamine, N, N-bis (2-acetoxyethyl ) 2- (2-methoxyethoxycarbonyl) ethylamine, N, N-bis (2-hydroxyethyl) 2- (2-hydroxyethoxycarbonyl) ethylamine, N, N-bis (2-acetoxyethyl) 2- (2- Acetoxyethoxycarbonyl) ethylamine, N, N-bis (2-hydroxyethyl) 2-[(methoxycarbonyl) methoxycarbonyl] ethylamine, N, N-bis (2-acetoxyethyl) 2-[(methoxycarbonyl) methoxycarbonyl] Ethylamine, N, N-bis (2-hydroxyethyl) 2- (2-oxopropoxycarbonyl) ethylamine, N, N-bis (2-acetoxyethyl) 2- (2-oxopropoxycarbonyl) ethylamine, N, N- Bis (2-hydroxyethyl) 2- (tetrahydrofurf Ruoxycarbonyl) ethylamine, N, N-bis (2-acetoxyethyl) 2- (tetrahydrofurfuryloxycarbonyl) ethylamine, N, N-bis (2-hydroxyethyl) 2-[(2-oxotetrahydrofuran-3- Yl) oxycarbonyl] ethylamine, N, N-bis (2-acetoxyethyl) 2-[(2-oxotetrahydrofuran-3-yl) oxycarbonyl] ethylamine, N, N-bis (2-hydroxyethyl) 2- ( 4-hydroxybutoxycarbonyl) ethylamine, N, N-bis (2-formyloxyethyl) 2- (4-formyloxybutoxycarbonyl) ethylamine, N, N-bis (2-formyloxyethyl) 2- (2-formyl) Oxyethoxycarbonyl) ethylamine, N, N-bis (2 Methoxyethyl) 2- (methoxycarbonyl) ethylamine, N- (2-hydroxyethyl) bis [2- (methoxycarbonyl) ethyl] amine, N- (2-acetoxyethyl) bis [2- (methoxycarbonyl) ethyl] amine N- (2-hydroxyethyl) bis [2- (ethoxycarbonyl) ethyl] amine, N- (2-acetoxyethyl) bis [2- (ethoxycarbonyl) ethyl] amine, N- (3-hydroxy-1- Propyl) bis [2- (methoxycarbonyl) ethyl] amine, N- (3-acetoxy-1-propyl) bis [2- (methoxycarbonyl) ethyl] amine, N- (2-methoxyethyl) bis [2- ( Methoxycarbonyl) ethyl] amine, N-butylbis [2- (methoxycarbonyl) ethyl] amine, N-butyl Tylbis [2- (2-methoxyethoxycarbonyl) ethyl] amine, N-methylbis (2-acetoxyethyl) amine, N-ethylbis (2-acetoxyethyl) amine, N-methylbis (2-pivaloyloxyethyl) amine N-ethylbis [2- (methoxycarbonyloxy) ethyl] amine, N-ethylbis [2- (tert-butoxycarbonyloxy) ethyl] amine, tris (methoxycarbonylmethyl) amine, tris (ethoxycarbonylmethyl) amine, N -Butylbis (methoxycarbonylmethyl) amine, N-hexylbis (methoxycarbonylmethyl) amine, and β- (diethylamino) -δ-valerolactone can be exemplified, but are not limited thereto.

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

（式中、Ｘは前述の通り、Ｒ³⁰⁷は炭素数２〜２０の直鎖状、分岐状のアルキレン基であり、カルボニル基、エーテル基、エステル基、スルフィドを１個あるいは複数個含んでいてもよい。）

(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. May be good.)

