JP5402651B2 - Positive resist material and pattern forming method using the same - Google Patents

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 time when the light used for exposure was g-line, and the reduction magnification was 1/5. 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 an accuracy equivalent to that of a substantially equal magnification 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.

It has been reported that there is little absorption of carbon atoms in difficult X-ray (EUV) exposure at a wavelength of 5 to 20 nm. 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.
As miniaturization progresses, image blur due to acid diffusion has become a problem. 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 improvement of dissolution contrast conventionally proposed but also the control of acid diffusion is important. However, chemically amplified resist materials 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. There is a close relationship between the type of acid labile group and the acid diffusion distance, and development of an acid labile group in which the deprotection reaction proceeds with an extremely short acid diffusion distance is desired.

  JP 2007-171895 A (Patent Document 3) exemplifies methacrylic ester in which indane, acenaphthene, fluorene, 9,10-dihydroanthracene is pendant as a copolymerization monomer for use in a photoresist underlayer film. Acid labile groups of (meth) acrylic acid esters of indane and tetrahydronaphthalene have been proposed. Since this has an aromatic group in the acid labile group, it improves etching resistance and EUV transmittance. Japanese Patent Application Laid-Open No. 2007-279699 (Patent Document 4) discloses a secondary or tertiary ester bond moiety, and proposes a resist material copolymerized with hydroxystyrene. In particular, since the steric free volume of the second grade is small, deprotection proceeds by short acid diffusion. However, indane and tetrahydronaphthalene do not have sufficient dissolution inhibiting properties, resulting in film loss after development and sufficient resolution cannot be obtained.

A trade-off relationship between sensitivity, edge roughness and resolution has been reported. Increasing sensitivity degrades edge roughness and resolution, and suppressing acid diffusion improves resolution but decreases edge roughness and sensitivity.
Although it is effective to suppress acid diffusion by adding an acid generator that generates a bulky acid, as described above, the edge roughness and sensitivity are reduced. 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 polymerization property that generates a specific sulfonic acid. Sulfonium salts and iodonium salts having olefins have been proposed. Photoresists using a base polymer copolymerized with a polymerizable acid generator have low acid diffusion because the acid diffusion is small and the acid generator is uniformly dispersed in the polymer, so both edge resolution and resolution are low. The characteristics can be improved at the same time.

Japanese Patent No. 3865048 JP 2006-169302 A JP 2007-171895 A JP 2007-279699 A JP-A-4-230645 JP 2005-84365 A JP 2006-045311 A

  The present invention has been made in view of the above circumstances, and provides a resist film having higher resolution than conventional positive resist materials, low line edge roughness, good pattern shape after exposure, and excellent etching resistance. An object of the present invention is to provide a positive resist material using a polymer compound suitable as a base resin for a positive resist material, particularly a chemically amplified positive resist material, and a pattern forming method.

  The inventors of the present invention obtain a positive resist material that has recently desired high resolution, low edge roughness (line width roughness; LWR, line edge roughness; LER), good etching shape, and excellent etching resistance. As a result of repeated intensive studies, this includes a polymer having a carboxyl group substituted with hydrobenzoanthracene, in particular, a polymer having a repeating unit selected from (meth) acrylic acid and derivatives thereof, styrene carboxylic acid, and vinyl naphthalene carboxylic acid. The present invention has been completed by discovering that it is extremely effective when used as a base resin of a positive resist material, particularly a chemically amplified positive resist material.

  In view of the above, the present inventors used the above polymer as a base resin for a positive resist material, particularly a chemically amplified positive resist material, in order to suppress acid diffusion and improve dissolution contrast and etching resistance. The alkali dissolution rate contrast before and after is significantly high, the effect of suppressing acid diffusion is high, the resolution is high, the pattern shape and edge roughness after exposure are good, and the etching resistance is excellent. It has been found that a positive resist material suitable for LSI manufacturing or a photomask fine pattern forming material, particularly 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 and exhibits better etching resistance. 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、炭素数１〜４のアルキル基、アルコキシ基、アルカノイル基、アルコキシカルボニル基、ヒドロキシ基、ニトロ基、炭素数６〜１０のアリール基、ハロゲン原子、又はシアノ基である。Ｒは水素原子、酸素原子又は硫黄原子を有していてもよい炭素数１〜１２の直鎖状、分岐状又は環状のアルキル基、炭素数２〜１２のアルケニル基、炭素数２〜１２のアルキニル基、又は炭素数６〜１０のアリール基である。ｍ、ｎは１〜４の整数である。）
請求項２：
下記一般式（２）で示される繰り返し単位ａを有す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に記載のポジ型レジスト材料。

（式中、Ｒ¹、Ｒ²、Ｒ、ｍ、ｎは前述の通りである。Ｘ¹は単結合、又は−Ｃ（＝Ｏ）−Ｏ−Ｒ⁴−、フェニレン基又はナフチレン基であり、Ｒ⁴は炭素数１〜１０の直鎖状、分岐状又は環状のアルキレン基であり、エステル基、エーテル基又はラクトン環を有していてもよい。Ｒ³は水素原子又はメチル基である。）
請求項３：
一般式（２）で示される繰り返し単位ａ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を有する繰り返し単位ｂ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（但し、０＜ａ＜１．０、０＜ｂ＜１．０、０．０５≦ａ＋ｂ≦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２に記載のレジスト材料。
請求項４：
繰り返し単位ｂが、フェノール性水酸基を有する繰り返し単位であることを特徴とする請求項３に記載のレジスト材料。
請求項５：
フェノール性水酸基を有する繰り返し単位が、下記一般式（３）で示されるｂ１〜ｂ８から選ばれるものであることを特徴とする請求項４に記載のレジスト材料。

（式中、Ｘ²、Ｘ³は単結合、又は−Ｃ（＝Ｏ）−Ｏ−Ｒ⁶−であり、Ｘ⁴、Ｘ⁵は−Ｃ（＝Ｏ）−Ｏ−Ｒ⁶−であり、Ｒ⁶は単結合、又は炭素数１〜１０の直鎖状、分岐状又は環状のアルキレン基である。Ｒ⁵は同一又は異種の水素原子又はメチル基である。Ｙ¹、Ｙ²はメチレン基又はエチレン基、Ｚはメチレン基、酸素原子又は硫黄原子、ｐは１又は２である。）
請求項６：
高分子化合物が、更に下記一般式（４）で示される繰り返し単位ｃ１〜ｃ５から選ばれる繰り返し単位を共重合してなることを特徴とする請求項３〜５のいずれか１項に記載のレジスト材料。

（式中、Ｒ⁹〜Ｒ¹³は水素原子、それぞれ炭素数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、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、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。Ｚはメチレン基、酸素原子又は硫黄原子である。）
請求項７：
高分子化合物が、一般式（２）で示される繰り返し単位ａ、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ｂに加えて、下記一般式（５）で示される繰り返し単位ｄ１〜ｄ３のいずれかを共重合してなることを特徴とする請求項３〜６のいずれか１項に記載のレジスト材料。

（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−Ｒ³³−、又は−Ｃ（＝Ｏ）−Ｙ−Ｒ³³−である。Ｙは酸素原子又はＮＨ、Ｒ³³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のアリール基もしくは炭素数７〜２０のアラルキル基を表す。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。０≦ｄ１≦０．３、０≦ｄ２≦０．３、０≦ｄ３≦０．３、０＜ｄ１＋ｄ２＋ｄ３≦０．３の範囲である。）
請求項８：
更に、有機溶剤及び酸発生剤を含有する化学増幅ポジ型レジスト材料であることを特徴とする請求項１〜７のいずれか１項に記載のポジ型レジスト材料。
請求項９：
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８に記載のポジ型レジスト材料。
請求項１０：
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８又は９に記載のポジ型レジスト材料。
請求項１１：
請求項１〜１０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。
That is, the present invention provides the following positive resist material and a pattern forming method using the same.
Claim 1:
A positive resist material characterized in that a resin in which a hydrogen atom of a carboxyl group is substituted with an acid labile group represented by the following general formula (1) is used as a base resin.

