JP4488174B2 - Resist material and pattern forming method - Google Patents

Description

The present invention relates to a chemically amplified positive resist material used for microfabrication in a manufacturing process of a semiconductor element, particularly far ultraviolet rays, KrF excimer laser light (248 nm), ArF excimer laser light (193 nm), F ₂ laser light (157 nm). The present invention relates to a resist material such as a chemically amplified positive resist material suitable for use as a light source for exposure, and a pattern forming method.

  With the high integration and high speed of LSI, pattern rule miniaturization is progressing rapidly. The background of rapid progress in miniaturization includes higher NA of projection lenses, improved performance of resist materials, and shorter wavelengths. In particular, the shortening of the wavelength from i-line (365 nm) to KrF excimer laser (248 nm) has brought about a major change and has greatly contributed to device mass production after the 0.25 micron rule. At this time, in order to increase the resolution and sensitivity of the resist material, an acid-catalyzed chemically amplified positive resist material (Patent Document 1: Japanese Patent Publication No. 2-27660, Patent Document 2: JP-A 63-63) No. 27829) has excellent characteristics and has become a mainstream resist material particularly for deep ultraviolet lithography.

Resist materials for KrF excimer lasers are generally used in the 0.3 micron process, passed through the 0.25 micron rule, and are now applied to the mass production of the 0.18 micron rule. The 0.13 micron rule has been studied, and the momentum of miniaturization is increasingly accelerated. The shortening of the wavelength from the KrF excimer laser to the ArF excimer laser (193 nm) is expected to make the design rule finer than 0.13 μm, but novolak and polyvinylphenol resins that have been used in the past are around 193 nm. Therefore, it cannot be used as a base resin for resist. In order to ensure transparency and necessary dry etching resistance, acrylic resins and cycloolefin-based alicyclic resins have been studied (Patent Document 3: Japanese Patent Laid-Open No. 9-73173, Patent Document 4: Japanese Laid-open Patent Application No. Hei 5 (1998)). 10-10739 gazette, patent document 5: Unexamined-Japanese-Patent No. 9-230595, patent document 6: international publication 97/33198 pamphlet). Furthermore, with regard to the F ₂ laser (157 nm) that can be expected to be miniaturized to 0.10 μm or less, it becomes increasingly difficult to ensure transparency, acrylic resin does not transmit light at all, and carbonyl bonds are also formed in cycloolefins. It turns out that what it has has strong absorption. A polymer having a benzene ring has slightly improved absorption near a wavelength of 160 nm, but is far from a practical value. In a single-layer resist, a carbon-carbon double bond represented by a benzene ring and a carbon represented by a carbonyl group are represented. It has been found that reducing oxygen double bonds is a necessary condition for ensuring the transmittance (Non-patent Document 1: International Work Shop 157 nm Lithography MIT-LL Boston, MA May 5, 1999). It has been shown that introduction of fluorine is effective for improving the transmittance (Non-Patent Document 2: J. Vac. Sci. Technol. B 17 (6), Nov / Dec 1999). Many fluorine-containing polymers have been proposed as a polymer (Non-patent document 3: J. Photopolymer Sci. And Technol. Vol. 13 No. 4 (2000) p657-664 and Vol. 13 No. 4 (2000) p451-458. ) Does not reach the transmittance of polyhydroxystyrene and its derivatives in KrF excimer laser exposure, and poly (meth) acryl derivatives or polycycloolefin derivatives in ArF exposure.

  On the other hand, it is known that the two-layer resist method is excellent for forming a pattern with a high aspect ratio on a conventional stepped substrate. Further, in order to develop a two-layer resist film with a general alkali developer. Requires a high molecular silicone compound having a hydrophilic group such as a hydroxy group or a carboxyl group.

As a silicone-based chemically amplified positive resist material, a base resin in which a part of the phenolic hydroxyl group of polyhydroxybenzylsilsesquioxane, which is a stable alkali-soluble silicone polymer, is protected with a t-Boc group is used. A silicone-based chemically amplified positive resist material for a KrF excimer laser combined with an acid generator has been proposed (Patent Document 7: JP-A-6-118651, Non-Patent Document 4: SPIE Vol. 1925 (1993) p377) ). For ArF excimer lasers, a positive resist material based on a silsesquioxane in which cyclohexyl carboxylic acid is substituted with an acid labile group has been proposed (Patent Document 8: JP-A-10-324748). Gazette, patent document 9: JP-A-11-302382, non-patent document 5: SPIE Vol. 3333 (1998) p62). Further, for F ₂ lasers, a positive resist material based on silsesquioxane having hexafluoroisopropanol as a soluble group has been proposed (Patent Document 10: Japanese Patent Application Laid-Open No. 2002-55456). The above polymer contains polysilsesquioxane having a ladder skeleton formed by condensation polymerization of trialkoxysilane or trihalogenated silane in the main chain.

  Silicon-containing (meth) acrylic esters have been proposed as the base polymer for resist in which silicon is pendant on the side chain (Patent Document 11: JP-A-9-110938, Non-Patent Document 6: J. Photopolymer Sci. and Technol., Vol. 9 No. 3 (1996) p435-446).

  A disadvantage of the (meth) acrylic ester type silicon-containing polymer is that the dry etching resistance in oxygen plasma is weaker than that of the silsesquioxane polymer. This is because the silicon content is low and the difference in the polymer main skeleton. In addition, the (meth) acrylic ester siloxane pendant type has the disadvantages that it easily repels the developer and has poor wettability. In view of this, there has been proposed a polymer containing a (meth) acrylic ester, which is a trisilane or tetrasilane pendant type, which has a high silicon content and further has an acid-eliminating property on a silicon-containing group to improve alkali solubility. (Non-patent document 7: SPIE Vol. 3678 (1999) p214, p241, p562). Since this has a silicon-silicon bond, it absorbs at a wavelength of 200 nm or less, but is sufficiently transparent for a 248 nm KrF excimer laser and is used as a silicon-containing acid leaving group having excellent etching resistance. Studies on silicon-containing acid labile groups other than those described above have also been conducted (SPIE Vol. 3678 (1999) p420).

  The present inventors have also proposed novel acid labile groups into which silicon has been introduced (Patent Document 12: JP 2001-278918 A, Patent Document 13: JP 2001-158808 A). This has the advantage that it has excellent acid detachment properties and can prevent the occurrence of T-top profile, and further has a carbon atom between silicon atoms and no silicon-silicon bond. Therefore, the wavelength of ArF excimer laser In addition, it has the feature that it is sufficiently transparent.

  Here, a bilayer resist having a pendant methacrylate having a polyhedral oligosilsesquioxane (POSS) pendant has been reported. POSS has a saddle type structure, and Non-Patent Document 8: Macromolecules, Vol. 31, no. 15, p4970 (1998) report its synthesis method and curing characteristics when an epoxy is pendant. Non-Patent Document 9: Mater. Res. Soc. Symp. Vol. 636 D6.5. 1 (2001) reports the characteristics of POSS pendant methacrylic polymer drawn by EB. The present inventors have also proposed an allyl POSS polymer in Patent Document 15: Japanese Patent Application Laid-Open No. 2002-256033.

Patent Document 14: Japanese Patent Application Laid-Open No. 2001-305737 introduces an example in which a hexafluoropentyl alcohol pendant POSS substituted with an acid labile group is exposed at 157 nm, and Non-Patent Document 10: Proc. SPIE Vol. 5039 (2003) Lecture No. 49 shows the 157 nm exposure characteristics of the POSS pendant αCF ₃ acrylic polymer. Until now, silicon-containing group methacrylic ester polymer-based resist has generated outgas containing silicon in 157 nm exposure, and silicon-containing material adheres to the projection lens surface to reduce transmittance, and cannot be removed even by O ₂ cleaning. However, only ladder polymers with a silsesquioxane skeleton in the main chain have been considered to have no outgassing containing silicon. It was found that there was no outgassing.

  In terms of resolving power in lithography, silicon pendant bilayer resists such as POSS pendant (meth) acrylic copolymer and silicon pendant polyolefin are superior to silsesquioxane bilayer resists of main chain silicon. On the other hand, a silsesquioxane type bilayer resist is more advantageous for etching resistance in dry development for processing a base organic film with oxygen gas.

  In the present invention, both the resolving power and the etching resistance are obtained by using a mixture of polysilsesquioxane and silicon pendant (meth) acrylic copolymer or a mixture of polysilsesquioxane and silicon pendant polyolefin. We propose bi-layer resists that are also available.

JP-B-2-27660 JP 63-27829 A JP-A-9-73173 Japanese Patent Laid-Open No. 10-10739 Japanese Patent Laid-Open No. 9-230595 International Publication No. 97/33198 Pamphlet JP-A-6-118651 Japanese Patent Laid-Open No. 10-324748 JP-A-11-302382 JP 2002-55456 A JP-A-9-110938 JP 2001-278918 A JP 2001-158808 A JP 2001-305737 A Japanese Patent Laid-Open No. 2002-256033 International Work Shop 157 nm Lithography MIT-LL Boston, MA May 5, 1999 J. et al. Vac. Sci. Technol. B 17 (6), Nov / Dec 1999 J. et al. Photopolymer Sci. and Technol. Vol. 13 No. 4 (2000) p657-664 and Vol. 13 No. 4 (2000) p451-458 SPIE Vol. 1925 (1993) p377 SPIE Vol. 3333 (1998) p62 J. et al. Photopolymer Sci. and Technol. Vol. 9 No. 3 (1996) p435-446 SPIE Vol. 3678 (1999) p214, p241, p420, p562 Macromolecules, Vol. 31, no. 15, p4970 (1998) Mater. Res. Soc. Symp. Vol. 636 D6.5. 1 (2001) Proc. SPIE Vol. 5039 (2003) Lecture number 49

  The present invention has been made in view of the above circumstances, and has a high sensitivity, a high resolution, a low line edge roughness even at a high silicon content, and a pattern having a particularly high aspect ratio that does not generate residues and the like. It is an object of the present invention to provide a resist material such as a chemically amplified positive resist material and a pattern forming method that can be suitably used as a material for a two-layer resist method suitable for the above.

  As a result of intensive studies to achieve the above object, the present inventors have found that polysilsesquioxane and silicon pendant (meth) acrylic copolymer are mixed, or polysilsesquioxane and silicon pendant polyolefin are mixed. It has been found that the use of the mixture as a base is effective as a bilayer resist having both resolution and etching resistance, and has led to the present invention.

［式中、Ｒ ² は水素原子、メチル基、フッ素原子、トリフルオロメチル基、シアノ基、−ＣＨ ₂ Ｃ（＝Ｏ）−Ｏ−Ｒ ³ 、又は−ＣＨ ₂ −Ｏ−Ｒ ⁴ である。Ｒ ³ は炭素数１〜４の直鎖状又は分岐状のアルキル基、Ｒ ⁴ は水素原子、炭素数１〜４の直鎖状又は分岐状のアルキル基、又は炭素数１〜４の直鎖状又は分岐状のアシル基であり、Ｒ ⁴³ は同一又は異種の水素原子、炭素数１〜１０の直鎖状、分岐状又は環状のアルキル基もしくはフッ素化されたアルキル基、又は炭素数６〜１０のアリール基であり、これらの基はエーテル基、ラクトン環、エステル基、ヒドロキシ基又はシアノ基を含んでいてもよい。Ｒ ⁴² は単結合、又は下記一般式（９）

で示される連結基である。一般式（９）中、Ｒ ⁵⁰ 、Ｒ ⁵¹ は炭素数１〜１０の直鎖状、分岐状又は環状のアルキル基であり、Ｒ ⁵² は単結合、酸素原子、又は炭素数１〜４のアルキレン基である。Ｘはエステル基又はエーテル基である。Ｒ ⁴⁴ 〜Ｒ ⁴⁶ は炭素数１〜６の直鎖状、分岐状又は環状のアルキル基、又は炭素数６〜１０のアリール基、Ｒ ⁴⁷ 〜Ｒ ⁴⁹ は炭素数１〜６の直鎖状、分岐状又は環状のアルキル基、炭素数６〜１０のアリール基、トリメチルシリル基、又は式中の珪素原子とシロキサン結合もしくはシルアルキレン結合している珪素含有基であり、Ｒ ⁴⁷ とＲ ⁴⁸ 、Ｒ ⁴⁷ とＲ ⁴⁹ 、Ｒ ⁴⁸ とＲ ⁴⁹ が結合してこれらが結合する珪素原子と共にポリシロキサン環を形成してもよい。ｍは４〜４０の整数であり、ｔは２〜３０の整数であり、ｎは１〜２０の整数である。］
請求項２：
下記一般式（１’）
Ｒ¹ＳｉＸ₃ （１’）
で示されるシランモノマー又は上記一般式（１’）のシランモノマーと下記一般式（１’’）
Ｒ⁰ＳｉＸ₃ （１’’）
（式中、Ｒ¹、Ｘ、Ｒ⁰は上記と同じ意味を示す。）
で示されるシランモノマーとを加水分解・縮合することによって得られるオルガノポリシロキサンと、下記一般式（８）のｃ−１〜ｃ−３から選ばれる１種以上の繰り返し単位と下記一般式（１０）中のｄ１〜ｄ７から選ばれる少なくとも１種以上の酸によってアルカリ溶解性が向上する基を有する繰り返し単位とを共重合してなる高分子化合物を添加することを特徴とするレジスト材料。

［式中、Ｒ²は水素原子、メチル基、フッ素原子、トリフルオロメチル基、シアノ基、−ＣＨ₂Ｃ（＝Ｏ）−Ｏ−Ｒ³、又は−ＣＨ₂−Ｏ−Ｒ⁴である。Ｒ³は炭素数１〜４の直鎖状又は分岐状のアルキル基、Ｒ⁴は水素原子、炭素数１〜４の直鎖状又は分岐状のアルキル基、又は炭素数１〜４の直鎖状又は分岐状のアシル基であり、Ｒ⁴³は同一又は異種の水素原子、炭素数１〜１０の直鎖状、分岐状又は環状のアルキル基もしくはフッ素化されたアルキル基、又は炭素数６〜１０のアリール基であり、これらの基はエーテル基、ラクトン環、エステル基、ヒドロキシ基又はシアノ基を含んでいてもよい。Ｒ⁴²は単結合、又は下記一般式（９）

で示される連結基である。一般式（９）中、Ｒ⁵⁰、Ｒ⁵¹は炭素数１〜１０の直鎖状、分岐状又は環状のアルキル基であり、Ｒ⁵²は単結合、酸素原子、又は炭素数１〜４のアルキレン基である。Ｘはエステル基又はエーテル基である。Ｒ⁴⁴〜Ｒ⁴⁶は炭素数１〜６の直鎖状、分岐状又は環状のアルキル基、又は炭素数６〜１０のアリール基、Ｒ⁴⁷〜Ｒ⁴⁹は炭素数１〜６の直鎖状、分岐状又は環状のアルキル基、炭素数６〜１０のアリール基、トリメチルシリル基、又は式中の珪素原子とシロキサン結合もしくはシルアルキレン結合している珪素含有基であり、Ｒ⁴⁷とＲ⁴⁸、Ｒ⁴⁷とＲ⁴⁹、Ｒ⁴⁸とＲ⁴⁹が結合してこれらが結合する珪素原子と共にポリシロキサン環を形成してもよい。ｍは４〜４０の整数であり、ｔは２〜３０の整数であり、ｎは１〜２０の整数である。一般式（１０）の繰り返し単位ｄ１〜ｄ７中、Ｒ⁵³〜Ｒ⁵⁷は水素原子、フッ素原子、炭素数１〜２０のアルキル基、炭素数６〜２０のアリール基、炭素数１〜２０のハロアルキル基、又はシアノ基であり、Ａは酸不安定基を示し、ｚは０又は１であり、ｙは１又は２である。Ａ¹とＡ²の両方又はどちらか一方が酸不安定基であり、酸不安定基でない場合は、水素原子、炭素数１〜２０のアルキル基、又は密着性基である。］
請求項３：
下記一般式（１’）
Ｒ¹ＳｉＸ₃ （１’）
で示されるシランモノマー又は上記一般式（１’）のシランモノマーと下記一般式（１’’）
Ｒ⁰ＳｉＸ₃ （１’’）
（式中、Ｒ¹、Ｘ、Ｒ⁰は上記と同じ意味を示す。）
で示されるシランモノマーとを加水分解・縮合することによって得られるオルガノポリシロキサンと、下記一般式（１１）で示される繰り返し単位ｅと下記一般式（１０）中のｄ１〜ｄ７から選ばれる少なくとも１種以上の酸によってアルカリ溶解性が向上する基を有する繰り返し単位とを共重合してなる高分子化合物を添加することを特徴とするレジスト材料。

［式中、式（１１）中のＲ⁵⁸は水素原子、又は炭素数１〜１０の直鎖状、分岐状又は環状のアルキル基、Ｒ⁵⁹は単結合、炭素数１〜１０の直鎖状、分岐状又は環状のアルキレン基、又は上記一般式（９）で示される連結基、Ｒ⁶⁰、Ｒ⁶¹、Ｒ⁶²は同一又は異種の水素原子、炭素数１〜２０のアルキル基、又はハロアルキル基、炭素数６〜２０のアリール基、トリメチルシリル基、又は式中の珪素原子とシロキサン結合もしくはシルアルキレン結合している珪素含有基であり、あるいはＲ⁶⁰とＲ⁶¹、Ｒ⁶⁰とＲ⁶²又はＲ⁶¹とＲ⁶²は、互いに結合してこれらが結合する珪素原子と共に珪素原子数３〜２０のポリシロキサン環を形成してもよい。一般式（１０）の繰り返し単位ｄ１〜ｄ７中、Ｒ⁵³〜Ｒ⁵⁷は水素原子、フッ素原子、炭素数１〜２０のアルキル基、炭素数６〜２０のアリール基、炭素数１〜２０のハロアルキル基、又はシアノ基であり、Ａは酸不安定基を示し、ｚは０又は１であり、ｙは１又は２である。Ａ¹とＡ²の両方又はどちらか一方が酸不安定基であり、酸不安定基でない場合は、水素原子、炭素数１〜２０のアルキル基、又は密着性基である。］
請求項４：
下記一般式（１）で示される繰り返し単位ａを有する高分子化合物と、下記一般式（８）のｃ−１〜ｃ−３から選ばれる１種以上の繰り返し単位を有する高分子化合物を添加することを特徴とするレジスト材料。

［式中、Ｒ ¹ は酸分解基を有する有機基、ｘは１．０〜１．５の範囲であり、Ｒ ² は水素原子、メチル基、フッ素原子、トリフルオロメチル基、シアノ基、−ＣＨ ₂ Ｃ（＝Ｏ）−Ｏ−Ｒ ³ 、又は−ＣＨ ₂ −Ｏ−Ｒ ⁴ である。Ｒ ³ は炭素数１〜４の直鎖状又は分岐状のアルキル基、Ｒ ⁴ は水素原子、炭素数１〜４の直鎖状又は分岐状のアルキル基、又は炭素数１〜４の直鎖状又は分岐状のアシル基であり、Ｒ ⁴³ は同一又は異種の水素原子、炭素数１〜１０の直鎖状、分岐状又は環状のアルキル基もしくはフッ素化されたアルキル基、又は炭素数６〜１０のアリール基であり、これらの基はエーテル基、ラクトン環、エステル基、ヒドロキシ基又はシアノ基を含んでいてもよい。Ｒ ⁴² は単結合、又は下記一般式（９）