  Specific examples of the formula (B) -2 include 1- [2- (methoxymethoxy) ethyl] pyrrolidine, 1- [2- (methoxymethoxy) ethyl] piperidine, 4- [2- (methoxymethoxy) ethyl]. Morpholine, 1- [2-[(2-methoxyethoxy) methoxy] ethyl] pyrrolidine, 1- [2-[(2-methoxyethoxy) methoxy] ethyl] piperidine, 4- [2-[(2-methoxyethoxy) Methoxy] ethyl] morpholine, 2- (1-pyrrolidinyl) ethyl acetate, 2-piperidinoethyl acetate, 2-morpholinoethyl acetate, 2- (1-pyrrolidinyl) ethyl formate, 2-piperidinoethyl propionate, 2-morpholinoethyl acetoxyacetate, 2- (1-pyrrolidinyl) ethyl methoxyacetate, 4- [2- (methoxycarbonyloxy) ethyl] Ruphorin, 1- [2- (t-butoxycarbonyloxy) ethyl] piperidine, 4- [2- (2-methoxyethoxycarbonyloxy) ethyl] morpholine, methyl 3- (1-pyrrolidinyl) propionate, 3-piperidi Methyl nopropionate, methyl 3-morpholinopropionate, methyl 3- (thiomorpholino) propionate, methyl 2-methyl-3- (1-pyrrolidinyl) propionate, ethyl 3-morpholinopropionate, 3-piperidinopropion Methoxycarbonylmethyl acid, 2-hydroxyethyl 3- (1-pyrrolidinyl) propionate, 2-acetoxyethyl 3-morpholinopropionate, 2-oxotetrahydrofuran-3-yl 3- (1-pyrrolidinyl) propionate, 3-morpholino Propionate tetrahydrofurf Glycidyl 3-piperidinopropionate, 2-methoxyethyl 3-morpholinopropionate, 2- (2-methoxyethoxy) ethyl 3- (1-pyrrolidinyl) propionate, butyl 3-morpholinopropionate, 3-pi Cyclohexyl peridinopropionate, α- (1-pyrrolidinyl) methyl-γ-butyrolactone, β-piperidino-γ-butyrolactone, β-morpholino-δ-valerolactone, methyl 1-pyrrolidinyl acetate, methyl piperidinoacetate, methyl morpholinoacetate, Examples thereof include methyl thiomorpholinoacetate, ethyl 1-pyrrolidinyl acetate, 2-methoxyethyl morpholinoacetate and the like.

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

（式中、Ｘ、Ｒ³⁰⁷、ｎは前述の通り、Ｒ³⁰⁸、Ｒ³⁰⁹は同一又は異種の炭素数１〜４の直鎖状、分岐状のアルキレン基である。）

(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 basic compound containing a cyano group include 3- (diethylamino) propiononitrile, N, N-bis (2-hydroxyethyl) -3-aminopropiononitrile, N, N-bis (2-acetoxy). Ethyl) -3-aminopropiononitrile, N, N-bis (2-formyloxyethyl) -3-aminopropiononitrile, N, N-bis (2-methoxyethyl) -3-aminopropiononitrile, N , N-bis [2- (methoxymethoxy) ethyl] -3-aminopropiononitrile, methyl N- (2-cyanoethyl) -N- (2-methoxyethyl) -3-aminopropionate, N- (2- Cyanoethyl) -N- (2-hydroxyethyl) -3-aminopropionic acid methyl, N- (2-acetoxyethyl) -N- (2-cyanoethyl) -3 Methyl aminopropionate, N- (2-cyanoethyl) -N-ethyl-3-aminopropiononitrile, N- (2-cyanoethyl) -N- (2-hydroxyethyl) -3-aminopropiononitrile, N- (2-acetoxyethyl) -N- (2-cyanoethyl) -3-aminopropiononitrile, N- (2-cyanoethyl) -N- (2-formyloxyethyl) -3-aminopropiononitrile, N- ( 2-cyanoethyl) -N- (2-methoxyethyl) -3-aminopropiononitrile, N- (2-cyanoethyl) -N- [2- (methoxymethoxy) ethyl] -3-aminopropiononitrile, N- (2-cyanoethyl) -N- (3-hydroxy-1-propyl) -3-aminopropiononitrile, N- (3-acetoxy-1-propyl -N- (2-cyanoethyl) -3-aminopropiononitrile, N- (2-cyanoethyl) -N- (3-formyloxy-1-propyl) -3-aminopropiononitrile, N- (2-cyanoethyl) ) -N-tetrahydrofurfuryl-3-aminopropiononitrile, N, N-bis (2-cyanoethyl) -3-aminopropiononitrile, diethylaminoacetonitrile, N, N-bis (2-hydroxyethyl) aminoacetonitrile, N, N-bis (2-acetoxyethyl) aminoacetonitrile, N, N-bis (2-formyloxyethyl) aminoacetonitrile, N, N-bis (2-methoxyethyl) aminoacetonitrile, N, N-bis [2 -(Methoxymethoxy) ethyl] aminoacetonitrile, N-cyanomethyl-N- (2-me Methyl toxiethyl) -3-aminopropionate, methyl N-cyanomethyl-N- (2-hydroxyethyl) -3-aminopropionate, methyl N- (2-acetoxyethyl) -N-cyanomethyl-3-aminopropionate, N-cyanomethyl-N- (2-hydroxyethyl) aminoacetonitrile, N- (2-acetoxyethyl) -N- (cyanomethyl) aminoacetonitrile, N-cyanomethyl-N- (2-formyloxyethyl) aminoacetonitrile, N- Cyanomethyl-N- (2-methoxyethyl) aminoacetonitrile, N-cyanomethyl-N- [2- (methoxymethoxy) ethyl] aminoacetonitrile, N- (cyanomethyl) -N- (3-hydroxy-1-propyl) aminoacetonitrile N- (3-acetoxy-1-propyl Pyr) -N- (cyanomethyl) aminoacetonitrile, N-cyanomethyl-N- (3-formyloxy-1-propyl) aminoacetonitrile, N, N-bis (cyanomethyl) aminoacetonitrile, 1-pyrrolidinepropiononitrile, 1- Piperidine propiononitrile, 4-morpholine propiononitrile, 1-pyrrolidine acetonitrile, 1-piperidine acetonitrile, 4-morpholine acetonitrile, cyanomethyl 3-diethylaminopropionate, N, N-bis (2-hydroxyethyl) -3-aminopropion Cyanomethyl acid, cyanomethyl N, N-bis (2-acetoxyethyl) -3-aminopropionate, cyanomethyl N, N-bis (2-formyloxyethyl) -3-aminopropionate, N, N-bis (2- Meto Cyethyl) -3-aminopropionic acid cyanomethyl, N, N-bis [2- (methoxymethoxy) ethyl] -3-aminopropionic acid cyanomethyl, 3-diethylaminopropionic acid (2-cyanoethyl), N, N-bis (2 -Hydroxyethyl) -3-aminopropionic acid (2-cyanoethyl), N, N-bis (2-acetoxyethyl) -3-aminopropionic acid (2-cyanoethyl), N, N-bis (2-formyloxyethyl) ) -3-Aminopropionic acid (2-cyanoethyl), N, N-bis (2-methoxyethyl) -3-aminopropionic acid (2-cyanoethyl), N, N-bis [2- (methoxymethoxy) ethyl] -3-aminopropionic acid (2-cyanoethyl), cyanomethyl 1-pyrrolidinepropionate, 1-piperidinepropiate Examples include cyanomethyl onate, 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 the basic compound to the resist material of this invention is 0.001-2 parts with respect to 100 parts of base resins, and 0.01-1 part is especially suitable. If the amount is 0.001 part or more, a sufficient blending effect is obtained, and if it is 2 parts or less, sufficient sensitivity is obtained.

