JP2010237645A - Positive resist material and patterning process using the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a positive resist material, typically, a chemically amplified positive resist comprising a specific a polymer compound as a base resin, which exhibits a high resolution surpassing conventional art positive resist compositions and forms a resist film having a minimal edge roughness and a good pattern profile after exposure, and to provide a patterning process. <P>SOLUTION: The positive resist material comprises, as a base resin, a polymer compound which has a recurring unit having carboxyl groups whose hydrogen is substituted by an acid labile group, and has a recurring unit having a group expressed by general formula (1) and has a weight average molecular weight of 1,000 to 500,000. In general formula (1), X represents -NH- or -S-. This positive resist material exhibits a remarkably high contrast of alkaline dissolution rate before and after exposure, a high resolution, a good pattern profile and a minimal line edge roughness after exposure, and a significant effect of suppressing acid diffusion rate. Consequently, the positive resist material, typically, the chemically amplified positive resist material suited as a fine pattern-forming material for the fabrication of VLSIs or photomasks and a pattern-forming material for EUV lithography can be obtained. <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

  The present invention relates to a positive resist material, particularly a positive resist material using a polymer compound suitable as a base resin for a chemically amplified positive resist material, 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 film, 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 resist materials are hardly absorbed by very short wavelength high energy rays such as electron beams (EB) and X-rays, and polyhydroxystyrene-based resist materials have been studied. ing.
The resist material for EB 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 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 film 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 the electron drawing energy is improved and the resolution and dimensional controllability are improved. Since it passes, the sensitivity of the resist film decreases. Since the mask exposure machine exposes by direct drawing with a single stroke, a decrease in sensitivity of the resist film leads to a decrease in productivity, which is not preferable. In view of the demand for higher sensitivity, chemically amplified resist materials are being studied.

With the miniaturization of patterns in mask manufacturing EB lithography, the resist film is becoming thinner in order to prevent pattern collapse during development with a high aspect ratio. In the case of photolithography, the thinning of the resist film greatly contributes to the improvement of the 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 film.

Here, it is generally said that there is a correlation between the carbon density of the resist film and the dry etching resistance. In EB drawing that is not affected by absorption, a resist material 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).

  As the miniaturization progresses, image blur 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 with a size 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: SPIE Vol. 6520 65203L-1 (2007)). However, chemically amplified resist materials have increased sensitivity and contrast due to acid diffusion. Therefore, reducing the post-exposure bake temperature (PEB) temperature and time to limit acid diffusion results in sensitivity and contrast. It drops significantly.

  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 onium salt acid generator having a polymerizable olefin in the polymer. 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 film is reduced by reducing shot noise due to an increase in exposure amount. SPIE Vol. In 5374 p74 (2004) (Non-Patent Document 6), a resist film with an increased amount of quencher is effective in reducing roughness, but at the same time the sensitivity deteriorates, so there is a trade-off relationship between sensitivity of EUV and roughness. 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 for generating an acid in electron beam exposure, in which electrons are transferred to the PAG by polymer excitation due to exposure and acid is released. 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) SPIE 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 a higher resolution than conventional positive resist materials, a small line edge roughness, and a good pattern shape after exposure, particularly a chemically amplified positive resist material. It is an object of the present invention to provide a positive resist material using a polymer compound suitable as a base resin for the above and a pattern forming method.

  As a result of intensive investigations to obtain a positive resist material having high resolution and low line edge roughness, which has recently been demanded, the inventors of the present invention include a polymer containing a specific repeating unit as a positive resist material, particularly a chemical resist. It has been found that it is extremely effective when used as a base resin for an amplified positive resist material, and the present invention has been completed.

  From the above, the present inventors further have a repeating unit in which a hydrogen atom of a carboxyl group is substituted with an acid labile group in order to further suppress acid diffusion and improve dissolution contrast, and the following general formula (1): By using a polymer obtained by copolymerization with a repeating unit having the indicated group as a base resin of a positive resist material, particularly a chemically amplified positive resist material, the alkali dissolution rate contrast before and after exposure is significantly high, and acid diffusion Positive resist material that has a high effect of suppressing image quality, has high resolution, and has a good pattern shape and edge roughness after exposure, and is particularly suitable as a fine pattern forming material for VLSI manufacturing or photomasks, particularly It has been found that a chemically amplified positive resist material can be obtained.

