JP2010002593A - Positive resist material and pattern forming method using the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a chemically amplified positive resist material which exhibits greatly high alkali dissolution rate contrast before and after exposure, has high sensitivity and high resolution, ensures a good pattern shape after exposure, controls acid diffusion velocity in particular, exhibits excellent etching resistance, and is suitable as a fine pattern forming material for VLSI manufacture or of a photomask and a pattern forming material for EUV exposure. <P>SOLUTION: The positive resist material includes as a base resin a polymer compound including a repeating unit in which the hydrogen atom of a carboxyl group is substituted by an acid-labile group and a repeating unit having a group represented by formula (1), and having a weight average molecular weight of 1,000-500,000, wherein R<SP>1</SP>and R<SP>2</SP>are H or R<SP>1</SP>and R<SP>2</SP>are bonded to each other to form methylene, ethylene or -O-; R<SP>3</SP>is a single bond or methylene; R<SP>4</SP>is H, 1-4C alkyl, acetyl or an acid-labile group; and m is an integer of 1-4. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to a polymer compound suitable as a base resin for a positive resist material, particularly a chemically amplified positive resist material, a positive resist material using the same, and a pattern forming method.

  With the high integration and high speed of LSI, pattern rule miniaturization is progressing rapidly. In particular, the expansion of the flash memory market and the increase in storage capacity are leading to miniaturization. The fine line for miniaturization is mass production of 65 nm node devices by ArF lithography, and preparation for mass production of 45 nm nodes by next generation ArF immersion lithography is in progress. Next generation 32nm node includes immersion lithography with ultra high NA lens combining liquid with higher refractive index than water, high refractive index lens and high refractive index resist, vacuum ultraviolet light (EUV) with wavelength of 13.5nm Lithography, double exposure of ArF lithography (double patterning lithography), and the like are candidates and are being studied.

Light elements such as hydrocarbons used in resists for high energy rays with very short wavelengths such as EB and X-rays hardly absorb, and polyhydroxystyrene-based resist materials have been studied.
The EB resist has been practically used for mask drawing. In recent years, mask manufacturing techniques have become a problem. Reduced projection exposure apparatuses have been used since the light used for exposure was g-line, and the reduction magnification was 1/5. However, both the enlargement of the chip size and the enlargement of the projection lens have a 1/4 magnification. Therefore, the influence of the dimensional deviation of the mask on the dimensional change of the pattern on the wafer has become a problem. It has been pointed out that with the miniaturization of the pattern, the dimensional deviation on the wafer has become larger than the value of the dimensional deviation of the mask. There is a need for a mask error enhancement factor (MEEF) calculated using a mask dimensional change as a denominator and a dimensional change on a wafer as a numerator. It is not uncommon for MEEF to exceed 4 for 45 nm-class patterns. If the reduction ratio is 1/4 and the MEEF is 4, it can be said that the mask production requires the same accuracy as that of the substantially equal-size mask.
In order to increase the accuracy of the line width in the mask manufacturing exposure apparatus, an exposure apparatus using an electron beam (EB) has been used from an exposure apparatus using a laser beam. Furthermore, since further miniaturization is possible by increasing the acceleration voltage in the electron gun of EB, 10 keV to 30 keV, and recently 50 keV is the mainstream, and studies of 100 keV are also underway.

  Here, as the acceleration voltage increases, lowering the sensitivity of the resist has become a problem. When the acceleration voltage is improved, the influence of forward scattering in the resist film is reduced, so that the contrast of electron drawing energy is improved and the resolution and dimensional controllability are improved. Since it passes, the sensitivity of the resist decreases. Since the mask exposure machine exposes with one stroke of direct drawing, a decrease in resist sensitivity leads to a decrease in productivity, which is not preferable. Chemically amplified resists are being studied because of the demand for higher sensitivity.

As the pattern of EB lithography becomes finer, the resist is becoming thinner to prevent pattern collapse during development with a high aspect ratio. In the case of optical lithography, the thinning of the resist greatly contributes to the improvement of resolution. This is because the planarization of the device has progressed with the introduction of CMP or the like. In the case of mask production, the substrate is flat, and the thickness of the substrate to be processed (for example, Cr, MoSi, SiO ₂ ) is determined for light shielding rate and phase difference control. In order to reduce the thickness, it is necessary to improve the dry etching resistance of the resist.

Here, it is generally said that there is a correlation between the carbon density of the resist and the dry etching resistance. For EB writing that is not affected by absorption, a resist based on a novolak polymer having excellent etching resistance has been developed.
The indene copolymerization disclosed in Japanese Patent No. 3865048 (Patent Document 1) and the acenaphthylene copolymer disclosed in Japanese Patent Application Laid-Open No. 2006-169302 (Patent Document 2) are not only high in carbon density but also rigid due to the cycloolefin structure. The main chain structure is expected to improve etching resistance.
In addition, the resolution is improved by the acetal group having a cyclic structure shown in the bulky acetal shown in Japanese Patent No. 3963625 (Patent Document 3) and Japanese Patent Application Laid-Open No. 2006-96965 (Patent Document 4). ing.

Further, it has been reported that the absorption of carbon atoms is small in difficult X-ray (EUV) exposure at a wavelength of 5 to 20 nm, which is expected as an exposure method in fine processing of 70 nm or later along with F ₂ exposure. Increasing the carbon density is effective not only for improving dry etching resistance but also for improving transmittance in the soft X-ray wavelength region (N. Matsuzawa et. Al .; Jp. J. Appl. Phys. Vol. 38). p7109-7113 (1999): Non-Patent Document 1).

  With the progress of miniaturization, blurring of images due to acid diffusion has become a problem (Non-patent Document 2: SPIE Vol. 5039 p1 (2003)). In order to ensure the resolution in a fine pattern having a dimension size of 45 nm or more, it is proposed that not only the conventionally proposed improvement in dissolution contrast but also the control of acid diffusion is important (non-patent document). 3: PIE Vol. 6520 65203L-1 (2007)). However, chemically amplified resists have increased sensitivity and contrast due to acid diffusion, so if you try to minimize acid diffusion by shortening the post-exposure bake (PEB) temperature and time, the sensitivity and contrast are remarkably high. descend.

  SPIE Vol. 5753 p269 (2005) (Non-patent Document 4) shows the relationship between sensitivity, resolution, and roughness triangle trade-off. Here, it is necessary to suppress acid diffusion in order to expand the exposure margin, but it has been reported that the roughness deteriorates rapidly when the acid diffusion distance is 50 nm or less.

  It is effective to suppress acid diffusion by adding an acid generator that generates a bulky acid. Therefore, it has been proposed to copolymerize an acid generator of an onium salt having a polymerizable olefin with an acid generator. JP-A-4-230645 (Patent Document 5), JP-A-2005-84365 (Patent Document 6) and JP-A-2006-045311 (Patent Document 7) describe a polymerizable olefin that generates a specific sulfonic acid. A sulfonium salt and an iodonium salt having the above have been proposed. Japanese Unexamined Patent Publication No. 2006-178317 (Patent Document 8) proposes a sulfonium salt in which a sulfonic acid is directly bonded to the main chain.

  The relationship between sensitivity and roughness trade-off is shown. For example, SPIE Vol. 3331 p531 (1998) (Non-Patent Document 5) shows an inversely proportional relationship between sensitivity and roughness, and it is predicted that the roughness of the resist will be reduced by reducing shot noise due to an increase in exposure amount. SPIE Vol. In 5374 p74 (2004) (Non-patent Document 6), a resist with an increased quencher is effective in reducing roughness, but at the same time the sensitivity deteriorates, so there is a trade-off relationship between sensitivity and roughness of EUV. There is a need to increase the quantum efficiency of acid generation to overcome this.

  SPIE Vol. 5753 p361 (2005) (Non-Patent Document 7) proposes a mechanism in which electrons are transferred to the PAG due to polymer excitation by exposure and acid is released as an acid generation mechanism in electron beam exposure. Both EB and EUV are higher than the ionization potential energy threshold of 10 eV, and it is estimated that the base polymer is easily ionized.

  SPIE Vol. 5753 p1034 (2005) (Non-Patent Document 8) shows that poly-4-hydroxystyrene has higher acid generation efficiency in EB exposure than poly-4-methoxystyrene, and poly-4-hydroxystyrene is irradiated with EB. This suggests that electrons are efficiently transferred to the PAG.

  Therefore, a material obtained by copolymerizing hydroxystyrene for enhancing acid generation efficiency by electron transfer, methacrylate of PAG in which sulfonic acid is directly bonded to the polymer main chain to suppress acid diffusion, and methacrylate having acid labile group is SPIE Vol. . 6519 p6519F1-1 (2007) (non-patent document 9).

Japanese Patent No. 3865048 JP 2006-169302 A Japanese Patent No. 3963625 JP 2006-96965 A JP-A-4-230645 JP 2005-84365 A JP 2006-045311 A JP 2006-178317 A N. Matsuzawa et. al. Jp. J. et al. Appl. Phys. Vol. 38 p7109-7113 (1999) SPIE Vol. 5039 p1 (2003) PIE Vol. 6520 65203L-1 (2007) SPIE Vol. 5753 p269 (2005) SPIE Vol. 3331 p531 (1998) SPIE Vol. 5374 p74 (2004) SPIE Vol. 5753 p361 (2005) SPIE Vol. 5753 p1034 (2005) SPIE Vol. 6519 p6519F1-1 (2007)

  The present invention has been made in view of the above circumstances, and has higher resolution, exposure margin, smaller density difference, process adaptability than conventional positive resist materials, good pattern shape after exposure, and It is an object of the present invention to provide a positive resist material exhibiting excellent etching resistance, particularly a polymer compound suitable as a base resin for a chemically amplified positive resist material, a positive resist material using the same, and a pattern forming method.

  As a result of intensive studies to obtain a positive resist material having high sensitivity and high resolution, exposure margin, etc. that have been recently requested, good etching shape, and excellent etching resistance, For this purpose, it has been found that it is extremely effective if a polymer containing a repeating unit having a specific phenolic hydroxyl group is used as a base resin of a positive resist material, particularly a chemically amplified positive resist material, and the present invention has been completed. It is.

