JP2004190036A - Polymeric silicone compound, resist material and pattern forming method - Google Patents

Abstract

（Ｚは非芳香族系の単環式もしくは多環式炭化水素基又は有橋環式炭化水素基、Ｚ’は炭化水素基、又は非芳香族系の単環式もしくは多環式炭化水素基又は有橋環式炭化水素基。ｘ、ｙ、ｚは上記Ｚ、Ｚ’の価数に応じ、１〜５の整数、Ｒ¹は−ＯＣＨＲ−Ｒ’−ＯＨ又は−ＮＨＣＨＲ−Ｒ’−ＯＨ、Ｒ²はアルキル基又はアルケニル基、又は非芳香族系の１価多環式炭化水素基又は有橋環式炭化水素基、ｐ１、ｐ２、ｐ３、ｐ４はｐ１、ｐ２が正数、ｐ３が０又は正数、ｐ４が０、又は、ｐ１、ｐ４が正数、ｐ３が０又は正数、ｐ２が０。）
【効果】 本発明の高分子シリコーン化合物をベース樹脂としたレジスト材料は、感度、解像性に優れており、電子線や遠紫外線による微細加工に有用である。
【選択図】 なしSOLUTION: The polymer silicone compound containing a repeating unit represented by the formula (1) or a polymer silicone compound in which part or all of the hydrogen atoms of the carboxyl group is substituted by an acid labile group.
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(Z is a non-aromatic monocyclic or polycyclic hydrocarbon group or a bridged cyclic hydrocarbon group, Z ′ is a hydrocarbon group, or a non-aromatic monocyclic or polycyclic hydrocarbon group Or a bridged cyclic hydrocarbon group, wherein x, y, and z are integers of ^{1 to} 5 according to the valences of Z and Z ', and R1 is -OCHR-R'-OH or -NHCHR-R'-OH. , R ² is an alkyl group or an alkenyl group, or a non-aromatic monovalent polycyclic hydrocarbon group or a bridged cyclic hydrocarbon group, p1, p2, p3, and p4 are p1 and p2 being positive numbers, and p3 is 0 or a positive number, p4 is 0, or p1 and p4 are positive numbers, p3 is 0 or a positive number, and p2 is 0.)
The resist material using the polymer silicone compound of the present invention as a base resin has excellent sensitivity and resolution, and is useful for fine processing using an electron beam or far ultraviolet rays.
[Selection diagram] None

Description

  The present invention relates to a polymer silicone compound suitable as a base resin for a resist material used in microfabrication in a manufacturing process of a semiconductor element, etc., far ultraviolet rays, KrF excimer laser light (248 nm), ArF excimer laser light (193 nm), The present invention relates to a resist material and a pattern forming method suitable for using high energy rays such as X-rays and X-rays as an exposure light source.

  In recent years, as the integration and speed of LSIs have increased, the pattern rules have been required to be finer. In light exposure, which is currently used as a general-purpose technology, the inherent limit of resolution derived from the wavelength of the light source Is approaching. In light exposure using a g-line (436 nm) or an i-line (365 nm) as a light source, a pattern rule of about 0.5 μm is a limit, and the integration degree of an LSI manufactured using this is up to a 16 Mbit DRAM equivalent. It becomes. However, LSI prototypes have already been made at this stage, and there is an urgent need to develop further miniaturization techniques.

  As one of means for miniaturizing a pattern, there is a method of shortening the wavelength of exposure light used for forming a resist pattern. A 256 Mbit DRAM (having a processing dimension of 0.25 μm or less) DRAM (Dynamic Random Access) In the mass production process of (memory), use of a short-wavelength KrF excimer laser (248 nm) instead of i-line (365 nm) as an exposure light source is currently being actively studied. However, in order to manufacture a DRAM having an integration degree of 1G or more that requires a finer processing technology (processing size of 0.2 μm or less), a shorter wavelength light source is required. In particular, an ArF excimer laser (193 nm) is used. Photography has recently been considered.

  Here, in the case of lithography using short-wavelength light of 220 nm or less typified by an ArF excimer laser, in order to form a fine pattern, a photoresist is required to have new characteristics that cannot be satisfied by conventional materials. Therefore, Ito et al. Developed a chemically amplified positive resist material in which an acid generator of an onium salt was added to a resin called PBOCST in which a hydroxyl group of polyhydroxystyrene was protected with a tert-butoxycarbonyloxy group (t-Boc group). Since the proposal, various high-sensitivity and high-resolution resist materials have been developed. However, although these resist materials are all of high sensitivity and high resolution, it is difficult to form a fine pattern with a high aspect ratio in view of the mechanical strength of the pattern obtained therefrom. .

  In addition, many resist materials using the above polyhydroxystyrene as a base resin and having sensitivity to far ultraviolet rays, electron beams and X-rays have been proposed. However, in order to form a pattern having a high aspect ratio on a stepped substrate, a two-layer resist method is excellent, whereas all of the resist materials are based on a single-layer resist method, and the problem of the substrate step is still high. There is a problem of light reflection from the substrate and a problem of difficulty in forming a pattern having a high aspect ratio, and at present it is difficult to use the pattern for practical use.

  On the other hand, conventionally, it is known that a two-layer resist method is excellent for forming a pattern having a high aspect ratio on a stepped substrate. Further, the two-layer resist film is developed with a general alkali developing solution. For this purpose, it is known that a high molecular silicone compound having a hydrophilic group such as a hydroxy group or a carboxyl group is required. However, in the case of silanol in which a hydroxyl group is directly bonded to a high molecular silicone compound, a cross-linking reaction occurs due to an acid, so that application to a chemically amplified positive resist material has been difficult.

  In recent years, as a silicone-based resist material that solves these problems, a base resin in which a part of phenolic hydroxyl groups of polyhydroxybenzylsilsesquioxane, a stable alkali-soluble silicone polymer, is protected with a t-Boc group has been used. However, a silicone-based chemically amplified positive resist material combining this with an acid generator has been proposed (Patent Document 1: Japanese Patent Application Laid-Open No. Hei 7-118651, Non-Patent Document 1: SPIE vol. 1952 (1993) 377). etc).

  However, the polymers used for these silicone resist materials have an aromatic ring, and the light absorption by the aromatic ring is extremely strong at a wavelength of 220 nm or less. It is not applicable to photography using light (that is, the resist also absorbs most of the exposure light on the surface and cannot form a fine resist pattern because the exposure does not reach the substrate [Non-Patent Document 2: Sasako et al., " ArF excimer laser lithography (3) -resist evaluation- ", Proceedings of the 35th Annual Conference of the Japan Society of Applied Physics, 1P-K4 (1989)].

  An example of a silicone-based resist material having no phenyl group in the base resin is described in Japanese Patent Application Laid-Open No. Hei 5-323611. This base polymer is used in order to enable alkali development. Since all necessary hydrophilic groups such as a carboxyl group and a hydroxy group are protected, many protective groups must be decomposed in order to dissolve the exposed part in a developing solution. For this reason, the amount of the acid generator to be added increases, or the sensitivity deteriorates. In addition, there is a high possibility of causing a change in film thickness or the generation of stress or bubbles in the film when a large number of protective groups are decomposed, and does not provide a resist material suitable for high sensitivity and fine processing. Was something.

JP-A-7-118651 JP-A-5-323611 SPIE vol. 1952 (1993) 377 Sasako et al., "ArF excimer laser lithography (3) -resist evaluation-", Proceedings of the 35th Japan Society of Applied Physics Related Lectures, 1P-K4 (1989)

  The present invention has been made in view of the above circumstances, has high sensitivity, high resolution, not only can be suitably used as a material of a two-layer resist method particularly suitable for forming a pattern of a high aspect ratio, It is an object of the present invention to provide a novel high molecular silicone compound useful as a base polymer of a resist material capable of forming a pattern having excellent heat resistance, a resist material containing the compound as a base polymer, and a pattern forming method.

  Means for Solving the Problems The present inventors have conducted intensive studies to achieve the above object, and as a result, have found that a polymer silicone compound having a repeating unit represented by the following general formula (1) or a carboxyl group or a carboxyl group in the polymer silicone compound Part or all of the hydrogen atoms of the hydroxyl group are substituted with one or more acid labile groups (that is, the carboxyl group of the high molecular silicone compound of the formula (1) or the hydrogen atom of the carboxyl group and the hydroxyl group is an acid). Substituted by an unstable group at a ratio of 0 to 100 mol%), a high molecular weight silicone compound having a weight average molecular weight of 1,000 to 50,000 and containing no aromatic ring, and a positive resist material obtained by adding an acid generator thereto Or a negative resist material to which a compound capable of being crosslinked by the action of an acid is added, particularly a resist containing a dissolution controlling agent in addition to an acid generator. Materials and resist materials obtained by further blending a basic compound with these compounds can enhance the resist dissolution contrast, in particular increase the dissolution rate after exposure, and furthermore, compounds having a group represented by ≡C-COOH in the molecule. The compounded resist material improves the PED stability of the resist and improves the edge roughness on the nitride film substrate, and the compounding of an acetylene alcohol derivative improves the applicability and storage stability. The silicone-based resist material according to the present invention has high transparency, is excellent in high resolution, exposure latitude, process adaptability, has high practicality, and is very effective as a resist material for VLSI which is advantageous for precise fine processing. This led to the achievement of the present invention.

［式中、Ｚは２価〜６価の炭素数５〜１２の非芳香族系の単環式もしくは多環式炭化水素基又は有橋環式炭化水素基、Ｚ’は２価〜６価の炭素数１〜２０の直鎖状もしくは分岐状の炭化水素基又は炭素数３〜２０の非芳香族系の単環式もしくは多環式炭化水素基又は有橋環式炭化水素基であり、これらの基は、炭素−炭素結合間に窒素原子、酸素原子又は硫黄原子が介在されていてもよく、炭素原子上の水素原子はハロゲン原子、アルコキシ基、ニトロ基、シアノ基又はアセチル基で置換されていてもよく、炭素骨格中のメチレン基はカルボニル基に置換されていてもよい。
ｘ、ｙ、ｚは上記Ｚ、Ｚ’の価数に応じ、それぞれ１〜５の整数を示す。
Ｒ¹は下記一般式（２ａ）又は（２ｂ）で示される基、Ｒ²は炭素数１〜８の直鎖状、分岐状又は環状の非置換もしくは置換のアルキル基又はアルケニル基、又は炭素数５〜１２の非芳香族系の１価の多環式炭化水素基又は有橋環式炭化水素基を示す。

（式中、Ｒは水素原子、水酸基又は炭素数１〜２０の直鎖状、分岐状又は環状のアルキル基を示し、Ｒ’は炭素数１〜２０の直鎖状、分岐状又は環状のアルキレン基を示し、これらアルキル基、アルキレン基は炭素−炭素結合中に酸素原子が介在されていてもよく、また炭素結合水素原子の一部が水酸基で置換されていてもよい。更に、ＲとＲ’はそれぞれ互いに環を形成してもよく、環を形成する場合には、Ｒ、Ｒ’はそれぞれ炭素数１〜８の直鎖状又は分岐状のアルキレン基を示す。）
式（１）において、ｐ１、ｐ２、ｐ３、ｐ４は、ｐ１＋ｐ２＋ｐ３＋ｐ４＝１で、ｐ１、ｐ２が正数、ｐ３が０又は正数、ｐ４が０であって、
０＜ｐ１／（ｐ１＋ｐ２＋ｐ３）≦０．９
０＜ｐ２／（ｐ１＋ｐ２＋ｐ３）≦０．８
０≦ｐ３／（ｐ１＋ｐ２＋ｐ３）≦０．７
を満足する数であるか、又は、ｐ１、ｐ４が正数、ｐ３が０又は正数、ｐ２が０であって、
０＜ｐ１／（ｐ１＋ｐ３＋ｐ４）≦０．９
０≦ｐ３／（ｐ１＋ｐ３＋ｐ４）≦０．７
０＜ｐ４／（ｐ１＋ｐ３＋ｐ４）≦０．９
を満足する数である。］
請求項２：
請求項１記載の一般式（１）で示される繰り返し単位からなる高分子シリコーン化合物のカルボキシル基又はカルボキシル基及び水酸基の水素原子の一部又は全部が１種又は２種以上の酸不安定基により置換されている重量平均分子量１，０００〜５０，０００の高分子シリコーン化合物。
請求項３：
カルボキシル基又はカルボキシル基及び水酸基の水素原子の一部が１種又は２種以上の酸不安定基により部分置換された上記一般式（１）で示される高分子シリコーン化合物の残りのカルボキシル基及び／又は水酸基の水素原子が、式（１）の高分子シリコーン化合物全体のカルボキシル基及び水酸基の水素原子の０モル％を超え５０モル％以下の割合で下記一般式（３ａ）又は（３ｂ）で示されるＣ−Ｏ−Ｃ基を有する基で置換されることにより分子内及び／又は分子間で架橋された請求項２記載の高分子シリコーン化合物。