で示される連結基である。一般式（９）中、Ｒ ⁵⁰ 、Ｒ ⁵¹ は炭素数１〜１０の直鎖状、分岐状又は環状のアルキル基であり、Ｒ ⁵² は単結合、酸素原子、又は炭素数１〜４のアルキレン基である。Ｘはエステル基又はエーテル基である。Ｒ ⁴⁴ 〜Ｒ ⁴⁶ は炭素数１〜６の直鎖状、分岐状又は環状のアルキル基、又は炭素数６〜１０のアリール基、Ｒ ⁴⁷ 〜Ｒ ⁴⁹ は炭素数１〜６の直鎖状、分岐状又は環状のアルキル基、炭素数６〜１０のアリール基、トリメチルシリル基、又は式中の珪素原子とシロキサン結合もしくはシルアルキレン結合している珪素含有基であり、Ｒ ⁴⁷ とＲ ⁴⁸ 、Ｒ ⁴⁷ とＲ ⁴⁹ 、Ｒ ⁴⁸ とＲ ⁴⁹ が結合してこれらが結合する珪素原子と共にポリシロキサン環を形成してもよい。ｍは４〜４０の整数であり、ｔは２〜３０の整数であり、ｎは１〜２０の整数である。］
請求項５：
下記一般式（１）で示される繰り返し単位ａを有する高分子化合物と、下記一般式（８）のｃ−１〜ｃ−３から選ばれる１種以上の繰り返し単位と下記一般式（１０）中のｄ１〜ｄ７から選ばれる少なくとも１種以上の酸によってアルカリ溶解性が向上する基を有する繰り返し単位とを共重合してなる高分子化合物を添加することを特徴とするレジスト材料。

［式中、Ｒ¹は酸分解基を有する有機基、ｘは１．０〜１．５の範囲であり、Ｒ²は水素原子、メチル基、フッ素原子、トリフルオロメチル基、シアノ基、−ＣＨ₂Ｃ（＝Ｏ）−Ｏ−Ｒ³、又は−ＣＨ₂−Ｏ−Ｒ⁴である。Ｒ³は炭素数１〜４の直鎖状又は分岐状のアルキル基、Ｒ⁴は水素原子、炭素数１〜４の直鎖状又は分岐状のアルキル基、又は炭素数１〜４の直鎖状又は分岐状のアシル基であり、Ｒ⁴³は同一又は異種の水素原子、炭素数１〜１０の直鎖状、分岐状又は環状のアルキル基もしくはフッ素化されたアルキル基、又は炭素数６〜１０のアリール基であり、これらの基はエーテル基、ラクトン環、エステル基、ヒドロキシ基又はシアノ基を含んでいてもよい。Ｒ⁴²は単結合、又は下記一般式（９）

で示される連結基である。一般式（９）中、Ｒ⁵⁰、Ｒ⁵¹は炭素数１〜１０の直鎖状、分岐状又は環状のアルキル基であり、Ｒ⁵²は単結合、酸素原子、又は炭素数１〜４のアルキレン基である。Ｘはエステル基又はエーテル基である。Ｒ⁴⁴〜Ｒ⁴⁶は炭素数１〜６の直鎖状、分岐状又は環状のアルキル基、又は炭素数６〜１０のアリール基、Ｒ⁴⁷〜Ｒ⁴⁹は炭素数１〜６の直鎖状、分岐状又は環状のアルキル基、炭素数６〜１０のアリール基、トリメチルシリル基、又は式中の珪素原子とシロキサン結合もしくはシルアルキレン結合している珪素含有基であり、Ｒ⁴⁷とＲ⁴⁸、Ｒ⁴⁷とＲ⁴⁹、Ｒ⁴⁸とＲ⁴⁹が結合してこれらが結合する珪素原子と共にポリシロキサン環を形成してもよい。ｍは４〜４０の整数であり、ｔは２〜３０の整数であり、ｎは１〜２０の整数である。一般式（１０）の繰り返し単位ｄ１〜ｄ７中、Ｒ⁵³〜Ｒ⁵⁷は水素原子、フッ素原子、炭素数１〜２０のアルキル基、炭素数６〜２０のアリール基、炭素数１〜２０のハロアルキル基、又はシアノ基であり、Ａは酸不安定基を示し、ｚは０又は１であり、ｙは１又は２である。Ａ¹とＡ²の両方又はどちらか一方が酸不安定基であり、酸不安定基でない場合は、水素原子、炭素数１〜２０のアルキル基、又は密着性基である。］
請求項６：
下記一般式（１）で示される繰り返し単位ａを有する高分子化合物と、下記一般式（１１）で示される繰り返し単位ｅと下記一般式（１０）中のｄ１〜ｄ７から選ばれる少なくとも１種以上の酸によってアルカリ溶解性が向上する基を有する繰り返し単位とを共重合してなる高分子化合物を添加することを特徴とするレジスト材料。

［式中、Ｒ¹は酸分解基を有する有機基、ｘは１．０〜１．５の範囲であり、式（１１）中のＲ⁵⁸は水素原子、又は炭素数１〜１０の直鎖状、分岐状又は環状のアルキル基、Ｒ⁵⁹は単結合、炭素数１〜１０の直鎖状、分岐状又は環状のアルキレン基、又は上記一般式（９）で示される連結基、Ｒ⁶⁰、Ｒ⁶¹、Ｒ⁶²は同一又は異種の水素原子、炭素数１〜２０のアルキル基、又はハロアルキル基、炭素数６〜２０のアリール基、トリメチルシリル基、又は式中の珪素原子とシロキサン結合もしくはシルアルキレン結合している珪素含有基であり、あるいはＲ⁶⁰とＲ⁶¹、Ｒ⁶⁰とＲ⁶²又はＲ⁶¹とＲ⁶²は、互いに結合してこれらが結合する珪素原子と共に珪素原子数３〜２０のポリシロキサン環を形成してもよい。一般式（１０）の繰り返し単位ｄ１〜ｄ７中、Ｒ⁵³〜Ｒ⁵⁷は水素原子、フッ素原子、炭素数１〜２０のアルキル基、炭素数６〜２０のアリール基、炭素数１〜２０のハロアルキル基、又はシアノ基であり、Ａは酸不安定基を示し、ｚは０又は１であり、ｙは１又は２である。Ａ¹とＡ²の両方又はどちらか一方が酸不安定基であり、酸不安定基でない場合は、水素原子、炭素数１〜２０のアルキル基、又は密着性基である。］
請求項７：
（１）請求項１乃至６のいずれか１項記載の高分子化合物混合物、
（２）酸発生剤、
（３）有機溶剤
を含有してなる化学増幅ポジ型レジスト材料。
請求項８：
（１）請求項１乃至６のいずれか１項記載の高分子化合物混合物、
（２）酸発生剤、
（３）有機溶剤、
（４）溶解阻止剤
を含有してなる化学増幅ポジ型レジスト材料。
請求項９：
更に、塩基性化合物を添加してなる請求項７又は８記載の化学増幅ポジ型レジスト材料。
請求項１０：
（１）請求項７乃至９のいずれか１項記載のレジスト材料を基板上に塗布する工程と、
（２）次いで、加熱処理後、フォトマスクを介して波長３００ｎｍ以下の高エネルギー線もしくは電子線で露光する工程と、
（３）必要に応じて加熱処理した後、現像液を用いて現像する工程と
を含むことを特徴とするパターン形成方法。
請求項１１：
請求項１０において、パターン形成後、酸素プラズマエッチングにより下地の加工を行うレジストパターン形成方法。
請求項１２：
請求項１０において、パターン形成後、塩素又は臭素を含むハロゲンガスによるエッチングにより下地の加工を行うレジストパターン形成方法。 That is, the present invention provides the following resist material and pattern forming method.
Claim 1:
The following general formula (1 ')
R ¹ SiX ₃ (1 ')
(Wherein R ¹ is an organic group having an acid-decomposable group, X is a halogen atom, a hydroxy group, an alkoxy group having 1 to 10 carbon atoms, or an acyl group having 1 to 10 carbon atoms.)
Or a silane monomer of the above general formula (1 ′) and the following general formula (1 ″)
R ⁰ SiX ₃ (1 ″)
(In the formula, R ⁰ is an organic group having an adhesive group, and X has the same meaning as described above.)
An organopolysiloxane obtained by hydrolyzing and condensing the silane monomer represented by formula (8), and a polymer compound having one or more repeating units selected from c-1 to c-3 of the following general formula (8): A resist material obtained by adding

[Wherein, R ² represents a hydrogen atom, a methyl group, a fluorine atom, a trifluoromethyl group, a cyano group, —CH ₂ C (═O) —O—R ³ , or —CH ₂ —O—R ⁴ . R ³ is a linear or branched alkyl group having 1 to 4 carbon atoms, R ⁴ is a hydrogen atom, a linear or branched alkyl group having 1 to 4 carbon atoms, or a linear chain having 1 to 4 carbon atoms. Or R ⁴³ is the same or different hydrogen atom, a linear, branched or cyclic alkyl group or fluorinated alkyl group having 1 to 10 carbon atoms, or 6 to 6 carbon atoms. 10 aryl groups, and these groups may contain an ether group, a lactone ring, an ester group, a hydroxy group or a cyano group. R ⁴² represents a single bond or the following general formula (9)

It is a coupling group shown by these. In General Formula (9), R ⁵⁰ and R ⁵¹ are linear, branched or cyclic alkyl groups having 1 to 10 carbon atoms, and R ⁵² is a single bond, an oxygen atom, or alkylene having 1 to 4 carbon atoms. It is a group. X is an ester group or an ether group. R ^{44 to} R ⁴⁶ are linear, branched or cyclic alkyl groups having 1 to 6 carbon atoms, or aryl groups having 6 to 10 carbon atoms, R ^{47 to} R ⁴⁹ are linear groups having 1 to 6 carbon atoms, A branched or cyclic alkyl group, an aryl group having 6 to 10 carbon atoms, a trimethylsilyl group, or a silicon-containing group in which a silicon atom in the formula is bonded to a siloxane bond or a silalkylene bond, and R ⁴⁷ and R ⁴⁸ , R ⁴⁷ And R ⁴⁹ , R ⁴⁸ and R ⁴⁹ may combine to form a polysiloxane ring together with the silicon atom to which they are bonded. m is an integer of 4 to 40, t is an integer of 2 to 30, and n is an integer of 1 to 20. ]
Claim 2:
The following general formula (1 ')
R ¹ SiX ₃ (1 ')
Or a silane monomer of the above general formula (1 ′) and the following general formula (1 ″)
R ⁰ SiX ₃ (1 ″)
(In the formula, R ¹ , X and R ⁰ have the same meaning as described above.)
An organopolysiloxane obtained by hydrolysis and condensation with a silane monomer represented by formula (1), one or more repeating units selected from c-1 to c-3 of the following general formula (8), and the following general formula (10 And a polymer compound obtained by copolymerizing a repeating unit having a group that improves alkali solubility with at least one acid selected from d1 to d7.

[Wherein, R ² represents a hydrogen atom, a methyl group, a fluorine atom, a trifluoromethyl group, a cyano group, —CH ₂ C (═O) —O—R ³ , or —CH ₂ —O—R ⁴ . R ³ is a linear or branched alkyl group having 1 to 4 carbon atoms, R ⁴ is a hydrogen atom, a linear or branched alkyl group having 1 to 4 carbon atoms, or a linear chain having 1 to 4 carbon atoms. Or R ⁴³ is the same or different hydrogen atom, a linear, branched or cyclic alkyl group or fluorinated alkyl group having 1 to 10 carbon atoms, or 6 to 6 carbon atoms. 10 aryl groups, and these groups may contain an ether group, a lactone ring, an ester group, a hydroxy group or a cyano group. R ⁴² represents a single bond or the following general formula (9)

It is a coupling group shown by these. In General Formula (9), R ⁵⁰ and R ⁵¹ are linear, branched or cyclic alkyl groups having 1 to 10 carbon atoms, and R ⁵² is a single bond, an oxygen atom, or alkylene having 1 to 4 carbon atoms. It is a group. X is an ester group or an ether group. R ^{44 to} R ⁴⁶ are linear, branched or cyclic alkyl groups having 1 to 6 carbon atoms, or aryl groups having 6 to 10 carbon atoms, R ^{47 to} R ⁴⁹ are linear groups having 1 to 6 carbon atoms, A branched or cyclic alkyl group, an aryl group having 6 to 10 carbon atoms, a trimethylsilyl group, or a silicon-containing group in which a silicon atom in the formula is bonded to a siloxane bond or a silalkylene bond, and R ⁴⁷ and R ⁴⁸ , R ⁴⁷ And R ⁴⁹ , R ⁴⁸ and R ⁴⁹ may combine to form a polysiloxane ring together with the silicon atom to which they are bonded. m is an integer of 4 to 40, t is an integer of 2 to 30, and n is an integer of 1 to 20. Among repeating units d1~d7 of general formula (10), R ⁵³ ~R ⁵⁷ is a hydrogen atom, a fluorine atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, haloalkyl having 1 to 20 carbon atoms A cyano group, A represents an acid labile group, z is 0 or 1, and y is 1 or 2. When both or ^one of A ¹ and A ² is an acid labile group and is not an acid labile group, it is a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, or an adhesive group. ]
Claim 3:
The following general formula (1 ')
R ¹ SiX ₃ (1 ')
Or a silane monomer of the above general formula (1 ′) and the following general formula (1 ″)
R ⁰ SiX ₃ (1 ″)
(In the formula, R ¹ , X and R ⁰ have the same meaning as described above.)
An organopolysiloxane obtained by hydrolysis / condensation with a silane monomer represented by the formula: at least 1 selected from the repeating unit e represented by the following general formula (11) and d1 to d7 in the following general formula (10): A resist material comprising a polymer compound obtained by copolymerizing a repeating unit having a group whose alkali solubility is improved by at least one kind of acid.

[Wherein, R ⁵⁸ in the formula (11) is a hydrogen atom, or a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms, R ⁵⁹ is a single bond, or a linear chain having 1 to 10 carbon atoms. , A branched or cyclic alkylene group, or a linking group represented by the general formula (9), R ⁶⁰ , R ⁶¹ and R ⁶² are the same or different hydrogen atoms, alkyl groups having 1 to 20 carbon atoms, or haloalkyl groups. , An aryl group having 6 to 20 carbon atoms, a trimethylsilyl group, or a silicon-containing group in which a silicon atom in the formula is bonded to a siloxane bond or a silalkylene bond, or R ⁶⁰ and R ⁶¹ , R ⁶⁰ and R ^62, or R ⁶¹ And R ⁶² may be bonded to each other to form a polysiloxane ring having 3 to 20 silicon atoms together with the silicon atom to which they are bonded. Among repeating units d1~d7 of general formula (10), R ⁵³ ~R ⁵⁷ is a hydrogen atom, a fluorine atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, haloalkyl having 1 to 20 carbon atoms A cyano group, A represents an acid labile group, z is 0 or 1, and y is 1 or 2. When both or ^one of A ¹ and A ² is an acid labile group and is not an acid labile group, it is a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, or an adhesive group. ]
Claim 4:
A polymer compound having a repeating unit a of the general formula (1), adding a high molecular compound having one or more repeating units selected from c-1 to c-3 of the following general formula (8) A resist material characterized by the above.

[Wherein, R ¹ is an organic group having an acid-decomposable group, x is in the range of 1.0 to 1.5, and R ² is a hydrogen atom, a methyl group, a fluorine atom, a trifluoromethyl group, a cyano group, — CH ₂ C (═O) —O—R ³ or —CH ₂ —O—R ⁴ . R ³ is a linear or branched alkyl group having 1 to 4 carbon atoms, R ⁴ is a hydrogen atom, a linear or branched alkyl group having 1 to 4 carbon atoms, or a linear chain having 1 to 4 carbon atoms. Or R ⁴³ is the same or different hydrogen atom, a linear, branched or cyclic alkyl group or fluorinated alkyl group having 1 to 10 carbon atoms, or 6 to 6 carbon atoms. 10 aryl groups, and these groups may contain an ether group, a lactone ring, an ester group, a hydroxy group or a cyano group. R ⁴² represents a single bond or the following general formula (9)

It is a coupling group shown by these. In General Formula (9), R ⁵⁰ and R ⁵¹ are linear, branched or cyclic alkyl groups having 1 to 10 carbon atoms, and R ⁵² is a single bond, an oxygen atom, or alkylene having 1 to 4 carbon atoms. It is a group. X is an ester group or an ether group. R ^{44 to} R ⁴⁶ are linear, branched or cyclic alkyl groups having 1 to 6 carbon atoms, or aryl groups having 6 to 10 carbon atoms, R ^{47 to} R ⁴⁹ are linear groups having 1 to 6 carbon atoms, A branched or cyclic alkyl group, an aryl group having 6 to 10 carbon atoms, a trimethylsilyl group, or a silicon-containing group in which a silicon atom in the formula is bonded to a siloxane bond or a silalkylene bond, and R ⁴⁷ and R ⁴⁸ , R ⁴⁷ And R ⁴⁹ , R ⁴⁸ and R ⁴⁹ may combine to form a polysiloxane ring together with the silicon atom to which they are bonded. m is an integer of 4 to 40, t is an integer of 2 to 30, and n is an integer of 1 to 20. ]
Claim 5:
In the polymer compound having the repeating unit a represented by the following general formula (1), one or more repeating units selected from c-1 to c-3 of the following general formula (8), and the following general formula (10) And a polymer compound obtained by copolymerizing a repeating unit having a group that improves alkali solubility with at least one acid selected from d1 to d7.

[Wherein, R ¹ is an organic group having an acid-decomposable group, x is in the range of 1.0 to 1.5, and R ² is a hydrogen atom, a methyl group, a fluorine atom, a trifluoromethyl group, a cyano group, — CH ₂ C (═O) —O—R ³ or —CH ₂ —O—R ⁴ . R ³ is a linear or branched alkyl group having 1 to 4 carbon atoms, R ⁴ is a hydrogen atom, a linear or branched alkyl group having 1 to 4 carbon atoms, or a linear chain having 1 to 4 carbon atoms. Or R ⁴³ is the same or different hydrogen atom, a linear, branched or cyclic alkyl group or fluorinated alkyl group having 1 to 10 carbon atoms, or 6 to 6 carbon atoms. 10 aryl groups, and these groups may contain an ether group, a lactone ring, an ester group, a hydroxy group or a cyano group. R ⁴² represents a single bond or the following general formula (9)

It is a coupling group shown by these. In General Formula (9), R ⁵⁰ and R ⁵¹ are linear, branched or cyclic alkyl groups having 1 to 10 carbon atoms, and R ⁵² is a single bond, an oxygen atom, or alkylene having 1 to 4 carbon atoms. It is a group. X is an ester group or an ether group. R ^{44 to} R ⁴⁶ are linear, branched or cyclic alkyl groups having 1 to 6 carbon atoms, or aryl groups having 6 to 10 carbon atoms, R ^{47 to} R ⁴⁹ are linear groups having 1 to 6 carbon atoms, A branched or cyclic alkyl group, an aryl group having 6 to 10 carbon atoms, a trimethylsilyl group, or a silicon-containing group in which a silicon atom in the formula is bonded to a siloxane bond or a silalkylene bond, and R ⁴⁷ and R ⁴⁸ , R ⁴⁷ And R ⁴⁹ , R ⁴⁸ and R ⁴⁹ may combine to form a polysiloxane ring together with the silicon atom to which they are bonded. m is an integer of 4 to 40, t is an integer of 2 to 30, and n is an integer of 1 to 20. Among repeating units d1~d7 of general formula (10), R ⁵³ ~R ⁵⁷ is a hydrogen atom, a fluorine atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, haloalkyl having 1 to 20 carbon atoms A cyano group, A represents an acid labile group, z is 0 or 1, and y is 1 or 2. When both or ^one of A ¹ and A ² is an acid labile group and is not an acid labile group, it is a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, or an adhesive group. ]
Claim 6:
At least one selected from a polymer compound having a repeating unit a represented by the following general formula (1), a repeating unit e represented by the following general formula (11), and d1 to d7 in the following general formula (10). A resist material, comprising a polymer compound obtained by copolymerizing a repeating unit having a group whose alkali solubility is improved by an acid.