  In view of the above, the present inventors have developed a polymer obtained by copolymerization with (meth) acrylate substituted with an acid labile group in order to further suppress acid diffusion and improve dissolution contrast and etching resistance. By using it as a base resin for resist materials, especially chemically amplified positive resist materials, the alkali dissolution rate contrast before and after exposure is significantly high, it has high sensitivity and high resolution, and the pattern shape after exposure is good. Further, the present inventors have found that a positive resist material, particularly a chemically amplified positive resist material, which is excellent in etching resistance and suitable for use as a fine pattern forming material for VLSI manufacturing or for photomasks, can be obtained.

  The positive resist material of the present invention has particularly high resist contrast, high sensitivity and high resolution, exposure margin, excellent process adaptability, and good pattern shape after exposure. In particular, the dimensional difference between the dense pattern and the sparse pattern is small, and more excellent etching resistance is exhibited. Therefore, since it has these excellent characteristics, it is very practical and is very effective as a resist material mask pattern forming material for VLSI.

（式中、Ｒ¹、Ｒ²は水素原子、又はＲ¹とＲ²は互いに結合してメチレン基、エチレン基又は−Ｏ−を形成する。Ｒ³は単結合又はメチレン基、Ｒ⁴は水素原子、炭素数１〜４のアルキル基、アセチル基、又は酸不安定基である。ｍは１〜４の整数である。）
請求項２：
少なくとも一般式（１）の基を有する繰り返し単位が、一般式（２）で示される重量平均分子量が１，０００〜５００，０００の範囲である高分子化合物をベース樹脂にしていることを特徴とする請求項１記載のポジ型レジスト材料。

（式中、Ｒ¹〜Ｒ⁴、ｍは前述の通り、Ｒ⁵は水素原子又はメチル基を表す。Ｚは単結合、フェニレン基又はナフチレン基である。ａは０＜ａ＜１．０である。）
請求項３：
少なくとも一般式（ａ）で示される繰り返し単位と、一般式（ｂ）で示される酸不安定基を有する繰り返し単位を共重合してなる一般式（３）で示される重量平均分子量が１，０００〜５００，０００の範囲である高分子化合物をベース樹脂にしていることを特徴とする請求項２記載のポジ型レジスト材料。

（式中、Ｒ¹〜Ｒ⁵、ｍ、Ｚは前述と同様である。Ｒ⁶は水素原子又はメチル基、Ｒ⁷は酸不安定基を表す。Ｘは単結合、エステル基、ラクトン環を有する炭素数１〜１２の連結基、フェニレン基、又はナフチレン基である。０＜ａ＜１．０、０＜ｂ＜１．０、０．１≦ａ＋ｂ≦１．０の範囲である。）
請求項４：
少なくとも上記一般式（３）中の繰り返し単位ａと、カルボキシル基の水酸基が酸不安定基で置換された繰り返し単位ｂに加えて、ヒドロキシ基、ラクトン環、エーテル基、エステル基、カルボニル基、又はシアノ基を有する密着性基の繰り返し単位ｃを共重合した重量平均分子量が１，０００〜５００，０００の範囲である高分子化合物（ここで０＜ａ＜１．０、０＜ｂ＜１．０、０＜ｃ≦０．９、０．２≦ａ＋ｂ＋ｃ≦１．０の範囲である。）をベース樹脂にしていることを特徴とする請求項３記載のポジ型レジスト材料。
請求項５：
更に、有機溶剤及び酸発生剤を含有する化学増幅型のレジスト材料であることを特徴とする請求項１乃至４のいずれか１項記載のポジ型レジスト材料。
請求項６：
更に、溶解阻止剤を含有するものであることを特徴とする請求項５記載のポジ型レジスト材料。
請求項７：
更に、添加剤として塩基性化合物及び／又は界面活性剤を配合してなることを特徴とする請求項５又は６記載のポジ型レジスト材料。
請求項８：
請求項１乃至７のいずれか１項に記載のポジ型レジスト材料を基板上に塗布する工程と、加熱処理後、高エネルギー線で露光する工程と、現像液を用いて現像する工程とを含むことを特徴とするパターン形成方法。
請求項９：
露光する高エネルギー線が、電子ビーム、波長３〜１５ｎｍの範囲の軟Ｘ線であることを特徴とする請求項８記載のパターン形成方法。 That is, the present invention provides the following polymer compound and positive resist material, and a pattern forming method using the same.
Claim 1:
A high weight average molecular weight in the range of 1,000 to 500,000 including a repeating unit in which a hydrogen atom of a carboxyl group is substituted with an acid labile group and a repeating unit having a group represented by the general formula (1) A positive resist material characterized in that a molecular compound is used as a base resin.

(Wherein R ¹ and R ² are hydrogen atoms, or R ¹ and R ² are bonded to each other to form a methylene group, ethylene group or —O—. R ³ is a single bond or a methylene group, and R ⁴ is hydrogen. An atom, an alkyl group having 1 to 4 carbon atoms, an acetyl group, or an acid labile group, and m is an integer of 1 to 4.)
Claim 2:
The repeating unit having at least a group of the general formula (1) is based on a polymer compound having a weight average molecular weight represented by the general formula (2) in the range of 1,000 to 500,000. The positive resist material according to claim 1.

(Wherein R ^{1 to} R ⁴ and m are as described above, R ⁵ represents a hydrogen atom or a methyl group. Z is a single bond, a phenylene group or a naphthylene group. A is 0 <a <1.0. is there.)
Claim 3:
The weight average molecular weight represented by the general formula (3) obtained by copolymerizing at least the repeating unit represented by the general formula (a) and the repeating unit having an acid labile group represented by the general formula (b) is 1,000. 3. The positive resist material according to claim 2, wherein the base resin is a polymer compound in the range of .about.500,000.

(In the formula, R ^{1 to} R ⁵ , m and Z are the same as described above. R ⁶ represents a hydrogen atom or a methyl group, R ⁷ represents an acid labile group. X represents a single bond, an ester group or a lactone ring. And a linking group having 1 to 12 carbon atoms, a phenylene group, or a naphthylene group, in a range of 0 <a <1.0, 0 <b <1.0, and 0.1 ≦ a + b ≦ 1.0.
Claim 4:
In addition to at least the repeating unit a in the general formula (3) and the repeating unit b in which the hydroxyl group of the carboxyl group is substituted with an acid labile group, a hydroxy group, a lactone ring, an ether group, an ester group, a carbonyl group, or A polymer compound having a weight average molecular weight in the range of 1,000 to 500,000 obtained by copolymerizing a repeating unit c of an adhesive group having a cyano group (where 0 <a <1.0, 0 <b <1. 4. The positive resist composition according to claim 3, wherein the base resin is 0, 0 <c ≦ 0.9, 0.2 ≦ a + b + c ≦ 1.0.
Claim 5:
5. The positive resist material according to claim 1, which is a chemically amplified resist material containing an organic solvent and an acid generator.
Claim 6:
6. The positive resist material according to claim 5, further comprising a dissolution inhibitor.
Claim 7:
The positive resist composition according to claim 5 or 6, further comprising a basic compound and / or a surfactant as an additive.
Claim 8:
A step of coating the positive resist material according to any one of claims 1 to 7 on a substrate, a step of exposing to high energy rays after heat treatment, and a step of developing using a developer. The pattern formation method characterized by the above-mentioned.
Claim 9:
9. The pattern forming method according to claim 8, wherein the high energy rays to be exposed are electron beams and soft X-rays having a wavelength in the range of 3 to 15 nm.

  Examples of the use of the positive resist material of the present invention as described above, particularly the chemically amplified positive resist material, include not only lithography in semiconductor circuit formation, but also mask circuit pattern formation, micromachines, and thin film magnetic head circuits. It can also be applied to formation.

  The positive resist material of the present invention has a significantly high alkali dissolution rate contrast before and after exposure, high sensitivity and high resolution, good pattern shape after exposure, and particularly suppresses the acid diffusion rate. Excellent etching resistance. Therefore, it is possible to obtain a positive resist material, particularly a chemically amplified positive resist material, which is particularly suitable as a fine pattern forming material for VLSI manufacturing or a photomask, and a pattern forming material for EUV exposure.

（式中、Ｒ¹、Ｒ²は水素原子、又はＲ¹とＲ²は互いに結合してメチレン基、エチレン基又は−Ｏ−を形成する。Ｒ³は単結合又はメチレン基、Ｒ⁴は水素原子、炭素数１〜４のアルキル基、アセチル基、又は酸不安定基である。ｍは１〜４の整数である。） Hereinafter, the present invention will be described in more detail.
The polymer compound according to the present invention is a resist material characterized in that a resin containing at least a repeating unit having a group represented by the following general formula (1) is used as a base resin.

(Wherein R ¹ and R ² are hydrogen atoms, or R ¹ and R ² are bonded to each other to form a methylene group, ethylene group or —O—. R ³ is a single bond or a methylene group, and R ⁴ is hydrogen. An atom, an alkyl group having 1 to 4 carbon atoms, an acetyl group, or an acid labile group, and m is an integer of 1 to 4.)

（式中、Ｒ¹〜Ｒ⁴、ｍは前述の通り、Ｒ⁵は水素原子又はメチル基を表す。Ｚは単結合、フェニレン基又はナフチレン基である。ａは０＜ａ＜１．０である。） The group represented by the general formula (1) is preferably one in which a hydrogen atom of a carboxyl group of (meth) acrylic acid is substituted, and can be represented by the following general formula (2).

(Wherein R ^{1 to} R ⁴ and m are as described above, R ⁵ represents a hydrogen atom or a methyl group. Z is a single bond, a phenylene group or a naphthylene group. A is 0 <a <1.0. is there.)

（式中、Ｒ¹〜Ｒ⁵、ｍ、Ｚは前述と同様である。Ｒ⁶は水素原子又はメチル基、Ｒ⁷は酸不安定基を表す。Ｘは単結合、エステル基、ラクトン環を有する炭素数１〜１２の連結基、フェニレン基、又はナフチレン基である。０＜ａ＜１．０、０＜ｂ＜１．０、０．１≦ａ＋ｂ≦１．０の範囲である。） In this case, in particular, the base resin is represented by the general formula (3) obtained by copolymerizing at least the repeating unit represented by the general formula (a) and the repeating unit having an acid labile group represented by the general formula (b). Polymer compounds having a weight average molecular weight in the range of 1,000 to 500,000 are preferred.