Wherein R ¹ and R ² are a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy group, an alkanoyl group, an alkoxycarbonyl group, a hydroxy group, a nitro group, an aryl group having 6 to 10 carbon atoms, a halogen atom, Or a cyano group, wherein R is a linear, branched or cyclic alkyl group having 1 to 12 carbon atoms which may have a hydrogen atom, an oxygen atom or a sulfur atom, an alkenyl group having 2 to 12 carbon atoms, A C2-C12 alkynyl group or a C6-C10 aryl group, m and n are integers of 1-4.)
Claim 2:
To claim 1 having a weight-average molecular weight having a unit a Ri return is that Repetitive represented by the following general formula (2) is characterized in that in the base resin a polymer compound ranges from 1,000 to 500,000 The positive resist material described.

(Wherein R ¹ , R ² , R, m and n are as described above. X ¹ is a single bond, or —C (═O) —O—R ⁴ —, a phenylene group or a naphthylene group, R ⁴ is a linear, branched or cyclic alkylene group having 1 to 10 carbon atoms and may have an ester group, an ether group or a lactone ring, and R ³ is a hydrogen atom or a methyl group. )
Claim 3:
Formula in addition to the indicated that Repetitive return unit a in (2), hydroxy group, lactone ring, an ether group, an ester group, by copolymerizing repeating units b having a carbonyl group, an adhesive group selected from cyano group Polymer compound having a weight average molecular weight in the range of 1,000 to 500,000 (provided that 0 <a <1.0, 0 <b <1.0, 0.05 ≦ a + b ≦ 1.0) The resist material according to claim 2, wherein a base resin is used.
Claim 4:
The resist material according to claim 3, wherein the repeating unit b is a repeating unit having a phenolic hydroxyl group.
Claim 5:
The resist material according to claim 4, wherein the repeating unit having a phenolic hydroxyl group is selected from b1 to b8 represented by the following general formula (3).

(Wherein X ² and X ³ are a single bond or —C (═O) —O—R ⁶ —, X ⁴ and X ⁵ are —C (═O) —O—R ⁶ —, R ⁶ is a single bond or a linear, branched or cyclic alkylene group having 1 to 10 carbon atoms, R ⁵ is the same or different hydrogen atom or methyl group, and Y ¹ and Y ² are methylene groups. Or an ethylene group, Z is a methylene group, an oxygen atom or a sulfur atom, and p is 1 or 2.)
Claim 6:
The resist according to any one of claims 3 to 5, wherein the polymer compound is obtained by copolymerizing a repeating unit selected from repeating units c1 to c5 represented by the following general formula (4). material.

(In the formula, R ^{9 to} R ¹³ are each a hydrogen atom, an alkyl group having 1 to 30 carbon atoms, an alkyl group partially or entirely substituted with a halogen atom, an alkoxy group, an alkanoyl group, or an alkoxycarbonyl group; -10 aryl group, halogen atom, or 1,1,1,3,3,3-hexafluoro-2-propanol group, Z is a methylene group, oxygen atom or sulfur atom.)
Claim 7:
Polymer compound, general formula (2) indicated that Repetitive return unit a, hydroxyl group, lactone ring, ether group, an ester group, a carbonyl group, in addition to the repeating units (b) of the adhesive group selected from cyano group The resist material according to any one of claims 3 to 6, which is obtained by copolymerizing any one of repeating units d1 to d3 represented by the following general formula (5).

(Wherein 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 ³³ —, or —C (═O) —Y—R ³³ —. Y is an oxygen atom or NH, R ³³ is a linear, branched or cyclic alkylene group, phenylene group or alkenylene group having 1 to 6 carbon atoms, including 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 , R ³¹ are the same or different linear, branched or cyclic alkyl groups having 1 to 12 carbon atoms. And may contain a carbonyl group, an ester group or an ether group, or represents an aryl group having 6 to 12 carbon atoms or an aralkyl group having 7 to 20 carbon atoms, Z ₀ is a single bond, a methylene group or an ethylene group. , phenylene, fluorinated phenylene group, -O-R ³² , Or _{-C (= O) -Z 1 -R} 32 - is a .Z ₁ is an oxygen atom or NH, R ³² represents a linear 1 to 6 carbon atoms, branched or cyclic alkylene group, 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 counterion, 0 ≦ d1 ≦ 0.3, 0 ≦ d2 ≦ 0.3; 0 ≦ d3 ≦ 0.3 and 0 <d1 + d2 + d3 ≦ 0.3.)
Claim 8:
The positive resist composition according to claim 1, further comprising a chemically amplified positive resist composition containing an organic solvent and an acid generator.
Claim 9:
The positive resist composition according to claim 8, further comprising a dissolution control agent.
Claim 10:
The positive resist composition according to claim 8 or 9, further comprising a basic compound and / or a surfactant as an additive.
Claim 11:
A step of applying the positive resist material according to any one of claims 1 to 10 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.

  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 and edge roughness 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、炭素数１〜４のアルキル基、アルコキシ基、アルカノイル基、アルコキシカルボニル基、ヒドロキシ基、ニトロ基、炭素数６〜１０のアリール基、ハロゲン原子、又はシアノ基である。Ｒは水素原子、酸素原子又は硫黄原子を有していてもよい炭素数１〜１２の直鎖状、分岐状又は環状のアルキル基、炭素数２〜１２のアルケニル基、炭素数２〜１２のアルキニル基、又は炭素数６〜１０のアリール基である。ｍ、ｎは１〜４の整数である。） 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 in which a hydrogen atom of a carboxyl group is substituted with at least an acid labile group represented by the following general formula (1).

Wherein R ¹ and R ² are a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy group, an alkanoyl group, an alkoxycarbonyl group, a hydroxy group, a nitro group, an aryl group having 6 to 10 carbon atoms, a halogen atom, Or a cyano group, wherein R is a linear, branched or cyclic alkyl group having 1 to 12 carbon atoms which may have a hydrogen atom, an oxygen atom or a sulfur atom, an alkenyl group having 2 to 12 carbon atoms, A C2-C12 alkynyl group or a C6-C10 aryl group, m and n are integers of 1-4.)

In this case, specific examples of R ¹ and R ² include a hydrogen atom, a methyl group, an ethyl group, a propyl group, a butyl group, a methoxy group, an ethoxy group, an acetoxy group, and a methoxycarbonyl group. Group, methoxy group, acetoxy group and methoxycarbonyl group are preferred.

（式中、Ｒ¹、Ｒ²、Ｒ、ｍ、ｎは前述の通りである。Ｘ¹は単結合、又は−Ｃ（＝Ｏ）−Ｏ−Ｒ⁴−、フェニレン基又はナフチレン基であり、Ｒ⁴は炭素数１〜１０の直鎖状、分岐状又は環状のアルキレン基であり、エステル基（−ＣＯＯ−）、エーテル基（−Ｏ−）又はラクトン環を有していてもよい。Ｒ³は水素原子又はメチル基である。） The acid labile group represented by the general formula (1) is preferably a hydrogen atom of a carboxyl group of (meth) acrylic acid or a derivative thereof (hereinafter collectively referred to as (meth) acrylate), styrene carboxylic acid, or vinyl naphthalene carboxylic acid. The polymer compound is preferably a polymer compound having a weight average molecular weight of the following general formula (2) in the range of 1,000 to 500,000.

(Wherein R ¹ , R ² , R, m and n are as described above. X ¹ is a single bond, or —C (═O) —O—R ⁴ —, a phenylene group or a naphthylene group, R ⁴ is a linear, branched or cyclic alkylene group having 1 to 10 carbon atoms and may have an ester group (—COO—), an ether group (—O—) or a lactone ring. ³ is a hydrogen atom or a methyl group.)

のものが挙げられる。 In addition, as a C1-C10 alkylene group which has a lactone ring, following formula

Can be mentioned.

（式中、Ｒ¹、Ｒ²、Ｒ³、Ｒ、ｍ、ｎは前述と同様である。Ｒ⁷は炭素数1〜１０の直鎖状、分岐状又は環状のアルキレン基であり、エステル基、エーテル基又はラクトン環を有していてもよい。０＜ａ１＋ａ２＋ａ３＋ａ４＜１．０の範囲である。）
これらの酸脱離基は、特にはＫｒＦ、ＥＢ、ＥＵＶリソグラフィーに適用することができる。 The repeating unit a represented by the general formula (2) can be represented by a1 to a4 in the following general formula (6).

(In the formula, R ¹ , R ² , R ³ , R, m and n are the same as described above. R ⁷ is a linear, branched or cyclic alkylene group having 1 to 10 carbon atoms, and an ester group. And may have an ether group or a lactone ring. 0 <a1 + a2 + a3 + a4 <1.0.)
These acid leaving groups are particularly applicable to KrF, EB, EUV lithography.