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

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

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

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

[Group II]
Compounds represented by the following general formulas (A11) to (A15).

（式中、Ｒ⁴⁰²、Ｒ⁴⁰³、Ｒ⁴¹¹は上記と同様の意味を示す。Ｒ⁴¹²は水素原子又は水酸基を示す。ｓ５、ｔ５は、ｓ５≧０、ｔ５≧０で、ｓ５＋ｔ５＝５を満足する数である。ｈ’は０又は１である。）

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

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

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

(Wherein R ″ represents a hydrogen atom or a —CH ₂ COOH group, and in each compound, 10 to 100 mol% of R ″ is a —CH ₂ COOH group. Show.)

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

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

  Examples of the surfactant include, but are not limited to, polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether, polyethylene stearyl ether, polyoxyethylene cetyl ether, polyoxyethylene olein ether, and polyoxyethylene Polyoxyethylene alkyl allyl ethers such as octylphenol ether and polyoxyethylene nonylphenol, polyoxyethylene polyoxypropylene block copolymers, sorbitan fatty acid esters such as sorbitan monolaurate, sorbitan monovalmitate, sorbitan monostearate, poly Oxyethylene sorbitan monolaurate, polyoxyethylene sorbitan monovalmitate, polyoxyethylene sorbitan monostearate Non-ionic surfactants of polyoxyethylene sorbitan fatty acid esters such as polyoxyethylene sorbitan trioleate and polyoxyethylene sorbitan tristearate, F-top EF301, EF303, EF352 (Tokemuputtokutsu), Megafuck F171, F172, F173 (Dainippon Ink and Chemicals), Florard FC430, FC431 (Sumitomo 3M), Asahi Guard AG710, Surflon S-381, S-382, SC101, SC102, SC103, SC104, SC105, SC106, Surfinol E1004, KH-10, Fluorosurfactants such as KH-20, KH-30, KH-40 (Asahi Glass), organosiloxane polymers KP-341, X-70-092, X-70-093 (Shin-Etsu Chemical) Work), acrylic acid-based or methacrylic acid-based Polyflow No. 75, no. 95 (Kyoeisha Yushi Chemical Co., Ltd.) and the like, among which Fluorard FC430, Surflon S-381, Surfynol E1004, KH-20, and KH-30 are preferable. These can be used alone or in combination of two or more.

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

  When using the resist material of the present invention, in particular, a chemically amplified positive resist material containing an organic solvent, the above polymer compound, an acid generator and the like for manufacturing various integrated circuits, there is no particular limitation, but a known lithography technique. Can be used.