[Wherein, R ¹ is an organic group having an acid-decomposable group, x is in the range of 1.0 to 1.5, and R ⁵⁸ in formula (11) is a hydrogen atom or a straight chain having 1 to 10 carbon atoms. , Branched or cyclic alkyl group, R ⁵⁹ is a single bond, a linear, branched or cyclic alkylene group having 1 to 10 carbon atoms, or a linking group represented by the above general formula (9), R ⁶⁰ , R ⁶¹ and R ⁶² are the same or different hydrogen atoms, alkyl groups having 1 to 20 carbon atoms, or haloalkyl groups, aryl groups having 6 to 20 carbon atoms, trimethylsilyl groups, or silicon atoms and siloxane bonds or silalkylenes in the formula Bonded silicon-containing groups, or R ⁶⁰ and R ⁶¹ , R ⁶⁰ and R ^62, or R ⁶¹ and R ⁶² are bonded together, and together with the silicon atoms to which they are bonded, the polysiloxane having 3 to 20 silicon atoms A ring may be formed. Among repeating units d1~d7 of general formula (10), R ⁵³ ~R ⁵⁷ is a hydrogen atom, a fluorine atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, haloalkyl having 1 to 20 carbon atoms A cyano group, A represents an acid labile group, z is 0 or 1, and y is 1 or 2. When both or ^one of A ¹ and A ² is an acid labile group and is not an acid labile group, it is a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, or an adhesive group. ]
Claim 7:
(1) The polymer compound mixture according to any one of claims 1 to 6,
(2) an acid generator,
(3) A chemically amplified positive resist material containing an organic solvent.
Claim 8:
(1) The polymer compound mixture according to any one of claims 1 to 6,
(2) an acid generator,
(3) organic solvent,
(4) A chemically amplified positive resist material containing a dissolution inhibitor.
Claim 9:
The chemically amplified positive resist material according to claim 7 or 8, further comprising a basic compound.
Claim 10:
(1) applying a resist material according to any one of claims 7 to 9 on a substrate;
(2) Next, after the heat treatment, a step of exposing with a high energy beam or an electron beam having a wavelength of 300 nm or less through a photomask;
(3) A pattern forming method comprising a step of performing heat treatment as necessary and then developing using a developer.
Claim 11:
11. The resist pattern forming method according to claim 10, wherein after the pattern is formed, the base is processed by oxygen plasma etching.
Claim 12:
11. The resist pattern forming method according to claim 10, wherein after the pattern is formed, the base is processed by etching with a halogen gas containing chlorine or bromine.

  The resist material of the present invention is sensitive to high energy rays and is excellent in sensitivity, resolution and oxygen plasma etching resistance at a wavelength of 300 nm or less. Therefore, the resist material of the present invention can be a material for a two-layer resist that is particularly excellent from these characteristics, and can easily form a fine pattern perpendicular to the substrate. It is suitable as a fine pattern forming material.

Hereinafter, the present invention will be described in more detail.
In the resist material of the present invention, the polymer compound used as the base resin is a polymer compound mixture of the following (I), (II) or (III).
(I) A mixture of the following polymer compound A and polymer compound B comprising the repeating unit b represented by the following general formula (2).
(II) at least 1 selected from the following polymer compound A, one or more repeating units selected from c-1 to c-3 of the following general formula (8), and d1 to d7 in the following general formula (10) A mixture with a polymer compound C obtained by copolymerizing a repeating unit having a group whose alkali solubility is improved by an acid of at least one species.
(III) Alkali solubility is improved by the following polymer compound A, the repeating unit e represented by the following general formula (11), and at least one acid selected from d1 to d7 in the following general formula (10). A mixture with a polymer compound D obtained by copolymerizing a repeating unit having a group.

[Polymer Compound A]
The following general formula (1 ')
R ¹ SiX ₃ (1 ')
(Wherein R ¹ is an organic group having an acid-decomposable group, X is a halogen atom, a hydroxy group, an alkoxy group having 1 to 10 carbon atoms, or an acyl group having 1 to 10 carbon atoms.)
Or a silane monomer of the above general formula (1 ′) and the following general formula (1 ″)
R ⁰ SiX ₃ (1 ″)
(In the formula, R ⁰ is an organic group having an adhesive group, and X has the same meaning as described above.)
Is an organopolysiloxane obtained by hydrolysis and condensation with a silane monomer represented by

In this case, examples of the organic group having an acid-decomposable group for R ¹ include those selected from the following a′-1 to a′-5.

Here, R ⁶³ and R ⁶⁴ are a linear, branched or cyclic alkylene group having 2 to 20 carbon atoms, a vinylene group, or an arylene group having 6 to 20 carbon atoms, and one of the hydrogen atoms of these groups. Part or all may be substituted with a fluorine atom or a trifluoromethyl group. Moreover, an oxygen atom or a sulfur atom may be interposed. R ⁶⁵ is a single bond or an alkylene group having 1 to 4 carbon atoms. R ⁶⁶ and R ⁶⁷ are a hydrogen atom, a fluorine atom, a linear or branched alkyl group having 1 to 4 carbon atoms or a fluorinated alkyl group, and 1 is present in at least one of R ⁶⁶ and R ^67. Contains one or more fluorine atoms. R ⁶⁸ is a methylene group, an ethylene group, a linear, branched or cyclic alkylene group having 3 to 20 carbon atoms, or an arylene group having 6 to 20 carbon atoms, and part or all of the hydrogen atoms of these groups May be substituted with a fluorine atom or a trifluoromethyl group. Moreover, an oxygen atom or a sulfur atom may be interposed. R ⁶⁹ is a fluorine atom or a trifluoromethyl group. A is an acid labile group, g, h, i are 1 or 2, and j is an integer of 0-4.

The a′-1 group can be exemplified below.

Next, a'-2 group can be illustrated below.

Next, a'-3 group can be illustrated below.

Next, a'-4 group can be illustrated next.

なお、上記式において、Ａは酸不安定基を示すが、酸不安定基の具体例は後述する。 Furthermore, a'-5 group can be illustrated next.

In the above formula, A represents an acid labile group, and specific examples of the acid labile group will be described later.

In the polymer compound of the present invention, in addition to the monomer having a group whose alkali solubility is improved by the acid, the organic compound R ⁰ having an adhesive group having hydrophilicity has the formula (1 ″). Monomers can be copolymerized. As the adhesive group, the main component is an oxygen atom such as alcohol group, carboxyl group, ether group, ester group, acetyl group, formyl group, carbonate group, lactone ring, sulfonamide group, cyano group, carboxylic acid anhydride, etc. . Specific examples of the organic group R ⁰ include the following groups in which the acid labile group A of a′-1, a′-2, and a′-3 is a hydrogen atom.

（Ｒ⁶³〜Ｒ⁶⁹、ｇは上記の通り。）

(R ^{63 to} R ⁶⁹ and g are as described above.)

Organic groups R ⁰ having other adhesive groups can be exemplified below.

  Furthermore, in order to improve transparency or optimize the molecular weight, a monomer q ′ pendant with an alkyl group or a fluorinated alkyl group represented by the following formulas (12 ′)-1 to (12 ′)-4 is copolymerized. You can also.

（式中、Ｒ⁷⁰は同一又は異種の炭素数１〜２０の直鎖状、分岐状もしくは環状の非置換又は置換の炭素数１〜１０のアルキル基であり、フッ素化されたアルキル基であってもよく、Ｒ⁷¹は酸素原子、炭素数１〜１０のアルキレン基、又は炭素数６〜１０のアリーレン基である。Ｘは上記の通りである。）

(In the formula, R ⁷⁰ is the same or different linear, branched or cyclic unsubstituted or substituted alkyl group having 1 to 10 carbon atoms, and is a fluorinated alkyl group. R ⁷¹ is an oxygen atom, an alkylene group having 1 to 10 carbon atoms, or an arylene group having 6 to 10 carbon atoms, X is as described above.)

A synthesis example of a silane monomer used for the repeating unit a of the general formula (1) is shown below.

Here, a platinum-catalyzed hydrosilylation reaction is performed on norbornene having a carboxylate and hydrosilane. R ⁷² may be an acid labile group, a hydrogen atom, or an alkali hydrolyzable group. In the above reaction formula, each X is the same or different halogen atom, hydroxy group, alkoxy group having 1 to 10 carbon atoms, or acyl group having 1 to 10 carbon atoms. The reaction temperature is room temperature, in some cases, heated to a maximum of about 150 ° C., and pressurized to about 10 atmospheres in an autoclave. The catalyst is preferably chloroplatinic acid.

Examples of the silane monomer represented by the general formula (1 ′) are shown below.

（式中、Ｒ⁷²、Ｘは上記の通り。ｈは１又は２、ｉｉは１〜３の整数である。）

(Wherein R ⁷² and X are as described above. H is 1 or 2, and ii is an integer of 1 to 3)

Here, R ⁷² may be an acid labile group represented by A, or may be a hydrogen atom or an acyl group having 1 to 6 carbon atoms. In the case of an acyl group, —OR ⁷² is obtained by alkali hydrolysis after polymerization. A hydroxy group may be substituted with an acid labile group.
Furthermore, in addition to the silane monomer represented by the above formula (1 ′) and the silane monomer having an adhesive group represented by the formula (1 ″), the following silane compound r can be co-condensed.

Still further, a silane compound s having a tetrafunctional or higher functional condensation group shown below can be copolymerized.

  As a synthesis method of the polymer compound A, co-condensation by hydrolysis is performed using the silane monomer. The amount of water in the hydrolysis reaction is preferably 0.2 to 10 moles per mole of monomer. At this time, a catalyst can also be used. Acetic acid, propionic acid, oleic acid, stearic acid, linoleic acid, salicylic acid, benzoic acid, formic acid, malonic acid, phthalic acid, fumaric acid, citric acid, tartaric acid, hydrochloric acid, sulfuric acid, nitric acid Acid such as sulfonic acid, methylsulfonic acid, tosylic acid, trifluoromethanesulfonic acid, ammonia trimethylamine, triethylamine, triethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, choline hydroxide 1,8-diazabicyclo [5. 4.0] -7-undecene (DBU), 1,5-diazabicyclo [4.3.0] -5-nonenone (DBN), bases such as sodium hydroxide, potassium hydroxide, barium hydroxide, calcium hydroxide , Tetraalkoxy titanium, trialkoxy It may be mentioned mono (acetylacetonato) titanium, tetraalkoxy zirconium, a metal chelate compound such as trialkoxy mono (acetylacetonato) zirconium.

  As the reaction operation, the monomer is dissolved in an organic solvent, and water is added to start the hydrolysis reaction. The catalyst may be added to water or may be added to an organic solvent. The reaction temperature is 0 to 100 ° C, preferably 10 to 80 ° C. A method of heating to 10 to 50 ° C. at the time of dropping the water and then raising the temperature to 40 to 80 ° C. for aging is preferable. As the organic solvent, those hardly soluble or insoluble in water are preferable, tetrahydrofuran, toluene, hexane, ethyl acetate, cyclohexanone, methyl-2-n-amyl ketone, propylene glycol monomethyl ether, ethylene glycol monomethyl ether, propylene glycol monoethyl ether. , Ethylene glycol monoethyl ether, propylene glycol dimethyl ether, diethylene glycol dimethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, ethyl pyruvate, butyl acetate, methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, tert-acetate -Butyl, tert-butyl propionate, propylene glycol mono tert Butyl ether acetate, γ- butyrolactone are preferred.

  Thereafter, the catalyst is neutralized, and the organic solvent layer is separated and dehydrated. It is necessary to sufficiently perform the remaining of water in order to advance the condensation reaction of the remaining silanol. Preferable examples include an adsorption method using a salt such as magnesium sulfate and molecular sieve, and an azeotropic dehydration method while removing the solvent.

In this case, the ratio of the amount of the monomer used is Ta ′, where the total amount of the monomer a ′ of the formula (1 ′), the monomer p ′ of the formula (1 ″), the monomer q ′, the silane compounds r and s is In the case (Ta ′ = a ′ + p ′ + q ′ + r + s), the molar ratio is 0.05 <a ′ / Ta ′ ≦ 1.0, especially 0.1 <a ′ / Ta ′ ≦ 0.8.
0.05 ≦ p ′ / Ta ′ ≦ 0.9, especially 0.1 ≦ p ′ / Ta ′ ≦ 0.8
0 ≦ q ′ / Ta ′ ≦ 0.8, especially 0 ≦ q ′ / Ta ′ ≦ 0.5
0 ≦ r / Ta ′ ≦ 0.8, especially 0 ≦ r / Ta ′ ≦ 0.6
0 ≦ s / Ta ′ ≦ 0.8, especially 0 ≦ s / Ta ′ ≦ 0.7
It is preferable that

  The polymer compound A is obtained by hydrolyzing and condensing the monomer of the above formula (1 ′) as an essential monomer. In this case, the polymer compound A usually comprises the following repeating unit a: It is what you have.

上記式中、Ｒ¹は酸分解基を有する有機基、ｘは１．０〜１．５、好ましくは１．２〜１．５、更に好ましくは１．３〜１．５の範囲であり、特に下記ａ−１〜ａ−５から選ばれる１種又は２種以上のシルセスキオキサンの繰り返し単位であることが好ましい。

In the above formula, R ¹ is an organic group having an acid-decomposable group, x is 1.0 to 1.5, preferably 1.2 to 1.5, more preferably 1.3 to 1.5, In particular, it is preferably a repeating unit of one or more silsesquioxanes selected from the following a-1 to a-5.

ここで、Ｒ⁶³〜Ｒ⁶⁹、Ａ、ｇ、ｈ、ｉ、ｊは上記の通りである。

Here, R ^{63 to} R ⁶⁹ , A, g, h, i, and j are as described above.

The repeating unit a-1 can be exemplified below.

Next, repeating unit a-2 can be illustrated below.

Next, repeating unit a-3 can be illustrated below.

Next, the repeating unit a-4 can be illustrated next.

Further, the repeating unit a-5 can be exemplified as follows.

（但し、Ｒ⁰は上記の通り。）
で示される繰り返し単位ｐを有することが好ましい。 In addition to the repeating unit of the above formula (1), the polymer compound A has the following general formula (1 ′ ″) which can be obtained by hydrolysis and condensation of the monomer of the above formula (1 ″).

(However, R ⁰ is as described above.)
It is preferable to have the repeating unit p shown by these.

  Specific examples include the following repeating units in which the acid labile group A of a-1, a-2, and a-3 is a hydrogen atom.

（Ｒ⁶³〜Ｒ⁶⁹、ｇは上記の通り。）

(R ^{63 to} R ⁶⁹ and g are as described above.)

The repeating unit which has another adhesive group can be illustrated below.

  Furthermore, a repeating unit q in which an alkyl group or a fluorinated alkyl group represented by the following formulas (12) -1 to (12) -4 derived from the monomer g is pendant is added to the repeating unit of the general formula (1). It can also be copolymerized.

（式中、Ｒ⁷⁰、Ｒ⁷¹は上記の通りであり、０≦ｊｊ＜１、０≦ｋ＜１、０≦ｌ＜１、０≦ｍｍ＜１の範囲である。）

(In the formula, R ⁷⁰ and R ⁷¹ are as described above, and 0 ≦ jj <1, 0 ≦ k <1, 0 ≦ l <1, 0 ≦ mm <1.)

  In addition, it is preferable that the weight average molecular weight of the high molecular compound A is 1,000-100,000 of polystyrene conversion by the measuring method by a gel permeation chromatography. The molecular weight distribution is preferably 1.0 to 5.0.

Further, in this polymer compound A, assuming that the repeating units derived from the above repeating units a, p, q and the silane compounds r, s are r, s, when a + p + q + r + s = Ta, the molar ratio is 0.05 <a /Ta≦1.0, especially 0.1 <a / Ta ≦ 0.8
0.05 ≦ p / Ta ≦ 0.9, especially 0.1 ≦ p / Ta ≦ 0.8
0 ≦ q / Ta ≦ 0.8, especially 0 ≦ q / Ta ≦ 0.5
0 ≦ r / Ta ≦ 0.8, especially 0 ≦ r / Ta ≦ 0.6
0 ≦ s / Ta ≦ 0.8, especially 0 ≦ s / Ta ≦ 0.7
It is preferable that

［式中、Ｒ²は水素原子、メチル基、フッ素原子、トリフルオロメチル基、シアノ基、−ＣＨ₂Ｃ（＝Ｏ）−Ｏ−Ｒ³、又は−ＣＨ₂−Ｏ−Ｒ⁴である。Ｒ³は炭素数１〜４の直鎖状又は分岐状のアルキル基、Ｒ⁴は水素原子、炭素数１〜４の直鎖状又は分岐状のアルキル基、又は炭素数１〜４の直鎖状又は分岐状のアシル基であり、Ｒ⁵は一般式（３）、（４）、（５）、（６）、（７）の中から選ばれる珪素含有基である。

（式中、Ｒ⁶、Ｒ⁷、Ｒ¹¹は水素原子、又は炭素数１〜１０、特に１〜８の直鎖状、分岐状又は環状のアルキル基であり、Ｒ⁸、Ｒ⁹、Ｒ¹⁰、Ｒ¹²、Ｒ¹³、Ｒ¹⁴、Ｒ¹⁵、Ｒ¹⁶、Ｒ¹⁷は炭素数１〜１０、特に１〜８の直鎖状、分岐状又は環状のアルキル基、炭素数６〜１４、特に６〜１０のアリール基、好ましくは各アルキル基が炭素数１〜６、特に１〜４であるトリアルキルシリル基、又は式中の珪素原子とシロキサン結合もしくはシルアルキレン結合している珪素含有基である。また、Ｒ⁶とＲ⁷とは、これらが結合する炭素原子と共に結合して炭素数３〜１０の脂肪族炭素環を形成してもよい。更に、Ｒ⁸とＲ⁹、Ｒ⁸とＲ¹⁰、Ｒ⁹とＲ¹⁰、Ｒ¹²とＲ¹³、Ｒ¹²とＲ¹⁴、Ｒ¹³とＲ¹⁴、Ｒ¹⁵とＲ¹⁶、Ｒ¹⁵とＲ¹⁷、Ｒ¹⁶とＲ¹⁸は、互いに結合してこれらが結合する珪素原子と共に珪素原子数３〜１０のポリシロキサン環を形成してもよい。）

（式中、Ｒ²⁸、Ｒ²⁹、Ｒ³⁰は炭素数１〜２０、特に１〜１２の直鎖状、分岐状又は環状のアルキル基、Ｒ¹⁸、Ｒ¹⁹、Ｒ²²、Ｒ²³、Ｒ²⁶、Ｒ²⁷、Ｒ³¹、Ｒ³²、Ｒ³⁵、Ｒ³⁶、Ｒ³⁹、Ｒ⁴⁰、Ｒ⁴¹は水素原子、又は炭素数１〜２０、特に１〜１２の直鎖状、分岐状又は環状のアルキル基、Ｒ²⁰、Ｒ²¹、Ｒ²⁴、Ｒ²⁵、Ｒ³³、Ｒ³⁴、Ｒ³⁷、Ｒ³⁸は水素原子、炭素数１〜２０、特に１〜１２の直鎖状、分岐状又は環状のアルキル基、フッ素化した炭素数１〜２０、特に１〜１２のアルキル基、又は炭素数６〜２０、特に６〜１０のアリール基、ｐ、ｑ、ｒ、ｓは０〜１０、特に０〜８の整数であるが、１≦ｐ＋ｑ＋ｓ≦２０、特に１≦ｐ＋ｑ＋ｓ≦１０である。）］ [Polymer Compound B Composed of Repeating Unit b of General Formula (2)]

[Wherein, R ² represents a hydrogen atom, a methyl group, a fluorine atom, a trifluoromethyl group, a cyano group, —CH ₂ C (═O) —O—R ³ , or —CH ₂ —O—R ⁴ . R ³ is a linear or branched alkyl group having 1 to 4 carbon atoms, R ⁴ is a hydrogen atom, a linear or branched alkyl group having 1 to 4 carbon atoms, or a linear chain having 1 to 4 carbon atoms. Or R ⁵ is a silicon-containing group selected from general formulas (3), (4), (5), (6), and (7).