（式中、Ｒ³、Ｒ⁴は水素原子又は炭素数１〜８の直鎖状、分岐状又は環状のアルキル基を示す。又は、Ｒ³とＲ⁴とは環を形成してもよく、環を形成する場合にはＲ³、Ｒ⁴は炭素数１〜８の直鎖状又は分岐状のアルキレン基を示す。Ｒ⁵は炭素数１〜１０の直鎖状、分岐状又は環状のアルキレン基、ｄは０又は１〜１０の整数である。Ａは、ｃ価の炭素数１〜５０の脂肪族もしくは脂環式飽和炭化水素基、芳香族炭化水素基又はヘテロ環基を示し、これらの基はヘテロ原子を介在していてもよく、またその炭素原子に結合する水素原子の一部が水酸基、カルボキシル基、アシル基又はフッ素原子によって置換されていてもよい。Ｂは−ＣＯ−Ｏ−、−ＮＨＣＯ−Ｏ−又は−ＮＨＣＯＮＨ−を示す。ｃは２〜８、ｃ’は１〜７の整数である。）
請求項４：
一般式（３ａ）又は（３ｂ）で示されるＣ−Ｏ−Ｃ基を有する架橋基が、下記一般式（３ａ’’’）又は（３ｂ’’’）で示される請求項３記載の高分子シリコーン化合物。

（式中、Ｒ³、Ｒ⁴は水素原子又は炭素数１〜８の直鎖状、分岐状又は環状のアルキル基を示す。又は、Ｒ³とＲ⁴とは環を形成してもよく、環を形成する場合にはＲ³、Ｒ⁴は炭素数１〜８の直鎖状又は分岐状のアルキレン基を示す。Ｒ⁵は炭素数１〜１０の直鎖状、分岐状又は環状のアルキレン基、ｄは０又は１〜５の整数である。Ａ’は、ｃ’’価の炭素数１〜２０の直鎖状、分岐状又は環状のアルキレン基、アルキルトリイル基、アルキルテトライル基又は炭素数６〜３０のアリーレン基を示し、これらの基はヘテロ原子を介在していてもよく、またその炭素原子に結合する水素原子の一部が水酸基、カルボキシル基、アシル基又はフッ素原子によって置換されていてもよい。Ｂは−ＣＯ−Ｏ−、−ＮＨＣＯ−Ｏ−又は−ＮＨＣＯＮＨ−を示す。ｃ’’は２〜４、ｃ’’’は１〜３の整数である。）
請求項５：
酸不安定基が、下記一般式（４）で示される基、下記一般式（５）で示される基、炭素数４〜２０の三級アルキル基、各アルキル基の炭素数が１〜６のトリアルキルシリル基及び炭素数４〜２０のオキソアルキル基より選ばれる１種又は２種以上の基である請求項２、３又は４記載の高分子シリコーン化合物。

（Ｒ⁶、Ｒ⁷は水素原子又は炭素数１〜１８の直鎖状、分岐状もしくは環状のアルキル基を示し、Ｒ⁸は炭素数１〜１８のヘテロ原子を有してもよい１価の炭化水素基を示し、Ｒ⁶とＲ⁷、Ｒ⁶とＲ⁸又はＲ⁷とＲ⁸とは環を形成していてもよく、環を形成する場合、Ｒ⁶、Ｒ⁷、Ｒ⁸はそれぞれ炭素数１〜１８の直鎖状又は分岐状のアルキレン基を示す。Ｒ⁹は炭素数４〜２０の三級アルキル基、各アルキル基の炭素数が１〜６のトリアルキルシリル基、炭素数４〜２０のオキソアルキル基又は上記一般式（４）で示される基を示す。ａは０〜６の整数である。）
請求項６：
請求項１乃至５のいずれか１項記載の高分子シリコーン化合物を含有してなることを特徴とするレジスト材料。
請求項７：
（Ａ）有機溶剤
（Ｂ）下記一般式（１）で示される繰り返し単位を有する高分子シリコーン化合物又はこの高分子シリコーン化合物のカルボキシル基又はカルボキシル基及び水酸基の水素原子の一部又は全部が１種又は２種以上の酸不安定基により置換されている重量平均分子量１，０００〜５０，０００の高分子シリコーン化合物、

［式中、Ｚは２価〜６価の炭素数５〜１２の非芳香族系の単環式もしくは多環式炭化水素基又は有橋環式炭化水素基、Ｚ’は２価〜６価の炭素数１〜２０の直鎖状もしくは分岐状の炭化水素基又は炭素数３〜２０の非芳香族系の単環式もしくは多環式炭化水素基又は有橋環式炭化水素基であり、これらの基は、炭素−炭素結合間に窒素原子、酸素原子又は硫黄原子が介在されていてもよく、炭素原子上の水素原子はハロゲン原子、アルコキシ基、ニトロ基、シアノ基又はアセチル基で置換されていてもよく、炭素骨格中のメチレン基はカルボニル基に置換されていてもよい。
ｘ、ｙ、ｚは上記Ｚ、Ｚ’の価数に応じ、それぞれ１〜５の整数を示す。
Ｒ¹は下記一般式（２ａ）又は（２ｂ）で示される基、Ｒ²は炭素数１〜８の直鎖状、分岐状又は環状の非置換もしくは置換のアルキル基又はアルケニル基、又は炭素数５〜１２の非芳香族系の１価の多環式炭化水素基又は有橋環式炭化水素基を示す。

（式中、Ｒは水素原子、水酸基又は炭素数１〜２０の直鎖状、分岐状又は環状のアルキル基を示し、Ｒ’は炭素数１〜２０の直鎖状、分岐状又は環状のアルキレン基を示し、これらアルキル基、アルキレン基は炭素−炭素結合中に酸素原子が介在されていてもよく、また炭素結合水素原子の一部が水酸基で置換されていてもよい。更に、ＲとＲ’はそれぞれ互いに環を形成してもよく、環を形成する場合には、Ｒ、Ｒ’はそれぞれ炭素数１〜８の直鎖状又は分岐状のアルキレン基を示す。）
式（１）において、ｐ１、ｐ２、ｐ３、ｐ４は、ｐ１＋ｐ２＋ｐ３＋ｐ４＝１で、ｐ１、ｐ２が正数、ｐ３が０又は正数、ｐ４が０であって、
０＜ｐ１／（ｐ１＋ｐ２＋ｐ３）≦０．９
０＜ｐ２／（ｐ１＋ｐ２＋ｐ３）≦０．８
０≦ｐ３／（ｐ１＋ｐ２＋ｐ３）≦０．７
を満足する数であるか、又は、ｐ１、ｐ４が正数、ｐ３が０又は正数、ｐ２が０であって、
０＜ｐ１／（ｐ１＋ｐ３＋ｐ４）≦０．９
０≦ｐ３／（ｐ１＋ｐ３＋ｐ４）≦０．７
０＜ｐ４／（ｐ１＋ｐ３＋ｐ４）≦０．９
を満足する数である。
また、カルボキシル基又はカルボキシル基及び水酸基の水素原子の一部が１種又は２種以上の酸不安定基により部分置換された上記一般式（１）で示される高分子シリコーン化合物の残りのカルボキシル基及び／又は水酸基の水素原子全体の０モル％を超え５０モル％以下の割合で下記一般式（３ａ）又は（３ｂ）で示されるＣ−Ｏ−Ｃ基を有する基で置換することにより分子内及び／又は分子間で架橋されていてもよい。

（式中、Ｒ³、Ｒ⁴は水素原子又は炭素数１〜８の直鎖状、分岐状又は環状のアルキル基を示す。又は、Ｒ³とＲ⁴とは環を形成してもよく、環を形成する場合にはＲ³、Ｒ⁴は炭素数１〜８の直鎖状又は分岐状のアルキレン基を示す。Ｒ⁵は炭素数１〜１０の直鎖状、分岐状又は環状のアルキレン基、ｄは０又は１〜１０の整数である。Ａは、ｃ価の炭素数１〜５０の脂肪族もしくは脂環式飽和炭化水素基、芳香族炭化水素基又はヘテロ環基を示し、これらの基はヘテロ原子を介在していてもよく、またその炭素原子に結合する水素原子の一部が水酸基、カルボキシル基、アシル基又はフッ素原子によって置換されていてもよい。Ｂは−ＣＯ−Ｏ−、−ＮＨＣＯ−Ｏ−又は−ＮＨＣＯＮＨ−を示す。ｃは２〜８、ｃ’は１〜７の整数である。）］
（Ｃ）酸発生剤
を含有してなることを特徴とするレジスト材料。
請求項８：
酸不安定基が、下記一般式（４）で示される基、下記一般式（５）で示される基、炭素数４〜２０の三級アルキル基、各アルキル基の炭素数が１〜６のトリアルキルシリル基及び炭素数４〜２０のオキソアルキル基より選ばれる１種又は２種以上の基である請求項７記載のレジスト材料。

（Ｒ⁶、Ｒ⁷は水素原子又は炭素数１〜１８の直鎖状、分岐状もしくは環状のアルキル基を示し、Ｒ⁸は炭素数１〜１８のヘテロ原子を有してもよい１価の炭化水素基を示し、Ｒ⁶とＲ⁷、Ｒ⁶とＲ⁸又はＲ⁷とＲ⁸とは環を形成していてもよく、環を形成する場合、Ｒ⁶、Ｒ⁷、Ｒ⁸はそれぞれ炭素数１〜１８の直鎖状又は分岐状のアルキレン基を示す。Ｒ⁹は炭素数４〜２０の三級アルキル基、各アルキル基の炭素数が１〜６のトリアルキルシリル基、炭素数４〜２０のオキソアルキル基又は上記一般式（４）で示される基を示す。ａは０〜６の整数である。）
請求項９：
更に、（Ｄ）溶解制御剤を配合したことを特徴とする請求項７又は８記載のレジスト材料。
請求項１０：
更に、（Ｅ）塩基性化合物を配合したことを特徴とする請求項７、８又は９記載のレジスト材料。
請求項１１：
更に、（Ｆ）：分子内に≡Ｃ−ＣＯＯＨで示される基を有する化合物を配合したことを特徴とする請求項７乃至１０のいずれか１項記載のレジスト材料。
請求項１２：
更に、（Ｇ）：アセチレンアルコール誘導体を配合したことを特徴とする請求項７乃至１１のいずれか１項記載のレジスト材料。
請求項１３：
（Ａ）有機溶剤
（Ｂ）下記一般式（１）で示される繰り返し単位を有する高分子シリコーン化合物又はこの高分子シリコーン化合物のカルボキシル基又はカルボキシル基及び水酸基の水素原子の一部が１種又は２種以上の酸不安定基により置換されている重量平均分子量１，０００〜５０，０００の高分子シリコーン化合物、

［式中、Ｚは２価〜６価の炭素数５〜１２の非芳香族系の単環式もしくは多環式炭化水素基又は有橋環式炭化水素基、Ｚ’は２価〜６価の炭素数１〜２０の直鎖状もしくは分岐状の炭化水素基又は炭素数３〜２０の非芳香族系の単環式もしくは多環式炭化水素基又は有橋環式炭化水素基であり、これらの基は、炭素−炭素結合間に窒素原子、酸素原子又は硫黄原子が介在されていてもよく、炭素原子上の水素原子はハロゲン原子、アルコキシ基、ニトロ基、シアノ基又はアセチル基で置換されていてもよく、炭素骨格中のメチレン基はカルボニル基に置換されていてもよい。
ｘ、ｙ、ｚは上記Ｚ、Ｚ’の価数に応じ、それぞれ１〜５の整数を示す。
Ｒ¹は下記一般式（２ａ）又は（２ｂ）で示される基、Ｒ²は炭素数１〜８の直鎖状、分岐状又は環状の非置換もしくは置換のアルキル基又はアルケニル基、又は炭素数５〜１２の非芳香族系の１価の多環式炭化水素基又は有橋環式炭化水素基を示す。

（式中、Ｒは水素原子、水酸基又は炭素数１〜２０の直鎖状、分岐状又は環状のアルキル基を示し、Ｒ’は炭素数１〜２０の直鎖状、分岐状又は環状のアルキレン基を示し、これらアルキル基、アルキレン基は炭素−炭素結合中に酸素原子が介在されていてもよく、また炭素結合水素原子の一部が水酸基で置換されていてもよい。更に、ＲとＲ’はそれぞれ互いに環を形成してもよく、環を形成する場合には、Ｒ、Ｒ’はそれぞれ炭素数１〜８の直鎖状又は分岐状のアルキレン基を示す。）
式（１）において、ｐ１、ｐ２、ｐ３、ｐ４は、ｐ１＋ｐ２＋ｐ３＋ｐ４＝１で、ｐ１、ｐ２が正数、ｐ３が０又は正数、ｐ４が０であって、
０＜ｐ１／（ｐ１＋ｐ２＋ｐ３）≦０．９
０＜ｐ２／（ｐ１＋ｐ２＋ｐ３）≦０．８
０≦ｐ３／（ｐ１＋ｐ２＋ｐ３）≦０．７
を満足する数であるか、又は、ｐ１、ｐ４が正数、ｐ３が０又は正数、ｐ２が０であって、
０＜ｐ１／（ｐ１＋ｐ３＋ｐ４）≦０．９
０≦ｐ３／（ｐ１＋ｐ３＋ｐ４）≦０．７
０＜ｐ４／（ｐ１＋ｐ３＋ｐ４）≦０．９
を満足する数である。
また、カルボキシル基又はカルボキシル基及び水酸基の水素原子の一部が１種又は２種以上の酸不安定基により部分置換された上記一般式（１）で示される高分子シリコーン化合物の残りのカルボキシル基及び／又は水酸基の水素原子全体の０モル％を超え５０モル％以下の割合で下記一般式（３ａ）又は（３ｂ）で示されるＣ−Ｏ−Ｃ基を有する基で置換することにより分子内及び／又は分子間で架橋されていてもよい。