(In the formula, R ^{1 to} R ⁵ , m and Z are the same as described above. R ⁶ represents a hydrogen atom or a methyl group, R ⁷ represents an acid labile group. X represents a single bond, an ester group or a lactone ring. And a linking group having 1 to 12 carbon atoms, a phenylene group, or a naphthylene group, in a range of 0 <a <1.0, 0 <b <1.0, and 0.1 ≦ a + b ≦ 1.0.

Specific examples of the monomer for obtaining the repeating unit represented by the general formula (a) are shown below.

（式中、Ｒ⁴は上記の通り。）

(Wherein R ⁴ is as described above.)

  The repeating unit a in the positive resist material of the present invention is characterized by having a cyclo ring and a phenolic hydroxy group in the same repeating unit. The phenol group has alkali solubility, prevents swelling in the developer, has a sensitizing action that increases the efficiency of acid generation by generating phenoxy radicals during EUV light and EB drawing, and transferring energy to the PAG. There is an advantage, but there is a disadvantage that the resolution is lowered due to an increase in the acid diffusion distance. The cyclo ring has a feature of reducing the acid diffusion distance by a rigid structure, and has an advantage of improving resolution. By combining a cyclo ring and a phenolic hydroxy group, a highly sensitive and high resolution base polymer for resist can be constructed. In particular, a copolymer of monomers shown in the right three columns having a plurality of phenolic hydroxyl groups has a high sensitizing effect.

ここで、Ｒ⁶、Ｒ⁷、Ｘは前述の通りである。 The monomer for obtaining the repeating unit b having an acid labile group in the general formula (3) can be represented by the following general formula (4).

Here, R ⁶ , R ⁷ and X are as described above.

The acid labile group (the acid labile group of R ^{7 in} the general formulas (3) and (4)) is variously selected, and may be the same or different. In particular, the following formulas (A-1) to (A-1) to ( Examples thereof include those represented by the group substituted by A-3).

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

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

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

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

Furthermore, the substituent shown by following formula (A-1) -1-(A-1) -10 can also be mentioned.

Here, R ³⁷ is the same or different from each other, a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms, or an aryl group having 6 to 20 carbon atoms, R ³⁸ is a hydrogen atom, or 1 to 1 carbon atoms. 10 linear, branched or cyclic alkyl groups.
R ³⁹ is a linear, branched or cyclic alkyl group having 2 to 10 carbon atoms that is the same or different from each other, or an aryl group having 6 to 20 carbon atoms.
a1 is as described above.

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

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

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

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

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

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

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

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

Moreover, as a tertiary alkyl group, the formula (A-3) -1-(A-3) -18 shown below can also be specifically mentioned.

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

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

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

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

  In particular, the acid labile group of A-3 is preferably a repeating unit of (meth) acrylic acid ester having an exo structure represented by the following formula (A-3) -21.

（式中、Ｒ⁵、ｂは前述の通り、Ｒ^c3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。Ｒ^c4〜Ｒ^c9及びＲ^c12、Ｒ^c13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、Ｒ^c10、Ｒ^c11は水素原子を示す。あるいは、Ｒ^c4とＲ^c5、Ｒ^c6とＲ^c8、Ｒ^c6とＲ^c9、Ｒ^c7とＲ^c9、Ｒ^c7とＲ^c13、Ｒ^c8とＲ^c12、Ｒ^c10とＲ^c11又はＲ^c11とＲ^c12は互いに環を形成していてもよく、その場合には炭素数１〜１５のヘテロ原子を含んでもよい２価の炭化水素基を示す。またＲ^c4とＲ^c13、Ｒ^c10とＲ^c13又はＲ^c6とＲ^c8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。Ｒ^c14は水素原子、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 ⁵ and b are as described above, and R ^c3 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 ^{c4 to} R ^c9 and R ^c12 and R ^c13 each independently represent a hydrogen atom or a monovalent hydrocarbon group that may contain a hetero atom having 1 to 15 carbon atoms, and R ^c10 and R ^{c11 each} represent a hydrogen atom. . Alternatively, R ^c4 and R ^c5, R ^c6 and R ^c8, R ^c6 and R ^c9, R ^c7 and R ^c9, R ^c7 and R ^c13, R ^c8 and R ^c12, R ^c10 and R ^c11, or R ^c11 and R ^{c12 Represents} a divalent hydrocarbon group which may form a ring with each other and may contain a hetero atom having 1 to 15 carbon atoms, R ^c4 and R ^c13 , R ^c10 and R ^c13 or R ^c6 and R ^c8 is bonded without anything intervening in between those bonded to the adjacent carbon may also form a double bond .R ^c14 is a hydrogen atom, 1 to 15 carbon atoms Straight, branched or cyclic alkyl group. The formula also represents enantiomer.)

  Here, an ester monomer for obtaining a repeating unit having an exo structure represented by the general formula (A-3) -21 is disclosed in JP-A No. 2000-327633. Specific examples include the following, but are not limited thereto.

  Next, as the acid labile group represented by A-3, the acid labile group of (meth) acrylic acid ester having frangyl, tetrahydrofurandiyl or oxanorbornanediyl represented by the following formula (A-3) -22: Can be mentioned.

（式中、式中、Ｒ⁵、ｂは前述の通りである。Ｒ^c14、Ｒ^c15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、Ｒ^c14、Ｒ^c15は互いに結合してこれらが結合する炭素原子と共に脂肪族炭化水素環を形成してもよい。Ｒ^c16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。Ｒ^c17は水素原子又はヘテロ原子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。）

(In formula, R ^{< 5 >} , b is as above-mentioned. R ^<c14> , R ^{< c15 > shows} a C1-C10 linear, branched or cyclic monovalent hydrocarbon group each independently. R ^c14 and R ^c15 may be bonded to each other to form an aliphatic hydrocarbon ring together with the carbon atom to which they are bonded, and R ^c16 is a divalent group selected from ^flangedyl , tetrahydrofurandiyl or ^{oxanorbornanediyl.} R ^c17 represents a linear, branched or cyclic monovalent hydrocarbon group having 1 to 10 carbon atoms which may contain a hydrogen atom or a hetero atom.

  Monomers for obtaining repeating units substituted with acid labile groups having frangyl, tetrahydrofuraniyl or oxanorbornanediyl are exemplified below. Ac represents an acetyl group and Me represents a methyl group.

  In the present invention, the base resin includes at least the repeating unit a in the general formula (3) and the repeating unit b in which the hydroxyl group of the carboxyl group is substituted with an acid labile group, in addition to a hydroxy group, a lactone ring, and an ether. A polymer compound having a weight average molecular weight in the range of 1,000 to 500,000 obtained by copolymerizing a repeating unit c of an adhesive group having a group, an ester group, a carbonyl group or a cyano group (where 0 <a <1 0.0, 0 <b <1.0, 0 <c ≦ 0.9, 0.2 ≦ a + b + c ≦ 1.0.).

  Specific examples of the monomer for obtaining the repeating unit c of the adhesive group having a hydroxy group, a lactone ring, an ether group, an ester group, a carbonyl group, or a cyano group can be given below.

  In the case of a monomer having a hydroxy group, the hydroxy group may be substituted with an acetal that can be easily deprotected with an acid such as ethoxyethoxy during the polymerization, and then deprotected with a weak acid and water after the polymerization, or an acetyl group or a formyl group. Alternatively, it may be substituted with a pivaloyl group or the like and subjected to alkali hydrolysis after polymerization.

  Further, it can be copolymerized with a repeating unit d such as indene d1, acenaphthylene d2, chromone d3, coumarin d4, norbornadiene d5 represented by the following general formula (5).

（式中、Ｒ⁹〜Ｒ¹³は水素原子、炭素数１〜３０のアルキル基、一部又は全てがハロゲン原子で置換されたアルキル基、ヒドロキシ基、アルコキシ基、アルカノイル基又はアルコキシカルボニル基、又は炭素数６〜１０のアリール基、ハロゲン原子、又は１，１，１，３，３，３−ヘキサフルオロ−２−プロパノール基である。Ｘはメチレン基、酸素原子、又は硫黄原子である。ｄ１は０≦ｄ１≦０．４、ｄ２は０≦ｄ２≦０．４、ｄ３は０≦ｄ３≦０．４、ｄ４は０≦ｄ４≦０．４、ｄ５は０≦ｄ５≦０．４、０≦ｄ１＋ｄ２＋ｄ３＋ｄ４＋ｄ５≦０．４である。）

(Wherein R ^{9 to} R ¹³ are a hydrogen atom, an alkyl group having 1 to 30 carbon atoms, an alkyl group partially or entirely substituted with a halogen atom, a hydroxy group, an alkoxy group, an alkanoyl group or an alkoxycarbonyl group, or An aryl group having 6 to 10 carbon atoms, a halogen atom, or a 1,1,1,3,3,3-hexafluoro-2-propanol group, and X is a methylene group, an oxygen atom, or a sulfur atom. Is 0 ≦ d1 ≦ 0.4, d2 is 0 ≦ d2 ≦ 0.4, d3 is 0 ≦ d3 ≦ 0.4, d4 is 0 ≦ d4 ≦ 0.4, d5 is 0 ≦ d5 ≦ 0.4, 0 ≦ d1 + d2 + d3 + d4 + d5 ≦ 0.4)

（式中、Ｒ¹⁴は水素原子又はメチル基を表し、Ｒ¹⁵は酸不安定基である。ｑは１又は２である。ｅは０≦ｅ≦０．４である。） The repeating unit e represented by the following general formula (6) can be additionally copolymerized.

(In the formula, R ¹⁴ represents a hydrogen atom or a methyl group, R ¹⁵ is an acid labile group, q is 1 or 2, and e is 0 ≦ e ≦ 0.4.)

Examples of the repeating unit f that can be copolymerized in addition to the repeating units a, b, c, d, and e include styrene, vinyl naphthalene, vinyl anthracene, vinyl pyrene, and methylene indan.
An onium salt acid generator g having a polymerizable olefin may be copolymerized.
JP-A-4-230645, JP-A-2005-84365, and JP-A-2006-045311 propose sulfonium salts and iodonium salts having a polymerizable olefin that generates a specific sulfonic acid. Japanese Patent Application Laid-Open No. 2006-178317 proposes a sulfonium salt in which a sulfonic acid is directly bonded to the main chain.