For example, the resist material of the present invention is spun onto a substrate (Si, SiO ₂ , SiN, SiON, TiN, WSi, BPSG, SOG, organic antireflection film, Cr, CrO, CrON, MoSi, etc.) for manufacturing an integrated circuit. It is applied by a suitable coating method such as coating, roll coating, flow coating, dip coating, spray coating, doctor coating, etc. so that the coating film thickness is 0.1 to 2.0 μm, on a hot plate at 60 to 150 ° C., Pre-bake for 1 to 10 minutes, preferably 80 to 120 ° C. for 1 to 5 minutes. Next, the light source selected from ultraviolet rays, far ultraviolet rays, electron beams, X-rays, excimer lasers, γ rays, synchrotron radiation, etc. The pattern to be exposed is exposed through a predetermined mask. It is preferable to expose so that the exposure amount is about 1 to 200 mJ / cm ² , preferably about 10 to 100 mJ / cm ² . Next, post exposure baking (PEB) is performed on a hot plate at 60 to 150 ° C. for 1 to 5 minutes, preferably at 80 to 120 ° C. for 1 to 3 minutes.

  Further, 0.1 to 5% by weight, preferably 2 to 3% by weight, using an aqueous developer such as tetramethylammonium hydroxide (TMAH) for 0.1 to 3 minutes, preferably 0.5 to 2 minutes. The target pattern is formed on the substrate by development using a conventional method such as a dip method, a paddle method, or a spray method. In addition, the resist material of the present invention is a far ultraviolet ray having a wavelength of 254 to 193 nm, a vacuum ultraviolet ray having a wavelength of 157 nm, an electron beam, a soft X-ray, an X-ray, an excimer laser, a γ ray, a synchrotron radiation, among high energy rays. Preferably, it is optimal for fine patterning with a high energy beam having a wavelength of 200 nm or less, particularly in the range of 180 to 200 nm.

  The resist material of the present invention can also be applied to immersion lithography. In ArF immersion lithography, pure water is used as an immersion solvent. In immersion lithography, exposure is performed by inserting water between a pre-baked resist film and a projection lens. Since the numerical aperture (NA) of the projection lens can be increased to 1.0 or more and the resolution can be improved, this is an important technique for extending the life of ArF lithography to the 65 nm node, and development has been accelerated. The lactone ring conventionally used as the hydrophilic group of ArF resist is soluble in both alkaline aqueous solution and water. When water-soluble lactones or acid anhydrides such as maleic anhydride or itaconic anhydride are used as hydrophilic groups, water permeates from the resist surface due to immersion in water, causing the resist surface to swell. Will occur. However, although hydroxynaphthalene dissolves in an alkaline aqueous solution but does not dissolve in water at all, it is considered that the influence of dissolution and swelling by the above-mentioned immersion is small.

  EXAMPLES Hereinafter, although a synthesis example, a comparative synthesis example, an Example, and a comparative example are shown and this invention is demonstrated concretely, this invention is not restrict | limited to the following Example etc. In addition, a mass average molecular weight (Mw) shows the polystyrene conversion mass average molecular weight by GPC.

[Synthesis Example 1]
In a 100 mL flask, 1-hydroxy-5-naphthyl methacrylate 5.78 g, 4- (1-oxo-2-propenyloxy) phenyldiphenylphonium perfluoro-n-butanesulfonate 3.2 g, 3-ethyl methacrylate -3-Exotetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodecanyl 6.9 g, 3-oxo-2,7-dioxatricyclo [4.2.1.0 ^4,8 ] nonan-9-yl methacrylate 10.8 g, 30 g of tetrahydrofuran as a solvent Added. The reaction vessel was cooled to −70 ° C. in a nitrogen atmosphere, and vacuum degassing and nitrogen flow were repeated three times. After raising the temperature to room temperature, 0.2 g of AIBN (2,2′-azobisisobutyronitrile) was added as a polymerization initiator, and the temperature was raised to 60 ° C., followed by reaction for 15 hours. This reaction solution was precipitated in 500 mL of isopropyl alcohol, and the resulting white solid was filtered and dried under reduced pressure at 60 ° C. to obtain 23.5 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 (molar ratio)
a11: b11: c11: d11 = 0.25: 0.05: 0.45: 0.25
Mass average molecular weight (Mw) = 8,900
Molecular weight distribution (Mw / Mn) = 1.72
This polymer compound is designated as Polymer 1.

[Synthesis Example 2]
In a 100 mL flask, 4.6 g of 5-hydroxy-1-naphthyl methacrylate, 3.2 g of 4- (1-oxo-2-propenyloxy) phenyldiphenylphonium perfluoro-n-butanesulfonate, 2-methacrylic acid-2- 7.4 g of ethyl-2-adamantane, 4.7 g of 3-hydroxy-1-adamantyl methacrylate, 3-oxo-2,7-dioxatricyclomethacrylate [4.2.1.0 ^4,8 ] nonane 5.6 g of -9-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 500 mL of isopropyl alcohol, and the resulting white solid was filtered and dried under reduced pressure at 60 ° C. to obtain 22.7 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 (molar ratio)
a11: b11: c11: d12: e11 = 0.20: 0.05: 0.25: 0.30: 0.20
Mass average molecular weight (Mw) = 8,500
Molecular weight distribution (Mw / Mn) = 1.78
This polymer compound is designated as Polymer 2.