(Wherein R ⁶ , R ⁷ and R ¹¹ are a hydrogen atom or a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms, particularly 1 to 8 carbon atoms, and R ⁸ , R ⁹ , R ^10. , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ , R ¹⁶ , R ¹⁷ are linear, branched or cyclic alkyl groups having 1 to 10 carbon atoms, particularly 1 to 8 carbon atoms, 6 to 14 carbon atoms, particularly 6 carbon atoms. 10 to 10 aryl groups, preferably a trialkylsilyl group in which each alkyl group has 1 to 6 carbon atoms, particularly 1 to 4 carbon atoms, or a silicon-containing group having a siloxane bond or a silalkylene bond with a silicon atom in the formula R ⁶ and R ⁷ may be bonded together with the carbon atom to which they are bonded to form an aliphatic carbocycle having 3 to 10 carbon atoms, R ⁸ and R ⁹ , R ⁸ and R ^10, R ⁹ and R ^10, R ¹² and R ^13, R ¹² and R ^14, R ¹³ and R ^14, R ¹⁵ and R ^16, R ¹⁵ and R ^17, R ¹⁶ and R ¹⁸ are each Combined may form a polysiloxane ring of silicon atoms from 3 to 10 together with silicon atoms to which they are attached.)

(Wherein R ²⁸ , R ²⁹ and R ³⁰ are linear, branched or cyclic alkyl groups having 1 to 20 carbon atoms, particularly 1 to 12 carbon atoms, R ¹⁸ , R ¹⁹ , R ²² , R ²³ , R ^26. , R ²⁷ , R ³¹ , R ³² , R ³⁵ , R ³⁶ , R ³⁹ , R ⁴⁰ , R ⁴¹ are a hydrogen atom, or a linear, branched or cyclic alkyl having 1 to 20 carbon atoms, particularly 1 to 12 carbon atoms. The groups R ²⁰ , R ²¹ , R ²⁴ , R ²⁵ , R ³³ , R ³⁴ , R ³⁷ , R ³⁸ are hydrogen atoms, linear, branched or cyclic alkyls having 1 to 20 carbon atoms, especially 1 to 12 carbon atoms. Group, a fluorinated alkyl group having 1 to 20, especially 1 to 12 carbon atoms, or an aryl group having 6 to 20 carbon atoms, particularly 6 to 10 carbon atoms, p, q, r and s are 0 to 10, particularly 0 to 8; 1 ≦ p + q + s ≦ 20, especially 1 ≦ p + q + s ≦ 10)]

  In this case, as the alkyl group, methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, tert-butyl group, pentyl group, cyclopentyl group, hexyl group, cyclohexyl group, octyl group, decyl group, A dodecyl group, a myristyl group, a stearyl group, etc. are mentioned, As a fluorinated alkyl group, the group by which some or all of the hydrogen atoms of these alkyl groups were substituted by the fluorine atom is mentioned. Examples of the aryl group include a phenyl group, a tolyl group, a xylyl group, and a naphthyl group.

As the silicon-containing groups are the siloxane and silicon-bonded or silalkylene bond, the following formula _{-W- (SiR 2 -W) v -SiR} 3
(W represents O or CH ₂ , R represents an alkyl group or aryl group having 1 to 10 carbon atoms, particularly 1 to 6 carbon atoms, and v represents an integer of 0 to 10, particularly 0 to 6)
The group shown by these is mentioned.
Examples of the trialkylsilyl group represented by SiR ₃ include a trimethylsilyl group, a triethylsilyl group, a dimethyl-tert-butylsilyl group, and the like.

（但し、Ｒは上記と同様であり、ｗは２〜１０、特に３〜６の整数である。） Furthermore, the following are mentioned as a polysiloxane ring.

(However, R is the same as the above, and w is an integer of 2 to 10, particularly 3 to 6.)

  Here, the silicon-containing groups represented by the general formulas (3), (4), (5), (6), and (7) function as acid labile groups.

  The silicon-containing groups represented by the general formulas (3), (4), and (5) can be listed below.

The silicon-containing groups represented by the general formulas (6) and (7) can be listed below.

  In the case of producing a polymer compound having a repeating unit represented by the general formula (2), generally, the above monomers and a solvent are mixed, a catalyst is added, and a polymerization reaction may be performed while heating or cooling depending on the case. Do. The polymerization reaction is also governed by the type of initiator (or catalyst), the starting method (light, heat, radiation, plasma, etc.), the polymerization conditions (temperature, pressure, concentration, solvent, additives), etc. In the polymerization of the polymer compound of the present invention, radical copolymerization initiated by radicals such as AIBN (azobisisobutyronitrile), ionic polymerization (anionic polymerization) using a catalyst such as alkyl lithium, etc. are generally used. Is. These polymerizations can be carried out according to conventional methods.

  The weight average molecular weight of the polymer compound having the repeating unit represented by the general formula (2) is preferably in the range of 1,000 to 100,000 in terms of polystyrene as measured by gel permeation chromatography, more preferably 2 , 50,000 to 50,000. The molecular weight distribution is preferably 1.0 to 3.0, more preferably 2.0 or less, and it is a resist to cut the high molecular weight component or low molecular component of the polymer after polymerization into a narrow dispersion polymer of 1.5 or less. This is a more preferable method for improving the resolution.

[Alkali solubility is improved by one or more kinds of repeating units selected from c-1 to c-3 of the general formula (8) and at least one kind of acid selected from d1 to d7 in the general formula (10). Polymer compound C obtained by copolymerizing a repeating unit having a group]

［式中、Ｒ²は水素原子、メチル基、フッ素原子、トリフルオロメチル基、シアノ基、−ＣＨ₂Ｃ（＝Ｏ）−Ｏ−Ｒ³、又は−ＣＨ₂−Ｏ−Ｒ⁴である。Ｒ³は炭素数１〜４の直鎖状又は分岐状のアルキル基、Ｒ⁴は水素原子、炭素数１〜４の直鎖状又は分岐状のアルキル基、又は炭素数１〜４の直鎖状又は分岐状のアシル基であり、Ｒ⁴³は同一又は異種の水素原子、炭素数１〜１０、特に１〜８の直鎖状、分岐状又は環状のアルキル基もしくはフッ素化されたアルキル基、又は炭素数６〜１４、特に６〜１０のアリール基であり、これらの基はエーテル基、ラクトン環、エステル基、ヒドロキシ基又はシアノ基を含んでいてもよい。Ｒ⁴²は単結合、又は下記一般式（９）

で示される連結基である。一般式（９）中、Ｒ⁵⁰、Ｒ⁵¹は炭素数１〜１０、特に１〜８の直鎖状、分岐状又は環状のアルキル基であり、Ｒ⁵²は単結合、酸素原子、又は炭素数１〜４のアルキレン基である。Ｘはエステル基又はエーテル基である。Ｒ⁴⁴〜Ｒ⁴⁶は炭素数１〜６の直鎖状、分岐状又は環状のアルキル基、又は炭素数６〜１４、特に６〜１０のアリール基、Ｒ⁴⁷〜Ｒ⁴⁹は炭素数１〜６の直鎖状、分岐状又は環状のアルキル基、炭素数６〜１４、特に６〜１０のアリール基、トリメチルシリル基、又は式中の珪素原子とシロキサン結合もしくはシルアルキレン結合している珪素含有基であり、Ｒ⁴⁷とＲ⁴⁸、Ｒ⁴⁷とＲ⁴⁹、Ｒ⁴⁸とＲ⁴⁹が結合してこれらが結合する珪素原子と共にポリシロキサン環を形成してもよい。ｍは４〜４０、特に４〜２０の整数であり、ｔは２〜３０、特に３〜１０の整数であり、ｎは１〜２０、特に１〜１０の整数である。一般式（１０）の繰り返し単位ｄ１〜ｄ７中、Ｒ⁵³〜Ｒ⁵⁷は水素原子、フッ素原子、炭素数１〜２０、特に１〜１０のアルキル基、炭素数６〜２０、特に６〜１０のアリール基、炭素数１〜２０、特に１〜１０のハロアルキル基、又はシアノ基であり、Ａは酸不安定基を示し、ｚは０又は１であり、ｙは１又は２である。Ａ¹とＡ²の両方又はどちらか一方が酸不安定基であり、酸不安定基でない場合は、水素原子、炭素数１〜２０のアルキル基、又は密着性基である。］

[Wherein, R ² represents a hydrogen atom, a methyl group, a fluorine atom, a trifluoromethyl group, a cyano group, —CH ₂ C (═O) —O—R ³ , or —CH ₂ —O—R ⁴ . R ³ is a linear or branched alkyl group having 1 to 4 carbon atoms, R ⁴ is a hydrogen atom, a linear or branched alkyl group having 1 to 4 carbon atoms, or a linear chain having 1 to 4 carbon atoms. Or R ⁴³ is the same or different hydrogen atom, a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms, particularly 1 to 8 carbon atoms, or a fluorinated alkyl group, Alternatively, it is an aryl group having 6 to 14 carbon atoms, particularly 6 to 10 carbon atoms, and these groups may contain an ether group, a lactone ring, an ester group, a hydroxy group, or a cyano group. R ⁴² represents a single bond or the following general formula (9)

It is a coupling group shown by these. In the general formula (9), R ⁵⁰ and R ⁵¹ are linear, branched or cyclic alkyl groups having 1 to 10 carbon atoms, particularly 1 to 8 carbon atoms, and R ⁵² is a single bond, oxygen atom or carbon number. 1 to 4 alkylene groups. X is an ester group or an ether group. R ^{44 to} R ⁴⁶ are linear, branched or cyclic alkyl groups having 1 to 6 carbon atoms, or aryl groups having 6 to 14 carbon atoms, particularly 6 to 10 carbon atoms, and R ^{47 to} R ⁴⁹ are 1 to 6 carbon atoms. A linear, branched or cyclic alkyl group, an aryl group having 6 to 14 carbon atoms, particularly 6 to 10 carbon atoms, a trimethylsilyl group, or a silicon-containing group having a siloxane bond or a silalkylene bond with a silicon atom in the formula Yes, R ⁴⁷ and R ⁴⁸ , R ⁴⁷ and R ⁴⁹ , R ⁴⁸ and R ⁴⁹ may be bonded together to form a polysiloxane ring together with the silicon atom to which they are bonded. m is an integer of 4 to 40, particularly 4 to 20, t is an integer of 2 to 30, particularly 3 to 10, and n is an integer of 1 to 20, particularly 1 to 10. Among repeating units d1~d7 of general formula (10), R ⁵³ ~R ⁵⁷ is a hydrogen atom, a fluorine atom, having 1 to 20 carbon atoms, particularly 1 to 10 alkyl group, number 6 to 20, especially 6 to 10 carbon An aryl group, a haloalkyl group having 1 to 20 carbon atoms, particularly 1 to 10 carbon atoms, or a cyano group, A represents an acid labile group, z is 0 or 1, and y is 1 or 2. When both or ^one of A ¹ and A ² is an acid labile group and is not an acid labile group, it is a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, or an adhesive group. ]

  Here, examples of the alkyl group, the fluorinated alkyl group, the aryl group, the silicon-containing group having a siloxane bond or a silalkylene bond, and the polysiloxane ring include those exemplified above. Examples of the haloalkyl group include groups in which part or all of the hydrogen atoms of the alkyl group have been substituted with halogen atoms such as chlorine atoms and fluorine atoms. The ester group is a -COO- group, and the ether group is a -O- group. The acid labile group will be described later. The adhesive groups are as follows.

The repeating unit shown by repeating unit c-1 in the general formula (8) can be listed below. Here, R ² , R ⁴² , R ⁴³ , and X are as described above.

The linking group represented by the general formula (9) can be listed below.

ここで、Ｒ²、Ｒ⁴⁴、Ｒ⁴⁵、Ｒ⁴⁶、Ｘは前述の通りである。 The repeating unit shown by repeating unit c-2 in General formula (8) can be mentioned below.

Here, R ² , R ⁴⁴ , R ⁴⁵ , R ⁴⁶ , and X are as described above.

ここで、Ｒ²、Ｒ⁴⁴、Ｒ⁴⁵、Ｒ⁴⁶、Ｘは前述の通りである。 The repeating unit shown by repeating unit c-3 in the general formula (8) can be listed below.

Here, R ² , R ⁴⁴ , R ⁴⁵ , R ⁴⁶ , and X are as described above.

  There are various methods for synthesizing a silsesquioxane pendant (meth) acrylate (POSSMA) having a three-dimensional cage structure to obtain the repeating unit represented by the repeating unit c-1 in the general formula (8). As a typical synthesis method, as shown in Macromolecules 1995, 28, p8435, there is a coupling reaction of POSS trisilanol and methacryl pendant trichlorosilane. POSS silanol is described in J. Org. Am. Chem. Soc. As shown in 1989, 111, p1741, a synthesis method by a condensation reaction of cyclohexyltrichlorosilane in an aqueous acetone solution has been reported. POSS trisilanol having a purity of almost 100% can be obtained while removing impurities with low silanol by filtration. However, it takes several years to increase the purity while repeating the filtration, and there is a disadvantage that it is very poor in mass productivity. Here, a catalyst can be added in order to increase the condensation rate. Specifically, acetic acid, oxalic acid, propionic acid, oleic acid, stearic acid, linoleic acid, salicylic acid, benzoic acid, formic acid, malonic acid, phthalic acid, fumaric acid, citric acid, tartaric acid, hydrochloric acid, sulfuric acid, nitric acid, sulfonic acid , Acids such as methylsulfonic acid, tosylic acid, trifluoromethanesulfonic acid, ammonia, sodium hydroxide, potassium hydroxide, barium hydroxide, calcium hydroxide, trimethylamine, triethylamine, triethanolamine, tetramethylammonium hydroxide, choline hydroxy Metal bases such as copper, tetrabutylammonium hydroxide, tetraalkoxytitanium, trialkoxymono (acetylacetonato) titanium, tetraalkoxyzirconium, trialkoxymono (acetylacetonato) zirconium Mention may be made of the door compound. Further, the condensation rate can be increased by raising the temperature in the range of room temperature to 100 ° C.

The raw material to be condensed can be represented by the following general formula (12). Here, as described above, R ⁴³ is X ₁ , X ₂ , and X ₃ each independently a halogen atom, a hydroxy group, a linear or branched alkyl group having 1 to 6 carbon atoms, or an acyl group. J. et al. Am. Chem. Soc. According to 1989, 111, p1741, the condensation of cyclohexyltrichlorosilane produced (13) -a, (13) -b, (13) -c, and (13) -b and (13) -c were removed by filtration. However, the purity of (13) -a is increased.
Next, monomer (15) -1 is obtained by coupling of (13) -a with formula (14).
As another synthesis method for obtaining the monomer represented by the general formula (15) -1, a co-condensation reaction may be performed by mixing the silane compounds represented by the general formulas (14) and (12).

  In addition, examples of the monomer other than the monomer represented by the general formula (15) -1 include the following (15) -2 to (15) -8. In this case, the cage silsesquioxane does not necessarily have a complete cubic structure, and the siloxane bond may be cleaved to form silanol. Moreover, you may take the saddle type structure which the some octahedron connected. Moreover, it may be other than those listed in (15) -1 to (15) -8, or may be a mixture of these.

（Ｒ²、Ｘ、Ｒ⁴³、Ｒ⁵⁰、Ｒ⁵¹は上記の通り。）

(R ² , X, R ⁴³ , R ⁵⁰ and R ⁵¹ are as described above.)

R ⁴³ is the same or different hydrogen atom, a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms, a fluorinated alkyl group, an ether group, a lactone ring, an ester group, Hydroxy group and cyano group may be included, but specifically, methyl group, ethyl group, isopropyl group, cyclopentyl group, cyclohexyl group, norbornyl group, adamantyl group, trifluoropropyl group, cyanoethyl group, cyanopropyl group or The following groups can be mentioned.

Here, the repeating units c-1, c-2, or c-3 can be copolymerized with a polar monomer that further improves the adhesion.

（Ｒ²は上記の通り。）

(R ² is as described above.)

The polymer compound C may be produced by the same method as described above, but the repeating unit c selected from c-1 to c-3 and the repeating unit selected from d-1 to d-7. When the ratio of d to the repeating unit t derived from the polar monomer is c + d + t = Tc,
0.01 ≦ c / Tc ≦ 0.8, especially 0.05 ≦ c / Tc ≦ 0.7
0.1 ≦ d / Tc ≦ 0.8, especially 0.15 ≦ d / Tc ≦ 0.7
0.1 ≦ t / Tc ≦ 0.8, especially 0.2 ≦ t / Tc ≦ 0.7
It is preferable that

  In addition, it is preferable that the weight average molecular weights of the high molecular compound C are 2,000-100,000 of polystyrene conversion by the measuring method by a gel permeation chromatography. The molecular weight distribution is preferably 1.0 to 3.0.