（式中、Ｒ²⁰、Ｒ²⁴、Ｒ²⁸は水素原子又はメチル基、Ｒ²¹はフェニレン基、−Ｏ−Ｒ−、又は−Ｃ（＝Ｏ）−Ｙ−Ｒ−である。Ｙは酸素原子又はＮＨ、Ｒは炭素数１〜６の直鎖状、分岐状又は環状のアルキレン基、フェニレン基又はアルケニレン基であり、カルボニル基、エステル基、エーテル基又はヒドロキシ基を含んでいてもよい。Ｒ²²、Ｒ²³、Ｒ²⁵、Ｒ²⁶、Ｒ²⁷、Ｒ²⁹、Ｒ³⁰、Ｒ³¹は同一又は異種の炭素数１〜１２の直鎖状、分岐状又は環状のアルキル基であり、カルボニル基、エステル基又はエーテル基を含んでいてもよく、又は炭素数６〜１２のアリール基、炭素数７〜２０のアラルキル基又はチオフェニル基を表す。Ｚは単結合、メチレン基、エチレン基、フェニレン基、フッ素化されたフェニレン基、−Ｏ−Ｒ³²−、又は−Ｃ（＝Ｏ）−Ｚ₁−Ｒ³²−である。Ｚ₁は酸素原子又はＮＨ、Ｒ³²は炭素数１〜６の直鎖状、分岐状又は環状のアルキレン基、フェニレン基又はアルケニレン基であり、カルボニル基、エステル基、エーテル基又はヒドロキシ基を含んでいてもよい。Ｍ^-は非求核性対向イオンを表す。ｇ１は０≦ｇ１≦０．３、ｇ２は０≦ｇ２≦０．３、ｇ３は０≦ｇ３≦０．３、０≦ｇ１＋ｇ２＋ｇ３≦０．３である。） In the present invention, repeating units g1, g2, and g3 having a sulfonium salt represented by the following general formula (7) can be copolymerized.

(Wherein R ²⁰ , R ²⁴ , and R ²⁸ are a hydrogen atom or a methyl group, R ²¹ is a phenylene group, —O—R—, or —C (═O) —Y—R—, where Y is an oxygen atom. Alternatively, NH or R is a linear, branched or cyclic alkylene group having 1 to 6 carbon atoms, a phenylene group or an alkenylene group, and may contain a carbonyl group, an ester group, an ether group or a hydroxy group. ²² , R ²³ , R ²⁵ , R ²⁶ , R ²⁷ , R ²⁹ , R ³⁰ , R ³¹ are the same or different linear, branched or cyclic alkyl groups having 1 to 12 carbon atoms, An ester group or an ether group may be contained, or an aryl group having 6 to 12 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, or a thiophenyl group, wherein Z represents a single bond, a methylene group, an ethylene group, a phenylene group, A fluorinated phenylene group, —O—R ³² —, or Is —C (═O) —Z ₁ —R ³² —, wherein Z ₁ is an oxygen atom or NH, and R ³² is a linear, branched or cyclic alkylene group having 1 to 6 carbon atoms, a phenylene group or an alkenylene. Which may contain a carbonyl group, an ester group, an ether group or a hydroxy group, M ⁻ represents a non-nucleophilic counter ion, g1 is 0 ≦ g1 ≦ 0.3, and g2 is 0 ≦ g2 ≦. 0.3 and g3 are 0 ≦ g3 ≦ 0.3 and 0 ≦ g1 + g2 + g3 ≦ 0.3.)

Non-nucleophilic counter ions of M ⁻ include halide ions such as chloride ions and bromide ions, triflate, fluoroalkyl sulfonates such as 1,1,1-trifluoroethanesulfonate, nonafluorobutanesulfonate, tosylate, and benzene. Sulfonate, 4-fluorobenzene sulfonate, aryl sulfonate such as 1,2,3,4,5-pentafluorobenzene sulfonate, alkyl sulfonate such as mesylate and butane sulfonate, bis (trifluoromethylsulfonyl) imide, bis (perfluoroethyl) Mention acid such as imide) such as sulfonyl) imide, bis (perfluorobutylsulfonyl) imide, tris (trifluoromethylsulfonyl) methide, tris (perfluoroethylsulfonyl) methide It can be.

  In order to synthesize these polymer compounds, as one method, a desired monomer among the monomers giving the repeating units a to g is heated in an organic solvent with a radical polymerization initiator added, and the copolymer is heated. 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-methylpropionate) ), Benzoyl peroxide, lauroyl peroxide and the like, and preferably polymerized by heating to 50 to 80 ° C. The reaction time is 2 to 100 hours, preferably 5 to 20 hours.

  When copolymerizing hydroxystyrene and hydroxyvinylnaphthalene, acetoxystyrene and acetoxyvinylnaphthalene are used in place of hydroxystyrene and hydroxyvinylnaphthalene, and after polymerization, the acetoxy group is deprotected by the above alkaline hydrolysis to produce polyhydroxystyrene and hydroxyhydroxyl. There is also a method of making polyvinyl naphthalene.

  Ammonia water, triethylamine, etc. can be used as the base during the alkali hydrolysis. The reaction temperature is −20 to 100 ° C., preferably 0 to 60 ° C., and the reaction time is 0.2 to 100 hours, preferably 0.5 to 20 hours.

Here, the ratio of the repeating units a to c is 0 <a <1, 0 <b <1, 0 ≦ c ≦ 0.9, particularly 0 <c ≦ 0.9, 0.2 ≦ a + b + c ≦ 1.0. Preferably, 0.05 ≦ a ≦ 0.9, 0.1 ≦ b ≦ 0.8, 0.1 ≦ c ≦ 0.8, 0.3 ≦ a + b + c ≦ 1.0, more preferably 0.8. 1 ≦ a ≦ 0.8, 0.15 ≦ b ≦ 0.7, 0.15 ≦ c ≦ 0.7, and 0.4 ≦ a + b + c ≦ 1.0.
In this case, the ratio of the repeating units d to g is preferably 0 ≦ d + e + f + g ≦ 0.8, particularly preferably 0 ≦ d + e + f + g ≦ 0.7, and a + b + c + d + e + f + g = 1.
For example, a + b + c = 1 means that in a polymer compound containing repeating units a, b, and c, the total amount of repeating units a, b, and c is 100 mol% with respect to the total amount of all repeating units. A + b + c <1 means that the total amount of the repeating units a, b and c is less than 100 mol% with respect to the total amount of all the repeating units and has other repeating units in addition to a, b and c. It shows that.

  The polymer compound used in the positive resist material of the present invention must have a weight average molecular weight of 1,000 to 500,000, preferably 2,000 to 30,000. If the weight average molecular weight is too small, the resist material is inferior in heat resistance. If the weight average molecular weight is too large, the alkali solubility is lowered, and a trailing phenomenon is likely to occur after pattern formation.

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

  The polymer compound used in the present invention is suitable as a base resin for a positive resist material. Such a polymer compound is used as a base resin, and an organic solvent, an acid generator, a dissolution inhibitor, a basic compound, an interface. By combining the activator and the like appropriately in accordance with the purpose to form a positive resist material, the dissolution rate of the polymer compound in the developing solution is accelerated by a catalytic reaction in the exposed area, so that a highly sensitive positive resist is formed. Type resist material, resist film with high dissolution contrast and resolution, exposure margin, excellent process adaptability, good pattern shape after exposure, and better etching resistance In particular, since the acid diffusion can be suppressed, the difference in density between the layers is small, which makes it highly practical and very useful as a resist material for VLSI. It can be such things. In particular, when a chemically amplified positive resist material containing an acid generator and utilizing an acid catalyzed reaction is used, the sensitivity can be increased, and various characteristics are further improved and extremely useful. .

  Further, by adding a dissolution inhibitor to the positive resist material, the difference in dissolution rate between the exposed portion and the unexposed portion can be further increased, and the resolution can be further improved.

  Furthermore, by adding a basic compound, for example, the acid diffusion rate in the resist film can be suppressed to further improve the resolution, and by adding a surfactant, the coatability of the resist material can be further improved. Alternatively, it can be controlled.

  The positive resist material of the present invention includes an organic solvent, a compound that generates an acid in response to high energy rays (acid generator), a dissolution inhibitor, a basic compound, a surfactant, if necessary, Other components can be contained, but as the organic solvent used in the positive resist material of the present invention, particularly the chemically amplified positive resist material, a base resin, an acid generator, and other additives are dissolved. Any organic solvent can be used. 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 monoethyl ether, ethylene glycol monoethyl ether, propylene glycol dimethyl ether, diethylene glycol dimethyl ether, and other ethers, propylene glycol monomethyl ether acetate, propylene glycol mono Ethyl ether acetate, ethyl lactate, ethyl pyruvate, butyl acetate, methyl 3-methoxypropionate, 3-ethoxy Ethyl propionate, acetate tert- butyl, tert- butyl propionate, and propylene glycol monobutyl tert- butyl ether acetate, although lactones such as γ- butyl lactone, not being limited thereto.

  These organic solvents can be used individually by 1 type or in mixture of 2 or more types. In the present invention, among these organic solvents, diethylene glycol dimethyl ether, 1-ethoxy-2-propanol, propylene glycol monomethyl ether acetate, and mixed solvents thereof, which have the highest solubility of the acid generator in the resist component, are preferably used. .

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

As an acid generator blended in the positive resist material of the present invention,
(I) 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 derivative,
(Vii) a disulfone derivative,
(Viii) a nitrobenzyl sulfonate derivative,
(Ix) sulfonic acid ester derivatives and the like.