[Synthesis Example 3]
In a 100 mL flask, 4.6 g of 5-hydroxy-1-vinylnaphthalene, 3.2 g of 4- (1-oxo-2-propenyloxy) phenyldiphenylphonium perfluoro-n-butanesulfonate, -3-ethyl methacrylate- 3-exotetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodecanyl 6.9 g, 3-oxo-2,7-dioxatricyclo [4.2.1.0 ^4,8 ] nonan-9-yl methacrylate 10.8 g, 30 g of tetrahydrofuran as a solvent Added. The reaction vessel was cooled to −70 ° C. in a nitrogen atmosphere, and vacuum degassing and nitrogen flow were repeated three times. After raising the temperature to room temperature, 0.2 g of AIBN (2,2′-azobisisobutyronitrile) was added as a polymerization initiator, and the temperature was raised to 60 ° C., followed by reaction for 15 hours. This reaction solution was precipitated in a 500 mL solution of isopropyl alcohol, and the resulting white solid was filtered and dried under reduced pressure at 60 ° C. to obtain 22.8 g of a white polymer.

When the obtained polymer was measured by ¹³ C, ¹ H-NMR and GPC, the following analysis results were obtained.
Copolymer composition ratio (molar ratio)
a12: b11: c11: d11 = 0.25: 0.05: 0.45: 0.25
Mass average molecular weight (Mw) = 8,100
Molecular weight distribution (Mw / Mn) = 1.79
This polymer compound is designated as Polymer 3.

[Synthesis Example 4]
A 100 mL flask was charged with 6.8 g of methacrylic acid-1-hydroxy-5-naphthyl, 3.2 g of 4- (1-oxo-2-propenyloxy) phenyldiphenylphonium perfluoro-n-butanesulfonate, and 1- (methacrylic acid 1- ( 7-oxanorbornan-2-yl) cyclopentyl 6.3 g, methacrylate 3-oxo-2,7-dioxatricyclo [4.2.1.0 ^4,8 ] nonan-9-yl 9.0 g, solvent As a result, 30 g of tetrahydrofuran was added. The reaction vessel was cooled to −70 ° C. in a nitrogen atmosphere, and vacuum degassing and nitrogen flow were repeated three times. After raising the temperature to room temperature, 0.2 g of AIBN (2,2′-azobisisobutyronitrile) was added as a polymerization initiator, and the temperature was raised to 60 ° C., followed by reaction for 15 hours. This reaction solution was precipitated in a 500 mL solution of isopropyl alcohol, and the resulting white solid was filtered and dried under reduced pressure at 60 ° C. to obtain 22.3 g of a white polymer.

When the obtained polymer was measured by ¹³ C, ¹ H-NMR and GPC, the following analysis results were obtained.
Copolymer composition ratio (molar ratio)
a11: b11: c11: d13 = 0.30: 0.05: 0.40: 0.25
Mass average molecular weight (Mw) = 8,900
Molecular weight distribution (Mw / Mn) = 1.72
This polymer compound is designated as polymer 4.

[Synthesis Example 5]
In a 100 mL flask, 12.5 g of methacrylic acid-5-tbutoxycarbonyl-1-naphthyl, 3.2 g of 4- (1-oxo-2-propenyloxy) phenyldiphenylphonium perfluoro-n-butanesulfonate, 5 of methacrylic acid 5 -Oxo-4-oxatricyclo [4.2.1.0 ^3,7 ] nonan-2-yl 12.1 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 24.5 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 (molar ratio)
a13: b11: c12 = 0.40: 0.05: 0.55
Mass average molecular weight (Mw) = 8,100
Molecular weight distribution (Mw / Mn) = 1.67
This polymer compound is designated as polymer 5.

[Synthesis Example 6]
In a 100 mL flask, 12.5 g of methacrylic acid-5-tbutoxycarbonyl-1-naphthyl, 4- (1-oxo-2-propenyloxy) phenyldiphenylphonium perfluoro-n-butanesulfonate 3.2 g, 8 (9 ) -Methacrylic acid-4-oxatricyclo [5.2.2.0 ^2,8 ] undecan-3-one (13.8 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 30.2 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 (molar ratio)
a13: b11: c13 = 0.40: 0.05: 0.55
Mass average molecular weight (Mw) = 8,700
Molecular weight distribution (Mw / Mn) = 1.62
This polymer compound is designated as polymer 6.