  The positive resist material of the present invention has a high dissolution contrast of the resist film, a high effect of suppressing acid diffusion, a high resolution, an exposure margin, excellent process adaptability, and a post-exposure process. The pattern shape is good. 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、Ｘは−ＮＨ−又は−Ｓ−である。）
請求項２：
上記一般式（１）で示される基を有する繰り返し単位が、下記一般式（２）で示される繰り返し単位であ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、Ｘは−ＮＨ−又は−Ｓ−である。Ｒ¹は水素原子又はメチル基である。Ｙ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：
下記一般式（ａ）で示される繰り返し単位と、下記一般式（ｂ）で示される酸不安定基を有する繰り返し単位が共重合されてなる下記一般式（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、Ｘ、Ｙは前述と同様である。Ｒ²は水素原子又はメチル基、Ｒ³は酸不安定基を表す。Ｚ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。ａは０＜ａ＜１．０、ｂは０＜ｂ＜１．０、ａ＋ｂは０．１≦ａ＋ｂ≦１．０の範囲である。）
請求項４：
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、シアノ基から選ばれる密着性基の繰り返し単位ｃを共重合した（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。）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、溶解制御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 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.

(In the formula, X is —NH— or —S—).
Claim 2:
2. The positive resist material according to claim 1, wherein the repeating unit having a group represented by the general formula (1) is a repeating unit represented by the following general formula (2).

(Wherein X is —NH— or —S—, R ¹ is a hydrogen atom or a methyl group, Y 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 following general formula (3) obtained by copolymerizing a repeating unit represented by the following general formula (a) and a repeating unit having an acid labile group represented by the following general formula (b) is 1 3. The positive resist material according to claim 2, wherein the base resin is a polymer compound in the range of 1,000,000 to 500,000.

(In the formula, R ¹ , X and Y are the same as described above. R ² represents a hydrogen atom or a methyl group, R ³ represents an acid labile group. Z represents a carbon number having a single bond, an ester group or a lactone ring. 1 to 12 linking groups, phenylene groups, or naphthylene groups, a is 0 <a <1.0, b is 0 <b <1.0, and a + b is in the range of 0.1 ≦ a + b ≦ 1.0. is there.)
Claim 4:
In addition to 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, a cyano group The repeating unit c of the adhesive group selected from the above was copolymerized (where 0 <a <1.0, 0 <b <1.0, 0 <c ≦ 0.9, 0.2 ≦ a + b + c ≦ 1.0). 4. The positive resist composition according to claim 3, wherein the base resin is a polymer compound having a weight average molecular weight in the range of 1,000 to 500,000.
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 control agent.
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 applying 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. A pattern forming method characterized by the above.
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 resolution, good pattern shape after exposure and line edge roughness, and particularly suppresses acid diffusion rate. it can. 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、Ｘは−ＮＨ−又は−Ｓ−である。） Hereinafter, the present invention will be described in more detail.
The resist material according to the present invention is a resist material characterized in that a base resin is a resin containing a repeating unit having a group represented by the following general formula (1).

(In the formula, X is —NH— or —S—).

（式中、Ｘは上記の通り。Ｒ¹は水素原子又はメチル基である。Ｙ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).

(In the formula, X is as described above. R ¹ is a hydrogen atom or a methyl group. Y is a single bond, a phenylene group or a naphthylene group. A is 0 <a <1.0.)

（式中、Ｒ¹、Ｘ、Ｙは前述と同様である。Ｒ²は水素原子又はメチル基、Ｒ³は酸不安定基を表す。Ｚは単結合、エステル基（−ＣＯＯ−）、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。ａは０＜ａ＜１．０、ｂは０＜ｂ＜１．０、ａ＋ｂは０．１≦ａ＋ｂ≦１．０の範囲である。） In this case, particularly as the base resin, at least a repeating unit represented by the following general formula (a) and a repeating unit having an acid labile group represented by the following general formula (b) are copolymerized. The high molecular compound whose weight average molecular weight shown by 3) is the range of 1,000-500,000 is preferable.

(In the formula, R ¹ , X and Y are the same as described above. R ² represents a hydrogen atom or a methyl group, R ³ represents an acid labile group. Z represents a single bond, an ester group (—COO—), a lactone. A ring-containing linking group having 1 to 12 carbon atoms, a phenylene group, or a naphthylene group, a is 0 <a <1.0, b is 0 <b <1.0, and a + b is 0.1 ≦ a + b ≦ 1. .0 range.)