（式中、Ｒ³、Ｒ⁴は水素原子又は炭素数１〜８の直鎖状、分岐状又は環状のアルキル基を示す。又は、Ｒ³とＲ⁴とは環を形成してもよく、環を形成する場合にはＲ³、Ｒ⁴は炭素数１〜８の直鎖状又は分岐状のアルキレン基を示す。Ｒ⁵は炭素数１〜１０の直鎖状、分岐状又は環状のアルキレン基、ｄは０又は１〜１０の整数である。Ａは、ｃ価の炭素数１〜５０の脂肪族もしくは脂環式飽和炭化水素基、芳香族炭化水素基又はヘテロ環基を示し、これらの基はヘテロ原子を介在していてもよく、またその炭素原子に結合する水素原子の一部が水酸基、カルボキシル基、アシル基又はフッ素原子によって置換されていてもよい。Ｂは−ＣＯ−Ｏ−、−ＮＨＣＯ−Ｏ−又は−ＮＨＣＯＮＨ−を示す。ｃは２〜８、ｃ’は１〜７の整数である。）］
（Ｃ）酸発生剤、
（Ｈ）酸の作用によって架橋する化合物
を含有してなることを特徴とするレジスト材料。
請求項１４：
酸不安定基が、下記一般式（４）で示される基、下記一般式（５）で示される基、炭素数４〜２０の三級アルキル基、各アルキル基の炭素数が１〜６のトリアルキルシリル基及び炭素数４〜２０のオキソアルキル基より選ばれる１種又は２種以上の基である請求項１３記載のレジスト材料。

（Ｒ⁶、Ｒ⁷は水素原子又は炭素数１〜１８の直鎖状、分岐状もしくは環状のアルキル基を示し、Ｒ⁸は炭素数１〜１８のヘテロ原子を有してもよい１価の炭化水素基を示し、Ｒ⁶とＲ⁷、Ｒ⁶とＲ⁸又はＲ⁷とＲ⁸とは環を形成していてもよく、環を形成する場合、Ｒ⁶、Ｒ⁷、Ｒ⁸はそれぞれ炭素数１〜１８の直鎖状又は分岐状のアルキレン基を示す。Ｒ⁹は炭素数４〜２０の三級アルキル基、各アルキル基の炭素数が１〜６のトリアルキルシリル基、炭素数４〜２０のオキソアルキル基又は上記一般式（４）で示される基を示す。ａは０〜６の整数である。）
請求項１５：
（ｉ）請求項６乃至１４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、
（ｉｉ）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、
（ｉｉｉ）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。 That is, the present invention provides the following high molecular silicone compound, a resist material containing the same, and a pattern forming method.
Claim 1:
A polymeric silicone compound comprising a repeating unit represented by the following general formula (1) and having a weight average molecular weight of 1,000 to 50,000.

[In the formula, Z is a divalent to hexavalent non-aromatic monocyclic or polycyclic hydrocarbon group having 5 to 12 carbon atoms or a bridged cyclic hydrocarbon group, and Z ′ is a divalent to hexavalent hydrocarbon group. A linear or branched hydrocarbon group having 1 to 20 carbon atoms or a non-aromatic monocyclic or polycyclic hydrocarbon group or a bridged cyclic hydrocarbon group having 3 to 20 carbon atoms, In these groups, a nitrogen atom, an oxygen atom or a sulfur atom may be interposed between carbon-carbon bonds, and a hydrogen atom on the carbon atom is substituted with a halogen atom, an alkoxy group, a nitro group, a cyano group or an acetyl group. And the methylene group in the carbon skeleton may be substituted with a carbonyl group.
x, y, and z each represent an integer of 1 to 5, depending on the valence of Z and Z '.
R ¹ is a group represented by the following general formula (2a) or (2b); R ² is a linear, branched or cyclic unsubstituted or substituted alkyl or alkenyl group having 1 to 8 carbon atoms, or carbon number 5 to 12 non-aromatic monovalent polycyclic hydrocarbon groups or bridged cyclic hydrocarbon groups.

(In the formula, R represents a hydrogen atom, a hydroxyl group or a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms, and R ′ represents a linear, branched or cyclic alkylene having 1 to 20 carbon atoms. These alkyl groups and alkylene groups may have an oxygen atom interposed in the carbon-carbon bond, or a part of the carbon-bonded hydrogen atom may be substituted with a hydroxyl group. 'May form a ring with each other, and when forming a ring, R and R' each represent a linear or branched alkylene group having 1 to 8 carbon atoms.)
In the formula (1), p1, p2, p3, and p4 are p1 + p2 + p3 + p4 = 1, p1 and p2 are positive numbers, p3 is 0 or a positive number, and p4 is 0,
0 <p1 / (p1 + p2 + p3) ≦ 0.9
0 <p2 / (p1 + p2 + p3) ≦ 0.8
0 ≦ p3 / (p1 + p2 + p3) ≦ 0.7
Or p1 and p4 are positive numbers, p3 is 0 or a positive number, p2 is 0,
0 <p1 / (p1 + p3 + p4) ≦ 0.9
0 ≦ p3 / (p1 + p3 + p4) ≦ 0.7
0 <p4 / (p1 + p3 + p4) ≦ 0.9
Is a number that satisfies. ]
Claim 2:
A carboxyl group or a part or all of hydrogen atoms of a carboxyl group and a hydroxyl group of the high molecular silicone compound comprising a repeating unit represented by the general formula (1) according to claim 1 is one or more acid labile groups. A substituted high-molecular silicone compound having a weight average molecular weight of 1,000 to 50,000.
Claim 3:
The remaining carboxyl groups and / or the remaining carboxyl groups of the high molecular silicone compound represented by the above general formula (1) in which a part of the hydrogen atoms of the carboxyl group or the carboxyl group and the hydroxyl group are partially substituted by one or more acid labile groups. Alternatively, the hydrogen atom of the hydroxyl group is represented by the following general formula (3a) or (3b) at a ratio of more than 0 mol% and 50 mol% or less of the hydrogen atom of the carboxyl group and the hydroxyl group of the whole polymer silicone compound of the formula (1). The polymer silicone compound according to claim 2, wherein the polymer silicone compound is crosslinked intra- and / or intermolecularly by being substituted with a group having a C-O-C group.

(Wherein, R ³ and R ⁴ represent a hydrogen atom or a linear, branched or cyclic alkyl group having 1 to 8 carbon atoms. Alternatively, R ³ and R ⁴ may form a ring, When a ring is formed, R ³ and R ⁴ represent a linear or branched alkylene group having 1 to 8 carbon atoms, and R ⁵ represents a linear, branched or cyclic alkylene group having 1 to 10 carbon atoms. And d is an integer of 0 or 1 to 10. A represents a c-valent aliphatic or alicyclic saturated hydrocarbon group having 1 to 50 carbon atoms, an aromatic hydrocarbon group or a heterocyclic group, May have a hetero atom interposed, and a part of the hydrogen atom bonded to the carbon atom may be substituted by a hydroxyl group, a carboxyl group, an acyl group or a fluorine atom. -, -NHCO-O- or -NHCONH-, where c is an integer of 2 to 8 and c 'is an integer of 1 to 7.)
Claim 4:
The polymer according to claim 3, wherein the crosslinking group having a C-O-C group represented by the general formula (3a) or (3b) is represented by the following general formula (3a "") or (3b ""). Silicone compounds.

(Wherein, R ³ and R ⁴ represent a hydrogen atom or a linear, branched or cyclic alkyl group having 1 to 8 carbon atoms. Alternatively, R ³ and R ⁴ may form a ring, When a ring is formed, R ³ and R ⁴ represent a linear or branched alkylene group having 1 to 8 carbon atoms, and R ⁵ represents a linear, branched or cyclic alkylene group having 1 to 10 carbon atoms. And d is an integer of 0 or 1 to 5. A ′ is a linear, branched or cyclic alkylene group having 1 to 20 carbon atoms, an alkyltriyl group or an alkyltetrayl group having a c ″ valency. Or an arylene group having 6 to 30 carbon atoms, and these groups may have a hetero atom interposed, and a part of the hydrogen atoms bonded to the carbon atom is a hydroxyl group, a carboxyl group, an acyl group or a fluorine atom. B represents -CO-O-, -NHCO-O- or -NHCONH- C ″ is an integer of 2 to 4 and c ″ ′ is an integer of 1 to 3.)
Claim 5:
The acid labile group is a group represented by the following general formula (4), a group represented by the following general formula (5), a tertiary alkyl group having 4 to 20 carbon atoms, and a tertiary alkyl group having 1 to 6 carbon atoms in each alkyl group. The polymer silicone compound according to claim 2, which is one or more groups selected from a trialkylsilyl group and an oxoalkyl group having 4 to 20 carbon atoms.

(R ⁶ and R ^{7 each} represent a hydrogen atom or a linear, branched or cyclic alkyl group having 1 to 18 carbon atoms, and R ⁸ represents a monovalent group which may have a hetero atom having 1 to 18 carbon atoms. R ⁶ and R ⁷ , R ⁶ and R ⁸ or R ⁷ and R ⁸ may form a ring, and when forming a ring, R ⁶ , R ⁷ and R ⁸ each represent a hydrocarbon group; A linear or branched alkylene group having 1 to 18 carbon atoms, R ⁹ represents a tertiary alkyl group having 4 to 20 carbon atoms, a trialkylsilyl group having 1 to 6 carbon atoms in each alkyl group, Represents an oxoalkyl group of 4 to 20 or a group represented by the above general formula (4), and a is an integer of 0 to 6.)
Claim 6:
A resist material comprising the polymer silicone compound according to claim 1.
Claim 7:
(A) an organic solvent (B) a polymer silicone compound having a repeating unit represented by the following general formula (1), or a carboxyl group of the polymer silicone compound or part or all of a hydrogen atom of a carboxyl group and a hydroxyl group is one kind Or a high molecular weight silicone compound having a weight average molecular weight of 1,000 to 50,000 substituted by two or more acid labile groups,

[In the formula, Z is a divalent to hexavalent non-aromatic monocyclic or polycyclic hydrocarbon group having 5 to 12 carbon atoms or a bridged cyclic hydrocarbon group, and Z ′ is a divalent to hexavalent hydrocarbon group. A linear or branched hydrocarbon group having 1 to 20 carbon atoms or a non-aromatic monocyclic or polycyclic hydrocarbon group or a bridged cyclic hydrocarbon group having 3 to 20 carbon atoms, In these groups, a nitrogen atom, an oxygen atom or a sulfur atom may be interposed between carbon-carbon bonds, and a hydrogen atom on the carbon atom is substituted with a halogen atom, an alkoxy group, a nitro group, a cyano group or an acetyl group. And the methylene group in the carbon skeleton may be substituted with a carbonyl group.
x, y, and z each represent an integer of 1 to 5, depending on the valence of Z and Z '.
R ¹ is a group represented by the following general formula (2a) or (2b); R ² is a linear, branched or cyclic unsubstituted or substituted alkyl or alkenyl group having 1 to 8 carbon atoms, or carbon number 5 to 12 non-aromatic monovalent polycyclic hydrocarbon groups or bridged cyclic hydrocarbon groups.

(In the formula, R represents a hydrogen atom, a hydroxyl group or a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms, and R ′ represents a linear, branched or cyclic alkylene having 1 to 20 carbon atoms. These alkyl groups and alkylene groups may have an oxygen atom interposed in the carbon-carbon bond, or a part of the carbon-bonded hydrogen atom may be substituted with a hydroxyl group. 'May form a ring with each other, and when forming a ring, R and R' each represent a linear or branched alkylene group having 1 to 8 carbon atoms.)
In the formula (1), p1, p2, p3, and p4 are p1 + p2 + p3 + p4 = 1, p1 and p2 are positive numbers, p3 is 0 or a positive number, and p4 is 0,
0 <p1 / (p1 + p2 + p3) ≦ 0.9
0 <p2 / (p1 + p2 + p3) ≦ 0.8
0 ≦ p3 / (p1 + p2 + p3) ≦ 0.7
Or p1 and p4 are positive numbers, p3 is 0 or a positive number, p2 is 0,
0 <p1 / (p1 + p3 + p4) ≦ 0.9
0 ≦ p3 / (p1 + p3 + p4) ≦ 0.7
0 <p4 / (p1 + p3 + p4) ≦ 0.9
Is a number that satisfies.
Further, the carboxyl group or the remaining carboxyl group of the high molecular silicone compound represented by the general formula (1) in which a part of the hydrogen atom of the carboxyl group and the hydroxyl group is partially substituted with one or more acid labile groups. And / or substitution by a group having a C—O—C group represented by the following general formula (3a) or (3b) at a ratio of more than 0 mol% and not more than 50 mol% of all hydrogen atoms of a hydroxyl group. And / or may be cross-linked between molecules.