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

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 or an oxoalkenyl group, and an aryl having 6 to 20 carbon atoms. Group, an aralkyl group having 7 to 12 carbon atoms or an aryloxoalkyl group, part or all of hydrogen atoms of these groups may be substituted by an alkoxy group, etc. R ^101b and R ^{101c May} form a ring, and in the case of forming a ring, R ^101b and R ^101c each represent an alkylene group having 1 to 6 carbon atoms, 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 aryl group include a phenyl group, a naphthyl group, a p-methoxyphenyl group, an m-methoxyphenyl group, an o-methoxyphenyl group, an ethoxyphenyl group, a p-tert-butoxyphenyl group, and an m-tert-butoxyphenyl group. Alkylphenyl groups such as alkoxyphenyl groups, 2-methylphenyl groups, 3-methylphenyl groups, 4-methylphenyl groups, ethylphenyl groups, 4-tert-butylphenyl groups, 4-butylphenyl groups, dimethylphenyl groups, etc. Alkyl naphthyl groups such as methyl naphthyl group and ethyl naphthyl group, alkoxy naphthyl groups such as methoxy naphthyl group and ethoxy naphthyl group, dialkyl naphthyl groups such as dimethyl naphthyl group and diethyl naphthyl group, dimethoxy naphthyl group and diethoxy naphthyl group Dialkoxynaphthyl group And the like. Examples of the aralkyl group include a benzyl group, a phenylethyl group, and a phenethyl group. As the aryloxoalkyl group, 2-aryl-2-oxoethyl group such as 2-phenyl-2-oxoethyl group, 2- (1-naphthyl) -2-oxoethyl group, 2- (2-naphthyl) -2-oxoethyl group and the like Groups and the like. Non-nucleophilic counter ions of K ⁻ include halide ions such as chloride ion and bromide ion, fluoroalkyl sulfonates such as triflate, 1,1,1-trifluoroethane sulfonate, and nonafluorobutane sulfonate, tosylate, and benzene sulfonate. Arylsulfonates such as 4-fluorobenzenesulfonate, 1,2,3,4,5-pentafluorobenzenesulfonate, alkylsulfonates such as mesylate and butanesulfonate, bis (trifluoromethylsulfonyl) imide, bis (perfluoroethylsulfonyl) ) Imido acids such as imide and bis (perfluorobutylsulfonyl) imide, methide acids such as tris (trifluoromethylsulfonyl) methide and tris (perfluoroethylsulfonyl) methide, and Sulfonate position alpha represented by the formula (K-1) is fluoro substituted formula (K-1), shown in (K-2), α, β-position include sulfonates fluorine substituted.

In general formula (K-1), ^R102 is a hydrogen atom, a linear, branched or cyclic alkyl group having 1 to 30 carbon atoms, an acyl group, an alkenyl group having 2 to 20 carbon atoms, or 6 to 20 carbon atoms. An aryl group and an aryloxy group, which may have an ether group, an ester group, a carbonyl group, or a lactone ring. R ¹⁰³ in the general formula (K-2) is a hydrogen atom, a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, or an aryl group having 6 to 20 carbon atoms. And may have an ether group, an ester group, a carbonyl group, or a lactone ring.

（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 include a trifluoromethyl group, a 1,1,1-trifluoroethyl group, a 1,1,1-trichloroethyl group, and a nonafluorobutyl group. As the aryl group, an alkoxyphenyl group such as a phenyl group, p-methoxyphenyl group, m-methoxyphenyl group, o-methoxyphenyl group, ethoxyphenyl group, p-tert-butoxyphenyl group, m-tert-butoxyphenyl group, Examples thereof include alkylphenyl groups such as 2-methylphenyl group, 3-methylphenyl group, 4-methylphenyl group, ethylphenyl group, 4-tert-butylphenyl group, 4-butylphenyl group, and dimethylphenyl group. Examples of the halogenated aryl group include a fluorophenyl group, a chlorophenyl group, and 1,2,3,4,5-pentafluorophenyl group. Examples of the aralkyl group include a benzyl group and a phenethyl group.

（式中、Ｒ¹⁰⁷、Ｒ¹⁰⁸、Ｒ¹⁰⁹は炭素数１〜１２の直鎖状、分岐状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。）

(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. A linear or branched alkylene group.)

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

（式中、Ｒ^101a、Ｒ^101bは上記と同様である。）

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

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

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

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

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

  Examples of β-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.

  Further, 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-hydroxy Succinimide 2-chloroethane sulfonate, N-hydroxysuccinimide benzene sulfonate N-hydroxysuccinimide-2,4,6-trimethylbenzenesulfonic acid ester, N-hydroxysuccinimide 1-naphthalenesulfonic acid ester, N-hydroxysuccinimide 2-naphthalenesulfonic acid ester, N-hydroxy-2-phenylsuccinimide methanesulfonic acid Ester, N-hydroxymaleimide methanesulfonate, N-hydroxymaleimide ethanesulfonate, N-hydroxy-2-phenylmaleimide methanesulfonate, N-hydroxyglutarimide methanesulfonate, N-hydroxyglutarimide benzenesulfone Acid ester, N-hydroxyphthalimidomethanesulfonic acid ester, N-hydroxyphthalimidobenzenesulfonic acid ester, N-hydroxyl Phthalimide trifluoromethanesulfonate, N-hydroxyphthalimide p-toluenesulfonate, N-hydroxynaphthalimide methanesulfonate, N-hydroxynaphthalimidebenzenesulfonate, N-hydroxy-5-norbornene-2,3- Dicarboximide methanesulfonate, N-hydroxy-5-norbornene-2,3-dicarboximide trifluoromethanesulfonate, N-hydroxy-5-norbornene-2,3-dicarboximide p-toluenesulfonate Examples thereof include sulfonic acid ester derivatives of N-hydroxyimide compounds.

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

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

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

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

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

  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. %. 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、上記式中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が炭素数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。）

(In the above formulae, R ²⁰¹ and R ²⁰² each represent a hydrogen atom or a linear or branched alkyl group or alkenyl group having 1 to 8 carbon atoms. R ²⁰³ represents a hydrogen atom or 1 to 8 carbon atoms. Represents a linear or branched alkyl group or alkenyl group, or — (R ²⁰⁷ ) _h COOH, wherein R ²⁰⁴ is — (CH ₂ ) _i — (i = 2 to 10), arylene having 6 to 10 carbon atoms. A group, a carbonyl group, a sulfonyl group, an oxygen atom or a sulfur atom, and R ²⁰⁵ represents an alkylene group having 1 to 10 carbon atoms, an arylene group having 6 to 10 carbon atoms, a carbonyl group, a sulfonyl group, an oxygen atom or a sulfur atom. R ²⁰⁶ 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, and R ²⁰⁷ represents a straight chain having 1 to 10 carbon atoms. Chain or branched alkyl R ²⁰⁸ represents a hydrogen atom or a hydroxyl group, j is an integer of 0 to 5. u and h are 0 or 1. s, t, s ′, t ′, s ″, t ″ Is a number satisfying s + t = 8, s ′ + t ′ = 5, s ″ + t ″ = 4, respectively, and having at least one hydroxyl group in each phenyl skeleton. Α is a formula (D8 ), (D9) is a number that makes the molecular weight of the compound of 100 to 1,000.)

  The acid labile group of the dissolution inhibitor may be the acid labile group of the present invention represented by the general formula (1) or a conventional acid labile group represented by (A1) to (A3).

  To the positive resist material of the present invention, a dissolution inhibitor composed of a compound having a plurality of bisphenol groups substituted with an acid labile group represented by the following general formula BP- (1) can be added.

（式中、Ｒ⁵⁰¹は同一又は異種の水素原子、炭素数１〜１０の直鎖状、分岐状もしくは環状のアルキル基、炭素数６〜１０のアリール基、炭素数２〜１０のアルケニル基又はハロゲン原子であり、Ｒ⁵⁰²は同一又は異種の独立して水素原子又は酸不安定基であり、ｎは２〜４の整数である。Ｚは式中の炭素原子を合わせて炭素数５〜４０の環状構造を有するアルキル基、有橋環式炭化水素基、又は縮合多環式炭化水素基であり、硫黄などのヘテロ原子を有していてもよい。

(Wherein R ⁵⁰¹ is the same or different hydrogen atom, a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, or A halogen atom, R ⁵⁰² is the same or different independently a hydrogen atom or an acid labile group, n is an integer of 2 to 4. Z is a carbon number of 5 to 40 including the carbon atoms in the formula. An alkyl group having a cyclic structure, a bridged cyclic hydrocarbon group, or a condensed polycyclic hydrocarbon group, which may have a heteroatom such as sulfur.

As the acid labile group in the general formula BP- (1), those selected from the same groups as those described above for R ⁷ can be used. Specific examples of the compound represented by the general formula BP- (1) are shown below.

（式中、Ｒ⁵⁰¹、Ｒ⁵⁰²は上記と同様の意味を示す。）

(Wherein R ⁵⁰¹ and R ⁵⁰² have the same meaning as described above.)

  To the positive resist material of the present invention, a dissolution inhibitor composed of calixarenes and calixresorcinols substituted with acid labile groups described in JP-A No. 11-322656 can be added.

  The blending amount of the dissolution inhibitor is 0 to 50 parts, preferably 5 to 50 parts, more preferably 10 to 30 parts, based on 100 parts of the base resin, used alone or in combination of two or more. it can. If the blending amount is small, the resolution may not be improved. If the blending amount is too large, the pattern film is reduced and the resolution tends to decrease.

Furthermore, a basic compound can be mix | blended with the resist material of this invention.
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-pyridine, 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 mix | blended.
N (X) _n (Y) _3-n (B) -1
(In the formula, n is 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. The side chain Y is It represents the same or different hydrogen atom or linear, branched or cyclic alkyl group having 1 to 20 carbon atoms, and may contain an ether group or a hydroxyl group, and Xs may combine 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, a linear or branched alkylene group having 1 to 4 carbon atoms, R ³⁰⁶ is a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms, a hydroxy group, One or a plurality of ether groups, ester groups and lactone rings may be contained.

Specific examples of the compound represented by the general formula (B) -1 are given below.
Tris (2-methoxymethoxyethyl) amine, tris {2- (2-methoxyethoxy) ethyl} amine, tris {2- (2-methoxyethoxymethoxy) ethyl} amine, tris {2- (1-methoxyethoxy) ethyl } Amine, Tris {2- (1-ethoxyethoxy) ethyl} amine, Tris {2- (1-ethoxypropoxy) ethyl} amine, Tris [2- {2- (2-hydroxyethoxy) ethoxy} ethyl] amine, 4,7,13,16,21,24-hexaoxa-1,10-diazabicyclo [8.8.8] hexacosane, 4,7,13,18-tetraoxa-1,10-diazabicyclo [8.5.5] Eicosane, 1,4,10,13-tetraoxa-7,16-diazabicyclooctadecane, 1-aza-12-crown-4 1-aza-15-crown-5, 1-aza-18-crown-6, tris (2-formyloxyethyl) amine, tris (2-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] amine Tris [2- (tert-butoxycarbonylmethyloxy) ethyl] amine, tris [2- (cyclohexyloxycarbonylmethyloxy) ethyl] amine, tris (2-methoxycarbonylethyl) amine, tris (2-ethoxycarbonylethyl) amine N, N-bis (2-hydroxyethyl) 2- (methoxycarbonyl) ethylamine, N, N-bis (2-acetoxyethyl) 2- (methoxycarbonyl) ethylamine, N, N-bis (2-hydroxyethyl) 2- (ethoxycarbonyl) ethylamine, N, N-bis (2-acetoxyethyl) 2- (ethoxycarbonyl) ethylamine, N, N-bis (2-hydroxyethyl) 2- (2-methoxyethoxycarbonyl) 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-acetoxy) Ethoxycarbonyl) 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- (tetrahydrofurfuryl Oxycarbonyl) 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-formyloxy) Ethoxycarbonyl) ethylamine, N, N-bis (2- Toxiethyl) 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- (methoxy Carbonyl) ethyl] amine, N-butylbis [2- (methoxycarbonyl) ethyl] amine, N-butyl Rubis [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.