（式中、Ｒ¹は上記の通り。） Specific examples of the monomer for obtaining the repeating unit represented by the general formula (a) can be given below.

(Wherein R ¹ is as described above.)

  The repeating unit a in the positive resist material of the present invention has a phenyl ester having cyclic —O—C (═O) —S— or —O—C (═O) —NH— in the repeating unit. It is characterized by. Phenyl esters having cyclic —O—C (═O) —S— or —O—C (═O) —NH— are hydroxy-1,3-benzoxiathiol-2-one or hydroxy-2-benzo, respectively. It can be synthesized by esterifying the phenol of xazolinone. Both are highly hydrophilic and exhibit excellent properties as adhesive groups. The one synthesized from hydroxy 2-benzoxazolinone having —O—C (═O) —NH— is more preferably used because it has a nitrogen atom and has an effect of suppressing acid diffusion.

ここで、Ｒ²、Ｒ³、Ｚ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 ² , R ³ and Z are as described above.

In this case, the following can be illustrated as a C1-C12 coupling group which has a lactone ring.

The acid labile group (the acid labile group of R ^{3 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 ( 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 atom to which they are bonded. In the case of forming a ring, it participates in the formation of the ring. R ³¹ , R ³² , and R ³³ each represent 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. is there.

  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.

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

（式中、Ｒ²、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。）

(Wherein R ² and b are as described above, 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 the formula (A-3), the acid resistance of (meth) acrylic acid ester having frangyl, tetrahydrofurandiyl or oxanorbornanediyl represented by the following formula (A-3) -22 is used. Mention may be made of stabilizing groups.

（式中、Ｒ²、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。）

(Wherein R ² and b are as defined above. R ^c14 and R ^c15 each independently represent a linear, branched or cyclic monovalent hydrocarbon group having 1 to 10 carbon atoms. ^c14, R ^c15 good .R ^c16 also to form an aliphatic hydrocarbon ring is a divalent group selected from the flange-yl, tetrahydrofuran oxanorbornanediyl with the carbon atom to which they are attached. 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 a repeating unit a in the general formula (3) and a 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 group. , A polymer compound having a weight average molecular weight in the range of 1,000 to 500,000 (0 <a <1. 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 having a hydroxy group, a lactone ring, an ether group, an ester group, a carbonyl group, or a cyano group as an adhesive group can be given below.

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

  In addition, repeating units d such as indene d1, acenaphthylene d2, chromone d3, coumarin d4, norbornadiene d5 represented by the following general formula (5) can also be copolymerized.

（式中、Ｒ⁴〜Ｒ⁸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 ^{4 to} R ⁸ 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、Ｒ⁹は水素原子又はメチル基を表し、Ｒ¹⁰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 ⁹ represents a hydrogen atom or a methyl group, R ¹⁰ 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.

（上記式中、Ｒ²⁰、Ｒ²⁴、Ｒ²⁸は水素原子又はメチル基、Ｒ²¹は単結合、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。Ｚ₀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.

(In the above formula, R ²⁰ , R ²⁴ , and R ²⁸ are a hydrogen atom or a methyl group, R ²¹ is a single bond, a phenylene group, —O—R—, or —C (═O) —Y—R—. Y is an oxygen atom or NH, R is a linear, branched or cyclic alkylene group having 1 to 6 carbon atoms, a phenylene group or an alkenylene group, and includes a carbonyl group, an ester group, an ether group or a hydroxy group. R ²² , R ²³ , R ²⁵ , R ²⁶ , R ²⁷ , R ²⁹ , R ³⁰ and R ³¹ are the same or different linear, branched or cyclic alkyl groups having 1 to 12 carbon atoms. , A carbonyl group, an ester group or an ether group, or an aryl group having 6 to 12 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, or a thiophenyl group, Z ₀ is a single bond, a methylene group, ethylene Group, phenylene group, fluorinated phenylene group,- -R ³² -, or _{-C (= O) -Z 1 -R} 32 - is a .Z ₁ is an oxygen atom or NH, R ³² may a straight, branched or cyclic alkylene group of , A phenylene group or an alkenylene group, which may contain a carbonyl group, an ester group, an ether group or a hydroxy group, M ⁻ represents a non-nucleophilic counter ion, g 1 represents 0 ≦ g 1 ≦ 0.3, g 2 Is 0 ≦ g2 ≦ 0.3, g3 is 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.