(Wherein, R ³ and R ⁴ represent a hydrogen atom or a linear, branched or cyclic alkyl group having 1 to 8 carbon atoms. Alternatively, R ³ and R ⁴ may form a ring, When a ring is formed, R ³ and R ⁴ represent a linear or branched alkylene group having 1 to 8 carbon atoms, and R ⁵ represents a linear, branched or cyclic alkylene group having 1 to 10 carbon atoms. And d is an integer of 0 or 1 to 10. A represents a c-valent aliphatic or alicyclic saturated hydrocarbon group having 1 to 50 carbon atoms, an aromatic hydrocarbon group or a heterocyclic group, May have a hetero atom interposed, and a part of the hydrogen atom bonded to the carbon atom may be substituted by a hydroxyl group, a carboxyl group, an acyl group or a fluorine atom. -, -NHCO-O- or -NHCONH-, where c is an integer of 2 to 8 and c 'is an integer of 1 to 7.)
(C) A resist material comprising an acid generator.
Claim 8:
The acid labile group is a group represented by the following general formula (4), a group represented by the following general formula (5), a tertiary alkyl group having 4 to 20 carbon atoms, and a tertiary alkyl group having 1 to 6 carbon atoms in each alkyl group. The resist material according to claim 7, which is one or more groups selected from a trialkylsilyl group and an oxoalkyl group having 4 to 20 carbon atoms.

(R ⁶ and R ^{7 each} represent a hydrogen atom or a linear, branched or cyclic alkyl group having 1 to 18 carbon atoms, and R ⁸ represents a monovalent group which may have a hetero atom having 1 to 18 carbon atoms. R ⁶ and R ⁷ , R ⁶ and R ⁸ or R ⁷ and R ⁸ may form a ring, and when forming a ring, R ⁶ , R ⁷ and R ⁸ each represent a hydrocarbon group; A linear or branched alkylene group having 1 to 18 carbon atoms, R ⁹ represents a tertiary alkyl group having 4 to 20 carbon atoms, a trialkylsilyl group having 1 to 6 carbon atoms in each alkyl group, Represents an oxoalkyl group of 4 to 20 or a group represented by the above general formula (4), and a is an integer of 0 to 6.)
Claim 9:
9. The resist material according to claim 7, further comprising (D) a dissolution controlling agent.
Claim 10:
10. The resist material according to claim 7, further comprising (E) a basic compound.
Claim 11:
The resist material according to any one of claims 7 to 10, further comprising (F) a compound having a group represented by ≡C-COOH in the molecule.
Claim 12:
The resist material according to any one of claims 7 to 11, further comprising (G): an acetylene alcohol derivative.
Claim 13:
(A) an organic solvent (B) a polymer silicone compound having a repeating unit represented by the following general formula (1), or one or two of a carboxyl group or a hydrogen atom of a carboxyl group and a hydroxyl group of the polymer silicone compound are A high molecular weight silicone compound having a weight average molecular weight of 1,000 to 50,000 substituted by at least one kind of acid labile group,

[In the formula, Z is a divalent to hexavalent non-aromatic monocyclic or polycyclic hydrocarbon group having 5 to 12 carbon atoms or a bridged cyclic hydrocarbon group, and Z ′ is a divalent to hexavalent hydrocarbon group. A linear or branched hydrocarbon group having 1 to 20 carbon atoms or a non-aromatic monocyclic or polycyclic hydrocarbon group or a bridged cyclic hydrocarbon group having 3 to 20 carbon atoms, In these groups, a nitrogen atom, an oxygen atom or a sulfur atom may be interposed between carbon-carbon bonds, and a hydrogen atom on the carbon atom is substituted with a halogen atom, an alkoxy group, a nitro group, a cyano group or an acetyl group. And the methylene group in the carbon skeleton may be substituted with a carbonyl group.
x, y, and z each represent an integer of 1 to 5, depending on the valence of Z and Z '.
R ¹ is a group represented by the following general formula (2a) or (2b); R ² is a linear, branched or cyclic unsubstituted or substituted alkyl or alkenyl group having 1 to 8 carbon atoms, or carbon number 5 to 12 non-aromatic monovalent polycyclic hydrocarbon groups or bridged cyclic hydrocarbon groups.

(In the formula, R represents a hydrogen atom, a hydroxyl group or a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms, and R ′ represents a linear, branched or cyclic alkylene having 1 to 20 carbon atoms. These alkyl groups and alkylene groups may have an oxygen atom interposed in the carbon-carbon bond, or a part of the carbon-bonded hydrogen atom may be substituted with a hydroxyl group. 'May form a ring with each other, and when forming a ring, R and R' each represent a linear or branched alkylene group having 1 to 8 carbon atoms.)
In the formula (1), p1, p2, p3, and p4 are p1 + p2 + p3 + p4 = 1, p1 and p2 are positive numbers, p3 is 0 or a positive number, and p4 is 0,
0 <p1 / (p1 + p2 + p3) ≦ 0.9
0 <p2 / (p1 + p2 + p3) ≦ 0.8
0 ≦ p3 / (p1 + p2 + p3) ≦ 0.7
Or p1 and p4 are positive numbers, p3 is 0 or a positive number, p2 is 0,
0 <p1 / (p1 + p3 + p4) ≦ 0.9
0 ≦ p3 / (p1 + p3 + p4) ≦ 0.7
0 <p4 / (p1 + p3 + p4) ≦ 0.9
Is a number that satisfies.
Further, the carboxyl group or the remaining carboxyl group of the high molecular silicone compound represented by the general formula (1) in which a part of the hydrogen atom of the carboxyl group and the hydroxyl group is partially substituted with one or more acid labile groups. And / or substitution by a group having a C—O—C group represented by the following general formula (3a) or (3b) at a ratio of more than 0 mol% and not more than 50 mol% of all hydrogen atoms of a hydroxyl group. And / or may be cross-linked between molecules.

(Wherein, R ³ and R ⁴ represent a hydrogen atom or a linear, branched or cyclic alkyl group having 1 to 8 carbon atoms. Alternatively, R ³ and R ⁴ may form a ring, When a ring is formed, R ³ and R ⁴ represent a linear or branched alkylene group having 1 to 8 carbon atoms, and R ⁵ represents a linear, branched or cyclic alkylene group having 1 to 10 carbon atoms. And d is an integer of 0 or 1 to 10. A represents a c-valent aliphatic or alicyclic saturated hydrocarbon group having 1 to 50 carbon atoms, an aromatic hydrocarbon group or a heterocyclic group, May have a hetero atom interposed, and a part of the hydrogen atom bonded to the carbon atom may be substituted by a hydroxyl group, a carboxyl group, an acyl group or a fluorine atom. -, -NHCO-O- or -NHCONH-, where c is an integer of 2 to 8 and c 'is an integer of 1 to 7.)
(C) an acid generator,
(H) A resist material comprising a compound which is crosslinked by the action of an acid.
Claim 14:
The acid labile group is a group represented by the following general formula (4), a group represented by the following general formula (5), a tertiary alkyl group having 4 to 20 carbon atoms, and a tertiary alkyl group having 1 to 6 carbon atoms in each alkyl group. 14. The resist material according to claim 13, which is one or more groups selected from a trialkylsilyl group and an oxoalkyl group having 4 to 20 carbon atoms.

(R ⁶ and R ^{7 each} represent a hydrogen atom or a linear, branched or cyclic alkyl group having 1 to 18 carbon atoms, and R ⁸ represents a monovalent group which may have a hetero atom having 1 to 18 carbon atoms. R ⁶ and R ⁷ , R ⁶ and R ⁸ or R ⁷ and R ⁸ may form a ring, and when forming a ring, R ⁶ , R ⁷ and R ⁸ each represent a hydrocarbon group; A linear or branched alkylene group having 1 to 18 carbon atoms, R ⁹ represents a tertiary alkyl group having 4 to 20 carbon atoms, a trialkylsilyl group having 1 to 6 carbon atoms in each alkyl group, And represents an oxoalkyl group of 4 to 20 or a group represented by the general formula (4), and a is an integer of 0 to 6.)
Claim 15:
(I) applying the resist material according to any one of claims 6 to 14 onto a substrate;
(Ii) then, after the heat treatment, exposing with a high energy beam or an electron beam having a wavelength of 300 nm or less through a photomask;
(Iii) performing a heat treatment as necessary, and then developing using a developer.

  That is, the present inventors provide a high transmittance to light in the far ultraviolet region, except for a high molecular silicone compound having a phenyl group as disclosed in Japanese Patent Application Laid-Open No. 6-118651, and All of the polymers, which are partially protected instead of being protected by acid labile groups and give high resolution, have been studied and searched for. On the other hand, as the high molecular silicone compound having no phenyl group, a high molecular silicone compound having an ethyl carboxyl group as described in JP-A-5-323611 can be mentioned. When an unsaturated carboxylic acid such as methacrylic acid is reacted with the polysiloxane, an addition reaction occurs exclusively at the α-position of the unsaturated carboxylic acid, and it is difficult to obtain a high molecular silicone compound as exemplified. Further, it is difficult to quantitatively perform the hydrosilylation reaction in the polymer compound, it is difficult to stably supply the polymer silicone compound, and it is difficult to control the quality of the resist.

  For such a polymer compound, a resist material using a polymer silicone compound in which an acid labile group is introduced into a part of the carboxyl group of the polymer silicone compound having no aromatic ring as described above, The present inventors have found that they have high transparency even with light having a short wavelength of 220 nm or less and can form a pattern with such exposure light, and have accomplished the present invention.

  Further, a high molecular silicone compound crosslinked intramolecularly and / or intermolecularly by a crosslinking group having a C—O—C group obtained by a reaction of a carboxyl group with an alkenyl ether compound and / or a halogenated alkyl ether compound was used. The resist material exhibits a dissolution inhibiting property with a small amount of crosslinking, and the heat resistance is improved by an increase in molecular weight due to the crosslinking. Moreover, since the cross-linking group is eliminated after the exposure before the exposure, the dissolution contrast of the resist film can be increased by reducing the molecular weight of the polymer, resulting in high sensitivity and high resolution. . In addition, since there are few problems of the surface hardly soluble layer and the occurrence of footing, it is possible to arbitrarily control the dimension of the pattern and the shape of the pattern by the composition, and it becomes a resist material excellent in process adaptability. This has led to the achievement of the present invention.

  The resist material using the polymer silicone compound of the present invention as a base resin is sensitive to high energy rays, and has excellent sensitivity and resolution, and thus is useful for fine processing by electron beams or far ultraviolet rays. In particular, since the absorption at the exposure wavelength of the ArF excimer laser and the KrF excimer laser is small, a fine pattern perpendicular to the substrate can be easily formed. Further, because of its excellent oxygen plasma etching resistance, the two-layer resist in which the resist film of the present invention is applied on the lower resist film has a feature that a fine pattern can be formed with a high aspect ratio.

  Hereinafter, the present invention will be described in more detail. The novel high molecular silicone compound of the present invention is obtained by adding an acid labile group and / or a crosslinking group to a high molecular silicone compound having a repeating unit represented by the following general formula (1). Is introduced.

Here, Z is a divalent or hexavalent non-aromatic monocyclic or polycyclic hydrocarbon group having 5 to 12 carbon atoms or a bridged cyclic hydrocarbon group. Groups, but are not limited thereto. That is, as the hydrocarbon group, a cyclopentanediyl group, a cyclohexanediyl group, a cycloheptanediyl group, a cyclopentanetriyl group, a cyclohexanetriyl group, a cycloheptanetriyl group, a cyclohexanetetrayl group, a cyclohexanepentyl group, a cyclohexanepentyl group, cyclohexane Hexayl group, cyclooctanediyl group, cyclononanediyl group, cyclodecanediyl group, cyclooctanetriyl group, cyclononanetriyl group, cyclodecanetriyl group, norbornanediyl group, isobornanediyl group, norbornanetriyl group , isobornyl Nantes Riiru group, adamantane-diyl group, a tricyclo [5,2,1,0 ^2,6] decanediyl group, adamantanetricarboxylic yl group, tricyclo [5,2,1,0 ^2,6] Dekantoriiru group, tricyclo [ 5,2,1,0 ^{2, 6]} decane methylene diyl group, a tricyclo [5,2,1,0 ^2,6] decane-methylene tri-yl group, tetracyclo [4,4,0,1 ^2,5, 1 ^7,10] dodecanediyl group, tetracyclo [4 , 4,0,1 ^2,5, 1 ^2,10] dodecane tri-yl group and the like.

  Z ′ is a divalent to hexavalent linear or branched hydrocarbon group having 1 to 20 carbon atoms, a non-aromatic monocyclic or polycyclic hydrocarbon group having 3 to 20 carbon atoms, or a bridged These groups are cyclic hydrocarbon groups, and these groups may have a nitrogen atom, an oxygen atom or a sulfur atom interposed between carbon-carbon bonds, and the hydrogen atom on the carbon atom is a halogen atom, an alkoxy group, or a nitro group. , A cyano group or an acetyl group, and the methylene group in the carbon skeleton may be substituted with a carbonyl group.

  Here, as the divalent to hexavalent linear or branched hydrocarbon group having 1 to 20 carbon atoms, 1 is subtracted from the valence M according to the valence M from the alkyl group or the alkenyl group. Groups (the number of M-1) from which carbon-bonded hydrogen atoms have been eliminated. For example, in the case of divalence, an alkylene group and an alkenylene group can be exemplified. However, in the case of a hydrocarbon group having 1 carbon atom, the maximum valence is 4, and also in the case of an unsaturated hydrocarbon group having 2 carbon atoms, the maximum valence is 4.

  In addition, when a nitrogen atom is interposed between carbon-carbon bonds, it can be interposed as -C-NH-C-, and when an oxygen atom and a sulfur atom are present, -C-O-C- and -C-S-S respectively. -C- intervenes.