  Specific examples of the monomer for obtaining the repeating units represented by the general formulas a1 to a4 can be given below.

  The polymerizable acid labile ester compound for obtaining the repeating unit a1 of the present invention can be obtained by making the carbonyl group of benzanthrone a hydroxy group and reacting with methacrylic acid chloride. Moreover, the ester compound for obtaining other repeating units a2-a4 can be obtained similarly.

  In the acid labile group of the present invention, when the carbon atom of the bonding portion with the ester is secondary, both sides are sandwiched by benzene rings, so that an internal olefin is not generated. As shown in the following reaction formula I and reaction formula II, a carbocation compound is generated by elimination by an acid, and when this reacts with water, it becomes a hydroxy group, and the carbocation may be added to the ortho position of the phenol group. is there. When the carbon atom of the bonding portion with the ester is tertiary, an olefin is generated and elimination proceeds.

  The polymer compound having an acid labile group of the above formula (1) according to the present invention includes a hydroxy group in addition to the repeating unit a of the (meth) acrylate, styrene carboxylic acid and vinyl naphthalene carboxylic acid of the above formula (2). , A repeating unit b having an adhesive group selected from a lactone ring, an ether group, an ester group, a carbonyl group, and a cyano group is preferably copolymerized. In this case, the repeating unit b preferably has a phenolic hydroxyl group that has a sensitizing effect by electron beam and EUV exposure, and the repeating unit having a phenolic hydroxyl group is b1 represented by the following general formula (3). It is preferable to be selected from ~ b8.

（式中、Ｘ²、Ｘ³は単結合、又は−Ｃ（＝Ｏ）−Ｏ−Ｒ⁶−であり、Ｘ⁴、Ｘ⁵は−Ｃ（＝Ｏ）−Ｏ−Ｒ⁶−であり、Ｒ⁶は単結合、又は炭素数１〜１０の直鎖状、分岐状又は環状のアルキレン基である。Ｒ⁵は同一又は異種の水素原子又はメチル基である。Ｙ¹、Ｙ²はメチレン基又はエチレン基、Ｚはメチレン基、酸素原子又は硫黄原子、ｐは１又は２である。）

(Wherein X ² and X ³ are a single bond or —C (═O) —O—R ⁶ —, X ⁴ and X ⁵ are —C (═O) —O—R ⁶ —, R ⁶ is a single bond or a linear, branched or cyclic alkylene group having 1 to 10 carbon atoms, R ⁵ is the same or different hydrogen atom or methyl group, and Y ¹ and Y ² are methylene groups. Or an ethylene group, Z is a methylene group, an oxygen atom or a sulfur atom, and p is 1 or 2.)

  The monomer for obtaining the repeating units b1 to b8 having the phenolic hydroxyl group can be shown below.

  Further, hydroxy groups other than phenolic hydroxyl groups, lactone rings, ether groups, ester groups, carbonyl groups, cyano groups, cyclic —O—C (═O) —S— or —O—C (═O) —NH—. Specific examples of the monomer for obtaining the repeating unit b of the adhesive group selected from are shown 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 may be deprotected with a weak acid and water after the polymerization, Substitution with a formyl group, pivaloyl group or the like, and alkali hydrolysis may be performed after polymerization.

（式中、Ｒ⁹〜Ｒ¹³は水素原子、それぞれ炭素数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、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、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。Ｚはメチレン基、酸素原子又は硫黄原子である。） The polymer compound according to the present invention is preferably obtained by copolymerizing a repeating unit selected from indene, acenaphthylene, chromone, coumarin, norbornadiene and derivatives c1 to c5 thereof represented by the following general formula (4).

(In the formula, R ^{9 to} R ¹³ are each a hydrogen atom, an alkyl group having 1 to 30 carbon atoms, an alkyl group partially or entirely substituted with a halogen atom, an alkoxy group, an alkanoyl group, or an alkoxycarbonyl group; -10 aryl group, halogen atom, or 1,1,1,3,3,3-hexafluoro-2-propanol group, Z is a methylene group, oxygen atom or sulfur atom.)

In this case, the monomer for obtaining indene, acenaphthylene, chromone, coumarin, norbornadiene, and derivatives c1 to c5 thereof can be specifically exemplified below.

Furthermore, an onium salt acid generator d 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は単結合、フェニレン基、−Ｏ−Ｒ³³−、又は−Ｃ（＝Ｏ）−Ｙ−Ｒ³³−である。Ｙは酸素原子又はＮＨ、Ｒ³³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（−ＣＯ−）、エステル基（−ＣＯＯ−）、エーテル基（−Ｏ−）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。０≦ｄ１≦０．３、０≦ｄ２≦０．３、０≦ｄ３≦０．３、０≦ｄ１＋ｄ２＋ｄ３≦０．３の範囲である。） In the present invention, repeating units d1 to d3 having a sulfonium salt represented by the following general formula (5) can be copolymerized.

(Wherein 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 ³³ —, or —C (═O) —Y—R ³³ —. Y is an oxygen atom or NH, R ³³ is a linear, branched or cyclic alkylene group having 1 to 6 carbon atoms, a phenylene group or an alkenylene group, a carbonyl group (—CO—), an ester group (—COO) -), An ether group (-O-) or a hydroxy group, R ²² , R ²³ , R ²⁵ , R ²⁶ , R ²⁷ , R ²⁹ , R ³⁰ , R ³¹ may be the same or different. 1 to 12 linear, branched or cyclic alkyl group, which may contain a carbonyl group, an ester group or an ether group, or an aryl group having 6 to 12 carbon atoms or an aralkyl having 7 to 20 carbon atoms Z ₀ represents a single bond, a methylene group, an ethylene group, a phenyl group, or a thiophenyl group. Rene group, fluorinated phenylene group, —O—R ³² —, or —C (═O) —Z ₁ —R ³² —, wherein Z ₁ is an oxygen atom or NH, and R ³² has 1 to 6 carbon atoms. A linear, branched or cyclic alkylene group, a phenylene group or an alkenylene group, which may contain a carbonyl group, an ester group, an ether group or a hydroxy group, and M ⁻ represents a non-nucleophilic counter ion. 0 ≦ d1 ≦ 0.3, 0 ≦ d2 ≦ 0.3, 0 ≦ d3 ≦ 0.3, 0 ≦ d1 + d2 + d3 ≦ 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 edge roughness (LER, LWR) is improved by uniformly dispersing the acid generator.

（式中、Ｒ¹⁴、Ｒ¹⁶は水素原子又はメチル基を表し、Ｒ¹⁵、Ｒ¹⁷は一般式（１）で示される基以外の酸不安定基である。ｑは１又は２である。） The present invention essentially has a repeating unit a as a repeating unit having an acid labile group, but is a (meth) acrylic acid ester substituted with an acid labile group R ^{15 represented} by the following general formula (7) It is also possible to additionally copolymerize the repeating unit e and the repeating unit f of hydroxystyrene substituted with the acid labile group R ¹⁷ .

(In the formula, R ¹⁴ and R ¹⁶ represent a hydrogen atom or a methyl group, and R ¹⁵ and R ¹⁷ are acid labile groups other than the group represented by the general formula (1). Q is 1 or 2. )

  Examples of the repeating unit g that can be copolymerized in addition to the repeating units a, b, c, d, e, and f include repeating units derived from styrene, vinyl naphthalene, vinyl anthracene, vinyl pyrene, methylene indane, and the like.

The acid labile group (acid labile groups of R ¹⁵ and R ^{17 in} the general formula (7)) is variously selected and may be the same or different. Examples thereof include those represented by the group substituted in 3).

In the formula (A-1), R ^L30 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. Specific examples of the oxoalkyl group include a 3-oxocyclohexyl group, a 4-methyl-2-oxooxan-4-yl group, and a 5-methyl-2-oxooxolan-5-yl group. A1 is an integer of 0-6.

In the formula (A-2), R ^L31 and R ^L32 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 ^L33 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 ^L31 and R ^L32 , R ^L31 and R ^L33 , R ^L32 and R ^L33 may combine to form a ring with the carbon atom to which they are bonded, and in the case of forming a ring, it participates in the formation of the ring. R ^L31 , R ^L32 , and R ^L33 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 ^L37 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 ^L38 is a hydrogen atom, or 1 to 1 carbon atoms. 10 linear, branched or cyclic alkyl groups.
R ^L39 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.