  By binding an acid generator to the polymer main chain, acid diffusion can be reduced, and degradation of resolution due to blurring of acid diffusion can be prevented. Further, the line edge roughness (LER, LWR) is improved by uniformly dispersing the acid generator.

  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, 0 <b <1.0, 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, and more Preferably, 0.1 ≦ 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 has 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.
The weight average molecular weight (Mw) is a measured value in terms of polystyrene using gel permeation chromatography (GPC).

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 controller, 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. 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. .

  In addition, by adding a dissolution control agent to the positive resist material, the difference in dissolution rate between the exposed area and the unexposed area 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 may contain an acid generator for causing the chemically amplified positive resist material used in the pattern forming method of the present invention to function. For example, it generates an acid in response to actinic rays or radiation. May contain a compound (photoacid generator). The component of the photoacid generator may be any compound that generates an acid upon irradiation with high energy rays. Suitable photoacid generators include sulfonium salts, iodonium salts, sulfonyldiazomethane, N-sulfonyloxyimide, oxime-O-sulfonate type acid generators, and the like. Although described in detail below, these can be used alone or in admixture of two or more.
Specific examples of the acid generator are described in paragraphs [0122] to [0142] of JP-A-2008-111103.

The resist material of the present invention can further contain any one or more of an organic solvent, a basic compound, a dissolution controller, a surfactant, and acetylene alcohols.
Specific examples of the organic solvent include paragraphs [0144] to [0145] of JP-A-2008-111103, paragraphs [0146] to [0164] as the basic compound, and paragraphs [0165] to [0166] of the surfactant. ], The dissolution control agent is described in paragraphs [0155] to [0178] of JP-A-2008-122932, and the acetylene alcohols are described in paragraphs [0179] to [0182]. A polymer-type quencher described in JP-A-2008-239918 can also be added. This enhances the rectangularity of the patterned resist by being oriented on the coated resist surface. The polymer quencher also has an effect of preventing pattern film loss and pattern top rounding when a protective film for immersion exposure is applied.

  In addition, it is preferable that the compounding quantity of an acid generator shall be 0.01-100 mass parts with respect to 100 mass parts of base resins, especially 0.1-80 mass parts, and the compounding quantity of an organic solvent is 100 mass of base resins. The amount is preferably 50 to 10,000 parts by mass, particularly 100 to 5,000 parts by mass with respect to parts. Moreover, 0-100 mass parts, especially 0-40 mass parts, a basic compound are 0-100 mass parts with respect to 100 mass parts of base resins, especially 0.001-50 mass parts, surfactant is a surfactant. The blending amount is preferably 0 to 10 parts by mass, particularly 0.0001 to 5 parts by mass.

  Various positive resist materials of the present invention, for example, chemically amplified positive resist materials containing an organic solvent, a polymer compound having an acid leaving group represented by the general formula (1), an acid generator, and a basic compound When used for manufacturing an integrated circuit, a known lithography technique can be applied although it is not particularly limited.

For example, the positive resist material of the present invention is applied to a substrate for manufacturing an integrated circuit (Si, SiO ₂ , SiN, SiON, TiN, WSi, BPSG, SOG, organic antireflection film, etc.) or a substrate for manufacturing a mask circuit (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.

  Furthermore, 0.1 to 10% by weight, preferably 2 to 10% by weight, especially 2 to 5% by weight of tetramethylammonium hydroxide (TMAH), tetraethylammonium hydroxide (TEAH), tetrapropylammonium hydroxide (TPAH) 3 seconds to 3 minutes, preferably 5 seconds to 2 minutes, using a developing solution of an alkaline aqueous solution such as tetrabutylammonium hydroxide (TBAH), dip method, paddle method, spray method By developing by a conventional method such as the above, a portion irradiated with light is dissolved in the developer, and a portion not exposed is not dissolved, and a desired positive pattern is formed on the substrate. 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.

  TEAH, TPAH, and TBAH having a longer alkyl chain than the TMAH aqueous solution that is generally widely used have the effect of reducing the swelling during development and preventing pattern collapse. In Japanese Patent No. 3429592, a repeating unit having an alicyclic structure such as adamantane methacrylate is copolymerized with a repeating unit having an acid labile group such as t-butyl methacrylate, and has no hydrophilic group and is water repellent. An example using an aqueous TBAH solution for the development of high polymer is presented.