Further, examples of the halogen atom substituted with a hydrogen atom on a carbon atom include F, Cl, Br and the like, and examples of the alkoxy group include methoxy, ethoxy, propoxy, isopropoxy, n-butyloxy, isobutyloxy, tert- An alkoxy group having 1 to 6 carbon atoms such as butyloxy is preferred. A methylene group in the carbon skeleton is substituted with a carbonyl group, for example,
-CH ₂ -CH ₂ -CH ₂ -
There _{-CH 2 -C (= O) -CH} 2 -
It means that it becomes.

Specifically, as Z ′, a methylene group, an ethylene group, a propanediyl group, a butanediyl group, a pentanediyl group, a hexanediyl group, a heptanediyl group, an octanediyl group, a nonanediyl group, a decanediyl group, an isopropanediyl group, an isobutanediyl group , Sec-butanediyl group, tert-butanetriyl group, isopentanediyl group, neopentantriyl group, vinyl group, allyl group, propenediyl group, butenediyl group, hexenediyl group, cyclopentanediyl group, cyclopentenediyl group, cyclohexanediyl group, cyclohexene Diyl group, cycloheptanediyl group, cyclopentanetriyl group, cyclohexanetriyl group, cycloheptanetriyl group, cyclohexanetetrayl group, cyclohexanepentile group, cyclohexane Oxayl group, cyclooctanediyl group, cyclononanediyl group, cyclodecanediyl group, cyclooctanetriyl group, cyclononanthryl group, cyclodecanetriyl group, cyclopentanemethylenediyl group, cyclohexanemethylenediyl group, cyclohexane-4, 4-dimethylenetriyl group, norbornanediyl group, isobornanediyl group, norbornanetriyl group, isobornanetriyl group, norbornane-5,5-dimethylenetriyl group, adamantanediyl group, adamantanemethylenediyl group, adamantanetricarboxylic yl group, adamantan methylenetriphenylphosphorane yl group, tricyclo [5,2,1,0 ^2,6] decanediyl group, a tricyclo [5,2,1,0 ^2,6] Dekantoriiru group, tricyclo [5, 2, 1 , 0 ^2,6] decane-methylene-diyl group, Torishi B [5,2,1,0 ^2,6] decane-methylene tri-yl group, tetracyclo [4,4,0,1 ^2,5, 1 ^7,10] dodecanediyl group, tetracyclo [4,4,0,1 ^{2 , 5,1 7,10} ] dodecantriyl group and the like.

  x, y, and z each represent an integer of 1 to 5 according to the valence of Z and Z ', preferably 1 to 3, and more preferably 1 or 2.

R ¹ is a group represented by the following general formula (2a) or (2b).

（式中、Ｒは水素原子、水酸基又は炭素数１〜２０、好ましくは１〜１０、更に好ましくは１〜６の直鎖状、分岐状又は環状のアルキル基を示し、Ｒ’は炭素数１〜２０、好ましくは１〜１０、更に好ましくは１〜６の直鎖状、分岐状又は環状のアルキレン基を示し、これらアルキル基、アルキレン基は炭素−炭素結合中に酸素原子が介在されていてもよく、また炭素結合水素原子の一部が水酸基で置換されていてもよい。更に、ＲとＲ’はそれぞれ互いに環を形成してもよく、環を形成する場合には、Ｒ、Ｒ’はそれぞれ炭素数１〜８の直鎖状又は分岐状のアルキレン基を示す。）

(Wherein, R represents a hydrogen atom, a hydroxyl group or a linear, branched or cyclic alkyl group having 1 to 20, preferably 1 to 10, more preferably 1 to 6 carbon atoms, and R ′ has 1 carbon atom. -20, preferably 1-10, and more preferably 1-6, linear, branched or cyclic alkylene groups, wherein these alkyl groups and alkylene groups have an oxygen atom interposed in a carbon-carbon bond. And a part of the carbon-bonded hydrogen atom may be substituted with a hydroxyl group, and R and R 'may form a ring with each other, and when forming a ring, R and R' Represents a linear or branched alkylene group having 1 to 8 carbon atoms, respectively.

  Examples of the alkyl group include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, pentyl, cyclopentyl, hexyl, cyclohexyl, octyl, decyl, myristyl, and the like. Examples of the alkylene group include a methylene group, an ethylene group, a propylene group, an isopropylene group, a butylene group, an isobutylene group, a hexylene group, a cyclohexylene group, and an octylene group.

  Specific examples of the groups of the formulas (2a) and (2b) include the following groups, but are not limited thereto.

In the above formula (1), R ² is a linear, branched or cyclic unsubstituted or substituted alkyl or alkenyl group having 1 to 8 carbon atoms, or a non-aromatic group having 5 to 12 carbon atoms. It represents a monovalent polycyclic hydrocarbon group or a bridged cyclic hydrocarbon group.

Here, as the linear, branched or cyclic unsubstituted alkyl group or alkenyl group having 1 to 8 carbon atoms, methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, tert- Examples thereof include a butyl group, a cyclohexyl group, a cyclopentyl group, a vinyl group, an allyl group, a propenyl group, a butenyl group, a hexenyl group, and a cyclohexenyl group. Examples of the substituted alkyl group or alkenyl group include those in which part or all of the hydrogen atoms of these unsubstituted alkyl groups or alkenyl groups are substituted with, for example, a cyano group, a nitro group, or an alkoxy group having 1 to 5 carbon atoms. be able to. Similarly, examples of the non-aromatic monovalent polycyclic hydrocarbon group having 5 to 12 carbon atoms or the bridged cyclic hydrocarbon group include a cyclopentyl group, a cyclopentenyl group, a cyclohexyl group, a cyclohexenyl group, and a cycloheptyl group. , Cycloheptenyl group, cyclooctyl group, cyclononanyl group, cyclodecanyl group, norbornanyl group, norbornenyl group, isobornanyl group, adamantyl group, adamantylmethylene group, tricyclo [5,2,1,0 ^2,6 ] decanyl group, tricyclo [5, 2,1,0 ^2,6] Dekeniru group, tricyclo [5,2,1,0 ^2,6] decane methylene group, tetracyclo [4,4,0,1 ^2,5, 1 ^7,10] dodecanyl group, tetracyclo [4,4,0,1 ^2,5, 1 ^7,10] Dodekeniru group and the like.

  In the above formula (1), p1 is a positive number, p2, p3, and p4 are each 0 or a positive number, and are numbers satisfying p1 + p2 + p3 + p4 = 1. That is, p1, p2, p3, and p4 indicate the ratio of the p1 repeating unit, the p2 repeating unit, the p3 repeating unit, and the p4 repeating unit of the compound of the present invention, and 0 ≦ p3 / (p1 + p2 + p3 + p4). .Ltoreq.0.7, preferably 0.ltoreq.p3 / (p1 + p2 + p3 + p4) .ltoreq.0.6, more preferably 0.ltoreq.p3 / (p1 + p2 + p3 + p4) .ltoreq.0.5. Are not suitable as base polymers. On the other hand, if p3 / (p1 + p2 + p3 + p4) is too low, the heat resistance may decrease.

Also, 0 <p1 / (p1 + p2 + p3 + p4) ≦ 0.9, preferably 0.1 ≦ p1 / (p1 + p2 + p3 + p4) ≦ 0.85, more preferably 0.2 ≦ p1 / (p1 + p2 + p3 + p4) ≦ 0.8, 0 ≦ p2 /(P1+p2+p3+p4)≦0.8, preferably 0 ≦ p2 / (p1 + p2 + p3 + p4) ≦ 0.6, more preferably 0 ≦ p2 / (p1 + p2 + p3 + p4) ≦ 0.5, 0 ≦ p4 / (p1 + p2 + p3 + p4) ≦ 0.9, Preferably, 0 <p4 / (p1 + p2 + p3 + p4) ≦ 0.9, more preferably 0.1 ≦ p4 / (p1 + p2 + p3 + p4) ≦ 0.85, and still more preferably 0.2 ≦ p4 / (p1 + p2 + p3 + p4) ≦ 0.8. When p1 becomes 0, the contrast of the alkali dissolution rate decreases and the resolution deteriorates. On the other hand, if it exceeds 0.9, it will not be soluble in alkali, or it will cause a change in film thickness, the generation of stress in the film or the generation of bubbles during alkali development, and the adhesion to the substrate will be reduced because the number of hydrophilic groups will be reduced. May be inferior.
In this case, in the present invention, in the formula (1), p1, p2, p3, and p4 are p1 + p2 + p3 + p4 = 1, p1 and p2 are positive numbers, p3 is 0 or a positive number, and p4 is 0,
0 <p1 / (p1 + p2 + p3) ≦ 0.9
0 <p2 / (p1 + p2 + p3) ≦ 0.8
0 ≦ p3 / (p1 + p2 + p3) ≦ 0.7
Or p1 and p4 are positive numbers, p3 is 0 or a positive number, p2 is 0,
0 <p1 / (p1 + p3 + p4) ≦ 0.9
0 ≦ p3 / (p1 + p3 + p4) ≦ 0.7
0 <p4 / (p1 + p3 + p4) ≦ 0.9
Can be satisfied.

  The polymer silicone compound of the present invention is a polymer silicone compound having a repeating unit represented by the above general formula (1), or a carboxyl group of the polymer silicone compound or part or all of hydrogen atoms of a carboxyl group and a hydroxyl group are 1 or more. It has a weight average molecular weight of 1,000 to 50,000 substituted by one or more kinds of acid labile groups and / or crosslinking groups. That is, 0 to 100 mol% of the hydrogen atoms of the carboxyl group or the carboxyl group and the hydroxyl group of the high molecular silicone compound of the formula (1) are substituted by one or more acid labile groups.

  In this case, the acid labile group is variously selected, and in particular, a group represented by the following general formula (4), a group represented by the following general formula (5), a tertiary alkyl group having 4 to 20 carbon atoms, Preferably, each alkyl group is one or more groups selected from a trialkylsilyl group having 1 to 6 carbon atoms and an oxoalkyl group having 4 to 20 carbon atoms.

Wherein, R ^6, R ⁷ is a hydrogen atom or 1 to 18 carbon atoms, preferably 1 to 6, more preferably a straight, branched or cyclic alkyl group of 1 to 5, R ⁸ is the number of carbon atoms 1 to 18, preferably 1 to 10, more preferably 1 to 8, monovalent hydrocarbon groups which may have a hetero atom such as an oxygen atom, and R ⁶ and R ⁷ , R ⁶ and R ⁸ , R ⁷ and R ⁸ may form a ring, and when forming a ring, R ⁶ , R ⁷ and R ⁸ each have 1 to 18 carbon atoms, preferably 1 to 10 carbon atoms, more preferably 1 to 10 carbon atoms. 8 represents a linear or branched alkylene group. R ⁹ is a tertiary alkyl group having 4 to 20 carbon atoms, preferably 4 to 15, more preferably 4 to 10, each alkyl group is a trialkylsilyl group having 1 to 6 carbon atoms, and 4 to 20 carbon atoms, preferably Represents an oxoalkyl group of 4 to 15, more preferably 4 to 10, or a group represented by the general formula (4). A is an integer of 0 to 6.

As the linear, branched or cyclic alkyl group having 1 to 18 carbon atoms for R ⁶ and R ^7, the same groups as described for R can be mentioned.

R ⁸ is an unsubstituted or substituted aryl such as a linear, branched or cyclic alkyl group, phenyl group, p-methylphenyl group, p-ethylphenyl group, alkoxy-substituted phenyl group such as p-methoxyphenyl group. Group, benzyl group, aralkyl group such as phenethyl group, or those groups having an oxygen atom, or a hydrogen atom bonded to a carbon atom is substituted with a hydroxyl group, or two hydrogen atoms are substituted with an oxygen atom. Examples of the carbonyl group include groups such as an alkyl group represented by the following formula.

Examples of the tertiary alkyl group having 4 to 20 carbon atoms for R ⁹ include a tert-butyl group, a 1-methylcyclohexyl group, a 2- (2-methyl) adamantyl group, and a tert-amyl group.

  Examples of the trialkylsilyl group having 1 to 6 carbon atoms of each alkyl group include trimethylsilyl group, triethylsilyl group, dimethyl-tert-butyl group and the like. Examples of the oxoalkyl group having 4 to 20 carbon atoms include 3-methylsilyl group. An oxocyclohexyl group, a group represented by the following formula, and the like are given.

  Specific examples of the acid labile group represented by the above formula (4) include, for example, 1-methoxyethyl group, 1-ethoxyethyl group, 1-n-propoxyethyl group, 1-isopropoxyethyl group, 1-n -Butoxyethyl group, 1-isobutoxyethyl group, 1-sec-butoxyethyl group, 1-tert-butoxyethyl group, 1-tert-amyloxyethyl group, 1-ethoxy-n-propyl group, 1-cyclohexyloxy Linear or branched acetal groups such as ethyl group, methoxypropyl group, ethoxypropyl group, 1-methoxy-1-methyl-ethyl group, 1-ethoxy-1-methyl-ethyl group, tetrahydrofuranyl group, tetrahydropyranyl And a cyclic acetal group such as a group, preferably an ethoxyethyl group, a butoxyethyl group, or an ethoxypropyl group. It is. On the other hand, as the acid labile group of the above formula (5), for example, a tert-butoxycarbonyl group, a tert-butoxycarbonylmethyl group, a tert-amyloxycarbonyl group, a tert-amyloxycarbonylmethyl group, a 1-ethoxyethoxycarbonylmethyl group , 2-tetrahydropyranyloxycarbonylmethyl group, 2-tetrahydrofuranyloxycarbonylmethyl group and the like.