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

In the formula, R ^L40 and R ^{L41 each} represent a hydrogen atom or a linear, branched or cyclic alkyl group having 1 to 8 carbon atoms. Alternatively, R ^L40 and R ^L41 may be bonded to form a ring together with the carbon atom to which they are bonded, and when forming a ring, R ^L40 and R ^L41 involved in the formation of the ring have 1 to 8 carbon atoms. A linear or branched alkylene group. R ^L42 is a linear, branched or cyclic alkylene group having 1 to 10 carbon atoms, B1 and D1 are 0 or 1 to 10, preferably 0 or an integer of 1 to 5, and C1 is an integer of 1 to 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 ^L34 , R ^L35 and R ^L36 are monovalent hydrocarbon groups such as a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms, oxygen, sulfur, Hetero atoms such as nitrogen and fluorine may be included, and R ^L34 and R ^L35 , R ^L34 and R ^L36 , R ^L35 and R ^L36 are bonded to each other, and together with the carbon atom to which they are bonded, a ring having 3 to 20 carbon atoms 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.

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

In formulas (A-3) -1 to (A-3) -18, R ^L43 is the same or different linear, branched or cyclic alkyl group having 1 to 8 carbon atoms, or 6 to 20 carbon atoms. An aryl group such as a phenyl group or a naphthyl group is shown. R ^L44 and R ^L46 represent a hydrogen atom or a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms. R ^L45 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 bivalent or higher valent alkylene group and an arylene group R ^L47 are included, and the polymer molecule or between molecules is crosslinked. May be.

In formulas (A-3) -19 and (A-3) -20, R ^L43 is the same as described above, and R ^L47 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.

（式中、Ｒ¹⁴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。また、本式により、鏡像体も表す。） In particular, the acid labile group (A-3) is preferably a repeating unit of a (meth) acrylic acid ester having an exo structure represented by the following (A-3) -21.

(.R shown wherein, R ¹⁴ is as defined above, R ^c3 represents a linear 1 to 8 carbon atoms, branched or cyclic alkyl or optionally substituted aryl group having 6 to 20 carbon atoms ^{c4 to} R ^c9 and R ^c12 and R ^c13 each independently represent a hydrogen atom or a monovalent hydrocarbon group which may contain a hetero atom having 1 to 15 carbon atoms, and R ^c10 and R ^{c11 each} represent a hydrogen atom. , 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 are A divalent hydrocarbon group which may form a ring 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 ; R ^c8 may be bonded to adjacent carbons without any intervening bonds to form a double bond, and this formula also represents an 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.

（式中、Ｒ¹⁴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。） 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.

(In the formula, R ¹⁴ is as described above. R ^c14 and R ^c15 each independently represents a linear, branched or cyclic monovalent hydrocarbon group having 1 to 10 carbon atoms, or R ^c14 , 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 represents a divalent group selected from ^frangyl , tetrahydrofurandiyl or ^{oxanorbornanediyl.} 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 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 g is as follows.
a is 0 <a <1.0, preferably 0.05 ≦ a ≦ 0.8, more preferably 0.08 ≦ a ≦ 0.7,
b is 0 <b <1.0, preferably 0.1 ≦ b ≦ 0.9, more preferably 0.15 ≦ b ≦ 0.8,
c is 0 ≦ c <1.0, preferably 0 ≦ c ≦ 0.9, more preferably 0 ≦ c ≦ 0.8,
d is 0 ≦ d ≦ 0.5, preferably 0 ≦ d ≦ 0.4, more preferably 0 ≦ d ≦ 0.3,
e is 0 ≦ e ≦ 0.5, preferably 0 ≦ e ≦ 0.4, more preferably 0 ≦ e ≦ 0.3,
f is 0 ≦ f ≦ 0.5, preferably 0 ≦ f ≦ 0.4, more preferably 0 ≦ f ≦ 0.3,
g is 0 ≦ g ≦ 0.5, preferably 0 ≦ g ≦ 0.4, and more preferably 0 ≦ g ≦ 0.3.
0.2 ≦ a + b + c ≦ 1.0, preferably 0.3 ≦ a + b + c ≦ 1.0, 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 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 of the present invention is suitable as a base resin for a positive resist material, particularly a chemically amplified positive resist material. Such a polymer compound is used as a base resin, and an organic solvent, an acid generator, and a dissolution control agent are used therefor. In the exposed part, the dissolution rate of the polymer compound in the developing solution is accelerated by a catalytic reaction by composing a suitable combination of a basic compound, a surfactant and the like according to the purpose. , A positive resist material with extremely high sensitivity, high dissolution contrast and resolution of the resist film, exposure margin, excellent process adaptability, and good pattern shape after exposure, Excellent etching resistance, especially because acid diffusion can be suppressed, so the density difference is small. It can be very effective as bets materials. 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. The compound (photo acid generator) to be used may be contained. 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 ketones such as cyclohexanone and methyl-2-n-amyl ketone described in paragraphs [0144] to [0145] of JP-A-2008-111103, 3-methoxybutanol, 3-methyl- Alcohols such as 3-methoxybutanol, 1-methoxy-2-propanol, 1-ethoxy-2-propanol, propylene glycol monomethyl ether, ethylene glycol monomethyl ether, propylene glycol monoethyl ether, ethylene glycol monoethyl ether, propylene glycol dimethyl ether , Ethers such as diethylene glycol dimethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, ethyl lactate, pyruvic acid Esters such as chill, butyl acetate, methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, tert-butyl acetate, tert-butyl propionate, propylene glycol mono tert-butyl ether acetate, lactones such as γ-butyrolactone, and the like Examples of the basic compound include primary, secondary, and tertiary amine compounds described in paragraphs [0146] to [0164], particularly hydroxy groups, ether groups, ester groups, lactone rings, and cyano. And amine compounds having a sulfonic acid ester group, the surfactants are paragraphs [0165] to [0166], and the dissolution control agents are paragraphs [0155] to [0178] of JP-A-2008-122932. Acetylene alcohols are paragraphs [0179] to [0182]. It is described in. 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, SiO _2, etc.) by an appropriate coating method such as spin coating, roll coating, flow coating, dip coating, spray coating, doctor coating, etc., the coating film thickness becomes 0.1 to 2.0 μm. Apply as follows. 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 mass, preferably 2 to 10% by mass, especially 2 to 10% by mass 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, an aqueous solution of 2.38% by mass 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).

（Ｅｔはエチル基） [Monomer synthesis example]
The polymerizable acid labile compound of the present invention was synthesized as follows.
[Monomer Synthesis Example 1] Synthesis of methacrylic acid = 7H-benzo [de] anthracen-7-yl (monomer 1)

(Et is an ethyl group)

To a mixture of 120 g of methacrylic acid chloride, 240 g of 11H-benzo [de] anthracen-11-ol and 1,500 g of toluene, 111 g of triethylamine was added under ice cooling and stirring. Then, it stirred at room temperature for 16 hours. The crude product was obtained by ordinary aqueous work-up and solvent distillation. Purification was performed by column chromatography to obtain the target product, methacrylic acid = 7H-benzo [de] anthracen-7-yl.
Monomers 2 to 5 were obtained in the same manner.

モノマー１：メタクリル酸＝７Ｈ−ベンゾ［ｄｅ］アントラセン−７−イル
モノマー２：メタクリル酸＝９−（７Ｈ−ベンゾ［ｄｅ］アントラセン−７−イルオキシ
カルボニル）−４−オキサトリシクロ［４．２．１．０^3,7］ノナン−５−
オン−２−イル
モノマー３：（４−ビニル安息香酸＝７Ｈ−ベンゾ［ｄｅ］アントラセン−７−イル
モノマー４：５−ビニル−１−ナフトエ酸＝７Ｈ−ベンゾ［ｄｅ］アントラセン−７−イ
ル
モノマー５：メタクリル酸＝７−メチル−７Ｈ−ベンゾ［ｄｅ］アントラセン−７−イル

Monomer 1: methacrylic acid = 7H-benzo [de] anthracen-7-yl monomer 2: methacrylic acid = 9- (7H-benzo [de] anthracen-7-yloxy
Carbonyl) -4-oxatricyclo [4.2.1.0 ^3,7 ] nonane-5
On-2-yl monomer 3: (4-vinylbenzoic acid = 7H-benzo [de] anthracen-7-yl monomer 4: 5-vinyl-1-naphthoic acid = 7H-benzo [de] anthracene-7-i
Monomer 5: Methacrylic acid = 7-methyl-7H-benzo [de] anthracen-7-yl

ＰＡＧモノマー１：４−メタクリル酸オキシフェニルジフェニルスルホニウム パーフル
オロブタンスルホネート
ＰＡＧモノマー２：トリフェニルスルホニウム ２，３，５，６−テトラフルオロ−４−
メタクリロイルオキシベンゼンスルホナート
ＰＡＧモノマー３：トリフェニルスルホニウム １，１，３，３，３−ペンタフルオロ−
２−メタクリロイルオキシプロパン−１−スルホネート The PAG monomers 1 to 3 and the adhesion monomers 1 and 2 are as follows.