[Repeating unit e represented by general formula (11) and a repeating unit having a group whose alkali solubility is improved by at least one acid selected from d1 to d7 in general formula (10) Polymer compound D]

［式中、式（１１）のＲ⁵⁸は水素原子、又は炭素数１〜１０、特に１〜４の直鎖状、分岐状又は環状のアルキル基、Ｒ⁵⁹は単結合、炭素数１〜１０、特に１〜４の直鎖状、分岐状又は環状のアルキレン基、又は上記一般式（９）で示される連結基、Ｒ⁶⁰、Ｒ⁶¹、Ｒ⁶²は同一又は異種の水素原子、炭素数１〜２０、特に１〜１０のアルキル基、又はハロアルキル基、炭素数６〜２０、特に６〜１０のアリール基、トリメチルシリル基、又は式中の珪素原子とシロキサン結合もしくはシルアルキレン結合している珪素含有基であり、あるいはＲ⁶⁰とＲ⁶¹、Ｒ⁶⁰とＲ⁶²又はＲ⁶¹とＲ⁶²は、互いに結合してこれらが結合する珪素原子と共に珪素原子数３〜１０のポリシロキサン環を形成してもよい。一般式（１０）の繰り返し単位ｄ１〜ｄ７中、Ｒ⁵³〜Ｒ⁵⁷は水素原子、フッ素原子、炭素数１〜２０、特に１〜４のアルキル基、炭素数６〜２０、特に６〜１０のアリール基、炭素数１〜２０、特に１〜４ハロアルキル基、又はシアノ基であり、Ａは酸不安定基を示し、ｚは０又は１であり、ｙは１又は２である。Ａ¹とＡ²の両方又はどちらか一方が酸不安定基であり、酸不安定基でない場合は、水素原子、炭素数１〜２０、特に１〜４のアルキル基、又は密着性基である。］

[Wherein, R ⁵⁸ in the formula (11) is a hydrogen atom, or a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms, particularly 1 to 4 carbon atoms, R ⁵⁹ is a single bond, or 1 to 10 carbon atoms. In particular, a linear, branched or cyclic alkylene group having 1 to 4 or a linking group represented by the above general formula (9), R ⁶⁰ , R ⁶¹ and R ⁶² are the same or different hydrogen atoms, having 1 carbon atom. -20, especially 1-10 alkyl groups, or haloalkyl groups, C6-C20, especially 6-10 aryl groups, trimethylsilyl groups, or silicon containing siloxane bonds or silalkylene bonds with silicon atoms in the formula R ⁶⁰ and R ⁶¹ , R ⁶⁰ and R ^62, or R ⁶¹ and R ⁶² may be bonded to each other to form a polysiloxane ring having 3 to 10 silicon atoms together with the silicon atom to which they are bonded. Good. In the repeating units d1 to d7 of the general formula (10), R ^{53 to} R ⁵⁷ are a hydrogen atom, a fluorine atom, an alkyl group having 1 to 20 carbon atoms, particularly 1 to 4 carbon atoms, an alkyl group having 6 to 20 carbon atoms, particularly 6 to 10 carbon atoms. An aryl group, 1 to 20 carbon atoms, particularly a 1 to 4 haloalkyl group, or a cyano group, A represents an acid labile group, z is 0 or 1, and y is 1 or 2; When both or ^one of A ¹ and A ² is an acid labile group and is not an acid labile group, it is a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, particularly 1 to 4 carbon atoms, or an adhesive group. . ]

  Here, examples of each group of the formula (10) are as described above. In the formula (11), examples of the alkyl group, the haloalkyl group, the aryl group, the silicon-containing group having a siloxane bond or a silalkylene bond, and the polysiloxane ring include those exemplified above. Examples of the alkylene group include those in which one hydrogen atom is eliminated from the alkyl group.

The repeating unit represented by e in the general formula (11) can be listed below.

ここで、Ｒ⁴²、Ｒ⁴³は前述の通りである。

Here, R ⁴² and R ⁴³ are as described above.

The polymer compound D can further copolymerize the following repeating unit f.

The production method of the polymer compound D may be the same method as described above, but the ratio between the repeating unit e and the repeating unit d selected from d-1 to d-7 and the repeating unit u. However, when e + d + u = Td,
0.1 ≦ e / Td ≦ 0.8, especially 0.2 ≦ c / Td ≦ 0.7
0.1 ≦ d / Td ≦ 0.8, especially 0.15 ≦ d / Td ≦ 0.7
0.1 ≦ u / Td ≦ 0.8, especially 0.2 ≦ u / Td ≦ 0.7
It is preferable that

  In addition, it is preferable that the weight average molecular weights of the high molecular compound D are 2,000-100,000 of polystyrene conversion by the measuring method by a gel permeation chromatography. The molecular weight distribution is preferably 1.0 to 3.0.

  Here, various acid labile groups are selected, and those represented by the following general formulas (A-1), (A-2), and (A-3) are preferable.

In the formula (A-1), R ⁵⁰ is a tertiary alkyl group having 4 to 20 carbon atoms, preferably 4 to 15 carbon atoms, each alkyl group is a trialkylsilyl group having 1 to 6 carbon atoms, and 4 to 20 carbon atoms. An oxoalkyl group or a group represented by the above general formula (A-3) is shown. Specific examples of the tertiary alkyl group include a tert-butyl group, a tert-amyl group, a 1,1-diethylpropyl group, and 1-ethyl. Cyclopentyl group, 1-butylcyclopentyl group, 1-ethylcyclohexyl group, 1-butylcyclohexyl group, 1-ethyl-2-cyclopentenyl group, 1-ethyl-2-cyclohexenyl group, 2-methyl-2-adamantyl group, etc. Specific examples of the trialkylsilyl group include a trimethylsilyl group, a triethylsilyl group, a dimethyl-tert-butylsilyl group, and the like. Specifically oxoalkyl group, 3-oxo-cyclohexyl group, 4-methyl-2-oxooxan-4-yl group, and 5-methyl-2-oxooxolan-5-yl group. a1 is an integer of 0-6.

In the formula (A-2), R ⁵¹ and R ⁵² represent a hydrogen atom or a linear, branched or cyclic alkyl group having 1 to 18, 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 ⁵³ 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 ⁵¹ and R ⁵² , R ⁵¹ and R ⁵³ , R ⁵² and R ⁵³ may form a ring, and in the case of forming a ring, R ⁵¹ , R ⁵² and R ⁵³ each have 1 to 18 carbon atoms, Preferably 1-10 linear or branched alkylene groups are shown.

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

  Furthermore, the substituent shown by following formula (A-1) -1-(A-1) -8 can also be mentioned.

R ⁵⁹ is a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms that is the same or different from each other, or an aryl group having 6 to 20 carbon atoms, and R ⁶⁰ is a hydrogen atom, the same or different carbon atoms that are mutually different. It is a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms, or an aryl group having 6 to 20 carbon atoms.

  Of the acid labile groups represented by the above formula (A-2), examples of the linear or branched groups include those of the following formulas (A-2) -1 to (A-2) -23. be able to.

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

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

In the formula, R ⁶¹ and R ⁶² represent a hydrogen atom or a linear, branched or cyclic alkyl group having 1 to 8 carbon atoms. Alternatively, R ⁶¹ and R ⁶² may be bonded to form a ring, and when forming a ring, R ⁶¹ and R ⁶² represent a linear or branched alkylene group having 1 to 8 carbon atoms. R ⁶³ 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) -24 to (A-2) -31.

Next, in the formula (A-3), R ⁵⁴ , R ⁵⁵ and R ⁵⁶ 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 contained, and R ⁵⁴ and R ⁵⁵ , R ⁵⁴ and R ⁵⁶ , R ⁵⁵ and R ⁵⁶ 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.

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

In formulas (A-3) -1 to (A-3) -18, R ⁶⁴ 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 is shown. R ⁶⁵ and R ^{67 each} represent a hydrogen atom or a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms. R ⁶⁶ represents an aryl group such as a phenyl group having 6 to 20 carbon atoms.

Furthermore the following formula (A-3) -19, as shown in (A-3) -20, 2 or more valences alkylene group, include R ⁶⁷ is an arylene group, within the molecule or between molecules of the polymer are crosslinked It may be. In formulas (A-3) -19 and (A-3) -20, R ⁶⁴ is the same as described above, and R ⁶⁸ 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. b2 is an integer of 1 to 3.

Further, R ⁵⁴ , R ⁵⁵ , and R ⁵⁶ in formula (A-3) may have a heteroatom such as oxygen, nitrogen, and sulfur, and specifically, the following formulas (A) -1 to (A ) -7.

Furthermore, R ⁵⁰ , R ⁵³ , and R ⁵⁶ in formulas (A-1), (A-2), and (A-3) are a phenyl group, a p-methylphenyl group, a p-ethylphenyl group, and p-methoxy. An unsubstituted or substituted aryl group such as an alkoxy-substituted phenyl group such as a phenyl group, an aralkyl group such as a benzyl group or a phenethyl group, or a hydrogen atom having an oxygen atom in these groups or bonded to a carbon atom is substituted with a hydroxyl group Or an alkyl group represented by the following formulas (A) -1 to (A) -7 in which two hydrogen atoms are substituted with oxygen atoms to form a carbonyl group, or formula (A) -8, ( A) -9, an oxoalkyl group represented by -9 can be mentioned.

  Examples of the oxoalkyl group having 4 to 20 carbon atoms include a 3-oxocyclohexyl group and a group represented by the following formula.

（式中、Ａ⁰¹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。Ｒ⁰¹、Ｒ⁰²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、Ｒ⁰¹、Ｒ⁰²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。Ｒ⁰³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。） The acid labile group represented by the formula (A-3) may be an acid labile group represented by the following general formula (A-4).

(In the formula, A ⁰¹ represents a divalent group selected from flangyl, tetrahydrofurandiyl or oxanorbornanediyl. R ⁰¹ and R ⁰² are each independently a linear, branched or cyclic group having 1 to 10 carbon atoms. Represents a monovalent hydrocarbon group, or R ⁰¹ and R ⁰² may be bonded to each other to form an aliphatic hydrocarbon ring together with the carbon atom to which they are bonded, and R ⁰³ may contain a hydrogen atom or a hetero atom; A good straight chain, branched or cyclic monovalent hydrocarbon group having 1 to 10 carbon atoms is shown.)

（式中、Ｒ⁰¹、Ｒ⁰²は上記と同様である。Ｒ⁰³、Ｒ⁰⁴は単結合、又は炭素数１〜４のアルキレン基であり、Ｒ⁰³＋Ｒ⁰⁴が炭素数３〜６のアルキレン基であり、２重結合を含んでいてもよい。） The oxygen-containing acid labile group (A-4) is represented by formulas (A-4) -1 and (A-4) -2.

(Wherein R ⁰¹ and R ⁰² are the same as above. R ⁰³ and R ⁰⁴ are a single bond or an alkylene group having 1 to 4 carbon atoms, and R ⁰³ + R ⁰⁴ is an alkylene group having 3 to 6 carbon atoms. And may contain a double bond.)

Specific examples of the formulas (A-4) -1 and (A-4) -2 can be given below. In the following formulae, Me represents a methyl group, and Ac represents an acetyl group.

In the present invention, as described above, as the base resin of the resist material,
(I) Mixture of polymer compound A having repeating unit a represented by general formula (1) and polymer compound B comprising repeating unit b represented by general formula (2) (II) General formula (1) Selected from polymer compound A having a repeating unit a represented by formula (1), one or more repeating units selected from c-1 to c-3 in formula (8), and d1 to d7 in formula (10). A mixture with a polymer compound C obtained by copolymerizing a repeating unit having a group whose alkali solubility is improved by at least one acid (III) a polymer having a repeating unit a represented by the general formula (1) Compound A, a repeating unit e represented by general formula (11) and a repeating unit having a group whose alkali solubility is improved by at least one acid selected from d1 to d7 in general formula (10) are combined. polymerization But it is intended to use a mixture of a polymer compound D comprising Te, where the polymer compound A and the polymer compound B, the mixing ratio of the C or D is preferably as follows.
0.1 ≦ A / (A + B + C + D) ≦ 0.9, especially 0.2 ≦ A / (A + B + C + D) ≦ 0.8
0 ≦ B / (A + B + C + D) ≦ 0.9, especially 0 ≦ B / (A + B + C + D) ≦ 0.8
0 ≦ C / (A + B + C + D) ≦ 0.9, especially 0 ≦ C / (A + B + C + D) ≦ 0.8
0 ≦ D / (A + B + C + D) ≦ 0.9, especially 0 ≦ D / (A + B + C + D) ≦ 0.8
0.1 ≦ (B + C + D) / (A + B + C + D) ≦ 0.9, especially 0.2 ≦ (B + C + D) / (A + B + C + D) ≦ 0.8

The resist material of the present invention is suitably used as a chemically amplified, particularly chemically amplified positive resist material,
(1) the base resin,
(2) an acid generator,
(3) contains an organic solvent, and if necessary (4) a dissolution inhibitor,
(5) It can be set as the composition containing a basic compound.

  (2) Component acid generators include onium salts of the following general formula (i), diazomethane derivatives of formula (ii), glyoxime derivatives of formula (iii), β-ketosulfone derivatives, disulfone derivatives, nitrobenzyl sulfonate derivatives, Examples thereof include sulfonic acid ester derivatives and imido-yl sulfonate derivatives.

_{^{(R 100) w M + K}} - (i)
(However, R ¹⁰⁰ represents a linear 1 to 12 carbon atoms which may be the same or different, branched or cyclic alkyl group, an aryl group or an aralkyl group having 7 to 12 carbon atoms of 6 to 12 carbon atoms M ⁺ represents iodonium or sulfonium, K ⁻ represents a non-nucleophilic counter ion, and w is 2 or 3.)

Examples of the alkyl group for R ¹⁰⁰ include a methyl group, an ethyl group, a propyl group, a butyl group, a cyclohexyl group, a 2-oxocyclohexyl group, a norbornyl group, and an adamantyl group. As the aryl group, an alkoxyphenyl group such as a phenyl group, p-methoxyphenyl group, m-methoxyphenyl group, o-methoxyphenyl group, ethoxyphenyl group, p-tert-butoxyphenyl group, m-tert-butoxyphenyl group, Examples thereof include alkylphenyl groups such as -methylphenyl group, 3-methylphenyl group, 4-methylphenyl group, ethylphenyl group, 4-tert-butylphenyl group, 4-butylphenyl group and dimethylphenyl group. Examples of the aralkyl group include a benzyl group and a phenethyl group. Non-nucleophilic counter ions of K ⁻ include halide ions such as chloride ion and bromide ion, fluoroalkyl sulfonates such as triflate, 1,1,1-trifluoroethane sulfonate, and nonafluorobutane sulfonate, tosylate, and benzene sulfonate. And aryl sulfonates such as 4-fluorobenzene sulfonate and 2,3,4,5,6-pentafluorobenzene sulfonate, and alkyl sulfonates such as mesylate and butane sulfonate.

（但し、Ｒ¹⁰¹、Ｒ¹⁰²は同一でも異なっ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又はハロゲン化アルキル基、炭素数６〜１２のアリール基又はハロゲン化アリール基又は炭素数７〜１２のアラルキル基を表す。）

(However, R ¹⁰¹ and R ¹⁰² may be the same or different and each is a linear, branched or cyclic alkyl group or halogenated alkyl group having 1 to 12 carbon atoms, an aryl group having 6 to 12 carbon atoms, or a halogenated group. Represents an aryl group or an aralkyl group having 7 to 12 carbon atoms.)

^Examples of the alkyl group for R ¹⁰¹ and R ¹⁰² include a methyl group, an ethyl group, a propyl group, a butyl group, an amyl group, a cyclopentyl group, a cyclohexyl group, a norbornyl group, and an adamantyl group. Examples of the halogenated alkyl group include a trifluoromethyl group, a 2,2,2-trifluoroethyl group, a 2,2,2-trichloroethyl group, and a nonafluorobutyl group. As the aryl group, an alkoxyphenyl group such as a phenyl group, p-methoxyphenyl group, m-methoxyphenyl group, o-methoxyphenyl group, ethoxyphenyl group, p-tert-butoxyphenyl group, m-tert-butoxyphenyl group, Examples thereof include alkylphenyl groups such as 2-methylphenyl group, 3-methylphenyl group, 4-methylphenyl group, ethylphenyl group, 4-tert-butylphenyl group, 4-butylphenyl group, and dimethylphenyl group. Examples of the halogenated aryl group include a fluorophenyl group, a chlorophenyl group, and 2,3,4,5,6-pentafluorophenyl group. Examples of the aralkyl group include a benzyl group and a phenethyl group.

（但し、Ｒ¹⁰³、Ｒ¹⁰⁴、Ｒ¹⁰⁵は炭素数１〜１２の直鎖状、分岐状又は環状のアルキル基又はハロゲン化アルキル基、炭素数６〜１２のアリール基又はハロゲン化アリール基又は炭素数７〜１２のアラルキル基を表す。また、Ｒ¹⁰⁴、Ｒ¹⁰⁵は互いに結合して環状構造を形成してもよく、環状構造を形成する場合、Ｒ¹⁰⁴、Ｒ¹⁰⁵はそれぞれ炭素数１〜６の直鎖状又は分岐状のアルキレン基を表す。）

(However, R ¹⁰³ , R ¹⁰⁴ , and R ¹⁰⁵ are linear, branched or cyclic alkyl groups or halogenated alkyl groups having 1 to 12 carbon atoms, aryl groups or halogenated aryl groups having 6 to 12 carbon atoms, or carbon atoms. Represents an aralkyl group of 7 to 12. R ¹⁰⁴ and R ¹⁰⁵ may be bonded to each other to form a cyclic structure, and when forming a cyclic structure, R ¹⁰⁴ and R ¹⁰⁵ each have 1 to 6 carbon atoms. Represents a linear or branched alkylene group.)

Examples of the alkyl group, halogenated alkyl group, aryl group, halogenated aryl group, and aralkyl group of R ¹⁰³ , R ¹⁰⁴ , and R ¹⁰⁵ include the same groups as those described for R ¹⁰¹ and R ¹⁰² . ^Examples of the alkylene group for R ¹⁰⁴ and R ¹⁰⁵ include a methylene group, an ethylene group, a propylene group, a butylene group, and a hexylene group.