  As the tetramethylammonium hydroxide (TMAH) developer, a 2.38% by mass aqueous solution is most widely used. This corresponds to 0.26N, and it is preferable that the TEAH, TPAH, and TBAH aqueous solutions have the same normality. The masses of TEAH, TPAH, and TBAH that are 0.26N are 3.84 mass%, 5.31 mass%, and 6.78 mass%, respectively.

  In a pattern of 32 nm or less that is resolved by EB or EUV, a phenomenon occurs in which lines are twisted, the lines are stuck together, or the stuck lines are tilted. This is thought to be because the lines swollen and swollen in the developer are stuck together. Since the swollen line is soft like a sponge containing a developer, it tends to collapse due to the stress of rinsing. For this reason, the developer having a long alkyl chain has the effect of preventing swelling and preventing pattern collapse.

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.
The weight average molecular weight (Mw) is a measured value in terms of polystyrene using gel permeation chromatography (GPC).
Moreover, the monomers 1-4 and the PAG monomers 1-3 used by the following synthesis example are as follows.

Monomer 1: Methacrylic acid (2-oxo-1,3-benzooxathiol-5-yl)
Monomer 2: Methacrylic acid (2-oxo-2,3-dihydrobenzoxazole-5-i
Le)
Monomer 3: 4-vinylbenzoic acid (2-oxo-2,3-dihydrobenzoxazole-
5-yl)
Monomer 4: 5-vinylnaphthalene-1-carboxylic acid (2-oxo-2,3-dihydrobenzene)
Nzooxazol-5-yl)
PAG monomer 1: 4-oxyphenyldiphenylsulfonium methacrylate perful
Orobutanesulfonate 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

[Synthesis Example 1]
In a 2-L flask, methacrylic acid-3-ethyl-3-exotetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodecanyl 8.2g, 8.7g of methacrylic acid (5-hydroxyindan-2-yl), 6.7g of monomer 1 and 40g 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: methacrylic acid (5-hydroxyindan-2-yl): monomer 1 = 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, 5.3 g of 3-hydroxyphenyl methacrylate, 6.8 g of tetrahydro-2-oxofuran-3-yl methacrylate, 6.5 g of 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: 3-hydroxyphenyl methacrylate: tetrahydro-2-oxofuran-3-yl methacrylate: monomer 2 = 0.30: 0.30: 0.25: 0.15
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, 4-hydroxyphenyl methacrylate 5.3 g, methacrylate 5-oxo-4-oxatricyclo [4.2.1.0 ^3,7 ] nonan-2-yl 3 g, 7.4 g of 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: 4-hydroxyphenyl methacrylate: 5-oxo-4-oxatricyclo [4.2.1.0 ^3,7 ] nonan-2-yl methacrylate: monomer 2 = 0.30: 0.30: 0.40: 0.15
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, methacrylic acid-3-ethyl-3-exotetracyclo [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, methacrylic acid-3-ethyl-3-exotetracyclo [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 2 8.7 g, coumarin 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 2: coumarin: 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]
To a 2 L flask was added 7.4 g of 2-ethyl-2-adamantane methacrylate, 5.3 g of 4-hydroxyphenyl methacrylate, 6.5 g of monomer 2, 6.5 g of PAG monomer 1, and 40 g of tetrahydrofuran as a solvent. . 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: 4-hydroxyphenyl methacrylate: monomer 2: 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, 4-hydroxyphenyl methacrylate 5.3 g, monomer 2 6.5 g, PAG monomer 2 5.7 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: 4-hydroxyphenyl methacrylate: monomer 2: PAG monomer 2 = 0.30: 0.30: 0.30: 0.10
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 g, methacrylic acid (5-hydroxyindan-2-yl) 8.7 g, monomer 1 6.5 g, PAG monomer 3 5.6 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: methacrylic acid (5-hydroxyindan-2-yl): monomer 1: PAG monomer 3 = 0.30: 0.30: 0.30: 0.10
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 g, 4-hydroxyphenyl methacrylate 5.3 g, monomer 2 7.4 g, PAG monomer 3 5.6 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: 4-hydroxyphenyl methacrylate: monomer 2: PAG monomer 3 = 0.30: 0.30: 0.30: 0.10
Weight average molecular weight (Mw) = 7,800
Molecular weight distribution (Mw / Mn) = 1.72
This polymer compound is referred to as (Polymer 10).