[Synthesis Example 7]
In a 100 mL flask, 14.6 g of methacrylic acid-1-hydroxy-5-naphthyl, 4- (1-oxo-2-methyl-2-propenyloxy) phenyldiphenylphonium perfluoro-n-butanesulfonate 4-oxymethacrylate Phenyldiphenylsulfonium perfluoro-n-butanesulfonate 6.5 g, methacrylic acid-3-ethyl-3-exotetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodecanyl (6.9 g) and 40 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 24.8 g of a white polymer.

When the obtained polymer was measured by ¹³ C, ¹ H-NMR and GPC, the following analysis results were obtained.
Copolymer composition ratio (molar ratio)
a11: b12: d11 = 0.65: 0.10: 0.25
Mass average molecular weight (Mw) = 8,100
Molecular weight distribution (Mw / Mn) = 1.45
This polymer compound is designated as polymer 7.

[Synthesis Example 8]
In a 100 mL flask, 12.0 g of 5-hydroxy-1-vinylnaphthalene, 6.5 g of 4- (1-oxo-2-methyl-2-propenyloxy) phenyldiphenylphonium perfluoro-n-butanesulfonate, methacrylic acid- 3-ethyl-3-exotetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodecanyl (6.9 g) and 40 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 22.6 g of a white polymer.

When the obtained polymer was measured by ¹³ C, ¹ H-NMR and GPC, the following analysis results were obtained.
Copolymer composition ratio (molar ratio)
a12: b12: d11 = 0.65: 0.10: 0.25
Mass average molecular weight (Mw) = 7,300
Molecular weight distribution (Mw / Mn) = 1.46
This polymer compound is designated as polymer 8.

[Synthesis Example 9]
In a 100 mL flask, 8.0 g of methacrylic acid-1-hydroxy-5-naphthyl, 6.5 g of 4- (1-oxo-2-methyl-2-propenyloxy) phenyldiphenylphonium perfluoro-n-butanesulfonate, methacryl Acid-3-ethyl-3-exotetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodecanyl 6.9 g, 4-hydroxystyrene 3.6 g, and 40 g of tetrahydrofuran as a solvent were added. The reaction vessel was cooled to −70 ° C. in a nitrogen atmosphere, and vacuum degassing and nitrogen flow were repeated three times. After raising the temperature to room temperature, 0.2 g of AIBN was added as a polymerization initiator, and the temperature was raised to 60 ° C., followed by reaction for 15 hours. This reaction solution was precipitated in a 500 mL solution of isopropyl alcohol, and the obtained white solid was filtered and dried under reduced pressure at 60 ° C. to obtain 22.8 g of a white polymer.

When the obtained polymer was measured by ¹³ C, ¹ H-NMR and GPC, the following analysis results were obtained.
Copolymer composition ratio (molar ratio)
a11: b12: d11: e12 = 0.35: 0.10: 0.25: 0.30
Mass average molecular weight (Mw) = 9,300
Molecular weight distribution (Mw / Mn) = 1.63
This polymer compound is designated as polymer 9.

[Synthesis Example 10]
In a 100 mL flask, 9.2 g of 5-hydroxy-1-vinylnaphthalene, 6.5 g of 4- (1-oxo-2-methyl-2-propenyloxy) phenyldiphenylphonium perfluoro-n-butanesulfonate, methacrylic acid- 12.5 g of 5-t butoxycarbonyl-1-naphthyl and 40 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 25.5 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 (molar ratio)
a12: a13: b12 = 0.50: 0.40: 0.10
Mass average molecular weight (Mw) = 8,900
Molecular weight distribution (Mw / Mn) = 1.45
This polymer compound is designated as polymer 10.

[Synthesis Example 11]
In a 100 mL flask, 7.4 g of 6-acetoxy-2-vinylnaphthalene, 6.5 g of 4- (1-oxo-2-methyl-2-propenyloxy) phenyldiphenylphonium perfluoro-n-butanesulfonate, methacrylic acid- 3-ethyl-3-exotetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodecanyl 6.9 g, 4-acetoxystyrene 4.8 g, and 40 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. The obtained white solid was dissolved again in 50 mL of methanol and 80 mL of tetrahydrofuran, 5 g of triethylamine and 5 g of water were added, the acetyl group was deprotected at 40 ° C. for 5 hours, and neutralized with acetic acid. The reaction solution was concentrated and then dissolved in 50 mL of acetone, followed by precipitation, filtration and drying at 60 ° C. in the same manner as above to obtain 20.2 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 (molar ratio)
a14: b12: d11: e12 = 0.35: 0.10: 0.25: 0.30
Mass average molecular weight (Mw) = 8,600
Molecular weight distribution (Mw / Mn) = 1.84
This polymer compound is designated as polymer 11.