  Specifically, for example, diphenyliodonium trifluoromethanesulfonate, trifluoromethanesulfonic acid (p-tert-butoxyphenyl) phenyliodonium, diphenyliodonium p-toluenesulfonate, p-toluenesulfonic acid (p-tert-butoxyphenyl) phenyl Iodonium, triphenylsulfonium trifluoromethanesulfonate, trifluoromethanesulfonate (p-tert-butoxyphenyl) diphenylsulfonium, bis (p-tert-butoxyphenyl) phenylsulfonium trifluoromethanesulfonate, tris (p-tert) trifluoromethanesulfonate -Butoxyphenyl) sulfonium, p-toluenesulfonic acid triphenylsulfonium, p-toluenesulfonic acid (pt rt-butoxyphenyl) diphenylsulfonium, bis (p-tert-butoxyphenyl) phenylsulfonium p-toluenesulfonate, tris (p-tert-butoxyphenyl) sulfonium p-toluenesulfonate, triphenylsulfonium nonafluorobutanesulfonate, Triphenylsulfonium butanesulfonate, trimethylsulfonium trifluoromethanesulfonate, trimethylsulfonium p-toluenesulfonate, cyclohexylmethyl (2-oxocyclohexyl) sulfonium trifluoromethanesulfonate, cyclohexylmethyl (2-oxocyclohexyl) sulfonium p-toluenesulfonate , Dimethylphenylsulfonium trifluoromethanesulfonate, dimethylphenol p-toluenesulfonate Onyl salts such as nylsulfonium, dicyclohexylphenylsulfonium trifluoromethanesulfonate, dicyclohexylphenylsulfonium p-toluenesulfonate, bis (benzenesulfonyl) diazomethane, bis (p-toluenesulfonyl) diazomethane, bis (xylenesulfonyl) diazomethane, bis (cyclohexyl) Sulfonyl) diazomethane, bis (cyclopentylsulfonyl) diazomethane, bis (n-butylsulfonyl) diazomethane, bis (isobutylsulfonyl) diazomethane, bis (sec-butylsulfonyl) diazomethane, bis (n-propylsulfonyl) diazomethane, bis (isopropylsulfonyl) Diazomethane, bis (tert-butylsulfonyl) diazomethane, bis (n-amylsulfonyl) ) Diazomethane, bis (isoamylsulfonyl) diazomethane, bis (sec-amylsulfonyl) diazomethane, bis (tert-amylsulfonyl) diazomethane, 1-cyclohexylsulfonyl-1- (tert-butylsulfonyl) diazomethane, 1-cyclohexylsulfonyl-1- Diazomethane derivatives such as (tert-amylsulfonyl) diazomethane, 1-tert-amylsulfonyl-1- (tert-butylsulfonyl) diazomethane, bis-o- (p-toluenesulfonyl) -α-dimethylglyoxime, bis-o- (P-toluenesulfonyl) -α-diphenylglyoxime, bis-o- (p-toluenesulfonyl) -α-dicyclohexylglyoxime, bis-o- (p-toluenesulfonyl) -2,3-pentanedi Nglyoxime, bis-o- (p-toluenesulfonyl) -2-methyl-3,4-pentanedione glyoxime, bis-o- (n-butanesulfonyl) -α-dimethylglyoxime, bis-o- (n- Butanesulfonyl) -α-diphenylglyoxime, bis-o- (n-butanesulfonyl) -α-dicyclohexylglyoxime, bis-o- (n-butanesulfonyl) -2,3-pentanedioneglyoxime, bis-o -(N-butanesulfonyl) -2-methyl-3,4-pentanedione glyoxime, bis-o- (methanesulfonyl) -α-dimethylglyoxime, bis-o- (trifluoromethanesulfonyl) -α-dimethylglyme Oxime, bis-o- (1,1,1-trifluoroethanesulfonyl) -α-dimethylglyoxime, bis o- (tert-butanesulfonyl) -α-dimethylglyoxime, bis-o- (perfluorooctanesulfonyl) -α-dimethylglyoxime, bis-o- (cyclohexanesulfonyl) -α-dimethylglyoxime, bis-o -(Benzenesulfonyl) -α-dimethylglyoxime, bis-o- (p-fluorobenzenesulfonyl) -α-dimethylglyoxime, bis-o- (p-tert-butylbenzenesulfonyl) -α-dimethylglyoxime, Glyoxime derivatives such as bis-o- (xylenesulfonyl) -α-dimethylglyoxime, bis-o- (camphorsulfonyl) -α-dimethylglyoxime, 2-cyclohexylcarbonyl-2- (p-toluenesulfonyl) propane, 2 -Isopropylcarbonyl-2- (p-tolue Sulfonyl) propane and other β-ketosulfone derivatives, diphenyldisulfone, dicyclohexyldisulfone and other disulfone derivatives, p-toluenesulfonic acid 2,6-dinitrobenzyl, p-toluenesulfonic acid 2,4-dinitrobenzyl and other nitrobenzylsulfonate derivatives, Sulfonic acid ester derivatives such as 1,2,3-tris (methanesulfonyloxy) benzene, 1,2,3-tris (trifluoromethanesulfonyloxy) benzene, 1,2,3-tris (p-toluenesulfonyloxy) benzene Phthalimido-yl-triflate, phthalimido-yl-tosylate, 5-norbornene-2,3-dicarboximido-yl-triflate, 5-norbornene-2,3-dicarboximido-yl-tosylate, 5-norbol And imide-yl-sulfonate derivatives such as 2-phenylcarboxyl-yl-n-butylsulfonate, triphenylsulfonium trifluoromethanesulfonate, and trifluoromethanesulfonic acid (p-tert-butoxyphenyl). Diphenylsulfonium, trifluoromethanesulfonic acid tris (p-tert-butoxyphenyl) sulfonium, p-toluenesulfonic acid triphenylsulfonium, p-toluenesulfonic acid (p-tert-butoxyphenyl) diphenylsulfonium, p-toluenesulfonic acid tris ( Onium salts such as p-tert-butoxyphenyl) sulfonium, bis (benzenesulfonyl) diazomethane, bis (p-toluenesulfonyl) diazomethane, bis (cyclohexylsulfo) Lu) diazomethane, bis (n-butylsulfonyl) diazomethane, bis (isobutylsulfonyl) diazomethane, bis (sec-butylsulfonyl) diazomethane, bis (n-propylsulfonyl) diazomethane, bis (isopropylsulfonyl) diazomethane, bis (tert-butyl) Diazomethane derivatives such as sulfonyl) diazomethane, glyoxime derivatives such as bis-o- (p-toluenesulfonyl) -α-dimethylglyoxime, bis-o- (n-butanesulfonyl) -α-dimethylglyoxime, naphthoquinonediazidesulfonic acid Ester derivatives are preferably used. In addition, the said acid generator can be used individually by 1 type or in combination of 2 or more types. An onium salt is excellent in the effect of improving rectangularity, and a diazomethane derivative and a glyoxime derivative are excellent in a standing wave reducing effect. However, by combining both, the profile can be finely adjusted.

  The blending amount of the acid generator is preferably 0.2 to 50 parts, particularly preferably 0.5 to 40 parts, and less than 0.2 parts with respect to 100 parts (parts by mass) of the total base resin. The amount of acid generated during exposure is small, and the sensitivity and resolution may be inferior. When the amount exceeds 50 parts, the transmittance of the resist may be lowered and the resolution may be inferior.

  The organic solvent of component (3) used in the present invention may be any organic solvent that can dissolve acid generators, base resins, dissolution inhibitors, and the like. Examples of such an organic solvent include ketones such as cyclohexanone and methyl-2-n-amyl ketone, 3-methoxybutanol, 3-methyl-3-methoxybutanol, 1-methoxy-2-propanol, and 1-ethoxy-2. -Alcohols such as propanol, propylene glycol monomethyl ether, ethylene glycol monomethyl ether, propylene glycol monoethyl ether, ethylene glycol monoethyl ether, propylene glycol dimethyl ether, diethylene glycol dimethyl ether, and other ethers, propylene glycol monomethyl ether acetate, propylene glycol monoethyl Ether acetate, ethyl lactate, ethyl pyruvate, butyl acetate, methyl 3-methoxypropionate, 3-ethoxy Esters such as ethyl lopionate, tert-butyl acetate, tert-butyl propionate, propylene glycol mono-tert-butyl ether acetate, etc. are used, and one of these may be used alone or in combination of two or more. However, it is not limited to these. In the present invention, among these organic solvents, diethylene glycol dimethyl ether, 1-ethoxy-2-propanol, and ethyl lactate, which are most excellent in solubility of the acid generator in the resist component, as well as propylene glycol monomethyl ether acetate, which is a safety solvent, are used. And mixed solvents thereof are preferably used.

  The blending amount is preferably 100 to 5,000 parts, particularly 200 to 3,000 parts, based on 100 parts of the total base resin.

  (4) As a component dissolution inhibitor, a compound having a weight average molecular weight of 3,000 or less, particularly a low molecular weight phenol or carboxylic acid derivative having a molecular weight of 2,500 or less, whose solubility in an alkaline developer is changed by the action of an acid. Examples thereof include compounds in which part or all are substituted with an acid-labile substituent. As the acid labile group, those similar to the above formulas (A-1) to (A-3) can be used.

  Examples of phenol or carboxylic acid derivatives having a weight average molecular weight of 2,500 or less include 4,4 ′-(1-methylethylidene) bisphenol and [1,1′-biphenyl-4,4′-diol] 2,2′-methylenebis. [4-Methylphenol], 4,4-bis (4′-hydroxyphenyl) valeric acid, tris (4-hydroxyphenyl) methane, 1,1,1-tris (4′-hydroxyphenyl) ethane, 1,1 , 2-tris (4′-hydroxyphenyl) ethane, phenolphthalein, thymolphthalein, 3,3′difluoro [(1,1′biphenyl) 4,4′-diol], 3,3′5,5 ′ -Tetrafluoro [(1,1'-biphenyl) -4,4'-diol], 4,4 '-[2,2,2-trifluoro-1- (trifluoromethyl) Redene] bisphenol, 4,4′-methylenebis [2-fluorophenol], 2,2′-methylenebis [4-fluorophenol], 4,4′isopropylidenebis [2-fluorophenol], cyclohexylidenebis [2 -Fluorophenol], 4,4 '-[(4-fluorophenyl) methylene] bis [2-fluorophenol], 4,4'-methylenebis [2,6-difluorophenol], 4,4'-(4- Fluorophenyl) methylenebis [2,6-difluorophenol], 2,6-bis [(2-hydroxy-5-fluorophenyl) methyl] -4-fluorophenol, 2,6-bis [(4-hydroxy-3- Fluorophenyl) methyl] -4-fluorophenol, 2,4-bis [(3-hydroxy-4-hydroxy) Phenyl) methyl] -6-methylphenol and the like.

  Examples of the dissolution inhibitor preferably used include 3,3′5,5′-tetrafluoro [(1,1′-biphenyl) -4,4′-di-t-butoxycarbonyl], 4,4 ′. -[2,2,2-trifluoro-1- (trifluoromethyl) ethylidene] bisphenol-4,4'-di-t-butoxycarbonyl, bis (4- (2'-tetrahydropyranyloxy) phenyl) methane Bis (4- (2′-tetrahydrofuranyloxy) phenyl) methane, bis (4-tert-butoxyphenyl) methane, bis (4-tert-butoxycarbonyloxyphenyl) methane, bis (4-tert-butoxycarbonylmethyl) Oxyphenyl) methane, bis (4- (1′-ethoxyethoxy) phenyl) methane, bis (4- (1′-ethoxypropyloxy) ) Phenyl) methane, 2,2-bis (4 ′-(2 ″ -tetrahydropyranyloxy)) propane, 2,2-bis (4 ′-(2 ″ -tetrahydrofuranyloxy) phenyl) propane, 2 , 2-bis (4′-tert-butoxycarbonyloxyphenyl) propane, 2,2-bis (4′-tert-butoxycarbonyloxyphenyl) propane, 2,2-bis (4-tert-butoxycarbonylmethyloxyphenyl) propane 2,2-bis (4 ′-(1 ″ -ethoxyethoxy) phenyl) propane, 2,2-bis (4 ′-(1 ″ -ethoxypropyloxy) phenyl) propane, 4,4-bis ( 4 ′-(2 ″ -tetrahydropyranyloxy) phenyl) tert-butyl valerate, 4,4-bis (4 ′-(2 ″ -tetrahydrofuranyl chloride) Ii) Phenyl) tert-butyl valerate, tert-butyl 4,4-bis (4′-tert-butoxyphenyl) valerate, tert-butyl 4,4-bis (4-tert-butoxycarbonyloxyphenyl) valerate , Tert-butyl 4,4-bis (4′-tert-butoxycarbonylmethyloxyphenyl) valerate, tert-butyl 4,4-bis (4 ′-(1 ″ -ethoxyethoxy) phenyl) valerate, 4, , 4-Bis (4 ′-(1 ″ -ethoxypropyloxy) phenyl) tert-butyl valerate, tris (4- (2′-tetrahydropyranyloxy) phenyl) methane, tris (4- (2′- Tetrahydrofuranyloxy) phenyl) methane, tris (4-tert-butoxyphenyl) methane, tris (4-tert-buto Xycarbonyloxyphenyl) methane, tris (4-tert-butoxycarbonyloxymethylphenyl) methane, tris (4- (1′-ethoxyethoxy) phenyl) methane, tris (4- (1′-ethoxypropyloxy) phenyl) Methane, 1,1,2-tris (4 ′-(2 ″ -tetrahydropyranyloxy) phenyl) ethane, 1,1,2-tris (4 ′-(2 ″ -tetrahydrofuranyloxy) phenyl) ethane 1,1,2-tris (4′-tert-butoxyphenyl) ethane, 1,1,2-tris (4′-tert-butoxycarbonyloxyphenyl) ethane, 1,1,2-tris (4′- tert-Butoxycarbonylmethyloxyphenyl) ethane, 1,1,2-tris (4 ′-(1′-ethoxyethoxy) Enyl) ethane, 1,1,2-tris (4 ′-(1′-ethoxypropyloxy) phenyl) ethane, 2-trifluoromethylbenzenecarboxylic acid 1,1-tert-butyl ester, 2-trifluoromethylcyclohexane Carboxylic acid-t-butyl ester, decahydronaphthalene-2,6-dicarboxylic acid-t-butyl ester, cholic acid-t-butyl ester, deoxycholic acid-t-butyl ester, adamantanecarboxylic acid-t-butyl ester, And adamantane acetic acid-t-butyl ester and [1,1′-bicyclohexyl-3,3 ′, 4,4′-tetracarboxylic acid tetra-t-butyl ester].

  The addition amount of the dissolution inhibitor in the resist material of the present invention is 20 parts or less, preferably 15 parts or less, based on 100 parts of the total base resin. If it exceeds 20 parts, the monomer component increases, so the heat resistance of the resist material decreases.

  As the basic compound, a compound that can suppress the degree of diffusion when the acid generated from the acid generator diffuses into the resist film is suitable, and by adding such a basic compound, It is possible to improve the resolution by suppressing the diffusion rate of the acid, to suppress the sensitivity change after exposure, to reduce the substrate and environment dependency, and to improve the exposure margin, the pattern profile, etc. 232706, 5-249683, 5-158239, 5-24962, 5-257282, 5-289322, 5-289340, etc.).

  Examples of such basic compounds include primary, secondary, and tertiary aliphatic amines, hybrid amines, aromatic amines, heterocyclic amines, nitrogen-containing compounds having a carboxy group, and sulfonyl groups. A nitrogen-containing compound having a hydroxy group, a nitrogen-containing compound having a hydroxy group, a nitrogen-containing compound having a hydroxyphenyl group, an alcoholic nitrogen-containing compound, an amide derivative, an imide derivative, and the like. Particularly, an aliphatic amine is preferably used.

  Specifically, primary aliphatic amines include ammonia, methylamine, ethylamine, n-propylamine, isopropylamine, n-butylamine, isobutylamine, sec-butylamine, tert-butylamine, pentylamine, tert- Amylamine, cyclopentylamine, hexylamine, cyclohexylamine, heptylamine, octylamine, nonylamine, decylamine, dodecylamine, cetylamine, methylenediamine, ethylenediamine, tetraethylenepentamine, etc. are exemplified as secondary aliphatic amines. Dimethylamine, diethylamine, di-n-propylamine, diisopropylamine, di-n-butylamine, diisobutylamine, di-sec-butylamine, dipentylamine, disi Lopentylamine, dihexylamine, dicyclohexylamine, diheptylamine, dioctylamine, dinonylamine, didecylamine, didodecylamine, dicetylamine, N, N-dimethylmethylenediamine, N, N-dimethylethylenediamine, N, N-dimethyltetraethylenepenta Examples of tertiary aliphatic amines include trimethylamine, triethylamine, tri-n-propylamine, triisopropylamine, tri-n-butylamine, triisobutylamine, tri-sec-butylamine, and tripentylamine. , Tricyclopentylamine, trihexylamine, tricyclohexylamine, triheptylamine, trioctylamine, trinonylamine, tridecylamine, tridodecylamine, Examples include cetylamine, N, N, N ′, N′-tetramethylmethylenediamine, N, N, N ′, N′-tetramethylethylenediamine, N, N, N ′, N′-tetramethyltetraethylenepentamine and the like. Is done.

  Examples of hybrid amines include dimethylethylamine, methylethylpropylamine, benzylamine, phenethylamine, and benzyldimethylamine. Specific examples of aromatic amines and heterocyclic amines include aniline derivatives (eg, aniline, N-methylaniline, N-ethylaniline, N-propylaniline, N, N-dimethylaniline, 2-methylaniline, 3- Methylaniline, 4-methylaniline, ethylaniline, propylaniline, trimethylaniline, 2-nitroaniline, 3-nitroaniline, 4-nitroaniline, 2,4-dinitroaniline, 2,6-dinitroaniline, 3,5- Dinitroaniline, N, N-dimethyltoluidine, etc.), diphenyl (p-tolyl) amine, methyldiphenylamine, triphenylamine, phenylenediamine, naphthylamine, diaminonaphthalene, pyrrole derivatives (eg pyrrole, 2H-pyrrole, 1-methylpyrrole, 2,4-dim Lupyrrole, 2,5-dimethylpyrrole, N-methylpyrrole, etc.), oxazole derivatives (eg oxazole, isoxazole etc.), thiazole derivatives (eg thiazole, isothiazole etc.), imidazole derivatives (eg imidazole, 4-methylimidazole, 4 -Methyl-2-phenylimidazole, etc.), pyrazole derivatives, furazane derivatives, pyrroline derivatives (eg pyrroline, 2-methyl-1-pyrroline etc.), pyrrolidine derivatives (eg pyrrolidine, N-methylpyrrolidine, pyrrolidinone, N-methylpyrrolidone etc.) ), Imidazoline derivatives, imidazolidine derivatives, pyridine derivatives (eg pyridine, methylpyridine, ethylpyridine, propylpyridine, butylpyridine, 4- (1-butylpentyl) pyridine, dimethyl) Lysine, trimethylpyridine, triethylpyridine, phenylpyridine, 3-methyl-2-phenylpyridine, 4-tert-butylpyridine, diphenylpyridine, benzylpyridine, methoxypyridine, butoxypyridine, dimethoxypyridine, 1-methyl-2-pyridine, 4-pyrrolidinopyridine, 1-methyl-4-phenylpyridine, 2- (1-ethylpropyl) pyridine, aminopyridine, dimethylaminopyridine, etc.), pyridazine derivatives, pyrimidine derivatives, pyrazine derivatives, pyrazoline derivatives, pyrazolidine derivatives, piperidine Derivatives, piperazine derivatives, morpholine derivatives, indole derivatives, isoindole derivatives, 1H-indazole derivatives, indoline derivatives, quinoline derivatives (eg quinoline, 3-quinoline carbo Nitriles), isoquinoline derivatives, cinnoline derivatives, quinazoline derivatives, quinoxaline derivatives, phthalazine derivatives, purine derivatives, pteridine derivatives, carbazole derivatives, phenanthridine derivatives, acridine derivatives, phenazine derivatives, 1,10-phenanthroline derivatives, adenine derivatives, adenosine Examples include derivatives, guanine derivatives, guanosine derivatives, uracil derivatives, uridine derivatives and the like.

  Furthermore, examples of the nitrogen-containing compound having a carboxy group include aminobenzoic acid, indolecarboxylic acid, amino acid derivatives (for example, nicotinic acid, alanine, arginine, aspartic acid, glutamic acid, glycine, histidine, isoleucine, glycylleucine, leucine, methionine. , Phenylalanine, threonine, lysine, 3-aminopyrazine-2-carboxylic acid, methoxyalanine and the like) and nitrogen-containing compounds having a sulfonyl group include 3-pyridinesulfonic acid, pyridinium p-toluenesulfonate, and the like. , Nitrogen-containing compounds having a hydroxy group, nitrogen-containing compounds having a hydroxyphenyl group, and alcoholic nitrogen-containing compounds include 2-hydroxypyridine, aminocresol, 2,4-quinolinediol, 3-indoleme Nord hydrate, monoethanolamine, diethanolamine, triethanolamine, N-ethyldiethanolamine, N, N-diethylethanolamine, triisopropanolamine, 2,2'-iminodiethanol, 2-aminoethanol, 3-amino-1 -Propanol, 4-amino-1-butanol, 4- (2-hydroxyethyl) morpholine, 2- (2-hydroxyethyl) pyridine, 1- (2-hydroxyethyl) piperazine, 1- [2- (2-hydroxy) Ethoxy) ethyl] piperazine, piperidine ethanol, 1- (2-hydroxyethyl) pyrrolidine, 1- (2-hydroxyethyl) -2-pyrrolidinone, 3-piperidino-1,2-propanediol, 3-pyrrolidino-1,2 -Propanediol, 8-hydroxy Yurolidine, 3-cuincridinol, 3-tropanol, 1-methyl-2-pyrrolidine ethanol, 1-aziridine ethanol, N- (2-hydroxyethyl) phthalimide, N- (2-hydroxyethyl) isonicotinamide, etc. Illustrated. Examples of amide derivatives include formamide, N-methylformamide, N, N-dimethylformamide, acetamide, N-methylacetamide, N, N-dimethylacetamide, propionamide, benzamide and the like. Examples of imide derivatives include phthalimide, succinimide, maleimide and the like.