  When the polymer silicone compound of the above formula (1) is used as a base resin for a positive resist material, the introduction rate of the acid labile group is more than 0 mol% and not more than 100 mol% of all hydrogen atoms of a carboxyl group. It is more preferably 20 to 98 mol%, further preferably 30 to 95 mol%, and 0 to 100 mol%, more preferably 0 to 80 mol%, and still more preferably 0 to 100 mol% of all hydrogen atoms of the hydroxyl group. It is preferably 60 mol%. If the hydrogen atom of the carboxyl group is not replaced by an acid labile group (the introduction ratio of the acid labile group to the hydrogen atom of the carboxyl group is 0 mol%), the contrast of the alkali dissolution rate becomes small and the resolution becomes poor.

  On the other hand, when the polymer silicone compound of the above formula (1) is used as a base resin for a negative resist material, the introduction ratio of acid labile groups is 0 to 90 mol%, preferably 0 to 90 mol% of all hydrogen atoms of carboxyl groups. The content is preferably from 80 to 80 mol%, more preferably from 0 to 70 mol%. Further, the content is preferably 0 to 70 mol%, more preferably 0 to 60 mol%, and still more preferably 0 to 50 mol% of the whole hydrogen atoms of the hydroxyl group.

  In the high molecular silicone compound of the present invention, a part or all of hydrogen atoms of a carboxyl group or a carboxyl group and a hydroxyl group are substituted by one or more acid labile groups at a ratio of 0 mol% to 100 mol%. The remaining hydrogen atoms of the carboxyl group and / or hydroxyl group of the high molecular silicone compound represented by the above general formula (1) are more than 0 mol% and 50 mol% or less, more preferably all the hydrogen atoms of the carboxyl group and hydroxyl group. Is substituted with a group having a C—O—C group represented by the following general formula (3a) or (3b) at a ratio of 0.2 to 40 mol%, more preferably 0.25 to 30 mol%. It may be crosslinked intra- and / or intermolecularly.

（式中、Ｒ³、Ｒ⁴は水素原子又は炭素数１〜８の直鎖状、分岐状又は環状のアルキル基を示す。又は、Ｒ³とＲ⁴とは環を形成してもよく、環を形成する場合にはＲ³、Ｒ⁴は炭素数１〜８の直鎖状又は分岐状のアルキレン基を示す。Ｒ⁵は炭素数１〜１０の直鎖状、分岐状又は環状のアルキレン基、ｄは０又は１〜１０の整数である。Ａは、ｃ価の炭素数１〜５０の脂肪族もしくは脂環式飽和炭化水素基、芳香族炭化水素基又はヘテロ環基を示し、これらの基はヘテロ原子を介在していてもよく、またその炭素原子に結合する水素原子の一部が水酸基、カルボキシル基、アシル基又はフッ素原子によって置換されていてもよい。Ｂは−ＣＯ−Ｏ−、−ＮＨＣＯ−Ｏ−又は−ＮＨＣＯＮＨ−を示す。ｃは２〜８、ｃ’は１〜７の整数である。）

(Wherein, R ³ and R ⁴ represent a hydrogen atom or a linear, branched or cyclic alkyl group having 1 to 8 carbon atoms. Alternatively, R ³ and R ⁴ may form a ring, When a ring is formed, R ³ and R ⁴ represent a linear or branched alkylene group having 1 to 8 carbon atoms, and R ⁵ represents a linear, branched or cyclic alkylene group having 1 to 10 carbon atoms. And d is an integer of 0 or 1 to 10. A represents a c-valent aliphatic or alicyclic saturated hydrocarbon group having 1 to 50 carbon atoms, an aromatic hydrocarbon group or a heterocyclic group, May have a hetero atom interposed, and a part of the hydrogen atom bonded to the carbon atom may be substituted by a hydroxyl group, a carboxyl group, an acyl group or a fluorine atom. -, -NHCO-O- or -NHCONH-, where c is an integer of 2 to 8 and c 'is an integer of 1 to 7.)

Here, as the linear, branched or cyclic alkyl group having 1 to 8 carbon atoms, the same as those described above can be exemplified. Examples of the linear, branched or cyclic alkylene group having 1 to 10 carbon atoms of R ⁵ include a methylene group, an ethylene group, a propylene group, an isopropylene group, an n-butylene group, an isobutylene group, a cyclohexylene group, and a cycloalkyl group. Pentylene groups and the like can be exemplified. A specific example of A will be described later. The crosslinking groups (3a) and (3b) are derived from alkenyl ether compounds and halogenated alkyl ether compounds described below.

  As is clear from the value of c ′ in the above formulas (3a) and (3b), the crosslinking group is not limited to divalent, and may be a trivalent to octavalent group. For example, examples of the divalent crosslinking group include those represented by the following formulas (3a ′) and (3b ′), and examples of the trivalent crosslinking group include those represented by the following formulas (3a ″) and (3b ″). .

なお、好ましい架橋基は下記一般式（３ａ’’’）又は（３ｂ’’’）である。

In addition, a preferable crosslinking group is the following general formula (3a "") or (3b "").

（式中、Ｒ³、Ｒ⁴は水素原子又は炭素数１〜８の直鎖状、分岐状又は環状のアルキル基を示す。又は、Ｒ³とＲ⁴とは環を形成してもよく、環を形成する場合にはＲ³、Ｒ⁴は炭素数１〜８の直鎖状又は分岐状のアルキレン基を示す。Ｒ⁵は炭素数１〜１０の直鎖状、分岐状又は環状のアルキレン基、ｄは０又は１〜５の整数である。Ａ’は、ｃ’’価の炭素数１〜２０の直鎖状、分岐状又は環状のアルキレン基、アルキルトリイル基、アルキルテトライル基又は炭素数６〜３０のアリーレン基を示し、これらの基はヘテロ原子を介在していてもよく、またその炭素原子に結合する水素原子の一部が水酸基、カルボキシル基、アシル基又はフッ素原子によって置換されていてもよい。Ｂは−ＣＯ−Ｏ−、−ＮＨＣＯ−Ｏ−又は−ＮＨＣＯＮＨ−を示す。ｃ’’は２〜４、ｃ’’’は１〜３の整数である。）

(Wherein, R ³ and R ⁴ represent a hydrogen atom or a linear, branched or cyclic alkyl group having 1 to 8 carbon atoms. Alternatively, R ³ and R ⁴ may form a ring, When a ring is formed, R ³ and R ⁴ represent a linear or branched alkylene group having 1 to 8 carbon atoms, and R ⁵ represents a linear, branched or cyclic alkylene group having 1 to 10 carbon atoms. And d is an integer of 0 or 1 to 5. A ′ is a linear, branched or cyclic alkylene group having 1 to 20 carbon atoms, an alkyltriyl group or an alkyltetrayl group having a c ″ valency. Or an arylene group having 6 to 30 carbon atoms, and these groups may have a hetero atom interposed, and a part of the hydrogen atoms bonded to the carbon atom is a hydroxyl group, a carboxyl group, an acyl group or a fluorine atom. B represents -CO-O-, -NHCO-O- or -NHCONH- C ″ is an integer of 2 to 4 and c ″ ′ is an integer of 1 to 3.)

  As the polymer silicone compound of the present invention, those having a repeating unit represented by the following general formula (1a) are preferable.

In the formula, R ⁰ represents the above-described acid labile group. p11 + p12 = p1, p11 ≧ 0, p12> 0, preferably 0 <p12 / p1 ≦ 1, more preferably 0.2 ≦ p12 / p1 ≦ 0.98, even more preferably 0.3 ≦ p12 / p1 ≤ 0.95. Also, p41 + p42 = p4, and p41> 0 and p42 ≧ 0. In this case, it is preferable that 0 <(p12 + p42) / (p1 + p4) ≦ 1, more preferably 0.05 ≦ (p12 + p42) / (p1 + p4) ≦ 0.9, and even more preferably 0.1 ≦ (p12 + p42) / (P1 + p4) ≦ 0.8. Incidentally, Z, Z ', x, y, z, R 1, R 2, p1, p2, p3, p4 are as defined above.

  Examples of the polymer silicone compound having a crosslinkable group having a C—O—C group of the present invention include those represented by the following formulas (1b) to (1e). The following examples are examples in which x, y, and z are each 1. Compounds of formulas (1b) and (1d) are intermolecular bonds, and formulas (1c) and (1e) are intramolecular bonds. However, the present invention is not limited to the following example.

  In the above formula, Q is a cross-linking group having a C—O—C group, typically a cross-linking group represented by the above formula (3a) or (3b), especially formulas (3a ′), (3b ′) and (3a). '') And (3b ''), preferably (3a '' ') and (3b' ''). In this case, when the crosslinking group is trivalent or more, in the above formula, Q is bonded to three or more of the following units.

  In the above formulas (1b) to (1e), p111 + p112 = p11, p411 + p412 = p41, and 0 ≦ p112 / p1 ≦ 0.5, 0 ≦ p412 / p4 ≦ 0.5, 0 ≦ (p112 + p412) / ( (p1 + p4) ≦ 0.5, more preferably 0.002 ≦ p112 / p1 ≦ 0.5, 0 ≦ p412 / p4 ≦ 0.4, 0.001 ≦ (p112 + p412) / (p1 + p4) ≦ 0 .45, more preferably 0.0025 ≦ p112 / p1 ≦ 0.4, 0 ≦ p412 / p4 ≦ 0.3, and 0.001 ≦ (p112 + p412) / (p1 + p4) ≦ 0.4. In addition, (p12 + p112 + p42 + p412) / (p1 + p4) is more than 0 and 1 or less, more preferably 0.05 to 0.9, and still more preferably 0.1 to 0.8.

  When the proportion of the crosslinking group having a C—O—C group is 0 mol%, the contrast of the alkali dissolution rate is reduced, and the advantages of the crosslinking group cannot be brought out, and the resolution may be deteriorated. If the amount is too large, it crosslinks too much and gels, loses its solubility in alkali, causes a change in film thickness or the occurrence of stress or bubbles in the film during alkali development, and reduces the number of hydrophilic groups and the substrate. May have poor adhesion.

  On the other hand, when the proportion of the acid labile group is 0 mol%, the contrast of the alkali dissolution rate becomes small, and the resolution becomes poor. On the other hand, if the amount is too large, the solubility in alkali may be lost, or the affinity with a developing solution may be reduced during alkali development, resulting in poor resolution.

  In this case, the size of the pattern and the shape of the pattern can be arbitrarily controlled by appropriately selecting the values of the crosslinking group having a C—O—C group and the acid labile group within the above ranges. In the polymer silicone compound of the present invention, the content of the crosslinking group having a C—O—C group and the acid labile group affects the contrast of the dissolution rate of the resist film, and controls the resist dimensions such as pattern dimension control and pattern shape. It is related to the characteristics of

  Here, the high molecular silicone compound may have two or more acid labile groups in the molecule, or may blend two or more polymers having different acid labile groups.

  In this case, in the above formulas (1a) to (1e), as the units (u-1) and (u-2) having the following acid labile groups, the following groups (u-1 ′), u-2 ′).

  In the above formula, p121 + p122 = p12, and p121 / p12 is 0 to 1, more preferably 0.05 to 1, and still more preferably 0.1 to 1. Also, p421 + p422 = p42, and p421 / p42 is from 0 to 1, more preferably from 0.05 to 1, and even more preferably from 0.1 to 1, (p121 + p421) / (p12 + p42) is from 0 to 1. And more preferably 0.05 to 1, and still more preferably 0.1 to 1.

  The polymer silicone compound of the present invention has a weight average molecular weight of 1,000 to 50,000, preferably 1,500 to 30,000. When the weight average molecular weight is less than 1,000, the resist material has poor heat resistance, and when it exceeds 50,000, the resist material cannot be uniformly applied when spin-coated.

Next, the method for producing the high molecular silicone compound of the present invention will be described. The high molecular silicone compound is a divalent to hexavalent non-aromatic monocyclic monocyclic ring having 5 to 12 carbon atoms to which a carboxylic acid alkyl ester group is bonded. A trichlorosilane compound having a formula or polycyclic hydrocarbon group or a bridged cyclic hydrocarbon group, and a divalent to hexavalent linear or branched C1-C20 hydrocarbon having an alkylcarbonyloxy group bonded thereto Group, or a trichlorosilane compound having a non-aromatic monocyclic or polycyclic hydrocarbon group or a bridged cyclic hydrocarbon group having 3 to 20 carbon atoms, and further, if necessary, linear, branched or After hydrolyzing a trichlorosilane compound having a cyclic alkyl group and further thermally condensing the hydrolyzed condensate, the alkyl ester group and the alkylcarbonyloxy group are converted by a general method. It is possible to obtain a high molecular silicone compounds of formula (1 ') is hydrolyzed (KOH, NaOH, etc.) Te. Note that trimethylsilylation is preferable in order to protect the silanol group at the terminal of the main chain in consideration of storage stability. By introducing an acid labile group into the carboxyl group of the obtained high molecular silicone compound, the desired high molecular silicone compound can be obtained. Alternatively, a polymer silicone compound of interest can be obtained by introducing an acid labile group of R ⁰ or a group of R ^{1 into} a carboxyl group and a hydroxyl group, or by introducing a crosslinking group. The introduction of the group of R ¹ can be performed by a conventional method. For example, when R ¹ has an ester structure represented by the general formula (2a), a synthesis method by a dehydration reaction using an acid catalyst, Examples include a method using an active ester using trifluoroacetic anhydride or dicyclohexylcarbodiimide, a method for activating an alcohol using diethyl azodicarboxylate, and a method using an O-alkylating agent such as diazoalkane. .