[Synthesis Example 12]
In a 100 mL flask, 7.4 g of 6-acetoxy-2-vinylnaphthalene, 4- (1-oxo-2-methyl-2-propenyloxy) -1,6-dimethylphenyldiphenylphonium perfluoro-n-butanesulfonate 6 .9 g, methacrylic acid-3-ethyl-3-exotetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodecanyl 6.9 g, 4-acetoxystyrene 4.8 g, and 40 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. The obtained white solid was dissolved again in 50 mL of methanol and 80 mL of tetrahydrofuran, 5 g of triethylamine and 5 g of water were added, the acetyl group was deprotected at 40 ° C. for 5 hours, and neutralized with acetic acid. The reaction solution was concentrated and then dissolved in 50 mL of acetone, followed by precipitation, filtration, and drying at 60 ° C. as described above to obtain 20.5 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 (molar ratio)
a14: b13: d11: e12 = 0.35: 0.10: 0.25: 0.30
Mass average molecular weight (Mw) = 8,800
Molecular weight distribution (Mw / Mn) = 1.87
This polymer compound is designated as polymer 12.

[Comparative Synthesis Example 1]
In a 100 mL flask, 8.7 g of 2-ethyl-2-adamantane methacrylate, 7.5 g of 3-hydroxy-1-adamantyl methacrylate, 5-oxo-4-oxatricyclo methacrylate [4.2.1. 0 ^3,7 ] nonan-2-yl (7.3 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 19.5 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 (molar ratio)
c12: d12: e11 = 0.35: 0.35: 0.30
Mass average molecular weight (Mw) = 8,900
Molecular weight distribution (Mw / Mn) = 1.83
This polymer compound is referred to as comparative polymer 1.

(Examples and comparative examples)
[Preparation of positive resist material]
The above synthesized polymer compounds (Polymers 1-9, Comparative Polymer 1), acid generator (PAG1) represented by the following formula, basic compounds (triethanolamine, TMMEA, AAA, AACN), dissolution inhibitor (DRI- Resist solutions were prepared by dissolving 1) in an organic solvent with the composition shown in Table 1 to prepare a resist material, and further filtering each composition through a 0.2 μm size filter.

塩基性化合物： ＴＭＭＥＡ、ＡＡＡ、ＡＡＣＮ（下記構造式参照）

溶解阻止剤： ＤＲI−１（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） Each composition in Table 1 is as follows.
Polymers 1-9: From Synthesis Examples 1-9 Comparative Polymer 1: From Comparative Synthesis Example 1 Acid generator: PAG1 (see the following structural formula)

Basic compounds: TMMEA, AAA, AACN (see the structural formula below)

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

Organic solvent: PGMEA (propylene glycol methyl ether acetate)

[Exposure patterning evaluation]
The resist material solution thus prepared (Examples 1 to 15 and Comparative Example 1) was spin-coated on a silicon wafer subjected to HMDS vapor prime treatment, and baked at 120 ° C. for 60 seconds using a hot plate. The thickness was 250 nm.
This is exposed using an ArF excimer laser stepper (Nikon Corp., NSR-S305B, NA-0.68, σ0.85, 2/3 annular illumination, 6% halftone phase shift mask). The film was baked at 60 ° C. for 60 seconds and developed with an aqueous solution of 2.38 mass% tetramethylammonium hydroxide for 60 seconds to obtain a positive pattern.

And 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 the resist sensitivity, and the minimum line width of the line and space separated at this exposure amount was defined as the resolution of the evaluation resist.
Further, the line edge roughness of a 0.12 μm line and space was measured using a length measuring SEM (S-9220 manufactured by Hitachi, Ltd.), and the resist cross section was observed by SEM (S4200 manufactured by Hitachi, Ltd.).
The results are also shown in Table 1.

  From the results of Table 1, the resist materials of Examples 1 to 15 have high resolution, and in particular, when the base is a highly reflective substrate such as a Si substrate, unevenness due to the occurrence of standing waves is suppressed to a small level. It can be seen that the edge roughness is small.

[Observation of resist pattern shape by simulated immersion exposure]
Next, using the resist material solutions prepared above (Examples 1 to 15 and Comparative Example 1), a resist film was prepared, exposed and developed in the same manner as described above, and the developed 0.12 μm line and 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 0.12 μm line and space pattern after development was observed.
The results obtained are summarized in Table 2.

  From the results shown in Table 2, it was confirmed that the resist materials (Examples 1 to 15) of the present invention did not change in shape even when rinsed with water for a long time as compared with Comparative Example 1, and could sufficiently cope with immersion exposure. It was.