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

密着性モノマー１：メタクリル酸（２−オキソ−１，３−ベンゾオキサチオール−５−イ
ル）
密着性モノマー２：メタクリル酸（２−オキソ−２，３−ジヒドロベンゾオキサゾール−
５−イル）

Adhesive monomer 1: Methacrylic acid (2-oxo-1,3-benzooxathiol-5-i
Le)
Adhesive monomer 2: methacrylic acid (2-oxo-2,3-dihydrobenzoxazole-
5-yl)

[Example of polymer synthesis]
[Polymer synthesis example 1]
To a 2 L flask, 6.0 g of monomer 1, 13.0 g of 4-acetoxystyrene, 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 is precipitated in 1 L of isopropyl alcohol, and the resulting white solid is dissolved again in 100 mL of methanol and 200 mL of tetrahydrofuran. 10 g of triethylamine and 10 g of water are added, and the acetyl group is deprotected at 70 ° C. for 5 hours. And neutralized with acetic acid. The reaction solution was concentrated and then dissolved in 100 mL of acetone, followed by precipitation, filtration and drying at 60 ° C. as described above 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)
Monomer 1: 4-hydroxystyrene = 0.20: 0.80
Weight average molecular weight (Mw) = 8,900
Molecular weight distribution (Mw / Mn) = 1.69
This polymer compound is referred to as (Polymer 1).

[Polymer synthesis example 2]
To a 2 L flask, 5.4 g of monomer 1, 14.5 g of 3-hydroxyphenyl methacrylate, 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)
Monomer 1: 3-hydroxyphenyl methacrylate = 0.18: 0.82
Weight average molecular weight (Mw) = 8,200
Molecular weight distribution (Mw / Mn) = 1.97
This polymer compound is referred to as (Polymer 2).

[Polymer synthesis example 3]
To a 2 L flask, 5.4 g of monomer 1, 17.9 g of methacrylic acid (5-hydroxyindan-2-yl), 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)
Monomer 1: Methacrylic acid (5-hydroxyindan-2-yl) = 0.18: 0.82
Weight average molecular weight (Mw) = 8,900
Molecular weight distribution (Mw / Mn) = 1.91
This polymer compound is referred to as (Polymer 3).

[Polymer Synthesis Example 4]
In a 2 L flask, 9.0 g of monomer 1, 8.7 g of methacrylic acid (5-hydroxyindan-2-yl), 3-oxo-2,7-dioxatricyclomethacrylate [4.2.1.0 ^{4 , 8} ] nonane-9-yl 6.7 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)
Monomer 1: Methacrylic acid (5-hydroxyindan-2-yl): 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) = 8,900
Molecular weight distribution (Mw / Mn) = 1.81
This polymer compound is referred to as (Polymer 4).

[Polymer synthesis example 5]
To a 2 L flask, 6.9 g of monomer 1, 1.7 g of indene, 10.8 g of 4-acetoxystyrene, 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 is precipitated in 1 L of isopropyl alcohol, and the resulting white solid is dissolved again in 100 mL of methanol and 200 mL of tetrahydrofuran. 10 g of triethylamine and 10 g of water are added, and the acetyl group is deprotected at 70 ° C. for 5 hours. And neutralized with acetic acid. The reaction solution was concentrated and then dissolved in 100 mL of acetone, followed by precipitation, filtration and drying at 60 ° C. as described above 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)
Monomer 1: Indene: 4-hydroxystyrene = 0.23: 0.10: 0.67
Weight average molecular weight (Mw) = 8,700
Molecular weight distribution (Mw / Mn) = 1.72
This polymer compound is referred to as (Polymer 5).

[Polymer Synthesis Example 6]
To a 2 L flask, 8.4 g of monomer 1, 5.3 g of 4-hydroxyphenyl methacrylate, 6.8 g of 4-acetoxystyrene, 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 is precipitated in 1 L of isopropyl alcohol, and the resulting white solid is dissolved again in 100 mL of methanol and 200 mL of tetrahydrofuran. 10 g of triethylamine and 10 g of water are added, and the acetyl group is deprotected at 70 ° C. for 5 hours. And neutralized with acetic acid. The reaction solution was concentrated and then dissolved in 100 mL of acetone, followed by precipitation, filtration and drying at 60 ° C. as described above 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)
Monomer 1: 4-hydroxyphenyl methacrylate: 4-hydroxystyrene = 0.28: 0.30: 0.42
Weight average molecular weight (Mw) = 8,600
Molecular weight distribution (Mw / Mn) = 1.98
This polymer compound is referred to as (Polymer 6).

[Polymer Synthesis Example 7]
To a 2 L flask was added 7.8 g of monomer 1, 6.8 g of 1-hydroxynaphthalen-5-yl methacrylate, 7.5 g of tetrahydro-2-oxofuran-3-yl methacrylate, 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)
Monomer 1: 1-hydroxynaphthalen-5-yl methacrylate: tetrahydro-2-oxofuran-3-yl methacrylate = 0.26: 0.30: 0.44
Weight average molecular weight (Mw) = 6,800
Molecular weight distribution (Mw / Mn) = 1.65
This polymer compound is referred to as (Polymer 7).

[Polymer Synthesis Example 8]
6.9 g of monomer 1, 10.7 g of 4-acetoxystyrene, 1.7 g of acenaphthylene, and 20 g of tetrahydrofuran as a solvent were added to a 2 L flask. 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 is precipitated in 1 L of isopropyl alcohol, and the resulting white solid is dissolved again in 100 mL of methanol and 200 mL of tetrahydrofuran. 10 g of triethylamine and 10 g of water are added, and the acetyl group is deprotected at 70 ° C. for 5 hours. And neutralized with acetic acid. The reaction solution was concentrated and then dissolved in 100 mL of acetone, followed by precipitation, filtration and drying at 60 ° C. as described above 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)
Monomer 1: 4-hydroxystyrene: acenaphthylene = 0.23: 0.67: 0.10
Weight average molecular weight (Mw) = 6,500
Molecular weight distribution (Mw / Mn) = 1.93
This polymer compound is referred to as (Polymer 8).

[Polymer synthesis example 9]
To a 2 L flask, 7.2 g of monomer 1, 2.0 g of 7-acetoxyindene, 10.6 g of 4-acetoxystyrene, 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. This reaction solution is precipitated in 1 L of isopropyl alcohol, and the resulting white solid is dissolved again in 100 mL of methanol and 200 mL of tetrahydrofuran. 10 g of triethylamine and 10 g of water are added, and the acetyl group is deprotected at 70 ° C. for 5 hours. And neutralized with acetic acid. The reaction solution was concentrated and then dissolved in 100 mL of acetone, followed by precipitation, filtration and drying at 60 ° C. as described above 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)
Monomer 1: 7-hydroxyindene: 4-hydroxystyrene = 0.24: 0.10: 0.66
Weight average molecular weight (Mw) = 6,400
Molecular weight distribution (Mw / Mn) = 1.94
This polymer compound is referred to as (Polymer 9).

[Polymer Synthesis Example 10]
To a 2 L flask, 6.9 g of monomer 1, 8.3 g of 4-acetoxystyrene, 2.7 g of 6-hydroxycoumarin, 1.5 g of coumarin, and 20 g of tetrahydrofuran as a solvent were added. The reaction vessel was cooled to −70 ° C. in a nitrogen atmosphere, and vacuum degassing and nitrogen 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 is precipitated in 1 L of isopropyl alcohol, and the resulting white solid is dissolved again in 100 mL of methanol and 200 mL of tetrahydrofuran. 10 g of triethylamine and 10 g of water are added, and the acetyl group is deprotected at 70 ° C. for 5 hours. And neutralized with acetic acid. The reaction solution was concentrated and then dissolved in 100 mL of acetone, followed by precipitation, filtration and drying at 60 ° C. as described above 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)
Monomer 1: 4-hydroxystyrene: 6-hydroxycoumarin: coumarin = 0.23: 0.52: 0.15: 0.10
Weight average molecular weight (Mw) = 6,900
Molecular weight distribution (Mw / Mn) = 2.21
This polymer compound is referred to as (Polymer 10).