On the other hand, when R ¹ has an amide structure represented by the general formula (2b), a method using a condensing agent such as dicyclohexylcarbodiimide or N-ethyl-N′-3-dimethylaminopropylcarbodiimide or an active ester is used. Examples include a method via p-nitrophenyl ester and an azide method via peptide hydrazide.

（式中、Ｚ、Ｚ’、Ｒ²、ｐ１、ｐ２、ｐ３、ｐ４、ｘ、ｚは上記と同様の意味を示す。）

(In the formula, Z, Z ′, R ² , p1, p2, p3, p4, x, and z have the same meaning as described above.)

  Here, the introduction of the acid labile group can be performed by a known method. Examples of the method for crosslinking with a crosslinking group having a C—O—C group include a method using an alkenyl ether compound or a halogenated alkyl ether compound.

  That is, the method for producing the polymer silicone compound of the present invention having a crosslinkable group having a C—O—C group includes the carboxyl group or carboxyl group of the polymer silicone compound (1 ′) obtained by the above polymerization method. And an acid labile group represented by the general formula (4) is introduced into a hydroxyl group, and after isolation, is reacted with an alkenyl ether compound or a halogenated alkyl ether compound to form a C—O—C group within and / or between molecules. Or a reaction with an alkenyl ether compound or a halogenated alkyl ether compound, whereby the compound is cross-linked by a group represented by C—O—C within a molecule and / or between molecules, and isolated, and then subjected to the general formula (4) a method for introducing an acid labile group, or an alkenyl ether compound or a halogenated alkyl ether compound The reaction with an alkenyl ether compound or a halogenated alkyl ether compound and the reaction with an acid represented by the general formula (4) may be performed simultaneously. A method in which unstable groups are introduced at once is preferable. Further, an acid labile group, a tertiary alkyl group, a trialkylsilyl group, an oxoalkyl group, or the like represented by the general formula (5) may be introduced into the polymer silicone compound obtained as needed. It is possible.

  Specifically, as a first method, a polymer silicone compound having a repeating unit represented by the above formula (1 ′), an alkenyl ether compound represented by the following general formula (I) or (II), As a second method using the compound represented by (4a), a polymer silicone compound having a repeating unit represented by the above formula (1 ′) and a halogenated compound represented by the following general formula (VII) or (VIII) A method using an alkyl ether compound and a compound represented by the following general formula (4b) is exemplified.

Here, Z, Z ′, R ² , p 1, p ² , p 3, p 4, x, z and R ⁴ , R ⁵ , R ⁷ , R ⁸ have the same meaning as described above, and R ^3a , R ^6a Represents a hydrogen atom or a linear, branched or cyclic alkyl group having 1 to 7 carbon atoms.

Further, in the vinyl ether compound represented by the formula (I) or (II), A is an aliphatic or alicyclic saturated hydrocarbon group having 1 to 50 carbon atoms having a c value (c represents 2 to 8), or an aromatic group. a hydrocarbon group or heterocyclic group, B is -CO-O -, - NHCOO- or -NHCONH- indicates, R ⁵ is a straight or branched alkylene of 1 to 10 carbon atoms, d Represents 0 or an integer of 1 to 10.

Specifically, as the c-valent aliphatic or alicyclic saturated hydrocarbon group or aromatic hydrocarbon group of A, preferably, C, 1 to 50, particularly 1 to 40 O, NH, N (CH ₃ ), An unsubstituted or hydroxyl group, a carboxyl group, an acyl group or a fluorine atom-substituted alkylene group which may be intervened with a hetero atom such as S or SO ₂ , preferably an arylene group having 6 to 50, particularly 6 to 40, carbon atoms; A group in which an alkylene group and an arylene group are bonded, and a group having a c ″ value (c ″ is an integer of 3 to 8) in which a hydrogen atom bonded to a carbon atom of each of the above groups is eliminated. And a group in which the heterocyclic group is bonded to the hydrocarbon group.

  Specific examples include the following.

  The compound represented by the general formula (I) is described, for example, in Stephen. C. Lapin, Polymers Paint Color Journal Journal. 179 (4237) and 321 (1988), that is, by a reaction between a polyhydric alcohol or a polyhydric phenol and acetylene, or a reaction between a polyhydric alcohol or a polyhydric phenol and a halogenated alkyl vinyl ether. Can be.

  Specific examples of the compound of the formula (I) include ethylene glycol divinyl ether, triethylene glycol divinyl ether, 1,2-propanediol divinyl ether, 1,3-propanediol divinyl ether, 1,3-butanediol divinyl ether, 1,4-butanediol divinyl ether, tetramethylene glycol divinyl ether, neopentyl glycol divinyl ether, trimethylolpropane trivinyl ether, trimethylolethane trivinyl ether, hexanediol divinyl ether, 1,4-cyclohexanediol divinyl ether, tetraethylene glycol divinyl Vinyl ether, pentaerythritol divinyl ether, pentaerythritol trivinyl ether, pentaerythritol tetrabi Ether, sorbitol tetravinyl ether, sorbitol pentavinyl ether, ethylene glycol diethylene vinyl ether, triethylene glycol diethylene vinyl ether, ethylene glycol dipropylene vinyl ether, triethylene glycol diethylene vinyl ether, trimethylolpropane triethylene vinyl ether, trimethylolpropane diethylene vinyl ether, pentaerythritol diethylene vinyl ether Pentaerythritol triethylene vinyl ether, pentaerythritol tetraethylene vinyl ether, and the compounds represented by the following formulas (I-1) to (I-31), but are not limited thereto.

  On the other hand, when B is -CO-O-, the compound represented by the general formula (II) can be produced by reacting a polyvalent carboxylic acid with a halogenated alkyl vinyl ether. Specific examples of the compound represented by the formula (II) when B is -CO-O- include diethylene vinyl ether terephthalate, diethylene vinyl ether phthalate, diethylene vinyl ether isophthalate, dipropylene vinyl ether phthalate, and dipropylene vinyl ether terephthalate. Diethylene vinyl ether isophthalate, diethylene vinyl ether maleate, diethylene vinyl ether fumarate, diethylene vinyl ether itaconate, and the like, but are not limited thereto.

  Further, the alkenyl ether group-containing compound preferably used in the present invention includes an alkenyl ether compound having an active hydrogen represented by the following general formula (III), (IV) or (V) and a compound having an isocyanate group. And the alkenyl ether group-containing compound synthesized by the above reaction.

（Ｒ^3a、Ｒ⁴、Ｒ⁵は上記と同様の意味を示す。）

(R ^3a , R ⁴ and R ⁵ have the same meaning as described above.)

  When B is -NHCOO- or -NHCONH-, as the compound having an isocyanate group represented by the above general formula (II), for example, a compound described in a crosslinking agent handbook (published by Taiseisha, 1981) may be used. Can be. Specifically, triphenylmethane triisocyanate, diphenylmethane diisocyanate, tolylene diisocyanate, dimer of 2,4-tolylene diisocyanate, naphthalene-1,5-diisocyanate, o-tolylene diisocyanate Polyisocyanate type such as nate, polymethylene polyphenyl isocyanate, hexamethylene diisocyanate, adduct of tolylene diisocyanate and trimethylol propane, adduct of hexamethylene diisocyanate and water, xylene diisocyanate Examples thereof include polyisocyanate adducts such as adducts with trimethylolpropane. By reacting the above-mentioned isocyanate group-containing compound with an active hydrogen-containing alkenyl ether compound, various compounds having an alkenyl ether group at a terminal can be obtained. Examples of such compounds include, but are not limited to, those represented by the following formulas (II-1) to (II-11).

  In the first method, when a high molecular silicone compound cross-linked by a cross-linking group having a C—O—C group is obtained, the weight-average molecular weight is 1,000 to 50,000, and preferably the general formula (1 ′) ), The alkenyl ether compound represented by the general formula (I) or (II) having p112 + p412 mol and the general formula (4a) having p12 + p42 mol per mol of the carboxyl group or the carboxyl group and the hydroxyl group of the polymer compound represented by the formula (4a). By reacting the compounds, for example, polymer compounds represented by the following general formulas (3a'-1) and (3a'-2) can be obtained.

  In the first method, the reaction solvent is preferably an aprotic polar solvent such as dimethylformamide, dimethylacetamide, tetrahydrofuran, or ethyl acetate, and may be used alone or as a mixture of two or more.

  As the acid of the catalyst, hydrochloric acid, sulfuric acid, trifluoromethanesulfonic acid, p-toluenesulfonic acid, methanesulfonic acid, trifluoroacetic acid, pyridinium p-toluenesulfonate and the like are preferably used. It is preferable that the amount is 0.1 to 10 mol% based on 1 mol of the carboxyl group of the polymer compound represented by ').

  The reaction temperature is −20 to 100 ° C., preferably 0 to 60 ° C., and the reaction time is 0.2 to 100 hours, preferably 0.5 to 20 hours.

  When the above reaction is carried out collectively without isolation, the order of adding the alkenyl ether compound represented by the general formula (I) or (II) and the compound represented by the general formula (4a) is not particularly limited. It is preferable to add the compound represented by the general formula (4a) and, after the reaction has sufficiently proceeded, add the alkenyl ether compound represented by the general formula (I) or (II). For example, the alkenyl ether compound represented by the general formula (I) or (II) and the compound represented by the general formula (4a) are added simultaneously, or the alkenyl ether compound represented by the general formula (I) or (II) is added first. When added, some of the reaction points of the alkenyl ether compound represented by the general formula (I) or (II) are hydrolyzed by moisture in the reaction system, and the structure of the resulting polymer compound becomes complicated, Control may be difficult.

（式中、Ｚ、Ｚ’、Ｒ²、ｐ１、ｐ２、ｐ３、ｐ４、ｘ、ｚ及びＲ⁵、Ｒ^6a、Ｒ⁷、Ｒ⁸、ｃ、ｄはそれぞれ上記と同様の意味を示し、Ｄはハロゲン原子（Ｃｌ、Ｂｒ又はＩ）である。）

(Wherein, Z, Z ′, R ² , p1, p2, p3, p4, x, z, and R ⁵ , R ^6a , R ⁷ , R ⁸ , c, and d each have the same meaning as described above; Is a halogen atom (Cl, Br or I).

  The compounds of the formulas (VI) and (VII) and the compound of the formula (4b) can be obtained by adding the compound of the formulas (I) and (II) and the compound of the formula (4a) to hydrogen chloride, hydrogen bromide or iodide. It can be obtained by reacting hydrogen.

  In the second method, when a crosslinked high molecular silicone compound is obtained, a carboxyl group or a carboxyl group of a high molecular compound having a repeating unit represented by the above general formula (1 ′) having a weight average molecular weight of 1,000 to 500,000 is used. And the halogenated alkyl ether compound represented by the general formula (VI) or (VII) (p112 + p412 mol) and the compound represented by the general formula (4b) (p12 + p42 mol) with respect to 1 mol of the hydroxyl group are reacted with, for example, the above-mentioned formula ( Polymer compounds represented by 3a'-1) and (3a'-2) can be obtained.

  The above production method is preferably carried out in a solvent in the presence of a base. The reaction solvent is preferably an aprotic polar solvent such as acetonitrile, acetone, dimethylformamide, dimethylacetamide, tetrahydrofuran, dimethylsulfoxide, etc., and may be used alone or as a mixture of two or more.

  As the base, triethylamine, pyridine, diisopropylamine, potassium carbonate and the like are preferable. The amount of the base to be used is 1 mol or more, especially 1 mol, per 1 mol of the carboxyl group of the polymer compound represented by the general formula (1 ′). It is preferably at least 5 mole times.

  The reaction temperature is -50 to 100C, preferably 0 to 60C, and the reaction time is 0.5 to 100 hours, preferably 1 to 20 hours.

As described above, the polymer compound having the repeating unit represented by the formula (1 ′) or the polymer compound in which a part of the carboxyl group is substituted with a COR ¹ group is used as the compound of the formula (4a) or (4b). To obtain a compound having an acid labile group, for example, a compound represented by the following formula (1 ″), which is isolated, and then isolated from the compound represented by the formula (I), (II) or (VI). ) And (VII) may be used for crosslinking.

  The polymer represented by the formula (3a'-1) or (3a'-2) obtained by the above first or second method may, if necessary, be represented by the original formula (1 '). P122 + p422 mol of a dialkyl dicarbonate compound, an alkoxycarbonylalkyl halide or the like is reacted with 1 mol of the carboxyl group of the polymer compound to introduce an acid labile group represented by the general formula (5), By reacting a halide, a trialkylsilyl halide, an oxoalkyl compound, or the like, a polymer compound represented by, for example, general formulas (3b′-1) and (3b′-2) can be obtained.

  The method for introducing the acid labile group of the above formula (5) is preferably carried out in a solvent in the presence of a base.