Furthermore, 1 type, or 2 or more types chosen from the basic compound shown by the following general formula (B) -1 can also be mix | blended.
N (X) _n (Y) _3-n (B) -1
(In the formula, n is 1, 2 or 3. The side chain X may be the same or different and can be represented by the following general formulas (X) -1 to (X) -3. The side chain Y is It represents the same or different hydrogen atom or linear, branched or cyclic alkyl group having 1 to 20 carbon atoms, and may contain an ether group or a hydroxyl group, and Xs may combine to form a ring. May be.)

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

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

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

(In the formula, as described above, R ³⁰⁷ is a linear or branched alkylene group having 2 to 20 carbon atoms, and contains one or more carbonyl groups, ether groups, ester groups or sulfides. May be good.)

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

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

(Wherein, X, R ^307, n is an alkylene group of formula (B) as exemplified by -1, R ^308, R ³⁰⁹ is a straight-chain having 1 to 4 carbon atoms the same or different or branched. )

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

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

  In addition to the above components, a surfactant conventionally used for improving the coating property can be added to the resist material of the present invention. In addition, the addition amount of an arbitrary component can be made into a normal amount in the range which does not inhibit the effect of this invention.

  Here, the surfactant is preferably nonionic, and examples thereof include perfluoroalkyl polyoxyethylene ethanol, fluorinated alkyl ester, perfluoroalkylamine oxide, and fluorinated organosiloxane compound. For example, Florard “FC-430”, “FC-431” (all manufactured by Sumitomo 3M Limited), Surflon “S-141”, “S-145”, “S-381”, “S-383” (any Manufactured by Asahi Glass Co., Ltd.), Unidyne "DS-401", "DS-403", "DS-451" (all manufactured by Daikin Industries, Ltd.), MegaFuck "F-8151", "F-171" , “F-172”, “F-173”, “F-177” (all manufactured by Dainippon Ink and Co., Ltd.), “X-70-092”, “X-70-093” (all Shin-Etsu) Chemical Industry Co., Ltd.). Preferably, Florard “FC-430” (manufactured by Sumitomo 3M Co., Ltd.), “X-70-093” (manufactured by Shin-Etsu Chemical Co., Ltd.) can be used.

In order to form a pattern using the resist material of the present invention, a known lithography technique can be employed. For example, a film thickness of 0.1 to 0.1 can be formed on a substrate such as a silicon wafer by spin coating or the like. It is applied to a thickness of 1.0 μm and prebaked on a hot plate at 60 to 200 ° C. for 10 seconds to 10 minutes, preferably 80 to 150 ° C. for 30 seconds to 5 minutes. Next, a mask for forming a target pattern is placed over the resist film, and a high-energy ray such as far ultraviolet ray having a wavelength of 300 nm or less, an excimer laser, an X-ray or an electron beam is applied to an exposure amount of about 1 to 200 mJ / cm ² , Preferably, after irradiating to about 10 to 100 mJ / cm ^2, post exposure baking (PEB) on a hot plate at 60 to 150 ° C. for 10 seconds to 5 minutes, preferably 80 to 130 ° C. for 30 seconds to 3 minutes. ) Further, 0.1 to 5% by mass, preferably 2 to 3% by mass, using an alkaline aqueous developer such as tetramethylammonium hydroxide (TMAH) for 10 seconds to 3 minutes, preferably 30 seconds to 2 minutes. A target pattern is formed on the substrate by developing by a conventional method such as a (dip) method, a paddle method, or a spray method. The material of the present invention is an ultraviolet ray or excimer laser of 254 to 120 nm, particularly an excimer laser such as KrF of 248 nm, ArF of 193 nm, Kr _{2 of} 146 nm, KrAr of 134 nm, F _{2 of} 157 nm, It is optimal for fine patterning with a laser such as 126 nm Ar ₂ , X-rays and electron beams. In addition, when the above range deviates from the upper limit and the lower limit, the target pattern may not be obtained.

The pattern formation method of this invention is illustrated.
FIG. 1 shows a method of forming a silicon-containing resist pattern by exposure, PEB, and development, forming a base organic film pattern by oxygen gas etching, and processing a film to be processed by dry etching. Here, in FIG. 1 (A), 1 is a base substrate, 2 is a substrate to be processed (SiO ₂ , SiN, etc.), 3 is an organic film (novolak, polyhydroxystyrene, etc.), 4 is a silicon-containing material according to the present invention. It is a resist layer made of a resist material containing a molecular compound. As shown in FIG. 1 (B), the required portion of this resist layer is exposed 5 and further subjected to PEB and development as shown in FIG. 1 (C). Then, the exposed region is removed, and further, oxygen plasma etching is performed as shown in FIG. 1D, and a substrate to be processed is etched (CF-based gas) as shown in FIG. it can.

Here, oxygen gas etching is reactive plasma etching containing oxygen gas as a main component, and the underlying organic film can be processed with a high aspect ratio. In addition to the oxygen gas, SO ₂ , N ₂ , NO ₂ , NH ₃ , CO, and CO ₂ gases may be added for the purpose of protecting the sidewall in order to prevent the T-top shape due to overetching. In addition, in order to remove the scum of the resist after development, to smooth the line edge and prevent roughness, it is possible to perform etching with a short-time fluorocarbon gas before performing oxygen gas etching. Next, in the dry etching processing of the film to be processed, if the film to be processed is SiO ₂ or Si ₃ N ₄ , etching using a fluorocarbon gas as a main component is performed. Examples of the fluorocarbon gas include CF ₄ , CHF ₃ , CH ₂ F ₂ , C ₂ F ₆ , C ₃ F ₈ , C ₄ F ₁₀ , and C ₅ F ₁₂ . At this time, the silicon-containing resist film can be peeled off simultaneously with dry etching of the film to be processed. When the film to be processed is polysilicon, tungsten silicide, TiN / Al, or the like, etching using chlorine and bromine gas as main components is performed.

The silicon-containing resist material of the present invention exhibits excellent resistance to etching mainly composed of chlorine and bromine gas, and the same processing method as that for a single layer resist can be used.
FIG. 2 shows this. In FIG. 2 (A), 1 is a base substrate, 6 is a substrate to be processed, 4 is the resist layer, and as shown in FIGS. 2 (B) and 2 (C). Further, after performing exposure 5, PEB, and development, the substrate to be processed (Cl-based gas) can be etched as shown in FIG. 2D. Thus, the present invention is directly above the film to be processed. This silicon-containing resist film can be patterned, and the film to be processed can be processed by etching mainly containing chlorine and bromine gas.

  EXAMPLES Hereinafter, although a synthesis example and an Example are shown and this invention is demonstrated concretely, this invention is not restrict | limited to the following Example. In the following examples, the weight average molecular weight Mw and the number average molecular weight Mn are molecular weights in terms of polystyrene by gel permeation chromatography.

[Polymer synthesis example 1]
In 200 g of tetrahydrofuran and 100 g of pure water, 16.6 g of 2-tert-butoxycarbonyl-5 (6) -trimethoxysilylnorbornane (the following monomer 1) and 15 g of 4-hydroxybenzyltrimethoxysilane (the following monomer 2) are dissolved, The temperature was 35 ° C., 9.1 g of tetramethylammonium hydroxide was added dropwise over 1 hour, and then the temperature was raised to 80 ° C. to conduct a silanol condensation reaction.
200 g of diethyl ether was added to the reaction solution, the aqueous layer was separated, the organic liquid layer was washed twice with 1% acetic acid aqueous solution and twice with ultrapure water, and dried under reduced pressure to give 2-tert-butoxycarbonyl-norbornane- Co-4-hydroxybenzyl polysilsesquioxane was obtained. As a result of GPC and ¹ H-NMR analysis of the obtained polymer, it was confirmed that the obtained polymer had the following structure (Polymer 1).

[Polymer synthesis example 2]
200 g of tetrahydrofuran, 100 g of pure water, 2-tert-butoxycarbonyl-5 (6) -trimethoxysilylnorbornane (monomer 1) 16.6 g, 5-hydroxy-2 (3) -trimethoxysilylindane (monomer 3 below) 15 g The temperature of the solution was adjusted to 35 ° C., 9.1 g of tetramethylammonium hydroxide was added dropwise over 1 hour, and then the temperature was raised to 80 ° C. to conduct a condensation reaction of silanol.
200 g of diethyl ether was added to the reaction solution, the aqueous layer was separated, the organic liquid layer was washed twice with 1% acetic acid aqueous solution and twice with ultrapure water, and dried under reduced pressure to give 2-tert-butoxycarbonyl-norbornane- Co-5-hydroxyindane polysilsesquioxane was obtained. As a result of GPC and ¹ H-NMR analysis of the obtained polymer, it was confirmed that the obtained polymer had the following structure (Polymer 2).

[Polymer Synthesis Example 3]
To 200 g of tetrahydrofuran and 100 g of pure water, 16.6 g of 2-tert-butoxycarbonyl-5 (6) -trimethoxysilylnorbornane (monomer 1), 2-methoxycarbonyl-5 (6) -trimethoxysilylnorbornane (monomer 4 below) 38.8 g, 2-carboxyl-5 (6) -trimethoxysilylnorbornane (3.8 g of the following monomer) 3.8 g was dissolved, the liquid temperature was 35 ° C., and 9.1 g of tetramethylammonium hydroxide was added dropwise over 1 hour. Then, the temperature was raised to 80 ° C. to conduct a condensation reaction of silanol.
200 g of diethyl ether was added to the reaction solution, the aqueous layer was separated, the organic liquid layer was washed twice with 1% acetic acid aqueous solution and twice with ultrapure water, and dried under reduced pressure to give 2-tert-butoxycarbonyl-norbornane- Co-2-methoxycarbonyl-5 (6) -norbornane-co-2-carboxyl-5 (6) -norbornane polysilsesquioxane was obtained. As a result of GPC and ¹ H-NMR analysis of the obtained polymer, it was confirmed that the obtained polymer had the following structure (Polymer 3).

[Polymer Synthesis Example 4]
To 200 g of tetrahydrofuran and 100 g of pure water, 16.6 g of 2-tert-butoxycarbonyl-5 (6) -trimethoxysilylnorbornane (monomer 1), 2-methoxycarbonyl-5 (6) -trimethoxysilylnorbornane (monomer 4) 33 .4 g, (2-hydroxy-2,2-bistrifluoromethyl) ethyl-trimethoxysilylnorbornane (the following monomer 6) 18.2 g was dissolved, the liquid temperature was adjusted to 35 ° C., and tetramethylammonium hydroxide 9.1 g was dissolved. The mixture was added dropwise over 1 hour, and then the temperature was raised to 80 ° C. to conduct a condensation reaction of silanol.
200 g of diethyl ether was added to the reaction solution, the aqueous layer was separated, the organic liquid layer was washed twice with 1% acetic acid aqueous solution and twice with ultrapure water, and dried under reduced pressure to give 2-tert-butoxycarbonyl-norbornane- Co-2-methoxycarbonyl-5 (6) -norbornane-co- (2-hydroxy-2,2-bistrifluoromethyl) ethyl-norbornane polysilsesquioxane was obtained. As a result of GPC and ¹ H-NMR analysis of the obtained polymer, it was confirmed that the obtained polymer had the following structure (Polymer 4).

[Polymer synthesis example 5]
2-ethyl-2-adamantyl methacrylate and methacrylic acid-3-oxo-2,7-dioxatricyclo [4.2.1.0 ^4.8 ] -9-nonane (monomer 12 below) and methacrylic acid 3- (3,5,7,9,11,13,15-heptacyclopentylpentacyclo [9.5.1.1 ^3,9 .1 ^5,15 .1 ^7,13 ] octasiloxane-1-yl) propyl ( Synthesis of the following monomers 7) and (30:55:15) In a 1 L flask, 74 g of 2-ethyladamantyl methacrylate and 5-oxo-oxatricyclo [4.2.1.0 ^3,7 ] nonane methacrylate 2-yl (monomer 12) 120 g and methacrylic acid 3- (3,5,7,9,11,13,15-heptacyclopentylpentacyclo [9.5.1.1 ^3,9 .1 ^5,15 . 1 ^7,13] oct-1-siloxane (1) 120 g of propyl (monomer 7) was dissolved in 380 mL of tetrahydrofuran (hereinafter abbreviated as THF), and after sufficiently removing oxygen in the system, 8.2 g of initiator AIBN was charged, and then the temperature was raised to 60 ° C. The polymerization reaction was performed for 24 hours.
In order to purify the obtained polymer, the reaction mixture was poured into a mixed solvent of hexane / ether (3: 2), and the obtained polymer was precipitated and separated to obtain 266 g of a white polymer.
The white polymer thus obtained was obtained by the following steps: methacrylate-2-ethyladamantyl-methacrylic acid-3-oxo-2,7-dioxatricyclo [4.2.1.0 ^4.8 ] -9-nonane ( Monomer 1) -methacrylic acid 3- (3,5,7,9,11,13,15-heptacyclopentylpentacyclo [9.5.1.1 ^3,9 .1 ^5,15 .1 ^7,13 ] octa Siloxane-1-yl) propyl (monomer 3) copolymer (30:55:15), having a weight average molecular weight of 16,100 by light scattering method, and dispersity (= Mw / Mn) from GPC elution curve. It was confirmed that the polymer was 1.98. Furthermore, by measuring ¹ H-NMR, it was confirmed that the polymer was contained in a ratio of approximately 30:55:15 as described above (Polymer 5).

[Polymer Synthesis Example 6]
2-ethyladamantyl methacrylate and methacrylic acid-3-oxo-2,7-dioxatricyclo [4.2.1.0 ^4.8 ] -9-nonane (monomer 12) and methacrylic acid 3- [tris (trimethyl Synthesis of (siloxy) silyl] propyl (monomer 8 below) and (30:55:15) In a 1 L flask, 74 g of 2-ethyladamantyl methacrylate and 3-oxo-2,7-dioxatricyclomethacrylate [meth] 4.2.1.0 ^4.8 ] -9-nonane (monomer 12) 120 g and methacrylic acid 3- [tris (trimethylsiloxy) silyl] propyl (monomer 8) 64 g are dissolved in 380 mL of THF, and oxygen in the system is sufficiently dissolved. After the removal, 8.2 g of initiator AIBN was charged, and then the temperature was raised to 60 ° C. to conduct a polymerization reaction for 24 hours.
In order to purify the obtained polymer, the reaction mixture was poured into a mixed solvent of hexane / ether (3: 2), and the obtained polymer was precipitated and separated to obtain 210 g of a white polymer.
The white polymer thus obtained was obtained by the following steps: methacrylate-2-ethyladamantyl-methacrylic acid-3-oxo-2,7-dioxatricyclo [4.2.1.0 ^4.8 ] -9-nonane ( Monomer 12) -methacrylic acid 3- [tris (trimethylsiloxy) silyl] propyl (monomer 8) copolymer (30:55:15), having a weight average molecular weight of 12,100 by light scattering method, and GPC elution curve It was confirmed that the polymer had a dispersity (= Mw / Mn) of 1.88. Furthermore, by measuring ¹ H-NMR, it was confirmed that the polymer was contained in a ratio of approximately 30:55:15 as described above (Polymer 6).

[Polymer Synthesis Example 7]
Tris (trimethylsilyl) silylethyl methacrylate (monomer 9 below), methacrylic acid-3-oxo-2,7-dioxatricyclo [4.2.1.0 ^4.8 ] -9-nonane (monomer 12) and p-hydroxy Synthesis of Styrene Copolymer (15:25:60) In a 1 L flask, 60 g of tris (trimethylsilyl) silylethyl methacrylate (monomer 9) and 5-oxo-oxatricyclo methacrylate [4.2.1.0 ^{3, 7} ] 80 g of nonan-2-yl (monomer 12) and 100 g of p-hydroxystyrene were dissolved in 560 mL of THF, and after sufficiently removing oxygen in the system, 5.5 g of initiator AIBN was charged, and then the temperature was raised to 60 ° C. Then, the polymerization reaction was carried out for 24 hours.
In order to purify the obtained polymer, the reaction mixture was poured into a mixed solvent of hexane / ether (3: 2), and the obtained polymer was precipitated and separated. As a result, 168 g of white polymer tris (trimethylsilyl) methacrylate was obtained. Silylethyl (monomer 9), methacrylic acid-3-oxo-2,7-dioxatricyclo [4.2.1.0 ^4.8 ] -9-nonane (monomer 12) and p-hydroxystyrene copolymer (copolymerization) Ratio 15:25:60).
The white polymer thus obtained, tris (trimethylsilyl) silylethyl methacrylate, methacrylic acid-3-oxo-2,7-dioxatricyclo [4.2.1.0 ^4.8 ] -9-nonane and p- Hydroxystyrene copolymer (copolymerization ratio 15:25:60) is a polymer having a weight average molecular weight of 16,000 by light scattering method and a dispersity (= Mw / Mn) of 1.65 from the GPC elution curve. It was confirmed that there was. Furthermore, by measuring ¹ H-NMR, it was confirmed that the polymer was contained at a ratio of 15:25:60 (polymer 7).

[Polymer Synthesis Example 8]
5-norbornene-2-carboxylic acid 1- (7-oxanorbornan-2-yl) cyclopentyl (the following monomer 13), vinylheptamethylcyclotetrasiloxane (the following monomer 10), maleic anhydride copolymer (38:12: 50) Synthesis In a 200 mL flask, 30.2 g of 1- (7-oxanorbornan-2-yl) cyclopentyl 5-monbornene-2-carboxylate (monomer 13) and 10 g of vinylheptamethylcyclotetrasiloxane (monomer 10) Then, 20 g of maleic anhydride was added to 50 mL of propylene glycol monomethyl ether acetate. 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, 4.0 g of AIBN was added as a polymerization initiator, and the temperature was raised to 55 ° C., followed by reaction for 25 hours. The reaction solution was diluted by adding 5 mL of acetone, and then precipitated in a 4.5 L solution of isopropyl alcohol. The resulting white solid was filtered and dried under reduced pressure at 40 ° C. to obtain 36 g of a white polymer.
It was confirmed by a light scattering method that the polymer had a weight average molecular weight of 7,300 and a degree of dispersion (= Mw / Mn) of 1.68 from the GPC elution curve. Furthermore, by measuring ¹ H-NMR, in the polymer, 1- (7-oxanorbornan-2-yl) cyclopentyl (monomer 13), 5-heptorene-2-carboxylic acid (monomer 13), vinylheptamethylcyclotetrasiloxane (monomer) 10) It was confirmed that maleic anhydride repeating units were contained in a ratio of 37:13:50 (Polymer 8).