[Polymer Synthesis Example 11]
To a 2 L flask, 6.9 g of Monomer 1, 15.5 g of methacrylic acid (5-hydroxy-1,2,3,4-tetrahydronaphthalen-2-yl), 1.6 g of chromone, and 20 g of tetrahydrofuran as a solvent were added. The reaction vessel was cooled to −70 ° C. in a nitrogen atmosphere, and vacuum degassing and nitrogen 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)
Monomer 1: Methacrylic acid (5-hydroxy-1,2,3,4-tetrahydronaphthalen-2-yl): chromone = 0.23: 0.67: 0.10
Weight average molecular weight (Mw) = 5,800
Molecular weight distribution (Mw / Mn) = 1.88
This polymer compound is referred to as (Polymer 11).

[Polymer Synthesis Example 12]
8.4 g of monomer 3, 10.7 g of 4-acetoxystyrene, 1.6 g of chromone, and 20 g of tetrahydrofuran as a solvent were added to a 2 L flask. 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 is precipitated in 1 L of isopropyl alcohol, and the resulting white solid is dissolved again in 100 mL of methanol and 200 mL of tetrahydrofuran. 10 g of triethylamine and 10 g of water are added, and the acetyl group is deprotected at 70 ° C. for 5 hours. And neutralized with acetic acid. The reaction solution was concentrated and then dissolved in 100 mL of acetone, followed by precipitation, filtration and drying at 60 ° C. as described above 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)
Monomer 3: 4-hydroxystyrene: chromone = 0.23: 0.67: 0.10
Weight average molecular weight (Mw) = 7,700
Molecular weight distribution (Mw / Mn) = 1.77
This polymer compound is referred to as (Polymer 12).

[Polymer Synthesis Example 13]
9.5 g of monomer 4, 10.4 g of 4-acetoxystyrene, 1.8 g of coumarin, and 20 g of tetrahydrofuran as a solvent were added to a 2 L flask. 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 is precipitated in 1 L of isopropyl alcohol, and the resulting white solid is dissolved again in 100 mL of methanol and 200 mL of tetrahydrofuran. 10 g of triethylamine and 10 g of water are added, and the acetyl group is deprotected at 70 ° C. for 5 hours. And neutralized with acetic acid. The reaction solution was concentrated and then dissolved in 100 mL of acetone, followed by precipitation, filtration and drying at 60 ° C. as described above 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)
Monomer 4: 4-hydroxystyrene: coumarin = 0.23: 0.65: 0.12
Weight average molecular weight (Mw) = 7,200
Molecular weight distribution (Mw / Mn) = 1.94
This polymer is designated as (Polymer 13).

[Polymer Synthesis Example 14]
In a 2 L flask, 9.0 g of monomer 1, 5.3 g of 4-hydroxyphenyl methacrylate, 3-oxo-2,7-dioxatricyclo [4.2.1.0 ^4,8 ] nonane-9 methacrylate -6.7 g of 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)
Monomer 1: 4-hydroxyphenyl methacrylate: 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) = 8,100
Molecular weight distribution (Mw / Mn) = 1.99
This polymer compound is referred to as (Polymer 14).

[Polymer Synthesis Example 15]
In a 2 L flask, 9.0 g of monomer 1, 5.3 g of 4-hydroxyphenyl methacrylate, 3-oxo-2,7-dioxatricyclo [4.2.1.0 ^4,8 ] nonane-9 methacrylate -6.7 g of yl, 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)
Monomer 1: 4-hydroxyphenyl methacrylate: 3-oxo-2,7-dioxatricyclo [4.2.1.0 ^4,8 ] nonan-9-yl methacrylate: PAG monomer 2 = 0.30: 0.30: 0.30: 0.10
Weight average molecular weight (Mw) = 8,900
Molecular weight distribution (Mw / Mn) = 1.89
This polymer compound is referred to as (Polymer 15).

[Polymer Synthesis Example 16]
In a 2 L flask, 9.0 g of monomer 1, 5.3 g of 4-hydroxyphenyl methacrylate, 3-oxo-2,7-dioxatricyclo [4.2.1.0 ^4,8 ] nonane-9 methacrylate -6.7 g of yl, 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)
Monomer 1: 4-hydroxyphenyl methacrylate: 3-oxo-2,7-dioxatricyclo [4.2.1.0 ^4,8 ] nonan-9-yl methacrylate: PAG monomer 3 = 0.30: 0.30: 0.30: 0.10
Weight average molecular weight (Mw) = 7,700
Molecular weight distribution (Mw / Mn) = 1.93
This polymer compound is referred to as (Polymer 16).

[Polymer Synthesis Example 17]
In a 2 L flask, 4.5 g of monomer 1 and 3-ethyl-3-exotetracyclomethacrylate [4.4.0.1 ^2,5 . 1 ^7,10] dodecanyl 4.1 g, 4-hydroxyphenyl methacrylate 5.3 g, methacrylic acid-2,7-dihydro-2-oxobenzo [C] furan-5-yl 6.5 g, 5 of PAG monomer 3. 6 g of tetrahydrofuran as a solvent 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)
Monomer 1: Methacrylic acid-3-ethyl-3-exotetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodecanyl: 4-hydroxyphenyl methacrylate: methacrylic acid-2,7-dihydro-2-oxobenzo [C] furan-5-yl: PAG monomer 3 = 0.15: 0.15: 0.30 : 0.30: 0.10
Weight average molecular weight (Mw) = 7,900
Molecular weight distribution (Mw / Mn) = 1.79
This polymer compound is referred to as (Polymer 17).

[Polymer Synthesis Example 18]
In a 2 L flask, 9.0 g of monomer 1, 6.4 g of 6-acetoxy-2-vinylnaphthalene, 3-oxo-2,7-dioxatricyclo [4.2.1.0 ^4,8 ] nonane methacrylate 6.7 g of -9-yl, 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 is precipitated in 1 L of isopropyl alcohol, and the resulting white solid is dissolved again in 100 mL of methanol and 200 mL of tetrahydrofuran. 10 g of triethylamine and 10 g of water are added, and the acetyl group is deprotected at 70 ° C. for 5 hours. And neutralized with acetic acid. The reaction solution was concentrated and then dissolved in 100 mL of acetone, followed by precipitation, filtration and drying at 60 ° C. as described above 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)
Monomer 1: 6-hydroxy-2-vinylnaphthalene: 3-oxo-2,7-dioxatricyclo [4.2.1.0 ^4,8 ] nonan-9-yl methacrylate: PAG monomer 3 = 0. 30: 0.30: 0.30: 0.10
Weight average molecular weight (Mw) = 7,900
Molecular weight distribution (Mw / Mn) = 1.92
This polymer is designated as (Polymer 18).

[Polymer Synthesis Example 19]
In a 2 L flask, 9.0 g of monomer 1, 6.5 g of methacrylic acid (5-hydroxyindan-2-yl), 3-oxo-2,7-dioxatricyclomethacrylate [4.2.1.0 ^{4 , 8} ] Nonane-9-yl 6.7 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)
Monomer 1: Methacrylic acid (5-hydroxyindan-2-yl): 3-oxo-2,7-dioxatricyclo [4.2.1.0 ^4,8 ] nonan-9-yl methacrylate: PAG monomer 3 = 0.30: 0.30: 0.30: 0.10
Weight average molecular weight (Mw) = 8,100
Molecular weight distribution (Mw / Mn) = 1.91
This polymer compound is referred to as (Polymer 19).

[Polymer Synthesis Example 20]
In a 2 L flask, 9.0 g of monomer 1, 7.4 g of methacrylic acid (5,8-dihydroxy-1,2,3,4-tetrahydronaphthalen-2-yl), 3-oxo-2,7-dimethacrylate 6.7 g of oxatricyclo [4.2.1.0 ^4,8 ] nonan-9-yl, 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)
Monomer 1: Methacrylic acid (5,8-dihydroxy-1,2,3,4-tetrahydronaphthalen-2-yl): 3-oxo-2,7-dioxatricyclomethacrylic acid [4.2.1.0 ^4,8 ] nonan-9-yl: PAG monomer 3 = 0.30: 0.20: 0.40: 0.10
Weight average molecular weight (Mw) = 8,800
Molecular weight distribution (Mw / Mn) = 2.06
This polymer compound is referred to as (Polymer 20).