（式中、Ｘは前述の通り、Ｒ³⁰⁷は炭素数２〜２０の直鎖状又は分岐状のアルキレン基であり、カルボニル基、エーテル基、エステル基又はスルフィドを１個あるいは複数個含んでいてもよい。） Furthermore, 1 type, or 2 or more types of the basic compound which has a cyclic structure shown by the following general formula (B) -2 can also be added.

(In the formula, as described above, R ³⁰⁷ is a linear or branched alkylene group having 2 to 20 carbon atoms, and includes one or more carbonyl groups, ether groups, ester groups or 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 Morpholine, 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 Propionic acid tetrahydrofur Ryl, 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, Mention may be made of methyl thiomorpholinoacetate, ethyl 1-pyrrolidinyl acetate, 2-methoxyethyl morpholinoacetate.

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

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

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

  In addition, the compounding quantity of the base compound of this invention is 0.001-2 parts with respect to 100 parts of base resins, Especially 0.01-1 part is suitable. If the blending amount is less than 0.001 part, there is no blending effect, and if it exceeds 2 parts, the sensitivity may be too low.

  As the compound having a group represented by ≡C—COOH in the molecule that can be added to the positive resist material of the present invention, for example, one or more compounds selected from the following groups I and II are used. However, it is not limited to these. By blending this component, the PED 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.

（但し、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。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。κは式（Ａ６）の化合物を重量平均分子量１，０００〜５，０００とする数である。λは式（Ａ７）の化合物を重量平均分子量１，０００〜１０，０００とする数である。）

(In the formula, R ⁴⁰⁸ represents a hydrogen atom or a methyl group. R ⁴⁰² and R ⁴⁰³ each represents a hydrogen atom or a linear or branched alkyl group or alkenyl group having 1 to 8 carbon atoms. R ⁴⁰⁴ represents It represents a hydrogen atom, a linear or branched alkyl group or alkenyl group having 1 to 8 carbon atoms, or a — (R ⁴⁰⁹ ) _h —COOR ′ group (R ′ represents a hydrogen atom or —R ⁴⁰⁹ —COOH). ⁴⁰⁵ represents — (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, and R ⁴⁰⁶ represents an alkylene having 1 to 10 carbon atoms. Group, an arylene group having 6 to 10 carbon atoms, a carbonyl group, a sulfonyl group, an oxygen atom or a sulfur atom, R ⁴⁰⁷ is a hydrogen atom or a linear or branched alkyl group having 1 to 8 carbon atoms, an alkenyl group, Phenyls each substituted with a hydroxyl group Or .R ⁴⁰⁹ showing a naphthyl group is a straight or branched alkyl or alkenyl group or -R showing a ⁴¹¹ -COOH groups .R ⁴¹⁰ is hydrogen atom or a straight-1 to 8 carbon atoms A chain or branched alkyl group, an alkenyl group, or —R ⁴¹¹ —COOH group, R ⁴¹¹ represents a linear or branched alkylene group having 1 to 10 carbon atoms, j is 0 to 3, s1 s4 and t1 to t4 are numbers satisfying s1 + t1 = 8, s2 + t2 = 5, s3 + t3 = 4, s4 + t4 = 6, respectively, and having at least one hydroxyl group in each phenyl skeleton, κ is a formula (A6). Is a number with a weight average molecular weight of 1,000 to 5,000. Λ is a number with a weight average molecular weight of 1,000 to 10,000 for the compound of formula (A7).)

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

(R ⁴⁰² , R ⁴⁰³ , and R ⁴¹¹ have the same meanings as above. R ⁴¹² represents a hydrogen atom or a hydroxyl group. S5 and t5 are numbers satisfying s5 + t5 = 5 when 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。α、κは上記と同様の意味を示す。）

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

  In addition, the compound which has group shown by (≡C-COOH) in the said molecule | numerator can be used individually by 1 type or in combination of 2 or more types.

  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 3 parts, relative to 100 parts of the base resin. More preferably, it is 0.1 to 2 parts. If it exceeds 5 parts, the resolution of the resist material may be lowered.

  Examples of the surfactant added to the present invention are not particularly limited, but polyoxyethylene alkyl such as polyoxyethylene lauryl ether, polyethylene stearyl ether, polyoxyethylene cetyl ether, polyoxyethylene olein ether, etc. Ethers, polyoxyethylene octylphenol ether, polyoxyethylene alkyl allyl ethers such as polyoxyethylene nonylphenol, polyoxyethylene polyoxypropylene block copolymers, sorbitan monolaurate, sorbitan monovalmitate, sorbitan monostearate, etc. Sorbitan fatty acid esters, polyoxyethylene sorbitan monolaurate, polyoxyethylene sorbitan monovalmitate, polyoxyethylene sorbita Nonionic surfactants of polyoxyethylene sorbitan fatty acid esters such as monostearate, polyoxyethylene sorbitan trioleate, polyoxyethylene sorbitan tristearate, F-top EF301, EF303, EF352 (manufactured by Tochem Products) Megafuck F171, F172, F173 (manufactured by DIC Corporation), Florard FC430, FC431, FC-4430 (manufactured by Sumitomo 3M Corporation), Asahi Guard AG710, Surflon S-381, S-382, SC101, SC102, SC103 , SC104, SC105, SC106, Surfinol E1004, KH-10, KH-20, KH-30, KH-40 (manufactured by Asahi Glass Co., Ltd.) and the like, organosiloxane polymer KP- 41, X-70-092, X-70-093 (Shin-Etsu Chemical Co., Ltd.), acrylic acid or methacrylic acid Polyflow No. 75, no. 95 (manufactured by Kyoeisha Yushi Chemical Co., Ltd.), among which FC430, FC-4430, Surflon S-381, Surfynol E1004, KH-20, and KH-30 are preferred. These can be used alone or in combination of two or more.

  The addition amount of the surfactant in the positive resist material of the present invention, particularly 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.

  When the positive resist material of the present invention, for example, a chemically amplified positive resist material containing an organic solvent, a polymer compound represented by the general formula (1), an acid generator, and a basic compound is used for manufacturing various integrated circuits. Although there is no particular limitation, a known lithography technique can be applied.

For example, the positive resist material of the present invention is applied to an integrated circuit manufacturing substrate (Si, SiO ₂ , SiN, SiON, TiN, WSi, BPSG, SOG, organic antireflection film, etc.) or a mask circuit manufacturing substrate (Cr , CrO, CrON, MoSi, etc.) by a suitable coating method such as spin 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. To do. This is pre-baked on a hot plate at 60 to 150 ° C. for 10 seconds to 30 minutes, preferably 80 to 120 ° C. for 30 seconds to 20 minutes. Next, a target pattern is passed through a predetermined mask with a light source selected from high energy rays such as ultraviolet rays, far ultraviolet rays, electron beams, X-rays, excimer lasers, γ rays, synchrotron radiation, and vacuum ultraviolet rays (soft X-rays). Direct exposure is performed. It is preferable to expose so that the exposure amount is about 1 to 200 mJ / cm ² , preferably 10 to 100 mJ / cm ² , or 0.1 to 100 μC, and preferably about 0.5 to 50 μC. Next, post-exposure baking (PEB) is performed on a hot plate at 60 to 150 ° C. for 10 seconds to 30 minutes, preferably 80 to 120 ° C. for 30 seconds to 20 minutes.

  Further, 0.1 to 5% by mass, preferably 2 to 3% by mass of a developer of an alkaline aqueous solution such as tetramethylammonium hydroxide (TMAH) is used for 3 seconds to 3 minutes, preferably 5 seconds to 2 minutes. By developing by a conventional method such as a dip method, a paddle method, or a spray method, a portion irradiated with light is dissolved in the developer, and a portion not exposed to light is not dissolved. The desired positive pattern is formed on the top. The resist material of the present invention is particularly suitable for fine patterning using electron beams, vacuum ultraviolet rays (soft X-rays), X-rays, γ rays, and synchrotron radiation among high-energy rays.

  EXAMPLES Hereinafter, although a synthesis example, a comparative synthesis example, an Example, and a comparative example are shown and this invention is demonstrated concretely, this invention is not restrict | limited to the following Example.

[Synthesis Example 1]
In a 2-L flask, methacrylic acid-3-ethyl-3-exotetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodecanyl 8.2 g, monomer 1 8.7 g, methacrylic acid 3-oxo-2,7-dioxatricyclo [4.2.1.0 ^4,8 ] nonan-9-yl 7 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 blowing were repeated three times. After raising the temperature to room temperature, 1.2 g of AIBN (azobisisobutyronitrile) was added as a polymerization initiator, and the temperature was raised to 60 ° C. and reacted for 15 hours. This reaction solution was precipitated in 1 L of isopropyl alcohol, and the resulting white solid was filtered and dried under reduced pressure at 60 ° C. to obtain a white polymer.
When the obtained polymer was measured by ¹³ C, ¹ H-NMR and GPC, the following analysis results were obtained.
Copolymer composition ratio (molar ratio)
Methacrylic acid-3-ethyl-3-exotetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodecanyl: monomer 1: 3-oxo-2,7-dioxatricyclo [4.2.1.0 ^4,8 ] nonan-9-yl methacrylate = 0.30: 0.40: 0.30
Weight average molecular weight (Mw) = 8,200
Molecular weight distribution (Mw / Mn) = 1.83
This polymer compound is referred to as (Polymer 1).