[Polymer synthesis example 9]
In a 300 mL flask, 19.6 g of maleic anhydride, 1- (dimethylvinylsilyloxy) -3,5,7,9,11,13,15-heptacyclopentylpentacyclo [9.5.1.1 ^3,9 . 1 ^5,15 . 1 ^7,13 ] octasiloxane (the following monomer 11) 42 g, 5-norbornene-2-carboxylic acid 1- (7-oxanorbornan-2-yl) cyclopentyl (monomer 13) 60 g, and 100 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, 6.0 g of 2,2′-azobis (2,4-dimethylvaleronitrile) was added as a polymerization initiator, and the temperature was raised to 55 ° C., followed by reaction for 25 hours. The reaction solution was diluted by adding 15 mL of acetone and then precipitated in a 4.5 L solution of isopropyl alcohol. The resulting white solid was filtered and dried under reduced pressure at 40 ° C. to obtain 86 g of a white polymer.
When the obtained polymer was measured by ¹³ C, ¹ H-NMR and GPC, the following analysis results were obtained.
Copolymer composition ratio (molar ratio)
Maleic anhydride: monomer 11: monomer 13 = 51: 9: 40
Weight average molecular weight (Mw) = 13,100
Molecular weight distribution (Mw / Mn) = 1.81
This is designated as (Polymer 9).

Dry Etching Test 2 g of the polymers obtained in Synthesis Examples 1 to 9 were sufficiently dissolved in 20 g of propylene glycol monomethyl ether acetate and filtered through a 0.1 μm filter to prepare a polymer solution. The polymer solution was applied to a silicon wafer by spin coating and baked at 110 ° C. for 90 seconds to produce a 200 nm thick polymer film. Next, dry etching was performed on the wafer on which the polymer film was produced under the following two conditions, and the difference in film thickness between the polymer film before and after etching was determined.

(1) Etching test with O ₂ gas Using a dry etching apparatus TE-8500P manufactured by Tokyo Electron Limited, the difference in film thickness of the polymer before and after etching was determined.
Etching conditions are as shown below.
Chamber pressure 450mTorr
RF power 600W
Ar gas flow rate 40sccm
O ₂ gas flow rate 60sccm
Gap 9mm
60 sec

₍₂₎ using an etching test Nichiden Anelva Co., Ltd. dry etching apparatus L-507D-L with Cl 2 / BCl ₃ based gas was determined film thickness difference before and after etching the polymer.
Etching conditions are as shown below.
Chamber pressure 300mTorr
RF power 300W
Gap 9mm
Cl ₂ gas flow rate 30sccm
BCl ₃ gas flow rate 30sccm
CHF ₃ gas flow rate 100sccm
O ₂ gas flow rate 2sccm
60 sec
The etching test results are shown in Table 1.

Resist Evaluation Example Using propylene glycol monomethyl ether acetate (PGMEA) containing 0.01% by mass of FC-430 (manufactured by Sumitomo 3M) using the above polymer, an acid generator represented by PAG1, 2 and a dissolution inhibitor represented by DRI1,2. ) A resist solution was prepared by dissolving in 1,000 parts by mass of a solvent sufficiently with the composition shown in Table 2 and filtering a 0.1 μm Teflon filter. OFPR-800 (manufactured by Tokyo Ohka Kogyo Co., Ltd.) was applied to the silicon wafer as a lower novolak resist material, heated at 300 ° C. for 5 minutes, and cured to a thickness of 0.5 μm.
On top of this, an antireflection film (DUV-30) manufactured by Brewer Science was spin-coated and baked at 110 ° C. for 30 seconds and at 200 ° C. for 60 seconds to a thickness of 37 nm.
A silicon-containing resist was spin-coated on a DUV-30 / novolak resist obtained by curing the resist solution, and baked at 120 ° C. for 60 seconds to a thickness of 200 nm using a hot plate. This was exposed using a KrF excimer laser stepper; S203 (manufactured by Nikon Corporation, NA 0.68 σ0.75 2/3 annular illumination), baked at 110 ° C. for 60 seconds (PEB), and then 2.38 mass% tetramethyl. When development was performed with ammonium hydroxide (TMAH) for 60 seconds, a positive pattern could be obtained.

The obtained resist pattern was evaluated as follows. The results are shown in Tables 2 and 3.
Evaluation methods:
Using a mask pattern with a ratio of 1: 2 for line and space, the exposure amount at which the 130 nm line is resolved according to the dimension is the optimum exposure amount (Eop), and the minimum line width of the line and space that is separated at this exposure amount Was defined as the resolution of the evaluation resist.

It is explanatory drawing of the processing process using oxygen etching. It is explanatory drawing of the process using chlorine-type etching.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Base substrate 2 Substrate 3 Organic film 4 Resist layer 5 Exposure 6 Substrate

Claims (12)

The following general formula (1 ')
R ¹ SiX ₃ (1 ')
(Wherein R ¹ is an organic group having an acid-decomposable group, X is a halogen atom, a hydroxy group, an alkoxy group having 1 to 10 carbon atoms, or an acyl group having 1 to 10 carbon atoms.)
Or a silane monomer of the above general formula (1 ′) and the following general formula (1 ″)
R ⁰ SiX ₃ (1 ″)
(In the formula, R ⁰ is an organic group having an adhesive group, and X has the same meaning as described above.)
An organopolysiloxane obtained by hydrolyzing and condensing the silane monomer represented by formula (8), and a polymer compound having one or more repeating units selected from c-1 to c-3 of the following general formula (8): A resist material obtained by adding

[Wherein, R ² represents a hydrogen atom, a methyl group, a fluorine atom, a trifluoromethyl group, a cyano group, —CH ₂ C (═O) —O—R ³ , or —CH ₂ —O—R ⁴ . R ³ is a linear or branched alkyl group having 1 to 4 carbon atoms, R ⁴ is a hydrogen atom, a linear or branched alkyl group having 1 to 4 carbon atoms, or a linear chain having 1 to 4 carbon atoms. Or R ⁴³ is the same or different hydrogen atom, a linear, branched or cyclic alkyl group or fluorinated alkyl group having 1 to 10 carbon atoms, or 6 to 6 carbon atoms. 10 aryl groups, and these groups may contain an ether group, a lactone ring, an ester group, a hydroxy group or a cyano group. R ⁴² represents a single bond or the following general formula (9)

It is a coupling group shown by these. In General Formula (9), R ⁵⁰ and R ⁵¹ are linear, branched or cyclic alkyl groups having 1 to 10 carbon atoms, and R ⁵² is a single bond, an oxygen atom, or alkylene having 1 to 4 carbon atoms. It is a group. X is an ester group or an ether group. R ^{44 to} R ⁴⁶ are linear, branched or cyclic alkyl groups having 1 to 6 carbon atoms, or aryl groups having 6 to 10 carbon atoms, R ^{47 to} R ⁴⁹ are linear groups having 1 to 6 carbon atoms, A branched or cyclic alkyl group, an aryl group having 6 to 10 carbon atoms, a trimethylsilyl group, or a silicon-containing group in which a silicon atom in the formula is bonded to a siloxane bond or a silalkylene bond, and R ⁴⁷ and R ⁴⁸ , R ⁴⁷ And R ⁴⁹ , R ⁴⁸ and R ⁴⁹ may combine to form a polysiloxane ring together with the silicon atom to which they are bonded. m is an integer of 4 to 40, t is an integer of 2 to 30, and n is an integer of 1 to 20. ] The following general formula (1 ')
R ¹ SiX ₃ (1 ')
(Wherein R ¹ is an organic group having an acid-decomposable group, X is a halogen atom, a hydroxy group, an alkoxy group having 1 to 10 carbon atoms, or an acyl group having 1 to 10 carbon atoms.)
Or a silane monomer of the above general formula (1 ′) and the following general formula (1 ″)
R ⁰ SiX ₃ (1 ″)
(In the formula, R ⁰ is an organic group having an adhesive group, and X has the same meaning as described above.)
An organopolysiloxane obtained by hydrolysis and condensation with a silane monomer represented by formula (1), one or more repeating units selected from c-1 to c-3 of the following general formula (8), and the following general formula (10 And a polymer compound obtained by copolymerizing a repeating unit having a group that improves alkali solubility with at least one acid selected from d1 to d7.

[Wherein, R ² represents a hydrogen atom, a methyl group, a fluorine atom, a trifluoromethyl group, a cyano group, —CH ₂ C (═O) —O—R ³ , or —CH ₂ —O—R ⁴ . R ³ is a linear or branched alkyl group having 1 to 4 carbon atoms, R ⁴ is a hydrogen atom, a linear or branched alkyl group having 1 to 4 carbon atoms, or a linear chain having 1 to 4 carbon atoms. Or R ⁴³ is the same or different hydrogen atom, a linear, branched or cyclic alkyl group or fluorinated alkyl group having 1 to 10 carbon atoms, or 6 to 6 carbon atoms. 10 aryl groups, and these groups may contain an ether group, a lactone ring, an ester group, a hydroxy group or a cyano group. R ⁴² represents a single bond or the following general formula (9)

It is a coupling group shown by these. In General Formula (9), R ⁵⁰ and R ⁵¹ are linear, branched or cyclic alkyl groups having 1 to 10 carbon atoms, and R ⁵² is a single bond, an oxygen atom, or alkylene having 1 to 4 carbon atoms. It is a group. X is an ester group or an ether group. R ^{44 to} R ⁴⁶ are linear, branched or cyclic alkyl groups having 1 to 6 carbon atoms, or aryl groups having 6 to 10 carbon atoms, R ^{47 to} R ⁴⁹ are linear groups having 1 to 6 carbon atoms, A branched or cyclic alkyl group, an aryl group having 6 to 10 carbon atoms, a trimethylsilyl group, or a silicon-containing group in which a silicon atom in the formula is bonded to a siloxane bond or a silalkylene bond, and R ⁴⁷ and R ⁴⁸ , R ⁴⁷ And R ⁴⁹ , R ⁴⁸ and R ⁴⁹ may combine to form a polysiloxane ring together with the silicon atom to which they are bonded. m is an integer of 4 to 40, t is an integer of 2 to 30, and n is an integer of 1 to 20. Among repeating units d1~d7 of general formula (10), R ⁵³ ~R ⁵⁷ is a hydrogen atom, a fluorine atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, haloalkyl having 1 to 20 carbon atoms A cyano group, A represents an acid labile group, z is 0 or 1, and y is 1 or 2. When both or ^one of A ¹ and A ² is an acid labile group and is not an acid labile group, it is a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, or an adhesive group. ] The following general formula (1 ')
R ¹ SiX ₃ (1 ')
(Wherein R ¹ is an organic group having an acid-decomposable group, X is a halogen atom, a hydroxy group, an alkoxy group having 1 to 10 carbon atoms, or an acyl group having 1 to 10 carbon atoms.)
Or a silane monomer of the above general formula (1 ′) and the following general formula (1 ″)
R ⁰ SiX ₃ (1 ″)
(In the formula, R ⁰ is an organic group having an adhesive group, and X has the same meaning as described above.)
An organopolysiloxane obtained by hydrolysis / condensation with a silane monomer represented by the formula: at least 1 selected from the repeating unit e represented by the following general formula (11) and d1 to d7 in the following general formula (10): A resist material comprising a polymer compound obtained by copolymerizing a repeating unit having a group whose alkali solubility is improved by at least one kind of acid.

[Wherein, R ⁵⁸ in the formula (11) is a hydrogen atom, or a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms, R ⁵⁹ is a single bond, or a linear chain having 1 to 10 carbon atoms. , A branched or cyclic alkylene group, or a linking group represented by the general formula (9), R ⁶⁰ , R ⁶¹ and R ⁶² are the same or different hydrogen atoms, alkyl groups having 1 to 20 carbon atoms, or haloalkyl groups. , An aryl group having 6 to 20 carbon atoms, a trimethylsilyl group, or a silicon-containing group in which a silicon atom in the formula is bonded to a siloxane bond or a silalkylene bond, or R ⁶⁰ and R ⁶¹ , R ⁶⁰ and R ^62, or R ⁶¹ And R ⁶² may be bonded to each other to form a polysiloxane ring having 3 to 20 silicon atoms together with the silicon atom to which they are bonded. Among repeating units d1~d7 of general formula (10), R ⁵³ ~R ⁵⁷ is a hydrogen atom, a fluorine atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, haloalkyl having 1 to 20 carbon atoms A cyano group, A represents an acid labile group, z is 0 or 1, and y is 1 or 2. When both or ^one of A ¹ and A ² is an acid labile group and is not an acid labile group, it is a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, or an adhesive group. ] A polymer compound having a repeating unit a of the general formula (1), adding a high molecular compound having one or more repeating units selected from c-1 to c-3 of the following general formula (8) A resist material characterized by the above.

[Wherein, R ¹ is an organic group having an acid-decomposable group, x is in the range of 1.0 to 1.5, and R ² is a hydrogen atom, a methyl group, a fluorine atom, a trifluoromethyl group, a cyano group, — CH ₂ C (═O) —O—R ³ or —CH ₂ —O—R ⁴ . R ³ is a linear or branched alkyl group having 1 to 4 carbon atoms, R ⁴ is a hydrogen atom, a linear or branched alkyl group having 1 to 4 carbon atoms, or a linear chain having 1 to 4 carbon atoms. Or R ⁴³ is the same or different hydrogen atom, a linear, branched or cyclic alkyl group or fluorinated alkyl group having 1 to 10 carbon atoms, or 6 to 6 carbon atoms. 10 aryl groups, and these groups may contain an ether group, a lactone ring, an ester group, a hydroxy group or a cyano group. R ⁴² represents a single bond or the following general formula (9)

It is a coupling group shown by these. In General Formula (9), R ⁵⁰ and R ⁵¹ are linear, branched or cyclic alkyl groups having 1 to 10 carbon atoms, and R ⁵² is a single bond, an oxygen atom, or alkylene having 1 to 4 carbon atoms. It is a group. X is an ester group or an ether group. R ^{44 to} R ⁴⁶ are linear, branched or cyclic alkyl groups having 1 to 6 carbon atoms, or aryl groups having 6 to 10 carbon atoms, R ^{47 to} R ⁴⁹ are linear groups having 1 to 6 carbon atoms, A branched or cyclic alkyl group, an aryl group having 6 to 10 carbon atoms, a trimethylsilyl group, or a silicon-containing group in which a silicon atom in the formula is bonded to a siloxane bond or a silalkylene bond, and R ⁴⁷ and R ⁴⁸ , R ⁴⁷ And R ⁴⁹ , R ⁴⁸ and R ⁴⁹ may combine to form a polysiloxane ring together with the silicon atom to which they are bonded. m is an integer of 4 to 40, t is an integer of 2 to 30, and n is an integer of 1 to 20. ] In the polymer compound having the repeating unit a represented by the following general formula (1), one or more repeating units selected from c-1 to c-3 of the following general formula (8), and the following general formula (10) And a polymer compound obtained by copolymerizing a repeating unit having a group that improves alkali solubility with at least one acid selected from d1 to d7.

[Wherein, R ¹ is an organic group having an acid-decomposable group, x is in the range of 1.0 to 1.5, and R ² is a hydrogen atom, a methyl group, a fluorine atom, a trifluoromethyl group, a cyano group, — CH ₂ C (═O) —O—R ³ or —CH ₂ —O—R ⁴ . R ³ is a linear or branched alkyl group having 1 to 4 carbon atoms, R ⁴ is a hydrogen atom, a linear or branched alkyl group having 1 to 4 carbon atoms, or a linear chain having 1 to 4 carbon atoms. Or R ⁴³ is the same or different hydrogen atom, a linear, branched or cyclic alkyl group or fluorinated alkyl group having 1 to 10 carbon atoms, or 6 to 6 carbon atoms. 10 aryl groups, and these groups may contain an ether group, a lactone ring, an ester group, a hydroxy group or a cyano group. R ⁴² represents a single bond or the following general formula (9)

It is a coupling group shown by these. In General Formula (9), R ⁵⁰ and R ⁵¹ are linear, branched or cyclic alkyl groups having 1 to 10 carbon atoms, and R ⁵² is a single bond, an oxygen atom, or alkylene having 1 to 4 carbon atoms. It is a group. X is an ester group or an ether group. R ^{44 to} R ⁴⁶ are linear, branched or cyclic alkyl groups having 1 to 6 carbon atoms, or aryl groups having 6 to 10 carbon atoms, R ^{47 to} R ⁴⁹ are linear groups having 1 to 6 carbon atoms, A branched or cyclic alkyl group, an aryl group having 6 to 10 carbon atoms, a trimethylsilyl group, or a silicon-containing group in which a silicon atom in the formula is bonded to a siloxane bond or a silalkylene bond, and R ⁴⁷ and R ⁴⁸ , R ⁴⁷ And R ⁴⁹ , R ⁴⁸ and R ⁴⁹ may combine to form a polysiloxane ring together with the silicon atom to which they are bonded. m is an integer of 4 to 40, t is an integer of 2 to 30, and n is an integer of 1 to 20. Among repeating units d1~d7 of general formula (10), R ⁵³ ~R ⁵⁷ is a hydrogen atom, a fluorine atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, haloalkyl having 1 to 20 carbon atoms A cyano group, A represents an acid labile group, z is 0 or 1, and y is 1 or 2. When both or ^one of A ¹ and A ² is an acid labile group and is not an acid labile group, it is a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, or an adhesive group. ] At least one selected from a polymer compound having a repeating unit a represented by the following general formula (1), a repeating unit e represented by the following general formula (11), and d1 to d7 in the following general formula (10). A resist material, comprising a polymer compound obtained by copolymerizing a repeating unit having a group whose alkali solubility is improved by an acid.

[Wherein, R ¹ is an organic group having an acid-decomposable group, x is in the range of 1.0 to 1.5, and R ⁵⁸ in formula (11) is a hydrogen atom or a straight chain having 1 to 10 carbon atoms. , Branched or cyclic alkyl group, R ⁵⁹ is a single bond, a linear, branched or cyclic alkylene group having 1 to 10 carbon atoms, or a linking group represented by the above general formula (9), R ⁶⁰ , R ⁶¹ and R ⁶² are the same or different hydrogen atoms, alkyl groups having 1 to 20 carbon atoms, or haloalkyl groups, aryl groups having 6 to 20 carbon atoms, trimethylsilyl groups, or silicon atoms and siloxane bonds or silalkylenes in the formula Bonded silicon-containing groups, or R ⁶⁰ and R ⁶¹ , R ⁶⁰ and R ^62, or R ⁶¹ and R ⁶² are bonded together, and together with the silicon atoms to which they are bonded, the polysiloxane having 3 to 20 silicon atoms A ring may be formed. Among repeating units d1~d7 of general formula (10), R ⁵³ ~R ⁵⁷ is a hydrogen atom, a fluorine atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, haloalkyl having 1 to 20 carbon atoms A cyano group, A represents an acid labile group, z is 0 or 1, and y is 1 or 2. When both or ^one of A ¹ and A ² is an acid labile group and is not an acid labile group, it is a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, or an adhesive group. ] (1) The polymer compound mixture according to any one of claims 1 to 6,
(2) an acid generator,
(3) A chemically amplified positive resist material containing an organic solvent. (1) The polymer compound mixture according to any one of claims 1 to 6,
(2) an acid generator,
(3) organic solvent,
(4) A chemically amplified positive resist material containing a dissolution inhibitor.   The chemically amplified positive resist material according to claim 7 or 8, further comprising a basic compound. (1) applying a resist material according to any one of claims 7 to 9 on a substrate;
(2) Next, after the heat treatment, a step of exposing with a high energy beam or an electron beam having a wavelength of 300 nm or less through a photomask;
(3) A pattern forming method comprising a step of performing heat treatment as necessary and then developing using a developer.   11. The resist pattern forming method according to claim 10, wherein after the pattern is formed, the base is processed by oxygen plasma etching.   11. The resist pattern forming method according to claim 10, wherein after the pattern is formed, the base is processed by etching with a halogen gas containing chlorine or bromine.

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