[Polymer Synthesis Example 21]
In a 2 L flask, 9.0 g of monomer 1, 7.4 g of methacrylic acid (6-hydroxycoumarin-3-yl), 3-oxo-2,7-dioxatricyclomethacrylate [4.2.1.0 ^{4 , 8} ] Nonane-9-yl 6.7 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)
Monomer 1: methacrylic acid (6-hydroxycoumarin-3-yl): 3-oxo-2,7-dioxatricyclo [4.2.1.0 ^4,8 ] nonan-9-yl methacrylate: PAG monomer 3 = 0.30: 0.20: 0.40: 0.10
Weight average molecular weight (Mw) = 8,900
Molecular weight distribution (Mw / Mn) = 1.84
This polymer compound is referred to as (Polymer 21).

[Polymer Synthesis Example 22]
In a 2 L flask, 14.4 g of monomer 2, 5.3 g of methacrylate 4-hydroxyphenyl, 3-oxo-2,7-dioxatricyclo [4.2.1.0 ^4,8 ] nonane-9 methacrylate -6.7 g of yl, 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)
Monomer 2: 4-hydroxyphenyl methacrylate: 3-oxo-2,7-dioxatricyclo [4.2.1.0 ^4,8 ] nonan-9-yl methacrylate: PAG monomer 3 = 0.30: 0.30: 0.30: 0.10
Weight average molecular weight (Mw) = 8,700
Molecular weight distribution (Mw / Mn) = 1.99
This polymer compound is referred to as (Polymer 22).

[Polymer Synthesis Example 23]
In a 2 L flask, 9.0 g of monomer 1, 4.5 g of methacrylic acid-4-hydroxy-1-naphthalene, 3-oxo-2,7-dioxatricyclo methacrylate [4.2.1.0 ^4,8 6.7 g of nonan-9-yl, 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)
Monomer 1: methacrylic acid-4-hydroxy-1-naphthalene: 3-oxo-2,7-dioxatricyclo [4.2.1.0 ^4,8 ] nonan-9-yl methacrylate: PAG monomer 3 = 0.30: 0.20: 0.40: 0.10
Weight average molecular weight (Mw) = 7,500
Molecular weight distribution (Mw / Mn) = 1.76
This polymer is designated as (Polymer 23).

[Polymer Synthesis Example 24]
In a 2 L flask, 9.0 g of monomer 5, 5.3 g of 4-hydroxyphenyl methacrylate, 3-oxo-2,7-dioxatricyclo [4.2.1.0 ^4,8 ] nonane-9 methacrylate -6.7 g of yl, 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)
Monomer 5: 4-hydroxyphenyl methacrylate: 3-oxo-2,7-dioxatricyclo [4.2.1.0 ^4,8 ] nonan-9-yl methacrylate: PAG monomer 3 = 0.30: 0.30: 0.30: 0.10
Weight average molecular weight (Mw) = 7,700
Molecular weight distribution (Mw / Mn) = 1.98
This polymer is designated as (Polymer 24).

[Polymer Synthesis Example 25]
To a 2 L flask, 9.0 g of monomer 1, 5.3 g of 4-hydroxyphenyl methacrylate, 6.7 g of adhesion monomer 1, 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)
Monomer 1: 4-hydroxyphenyl methacrylate: Adhesive monomer 1: PAG monomer 3 = 0.30: 0.30: 0.30: 0.10
Weight average molecular weight (Mw) = 7,700
Molecular weight distribution (Mw / Mn) = 1.77
This polymer is designated as (Polymer 25).

[Polymer Synthesis Example 26]
9.0 g of monomer 1, 5.3 g of 4-hydroxyphenyl methacrylate, 7.4 g of adhesive monomer 2, 5.6 g of PAG monomer 3 and 40 g of tetrahydrofuran as a solvent were added to a 2 L flask. 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)
Monomer 1: 4-hydroxyphenyl methacrylate: Adhesive monomer 2: PAG monomer 3 = 0.30: 0.30: 0.30: 0.10
Weight average molecular weight (Mw) = 7,500
Molecular weight distribution (Mw / Mn) = 1.75
This polymer is designated as (Polymer 26).

[Polymer Synthesis Example 27]
In a 2 L flask, 4.5 g of monomer 1, 2- (7-oxanorbornan-2-yl) cyclopentyl methacrylate 5.0 g, 4-hydroxyphenyl methacrylate 4.4 g, methacrylic acid-2,7-dihydro-2 -6.5 g of oxobenzo [C] furan-5-yl, 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)
Monomer 1: 2- (7-oxanorbornan-2-yl) methacrylate methacrylate: 4-hydroxyphenyl methacrylate: methacrylate-2,7-dihydro-2-oxobenzo [C] furan-5-yl: PAG monomer 3 = 0.15: 0.20: 0.25: 0.30: 0.10
Weight average molecular weight (Mw) = 7,500
Molecular weight distribution (Mw / Mn) = 1.75
This polymer is designated as (Polymer 27).

[Polymer Synthesis Example 28]
In a 2 L flask, 4.5 g of monomer 1, 3.6 g of methacrylic acid 1-ethylcyclopentyl ester, 4.4 g of methacrylic acid 4-hydroxyphenyl, methacrylic acid-2,7-dihydro-2-oxobenzo [C] furan-5 -6.5 g of yl, 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)
Monomer 1: Methacrylic acid 1-ethylcyclopentyl ester: 4-hydroxyphenyl methacrylate: Methacrylic acid-2,7-dihydro-2-oxobenzo [C] furan-5-yl: PAG monomer 3 = 0.15: 0.20 : 0.25: 0.30: 0.10
Weight average molecular weight (Mw) = 7,300
Molecular weight distribution (Mw / Mn) = 1.73
This polymer is designated as (Polymer 28).

[Polymer Synthesis Example 29]
To a 2 L flask, 6.2 g of monomer 5, 13.0 g of 4-acetoxystyrene, 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 is precipitated in 1 L of isopropyl alcohol, and the resulting white solid is dissolved again in 100 mL of methanol and 200 mL of tetrahydrofuran. 10 g of triethylamine and 10 g of water are added, and the acetyl group is deprotected at 70 ° C. for 5 hours. And neutralized with acetic acid. The reaction solution was concentrated and then dissolved in 100 mL of acetone, followed by precipitation, filtration and drying at 60 ° C. as described above 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)
Monomer 5: 4-hydroxystyrene = 0.20: 0.80
Weight average molecular weight (Mw) = 8,300
Molecular weight distribution (Mw / Mn) = 1.63
This polymer is designated as (Polymer 29).

[Comparative Synthesis Example 1]
The following polymers were synthesized by the same method as in the above polymer synthesis example.
Copolymer composition ratio (molar ratio)
Hydroxystyrene: Methacrylic acid 1-ethylcyclopentyl ester = 0.70: 0.30
Weight average molecular weight (Mw) = 9,300
Molecular weight distribution (Mw / Mn) = 1.86
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 polymer synthesis example.
Copolymer composition ratio (molar ratio)
Hydroxystyrene: Methacrylic acid 1-ethyladamantyl ester = 0.77: 0.23
Weight average molecular weight (Mw) = 8,100
Molecular weight distribution (Mw / Mn) = 1.96
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 polymer synthesis example.
Copolymer composition ratio (molar ratio)
Hydroxystyrene: Methacrylic acid 1-ethylcyclopentyl ester: Indene = 0.73: 0.17: 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 3).

[Comparative Synthesis Example 4]
The following polymers were synthesized by the same method as in the above polymer synthesis example.
Copolymer composition ratio (molar ratio)
Hydroxystyrene: 1-ethylcyclopentyl ester of methacrylic acid: acenaphthylene = 0.75: 0.15: 0.10
Weight average molecular weight (Mw) = 7,200
Molecular weight distribution (Mw / Mn) = 1.79
This polymer compound is referred to as (Comparative Polymer 4).

[Comparative Synthesis Example 5]
The following polymers were synthesized by the same method as in the above polymer synthesis example.
Copolymer composition ratio (molar ratio)
Hydroxystyrene: Tetrahydronaphthalen-1-yl methacrylate = 0.70: 0.30
Weight average molecular weight (Mw) = 7,200
Molecular weight distribution (Mw / Mn) = 1.71
This polymer compound is referred to as (Comparative Polymer 5).