[Synthesis Example 2]
In a 2-L flask, methacrylic acid-3-ethyl-3-exotetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodecanyl 8.2 g, monomer 1 6.5 g, tetrahydro-2-oxofuran-3-yl methacrylate 6.8 g, and tetrahydrofuran 40 g as a solvent were added. The reaction vessel was cooled to −70 ° C. in a nitrogen atmosphere, and vacuum degassing and nitrogen blowing were repeated three times. After raising the temperature to room temperature, 1.2 g of AIBN (azobisisobutyronitrile) was added as a polymerization initiator, and the temperature was raised to 60 ° C. and reacted for 15 hours. This reaction solution was precipitated in 1 L of isopropyl alcohol, and the resulting white solid was filtered and dried under reduced pressure at 60 ° C. to obtain a white polymer.
When the obtained polymer was measured by ¹³ C, ¹ H-NMR and GPC, the following analysis results were obtained.
Copolymer composition ratio (molar ratio)
Methacrylic acid-3-ethyl-3-exotetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodecanyl: monomer 1: tetrahydro-2-oxofuran-3-yl methacrylate = 0.30: 0.30: 0.40
Weight average molecular weight (Mw) = 9,200
Molecular weight distribution (Mw / Mn) = 1.78
This polymer compound is referred to as (Polymer 2).

[Synthesis Example 3]
In a 2-L flask, methacrylic acid-3-ethyl-3-exotetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodecanyl 8.2 g, monomer 2 7.4 g, 5-oxo-4-oxatricyclo [4.2.1.0 ^3,7 ] nonan-2-yl methacrylate 13.3 g, solvent As a result, 40 g of tetrahydrofuran was added. The reaction vessel was cooled to −70 ° C. in a nitrogen atmosphere, and vacuum degassing and nitrogen blowing were repeated three times. After raising the temperature to room temperature, 1.2 g of AIBN (azobisisobutyronitrile) was added as a polymerization initiator, and the temperature was raised to 60 ° C. and reacted for 15 hours. This reaction solution was precipitated in 1 L of isopropyl alcohol, and the resulting white solid was filtered and dried under reduced pressure at 60 ° C. to obtain a white polymer.
When the obtained polymer was measured by ¹³ C, ¹ H-NMR and GPC, the following analysis results were obtained.
Copolymer composition ratio (molar ratio)
Methacrylic acid-3-ethyl-3-exotetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodecanyl: monomer 2: 5-oxo-4-oxatricyclomethacrylate [4.2.1.0 ^3,7 ] nonan-2-yl = 0.30: 0.30: 0.40
Weight average molecular weight (Mw) = 8,100
Molecular weight distribution (Mw / Mn) = 1.72
This polymer compound is referred to as (Polymer 3).

[Synthesis Example 4]
In a 2 L flask, add 3-ethyl-3-exotetracyclomethacrylate [4.4.0.1 ^2,5 . 1, ¹⁰ ] dodecanyl 8.2 g, monomer 3 9.7 g, 1-hydroxynaphthalen-5-yl methacrylate 4.6 g, methacrylate 3-oxo-2,7-dioxatricyclo [4.2. 1.0 ^4,8 ] nonan-9-yl 4.5 g and tetrahydrofuran 40 g as a solvent were added. The reaction vessel was cooled to −70 ° C. in a nitrogen atmosphere, and vacuum degassing and nitrogen blowing were repeated three times. After raising the temperature to room temperature, 1.2 g of AIBN (azobisisobutyronitrile) was added as a polymerization initiator, and the temperature was raised to 60 ° C. and reacted for 15 hours. This reaction solution was precipitated in 1 L of isopropyl alcohol, and the resulting white solid was filtered and dried under reduced pressure at 60 ° C. to obtain a white polymer.
When the obtained polymer was measured by ¹³ C, ¹ H-NMR and GPC, the following analysis results were obtained.
Copolymer composition ratio (molar ratio)
Methacrylic acid-3-ethyl-3-exotetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodecanyl: monomer 3: 1-hydroxynaphthalen-5-yl methacrylate: 3-oxo-2,7-dioxatricyclo [4.2.1.0 ^4,8 ] nonane-9 methacrylate -Ile = 0.30: 0.30: 0.20: 0.20
Weight average molecular weight (Mw) = 6,800
Molecular weight distribution (Mw / Mn) = 1.76
This polymer compound is referred to as (Polymer 4).

[Synthesis Example 5]
In a 2 L flask, add 3-ethyl-3-exotetracyclomethacrylate [4.4.0.1 ^2,5 . 1 ^7,10 ] dodecanyl 8.2 g, monomer 4 11.2 g, tetrahydro-2-oxofuran-3-yl methacrylate 6.8 g, and tetrahydrofuran 40 g as a solvent were added. The reaction vessel was cooled to −70 ° C. in a nitrogen atmosphere, and vacuum degassing and nitrogen blowing were repeated three times. After raising the temperature to room temperature, 1.2 g of AIBN (azobisisobutyronitrile) was added as a polymerization initiator, and the temperature was raised to 60 ° C. and reacted for 15 hours. This reaction solution was precipitated in 1 L of isopropyl alcohol, and the resulting white solid was filtered and dried under reduced pressure at 60 ° C. to obtain a white polymer.
When the obtained polymer was measured by ¹³ C, ¹ H-NMR and GPC, the following analysis results were obtained.
Copolymer composition ratio (molar ratio)
Methacrylic acid-3-ethyl-3-exotetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodecanyl: monomer 4: tetrahydro-2-oxofuran-3-yl methacrylate = 0.30: 0.30: 0.40
Weight average molecular weight (Mw) = 8,800
Molecular weight distribution (Mw / Mn) = 1.86
This polymer compound is referred to as (Polymer 5).

[Synthesis Example 6]
In a 2-L flask, methacrylic acid-3-ethyl-3-exotetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodecanyl 8.2 g, monomer 1 8.7 g, coumarone 1.6 g, tetrahydro-2-oxofuran-3-yl methacrylate 5.1 g and tetrahydrofuran 40 g as a solvent were added. The reaction vessel was cooled to −70 ° C. in a nitrogen atmosphere, and vacuum degassing and nitrogen blowing were repeated three times. After raising the temperature to room temperature, 1.2 g of AIBN (azobisisobutyronitrile) was added as a polymerization initiator, and the temperature was raised to 60 ° C. and reacted for 15 hours. This reaction solution was precipitated in 1 L of isopropyl alcohol, and the resulting white solid was filtered and dried under reduced pressure at 60 ° C. to obtain a white polymer.
When the obtained polymer was measured by ¹³ C, ¹ H-NMR and GPC, the following analysis results were obtained.
Copolymer composition ratio (molar ratio)
Methacrylic acid-3-ethyl-3-exotetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodecanyl: monomer 1: coumarone: tetrahydro-2-oxofuran-3-yl methacrylate = 0.30: 0.40: 0.1: 0.20
Weight average molecular weight (Mw) = 7,200
Molecular weight distribution (Mw / Mn) = 1.89
This polymer compound is referred to as (Polymer 6).

[Synthesis Example 7]
In a 2 L flask, 7.4 g of 2-ethyl-2-adamantane methacrylate, 6.5 g of monomer 1, 3-oxo-2,7-dioxatricyclo methacrylate [4.2.1.0 ^4,8 6.7 g of nonan-9-yl, 6.5 g of PAG monomer 1 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 blowing were repeated three times. After raising the temperature to room temperature, 1.2 g of AIBN (azobisisobutyronitrile) was added as a polymerization initiator, and the temperature was raised to 60 ° C. and reacted for 15 hours. This reaction solution was precipitated in 1 L of isopropyl alcohol, and the resulting white solid was filtered and dried under reduced pressure at 60 ° C. to obtain a white polymer.
When the obtained polymer was measured by ¹³ C, ¹ H-NMR and GPC, the following analysis results were obtained.
Copolymer composition ratio (molar ratio)
2-ethyl-2-adamantane methacrylate: monomer 1: 3-oxo-2,7-dioxatricyclo [4.2.1.0 ^4,8 ] nonan-9-yl methacrylate: PAG monomer 1 = 0.30: 0.30: 0.30: 0.10
Weight average molecular weight (Mw) = 7,800
Molecular weight distribution (Mw / Mn) = 1.81
This polymer compound is referred to as (Polymer 7).

[Synthesis Example 8]
In a 2-L flask, methacrylic acid-3-ethyl-3-exotetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodecanyl 8.2 g, monomer 1 6.5 g, methacrylic acid 3-oxo-2,7-dioxatricyclo [4.2.1.0 ^4,8 ] nonan-9-yl 7 g, 5.7 g of PAG monomer 2 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 blowing were repeated three times. After raising the temperature to room temperature, 1.2 g of AIBN (azobisisobutyronitrile) was added as a polymerization initiator, and the temperature was raised to 60 ° C. and reacted for 15 hours. This reaction solution was precipitated in 1 L of isopropyl alcohol, and the resulting white solid was filtered and dried under reduced pressure at 60 ° C. to obtain a white polymer.
When the obtained polymer was measured by ¹³ C, ¹ H-NMR and GPC, the following analysis results were obtained.
Copolymer composition ratio (molar ratio)
Methacrylic acid-3-ethyl-3-exotetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodecanyl: monomer 1: 3-oxo-2,7-dioxatricyclo [4.2.1.0 ^4,8 ] nonan-9-yl methacrylate: PAG monomer 2 = 0.30: 0.30: 0.30: 0.1
Weight average molecular weight (Mw) = 7,200
Molecular weight distribution (Mw / Mn) = 1.91
This polymer compound is referred to as (Polymer 8).

[Synthesis Example 9]
In a 2-L flask, methacrylic acid-3-ethyl-3-exotetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodecanyl 8.2, 6.5 g of monomer 1, 5.1 g of tetrahydro-2-oxofuran-3-yl methacrylate, 5.6 g of PAG monomer 3, 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 blowing were repeated three times. After raising the temperature to room temperature, 1.2 g of AIBN (azobisisobutyronitrile) was added as a polymerization initiator, and the temperature was raised to 60 ° C. and reacted for 15 hours. This reaction solution was precipitated in 1 L of isopropyl alcohol, and the resulting white solid was filtered and dried under reduced pressure at 60 ° C. to obtain a white polymer.
When the obtained polymer was measured by ¹³ C, ¹ H-NMR and GPC, the following analysis results were obtained.
Copolymer composition ratio (molar ratio)
Methacrylic acid-3-ethyl-3-exotetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodecanyl: monomer 1: tetrahydro-2-oxofuran-3-yl methacrylate: PAG monomer 3 = 0.30: 0.30: 0.30: 0.1
Weight average molecular weight (Mw) = 7,900
Molecular weight distribution (Mw / Mn) = 1.68
This polymer compound is referred to as (Polymer 9).