[Electron beam drawing evaluation]
In the drawing evaluation, using the polymer compound synthesized above, solutions (Examples 16 to 21, Comparative Example 2) dissolved in an organic solvent with the composition shown in Table 3 were filtered through a 0.2 μm size filter. Thus, a positive resist material was prepared.

Each composition in the following Table 3 is as follows.
Polymers 7 to 12: From Synthesis Examples 7 to 12 Comparative Polymer 1: From Comparative Synthesis Example 1 The acid generator (PAG1) and the organic solvent (PGMEA) are the same as described above.

  The obtained positive resist material was spin-coated on a Si substrate having a diameter of 6 inches (200 mm) using a clean track Mark 5 (manufactured by Tokyo Electron), prebaked at 110 ° C. for 90 seconds on a hot plate, and 100 nm in thickness. A resist film was prepared. 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 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の結果から、実施例１６〜２１のレジスト材料は、高感度、高解像力であることがわかる。

From the results of Table 3, it can be seen that the resist materials of Examples 16 to 21 have high sensitivity and high resolution.

[Dry etching resistance evaluation]
In the dry etching resistance test, a polymer solution obtained by dissolving 2 g of each of the synthesized polymer compounds (Polymer 1 to 12 and Comparative Polymer 1) in 10 g of PGMEA and filtering through a 0.2 μm size filter was applied to a Si substrate by spin coating. The film was formed into a film having a thickness of 300 nm and evaluated under two system conditions.

(1) Etching test with CHF ₃ / CF ₄ gas Using a dry etching apparatus TE-8500P manufactured by Tokyo Electron Co., Ltd., the difference in film thickness of the polymer film before and after etching was determined.
Etching conditions are as shown below.
Chamber pressure 40.0Pa
RF power 1,000W
Gap 9mm
CHF ₃ gas flow rate 30ml / min
CF ₄ gas flow rate 30ml / min
Ar gas flow rate 100ml / min
60 sec

₍₂₎ Cl ₂ / BCl ₃ system using an etching test Nichiden Anelva Co., Ltd. dry etching apparatus L-507D-L Gas was calculated the difference between the film thickness of before and after etching of the polymer film.
Etching conditions are as shown below.
Chamber pressure 40.0Pa
RF power 300W
Gap 9mm
Cl ₂ gas flow rate 30ml / min
BCl ₃ gas flow rate 30ml / min
CHF ₃ gas flow rate 100ml / min
O ₂ gas flow rate 2ml / min
60 sec
The results are shown in Table 4.

  From the results of Table 4, it was confirmed that the polymer compounds (Polymers 1 to 12) according to the present invention have higher dry etching resistance than Comparative Polymer 1.

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 (7)

A resist material comprising at least a polymer compound having a repeating unit represented by the following general formulas (a) and (b).

(In the formula, R ¹ represents the same or different hydrogen atom or methyl group. R ² represents a single bond, —O—, —C (═O) —O—, —C (═O) —NH—. R ³ is any one of a hydroxy group, an acid labile group, a hydroxy group substituted with an acetyl group, a carboxyl group, and a carboxyl group substituted with an acid labile group, R ⁴ is a phenylene group,- O—R ⁷ —, —C (═O) —X ¹ —R ⁷ —, —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) -X ¹ -R ⁷ -Z ^1- , X ¹ is an oxygen atom or NH, R ⁷ is a linear, branched or cyclic alkylene group having 1 to 6 carbon atoms, or carbon number An arylene group of 6 to 8, which may contain 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, and Z ¹ is a phenylene group. ⁵ , R ⁶ is the same or different 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 6 to 12 carbon atoms. Or an aryl group having 7 to 20 carbon atoms or a thiophenyl group, R ⁵ and R ⁶ may be bonded to form a ring, and K ⁻ represents a non-nucleophilic counter ion. Is 1 or 2, and a and b are in the range of 0 <a <1.0 and 0 <b ≦ 0.8.) The resist material according to claim 1, wherein the polymer compound further contains a repeating unit represented by the following general formula (c) and / or (d).

(In the formula, R ¹ represents a hydrogen atom or a methyl group. R ⁸ is an adhesive group having a lactone, R ⁹ is an acid labile group. R ¹⁰ is a hydrogen atom, a methyl group, —CH ₂ —C. (= O) -O-CH _3. c and d are in a range of 0 ≦ c ≦ 0.8, 0 ≦ d ≦ 0.8, and 0 <c + d ≦ 0.8.)   The resist material according to claim 1, wherein the resist material is a chemically amplified positive resist material.   4. The resist material according to claim 1, wherein the resist material contains one or more of an organic solvent, a basic compound, a dissolution inhibitor, and a surfactant. Resist 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. A pattern forming method comprising:   The pattern forming method according to claim 5, wherein the high energy ray has a wavelength in a range of 200 nm or less.   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.