[Synthesis Example 11]
To a 2 L flask, 7.1 g of 9-fluorenyl methacrylate, 5.3 g of 4-hydroxyphenyl methacrylate, 7.4 g of monomer 2, 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 9-fluorenyl: 4-hydroxyphenyl methacrylate: monomer 2: PAG monomer 3 = 0.30: 0.30: 0.30: 0.10
Weight average molecular weight (Mw) = 7,200
Molecular weight distribution (Mw / Mn) = 1.70
This polymer compound is referred to as (Polymer 11).

[Synthesis Example 12]
To a 2 L flask, 7.1 g of acenaphthenyl methacrylate, 5.3 g of 4-hydroxyphenyl methacrylate, 7.4 g of monomer 2, 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 acenaphthenyl: 4-hydroxyphenyl methacrylate: monomer 2: PAG monomer 3 = 0.30: 0.30: 0.30: 0.10
Weight average molecular weight (Mw) = 7,300
Molecular weight distribution (Mw / Mn) = 1.68
This polymer compound is referred to as (Polymer 12).

[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).

[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 Polymer 3).

[Examples and Comparative Examples]
A solution prepared by dissolving the composition shown in Table 1 in a solvent in which 100 ppm of a surfactant, manufactured by Sumitomo 3M Limited, as a surfactant, 100 ppm was used as a surfactant, using the polymer compound synthesized above, was added to the surface of the solution. 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 12: Polymer compound comparative polymers 1 to 3 obtained in Synthesis Examples 1 to 12: Polymer compounds organic solvents obtained in Comparative Synthesis Examples 1 to 3: PGMEA (propylene glycol monomethyl ether acetate)
EL (ethyl lactate)
CyH (cyclohexanone)
Acid generator: PAG1, PAG2 (see structural formula below)
Basic compounds: Amine1, Amine2, Amine3 (see the structural formula below)
Dissolution control agent: DRI1, DRI2 (see the following structural formula)

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 was spin-coated on a Si substrate having a diameter of 6 inches φ using a clean track Mark 5 (manufactured by Tokyo Electron Ltd.), prebaked on a hot plate at 110 ° C. for 60 seconds, and 100 nm. A resist film was prepared. For this, drawing in a vacuum chamber was performed at an HV voltage of 50 keV using HL-800D manufactured by Hitachi, Ltd.
Immediately after drawing, post-exposure baking (PEB) was performed on a hot plate using a clean truck Mark 5 (manufactured by Tokyo Electron Co., Ltd.) at 100 ° C. for 60 seconds and paddled with 2.38 mass% TMAH aqueous solution for 30 seconds. Development was performed to obtain a positive pattern.
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.

  From the results in Table 1, it was found that the resist material using the polymer compound of the present invention satisfies sufficient resolution, sensitivity, and edge roughness.

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.

(In the formula, X is —NH— or —S—). The positive resist material according to claim 1, wherein the repeating unit having a group represented by the general formula (1) is a repeating unit represented by the following general formula (2).

(Wherein X is —NH— or —S—, R ¹ is a hydrogen atom or a methyl group, Y 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 following general formula (3) obtained by copolymerizing a repeating unit represented by the following general formula (a) and a repeating unit having an acid labile group represented by the following general formula (b) is 1 3. The positive resist material according to claim 2, wherein the base resin is a polymer compound in the range of 1,000,000 to 500,000.

(In the formula, R ¹ , X and Y are the same as described above. R ² represents a hydrogen atom or a methyl group, R ³ represents an acid labile group. 1 to 12 linking groups, phenylene groups, or naphthylene groups, a is 0 <a <1.0, b is 0 <b <1.0, and a + b is in the range of 0.1 ≦ a + b ≦ 1.0. is there.)   In addition to 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, a cyano group The repeating unit c of the adhesive group selected from the above was copolymerized (where 0 <a <1.0, 0 <b <1.0, 0 <c ≦ 0.9, 0.2 ≦ a + b + c ≦ 1.0). 4. The positive resist composition according to claim 3, wherein the base resin is a polymer compound having a weight average molecular weight in the range of 1,000 to 500,000.   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 control agent.   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 applying 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. A pattern forming method characterized by the above.   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.