[Synthesis Example 10]
In a 2-L flask, methacrylic acid-3-ethyl-3-exotetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodecanyl 8.2, 7.4 g of monomer 2, 6.5 g of methacrylic acid-2,7-dihydro-2-oxobenzo [C] furan-5-yl, 5.6 g of PAG monomer 3, solvent As a result, 40 g of tetrahydrofuran was added. The reaction vessel was cooled to −70 ° C. in a nitrogen atmosphere, and vacuum degassing and nitrogen blowing were repeated three times. After raising the temperature to room temperature, 1.2 g of AIBN (azobisisobutyronitrile) was added as a polymerization initiator, and the temperature was raised to 60 ° C. and reacted for 15 hours. This reaction solution was precipitated in 1 L of isopropyl alcohol, and the resulting white solid was filtered and dried under reduced pressure at 60 ° C. to obtain a white polymer.
When the obtained polymer was measured by ¹³ C, ¹ H-NMR and GPC, the following analysis results were obtained.
Copolymer composition ratio (molar ratio)
Methacrylic acid-3-ethyl-3-exotetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodecanyl: monomer 2: methacrylic acid-2,7-dihydro-2-oxobenzo [C] furan-5-yl: PAG monomer 3 = 0.30: 0.30: 0.30: 0. 1
Weight average molecular weight (Mw) = 7,800
Molecular weight distribution (Mw / Mn) = 1.72
This polymer compound is referred to as (Polymer 10).

Monomer 1: Methacrylic acid (5-hydroxyindan-2-yl)
Monomer 2: Methacrylic acid (5,8-dihydroxy-1,2,3,4-tetrahydronaphthalen-2-yl)
Monomer 3: 4-vinylbenzoic acid (5,8-dihydroxy-1,2,3,4-tetrahydronaphthalen-2-yl)
Monomer 4: 5-vinylnaphthalene-1-carboxylic acid (5,8-dihydroxy-1,2,3,4-tetrahydronaphthalen-2-yl)
PAG monomer 1: 4-oxyphenyldiphenylsulfonium methacrylate perfluorobutanesulfonate PAG monomer 2: triphenylsulfonium 2,3,5,6-tetrafluoro-4-methacryloyloxybenzenesulfonate PAG monomer 3: triphenylsulfonium 1, 1,3,3,3-pentafluoro-2-methacryloyloxypropane-1-sulfonate

重量平均分子量（Ｍｗ）＝８，１００
分子量分布（Ｍｗ／Ｍｎ）＝１．７９
この高分子化合物を（比較ポリマー１）とする。 [Comparative Synthesis Example 1]
The following polymers were synthesized by the same method as in the above synthesis example.
Copolymer composition ratio (molar ratio)
Hydroxystyrene: Methacrylic acid 1-ethylcyclopentyl ester: Indene = 0.75: 0.15: 0.10

Weight average molecular weight (Mw) = 8,100
Molecular weight distribution (Mw / Mn) = 1.79
This polymer compound is referred to as (Comparative Polymer 1).

この高分子化合物を（比較ポリマー２）とする。 [Comparative Synthesis Example 2]
The following polymers were synthesized by the same method as in the above synthesis example.
Copolymer composition ratio (molar ratio)
1-ethylcyclopentyl methacrylate: 3-hydroxy-1-adamantyl methacrylate: 3-oxo-2,7-dioxatricyclo [4.2.1.0 ^4,8 ] nonan-9-yl methacrylate: methacryl Acid 3,5-bis (hexafluoro-2-hydroxy-2-propyl) cyclohexyl = 0.30: 0.20: 0.40: 0.10
Weight average molecular weight (Mw) = 8,200
Molecular weight distribution (Mw / Mn) = 1.72

This polymer compound is referred to as (Comparative Polymer 2).

[Comparative Synthesis Example 3]
The following polymers were synthesized by the same method as in the above synthesis example.
Copolymer composition ratio (molar ratio)
Methacrylic acid-3-ethyl-3-exotetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodecanyl: 4-hydroxystyrene: methacrylate 3-oxo-2,7-dioxatricyclo [4.2.1.0 ^4,8 ] nonan-9-yl = 0.30: 0. 40: 0.30
Weight average molecular weight (Mw) = 8,300
Molecular weight distribution (Mw / Mn) = 1.82
This polymer compound is referred to as “Comparative Example Polymer 3”.

この高分子化合物を（比較ポリマー３）とする。

This polymer compound is referred to as (Comparative Polymer 3).

[Examples and Comparative Examples]
Using the polymer compound synthesized above, a solution obtained by dissolving Sumitomo 3M Surfactant FC-4430 as a surfactant in a solvent in which 100 ppm was dissolved with a composition shown in Table 1 was used. A positive resist material was prepared by filtration through a 2 μm size filter.
Each composition in Table 1 is as follows.
Polymers 1 to 10: Synthesis examples 1 to 10
Comparative polymers 1-3: Comparative synthesis examples 1-3
Organic solvent: PGMEA (propylene glycol monomethyl ether acetate)
EL (ethyl lactate)
CyH (cyclohexanone)
Acid generator: PAG1, PAG2, PAG3 (see structural formula below)
Basic compounds: Amine1, Amine2, Amine3 (see the structural formula below)
Dissolution inhibitor: DRI1, DRI2 (see structural formula below)

Electron Beam Drawing Evaluation In the drawing evaluation, a positive resist material was prepared by filtering a solution dissolved in the composition shown in Table 1 using a polymer compound synthesized as described above with a 0.2 μm size filter.
The obtained positive resist material is spin-coated on a Si substrate having a diameter of 6 inches using a clean track Mark 5 (manufactured by Tokyo Electron), and pre-baked on a hot plate at 110 ° C. for 60 seconds to form a 100 nm resist film Was made. For this, drawing in a vacuum chamber was performed at an HV voltage of 50 keV using a Hitachi HL-800D.
Immediately after drawing, post-exposure baking (PEB) is performed on a hot plate at 100 ° C. for 60 seconds using a clean track Mark 5 (manufactured by Tokyo Electron Ltd.), and paddle development is performed for 30 seconds with a 2.38 mass% TMAH aqueous solution. A positive pattern was obtained.
The obtained resist pattern was evaluated as follows.
The minimum dimension at the exposure amount for resolving 100 nm line and space at 1: 1 was taken as the resolving power, and the edge roughness of 100 nm LS was measured by SEM.
Table 1 shows the results of resist composition, sensitivity and resolution in EB exposure.

Evaluation of dry etching resistance In the dry etching resistance test, 10 g of PGMEA was dissolved in 2 g of each of the above polymers, and a polymer solution filtered through a 0.2 μm size filter was formed on a Si substrate by spin coating. Films were evaluated under the following conditions.
(1) Etching test with CHF ₃ / CF ₄ 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

This evaluation shows that the film having a small difference in film thickness, that is, a film having a small decrease, has etching resistance.
The results of dry etching resistance are shown in Table 2.

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

Claims (9)

A high weight average molecular weight in the range of 1,000 to 500,000 including a repeating unit in which a hydrogen atom of a carboxyl group is substituted with an acid labile group and a repeating unit having a group represented by the general formula (1) A positive resist material characterized in that a molecular compound is used as a base resin.

(Wherein R ¹ and R ² are hydrogen atoms, or R ¹ and R ² are bonded to each other to form a methylene group, ethylene group or —O—. R ³ is a single bond or a methylene group, and R ⁴ is hydrogen. An atom, an alkyl group having 1 to 4 carbon atoms, an acetyl group, or an acid labile group, and m is an integer of 1 to 4.) The repeating unit having at least a group of the general formula (1) is based on a polymer compound having a weight average molecular weight represented by the general formula (2) in the range of 1,000 to 500,000. The positive resist material according to claim 1.

(Wherein R ^{1 to} R ⁴ and m are as described above, R ⁵ represents a hydrogen atom or a methyl group. Z is a single bond, a phenylene group or a naphthylene group. A is 0 <a <1.0. is there.) The weight average molecular weight represented by the general formula (3) obtained by copolymerizing at least the repeating unit represented by the general formula (a) and the repeating unit having an acid labile group represented by the general formula (b) is 1,000. 3. The positive resist material according to claim 2, wherein the base resin is a polymer compound in the range of .about.500,000.

(In the formula, R ^{1 to} R ⁵ , m and Z are the same as described above. R ⁶ represents a hydrogen atom or a methyl group, R ⁷ represents an acid labile group. X represents a single bond, an ester group or a lactone ring. And a linking group having 1 to 12 carbon atoms, a phenylene group, or a naphthylene group, in a range of 0 <a <1.0, 0 <b <1.0, and 0.1 ≦ a + b ≦ 1.0.   In addition to at least the repeating unit a in the general formula (3) and the repeating unit b in which the hydroxyl group of the carboxyl group is substituted with an acid labile group, a hydroxy group, a lactone ring, an ether group, an ester group, a carbonyl group, or A polymer compound having a weight average molecular weight in the range of 1,000 to 500,000 obtained by copolymerizing a repeating unit c of an adhesive group having a cyano group (where 0 <a <1.0, 0 <b <1. 4. The positive resist composition according to claim 3, wherein the base resin is 0, 0 <c ≦ 0.9, 0.2 ≦ a + b + c ≦ 1.0.   5. The positive resist material according to claim 1, which is a chemically amplified resist material containing an organic solvent and an acid generator.   6. The positive resist material according to claim 5, further comprising a dissolution inhibitor.   The positive resist composition according to claim 5 or 6, further comprising a basic compound and / or a surfactant as an additive.   A step of coating the positive resist material according to any one of claims 1 to 7 on a substrate, a step of exposing to high energy rays after heat treatment, and a step of developing using a developer. The pattern formation method characterized by the above-mentioned.   9. The pattern forming method according to claim 8, wherein the high energy rays to be exposed are electron beams and soft X-rays having a wavelength in the range of 3 to 15 nm.