[Comparative Synthesis Example 6]
The following polymers were synthesized by the same method as in the above polymer synthesis example.
Copolymer composition ratio (molar ratio)
Hydroxystyrene: Indan-1-yl methacrylate = 0.70: 0.30
Weight average molecular weight (Mw) = 7,300
Molecular weight distribution (Mw / Mn) = 1.79
This polymer compound is referred to as (Comparative Polymer 6).

[Comparative Synthesis Example 7]
The following polymers were synthesized by the same method as in the above polymer synthesis example.
Copolymer composition ratio (molar ratio)
Methacrylic acid 1-ethylcyclopentyl ester: 4-hydroxyphenyl methacrylate: 3-oxo-2,7-dioxatricyclo [4.2.1.0 ^4,8 ] nonan-9-yl methacrylate: PAG monomer 3 = 0.30: 0.30: 0.30: 0.10
Weight average molecular weight (Mw) = 7,900
Molecular weight distribution (Mw / Mn) = 1.89
This polymer compound is referred to as (Comparative Polymer 7).

[Examples and Comparative Examples]
Using the polymer compound synthesized above, a solution prepared by dissolving the composition shown in Tables 1 and 2 in a solvent in which 100 ppm of surfactant FC-4430 manufactured by Sumitomo 3M Limited was dissolved as a surfactant, A positive resist material was prepared by filtering through a 0.2 μm size filter.
Each composition in Tables 1 and 2 is as follows.
Polymers 1 to 29: Polymer compound comparison polymers obtained in the above polymer synthesis examples 1 to 29 Polymers 1 to 7: Polymer compound organic solvents obtained in the above comparison synthesis examples 1 to 7: PGMEA (propylene glycol monomethyl ether acetate)
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 using a clean track Mark 5 (manufactured by Tokyo Electron Co., Ltd.) on a Si substrate having a diameter of 6 inches and subjected to HMDS (hexamethyldisilazane) vapor prime treatment. A 100 nm resist film was prepared by pre-baking at 110 ° C. for 60 seconds. To 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 for 60 seconds on a hot plate using a clean track Mark 5 (manufactured by Tokyo Electron Ltd.), and paddle development was performed for 30 seconds with a 2.38 mass% TMAH aqueous solution. A positive pattern was obtained.
The obtained resist pattern was evaluated as follows.
The minimum dimension in the exposure amount for resolving 120 nm line and space at 1: 1 was taken as the resolving power, and 120 nm LS line width roughness (LWR) was measured by SEM.
Tables 1 and 2 show the results of resist composition, sensitivity and resolution in EB exposure.

Evaluation of dry etching resistance In the dry etching resistance test, a polymer solution prepared by dissolving 10 g of cyclohexanone in 2 g of each polymer and filtered through a 0.2 μm size filter was formed on a Si substrate by spin coating, and the thickness was 300 nm. The film was evaluated under the following conditions.
Etching test with CHF ₃ / CF ₄ gas:
Using a dry etching apparatus TE-8500P manufactured by Tokyo Electron Ltd., the film thickness difference between the polymer films 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 3.

  From the results shown in Tables 1 and 2, the resist material using the polymer compound of the present invention has sufficient resolution, sensitivity, and edge roughness, and when a polymer type acid generator is copolymerized, the conventional acid resistance is not obtained. Even if a stable group is used, the resolution performance and edge roughness performance are further improved and may be superior to the examples of the present invention that do not contain a polymer type acid generator. Due to the synergistic effect of copolymerizing the generator, it showed very good resolution performance and small edge roughness. Further, from the results of Table 3, it was found that the film has excellent dry etching resistance since the difference in film thickness after etching is small.

Claims (11)

A positive resist material characterized in that a resin in which a hydrogen atom of a carboxyl group is substituted with an acid labile group represented by the following general formula (1) is used as a base resin.

Wherein R ¹ and R ² are a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy group, an alkanoyl group, an alkoxycarbonyl group, a hydroxy group, a nitro group, an aryl group having 6 to 10 carbon atoms, a halogen atom, Or a cyano group, wherein R is a linear, branched or cyclic alkyl group having 1 to 12 carbon atoms which may have a hydrogen atom, an oxygen atom or a sulfur atom, an alkenyl group having 2 to 12 carbon atoms, A C2-C12 alkynyl group or a C6-C10 aryl group, m and n are integers of 1-4.) To claim 1 having a weight-average molecular weight having a unit a Ri return is that Repetitive represented by the following general formula (2) is characterized in that in the base resin a polymer compound ranges from 1,000 to 500,000 The positive resist material described.

(Wherein R ¹ , R ² , R, m and n are as described above. X ¹ is a single bond, or —C (═O) —O—R ⁴ —, a phenylene group or a naphthylene group, R ⁴ is a linear, branched or cyclic alkylene group having 1 to 10 carbon atoms and may have an ester group, an ether group or a lactone ring, and R ³ is a hydrogen atom or a methyl group. ) Formula in addition to the indicated that Repetitive return unit a in (2), hydroxy group, lactone ring, an ether group, an ester group, by copolymerizing repeating units b having a carbonyl group, an adhesive group selected from cyano group Polymer compound having a weight average molecular weight in the range of 1,000 to 500,000 (provided that 0 <a <1.0, 0 <b <1.0, 0.05 ≦ a + b ≦ 1.0) The resist material according to claim 2, wherein a base resin is used.   The resist material according to claim 3, wherein the repeating unit b is a repeating unit having a phenolic hydroxyl group. The resist material according to claim 4, wherein the repeating unit having a phenolic hydroxyl group is selected from b1 to b8 represented by the following general formula (3).

(Wherein X ² and X ³ are a single bond or —C (═O) —O—R ⁶ —, X ⁴ and X ⁵ are —C (═O) —O—R ⁶ —, R ⁶ is a single bond or a linear, branched or cyclic alkylene group having 1 to 10 carbon atoms, R ⁵ is the same or different hydrogen atom or methyl group, and Y ¹ and Y ² are methylene groups. Or an ethylene group, Z is a methylene group, an oxygen atom or a sulfur atom, and p is 1 or 2.) The resist according to any one of claims 3 to 5, wherein the polymer compound is obtained by copolymerizing a repeating unit selected from repeating units c1 to c5 represented by the following general formula (4). material.

(In the formula, R ^{9 to} R ¹³ are each a hydrogen atom, an alkyl group having 1 to 30 carbon atoms, an alkyl group partially or entirely substituted with a halogen atom, an alkoxy group, an alkanoyl group, or an alkoxycarbonyl group; -10 aryl group, halogen atom, or 1,1,1,3,3,3-hexafluoro-2-propanol group, Z is a methylene group, oxygen atom or sulfur atom.) Polymer compound, general formula (2) indicated that Repetitive return unit a, hydroxyl group, lactone ring, ether group, an ester group, a carbonyl group, in addition to the repeating units (b) of the adhesive group selected from cyano group The resist material according to any one of claims 3 to 6, which is obtained by copolymerizing any one of repeating units d1 to d3 represented by the following general formula (5).

(Wherein 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 ³³ —, or —C (═O) —Y—R ³³ —. Y is an oxygen atom or NH, R ³³ is a linear, branched or cyclic alkylene group, phenylene group or alkenylene group having 1 to 6 carbon atoms, including 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 , R ³¹ are the same or different linear, branched or cyclic alkyl groups having 1 to 12 carbon atoms. And may contain a carbonyl group, an ester group or an ether group, or represents an aryl group having 6 to 12 carbon atoms or an aralkyl group having 7 to 20 carbon atoms, Z ₀ is a single bond, a methylene group or an ethylene group. , phenylene, fluorinated phenylene group, -O-R ³² , Or _{-C (= O) -Z 1 -R} 32 - is a .Z ₁ is an oxygen atom or NH, R ³² represents a linear 1 to 6 carbon atoms, branched or cyclic alkylene group, 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 counterion, 0 ≦ d1 ≦ 0.3, 0 ≦ d2 ≦ 0.3; 0 ≦ d3 ≦ 0.3 and 0 <d1 + d2 + d3 ≦ 0.3.)   The positive resist composition according to claim 1, further comprising a chemically amplified positive resist composition containing an organic solvent and an acid generator.   The positive resist composition according to claim 8, further comprising a dissolution control agent.   The positive resist composition according to claim 8 or 9, 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 10 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.