  The reaction solvent is preferably an aprotic polar solvent such as acetonitrile, acetone, dimethylformamide, dimethylacetamide, tetrahydrofuran, dimethylsulfoxide, etc., and may be used alone or as a mixture of two or more.

  As the base, triethylamine, pyridine, imidazole, diisopropylamine, potassium carbonate and the like are preferable, and the amount of the base used is 1 mole or more per 1 mole of the carboxyl group of the polymer compound represented by the general formula (1 ′). In particular, it is preferably at least 5 mol times.

  The reaction temperature is 0-100 ° C, preferably 0-60 ° C. The reaction time is 0.2 to 100 hours, preferably 1 to 10 hours.

  Examples of the dialkyl dicarbonate compound include di-tert-butyl dicarbonate and di-tert-amyl dicarbonate. Examples of the alkoxycarbonylalkyl halide include tert-butoxycarbonylmethyl chloride, tert-amyloxycarbonylmethyl chloride, and tert-butoxy. Examples include carbonylmethyl bromide and tert-butoxycarbonylethyl chloride, and examples of the trialkylsilyl halide include trimethylsilyl chloride, triethylsilyl chloride, and dimethyl-tert-butylsilyl chloride.

  The polymer compound represented by the general formula (3a′-1) or (3a′-2) obtained by the above first or second method may be added with the original general formula (1 ′) as necessary. The tertiary alkylation or oxoalkylation can be carried out by reacting p12 + p42 mol of a tertiary alkylating agent and an oxoalkyl compound with respect to 1 mol of the carboxyl group of the polymer compound shown.

The above method is preferably performed in a solvent in the presence of an acid.
As the reaction solvent, aprotic polar solvents such as dimethylformamide, dimethylacetamide, tetrahydrofuran, and ethyl acetate are preferable, and they may be used alone or as a mixture of two or more.

  As the acid for the catalyst, hydrochloric acid, sulfuric acid, trifluoromethanesulfonic acid, p-toluenesulfonic acid, methanesulfonic acid, pyridinium p-toluenesulfonate and the like are preferable, and the amount of use is represented by the general formula (1 ′). It is preferably 0.1 to 10 mol% with respect to 1 mol of the carboxyl group of the polymer compound to be obtained.

  The reaction temperature is −20 to 100 ° C., preferably 0 to 60 ° C., and the reaction time is 0.2 to 100 hours, preferably 0.5 to 20 hours.

  Examples of the tertiary alkylating agent include isobutene, 2-methyl-1-butene, and 2-methyl-2-butene. Examples of the oxoalkyl compound include α-angelicalactone, 2-cyclohexen-1-one, and 5,6. -Dihydro-2H-pyran-2-one and the like.

  The repeating unit represented by the following general formula (3c'-1) or (3c'-2) directly without passing through the polymer compound represented by the general formula (3a'-1) or (3a'-2) After introducing an acid labile group represented by the general formula (5), a tertiary alkyl group, a trialkylsilyl group, an oxoalkyl group or the like into the polymer compound having the general formula (5), the acid represented by the general formula (4) is added as necessary. Unstable groups can also be introduced.

In the polymer compound of the present invention, the acid labile group of R ² is not limited to one type, and two or more types can be introduced. In this case, after introducing p41 mol of the acid labile group per 1 mol of the total hydroxyl groups of the polymer compound of the formula (1 ′) as described above, a different acid labile group is introduced in the same manner as described above. By introducing p42 mol of the above, a polymer compound in which two or more such acid labile groups are introduced, or by repeating such an operation appropriately, can be obtained.

The polymeric silicone compound of the present invention is effective as a base polymer of a resist material, and the resist material of the present invention contains the polymeric silicone compound as a base polymer. In this case, the resist material may be a positive type or a negative type, but is preferably a chemically amplified type. As such a resist material,
(A) an organic solvent,
(B) the above polymer silicone compound as a base resin,
(C) an acid generator and, if necessary,
(D) a dissolution controlling agent,
(E) a basic compound,
(F) a compound having a group represented by ≡C-COOH in the molecule,
(G) a chemically amplified positive resist material containing an acetylene alcohol derivative;
Or,
(A) an organic solvent,
(B) the above polymer silicone compound as a base resin,
(C) an acid generator,
(H) A chemically amplified negative resist material containing a compound which is crosslinked by the action of an acid can be used.

  Here, the organic solvent of the component (A) used in the present invention may be any organic solvent that can dissolve the acid generator, the base resin, the dissolution controlling agent 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, 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, ethers such as diethylene glycol dimethyl ether, 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, and propylene glycol-mono-tert-butyl ether acetate are used, and one of these may be used alone or in combination of two or more. However, the present invention is not limited to these. In the present invention, among these organic solvents, in addition to diethylene glycol dimethyl ether and 1-ethoxy-2-propanol in which the solubility of the acid generator in the resist component is the most excellent, propylene glycol monomethyl ether acetate as a safe solvent and a mixture thereof Solvents are preferably used.

  The amount of the organic solvent to be used is preferably 200 to 1,000 parts, more preferably 400 to 800 parts, per 100 parts (parts by weight, hereinafter the same) of the base resin (B).

As the acid generator of the component (C),
<1> Onium salt of the following general formula (6a-1), (6a-2) or (6b),
<2> a diazomethane derivative represented by the following general formula (7),
<3> a glyoxime derivative represented by the following general formula (8),
<4> a bissulfone derivative represented by the following general formula (9),
<5> a sulfonic acid ester of an N-hydroxyimide compound represented by the following general formula (10),
<6> β-ketosulfonic acid derivative,
<7> disulfone derivative,
<8> nitrobenzyl sulfonate derivative,
<9> Sulfonic acid ester derivatives and the like.

（式中、Ｒ^30a、Ｒ^30b、Ｒ^30cはそれぞれ炭素数１〜１２の直鎖状、分岐状又は環状のアルキル基、アルケニル基、オキソアルキル基又はオキソアルケニル基、炭素数６〜２０のアリール基又は炭素数７〜１２のアラルキル基又はアリールオキソアルキル基を表し、これら基の水素原子の一部又は全部がアルコキシ基等によって置換されていてもよい。また、Ｒ^30bとＲ^30cとは環を形成してもよく、環を形成する場合には、Ｒ^30b、Ｒ^30cはそれそれ炭素数１〜６のアルキレン基を示し、Ｋ^-は非求核性対向イオンを表す。）

(Wherein, R ^30a , R ^30b and R ^30c each represent a linear, branched or cyclic alkyl group, alkenyl group, oxoalkyl group or oxoalkenyl group having 1 to 12 carbon atoms, aryl having 6 to 20 carbon atoms) represents a group or an aralkyl group or an aryl oxoalkyl group having 7 to 12 carbon atoms, some or all of the hydrogen atoms in these groups may be substituted by alkoxy or other groups. Further, the ring and R ^30b and R ^30c And when forming a ring, R ^30b and R ^30c each represent an alkylene group having 1 to 6 carbon atoms, and K ⁻ represents a non-nucleophilic counter ion.)

R ^30a , R ^30b and R ^30c may be the same or different from each other, and specifically, as an alkyl group, a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, a sec-butyl group Group, tert-butyl group, pentyl group, hexyl group, heptyl group, octyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclopropylmethyl group, 4-methylcyclohexyl group, cyclohexylmethyl group, norbornyl group, adamantyl group, etc. Is mentioned. Examples of the alkenyl group include a vinyl group, an allyl group, a propenyl group, a butenyl group, a hexenyl group, and a cyclohexenyl group. Examples of the oxoalkyl group and the oxoalkenyl group include a 2-oxocyclopentyl group and a 2-oxocycloheptyl group, and a 2-oxopropyl group, a 2-cyclopentyl-2-oxoethyl group, and a 2-cyclohexyl-2-oxoethyl group. And 2-alkyl-2-oxoethyl groups such as a 2- (4-methylcyclohexyl) -2-oxoethyl group. Examples of the aryl group include a phenyl group, a naphthyl group, a p-methoxyphenyl group, an m-methoxyphenyl group, an o-methoxyphenyl group, an ethoxyphenyl group, a p-tert-butoxyphenyl group, and an m-tert-butoxyphenyl group. Alkylphenyl groups such as alkoxyphenyl group, 2-methylphenyl group, 3-methylphenyl group, 4-methylphenyl group, ethylphenyl group, 4-tert-butylphenyl group, 4-butylphenyl group and dimethylphenyl group Alkyl naphthyl groups such as methyl naphthyl group and ethyl naphthyl group, methoxy naphthyl group, alkoxy naphthyl group such as ethoxy naphthyl group, dimethyl naphthyl group, dialkyl naphthyl group such as diethyl naphthyl group, dimethoxy naphthyl group, diethoxy naphthyl group and the like Dialkoxynaphthyl group And the like. Examples of the aralkyl group include a benzyl group, a phenylethyl group, and a phenethyl group. Examples of the aryloxoalkyl group include 2-aryl-2 such as 2- (phenyl) -2-oxoethyl group, 2- (1-naphthyl) -2-oxoethyl group, and 2- (2-naphthyl) -2-oxoethyl group. -Oxoethyl group and the like. K ^- a non-nucleophilic counter chloride ions as the ion, halide ions such as bromide ion, triflate, perfluorooctyl sulfonate, 1,1,1-trifluoro ethanesulfonate, fluoroalkyl sulfonate such as nonafluorobutanesulfonate , Tosylate, benzenesulfonate, 4-fluorobenzenesulfonate, 4-trifluoromethylbenzenesulfonate, arylsulfonates such as 1,2,3,4,5-pentafluorobenzenesulfonate, and alkylsulfonates such as mesylate and butanesulfonate. .

（式中、Ｒ^31a、Ｒ^31bはそれぞれ炭素数１〜８の直鎖状、分岐状又は環状のアルキル基、Ｒ³²は炭素数１〜１０の直鎖状、分岐状又は環状のアルキレン基、Ｒ^33a、Ｒ^33bはそれぞれ炭素数３〜７の２−オキソアルキル基を示し、Ｋ^-は非求核性対向イオンを表す。）

(Wherein, R ^31a and R ^31b each represent a linear, branched or cyclic alkyl group having 1 to 8 carbon atoms, R ³² represents a linear, branched or cyclic alkylene group having 1 to 10 carbon atoms; R ^33a and R ^33b each represent a 2-oxoalkyl group having 3 to 7 carbon atoms, and K ⁻ represents a non-nucleophilic counter ion.)

Specific examples of R ^31a and R ^31b include a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, a tert-butyl group, a pentyl group, a hexyl group, a heptyl group, and an octyl group. , Cyclopentyl, cyclohexyl, cyclopropylmethyl, 4-methylcyclohexyl, cyclohexylmethyl and the like. R ³² is a methylene group, an ethylene group, a propylene group, a butylene group, a pentylene group, a hexylene group, a heptylene group, an octylene group, a nonylene group, a 1,4-cyclohexylene group, a 1,2-cyclohexylene A 1,3-cyclopentylene group, a 1,4-cyclooctylene group, a 1,4-cyclohexanedimethylene group, and the like. ^{Examples of} R ^33a and R ^33b include a 2-oxopropyl group, a 2-oxocyclopentyl group, a 2-oxocyclohexyl group, and a 2-oxocycloheptyl group. K ^- is can be exemplified the same as the equation (6a).

（式中、Ｒ³⁴、Ｒ³⁵は炭素数１〜１２の直鎖状、分岐状又は環状のアルキル基又はハロゲン化アルキル基、炭素数６〜２０のアリール基又はハロゲン化アリール基又は炭素数７〜１２のアラルキル基を表す。）

(Wherein, R ³⁴ and R ³⁵ represent a linear, branched or cyclic alkyl group or halogenated alkyl group having 1 to 12 carbon atoms, an aryl group or halogenated aryl group having 6 to 20 carbon atoms or a carbon atom having 7 carbon atoms). ~ 12 aralkyl groups.)

^Examples of the alkyl group for R ³⁴ and R ³⁵ include a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, a tert-butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group and an amyl group. Group, cyclopentyl group, cyclohexyl group, cycloheptyl group, norbornyl group, adamantyl group and the like. Examples of the halogenated alkyl group include a trifluoromethyl group, a 1,1,1-trifluoroethyl group, a 1,1,1-trichloroethyl group, a nonafluorobutyl group, and the like. Examples of the aryl group include an alkoxyphenyl group such as a phenyl group, a p-methoxyphenyl group, an m-methoxyphenyl group, an o-methoxyphenyl group, an ethoxyphenyl group, a p-tert-butoxyphenyl group, and a m-tert-butoxyphenyl group; Examples thereof include an alkylphenyl group such as a 2-methylphenyl group, a 3-methylphenyl group, a 4-methylphenyl group, an ethylphenyl group, a 4-tert-butylphenyl group, a 4-butylphenyl group, and a dimethylphenyl group. Examples of the halogenated aryl group include a fluorobenzene group, a chlorobenzene group, a 1,2,3,4,5-pentafluorobenzene group, and the like. Examples of the aralkyl group include a benzyl group and a phenethyl group.

（式中、Ｒ³⁶、Ｒ³⁷、Ｒ³⁸は炭素数１〜１２の直鎖状、分岐状又は環状のアルキル基又はハロゲン化アルキル基、炭素数６〜２０のアリール基又はハロゲン化アリール基又は炭素数７〜１２のアラルキル基を表す。また、Ｒ³⁷、Ｒ³⁸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、Ｒ³⁷、Ｒ³⁸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。）

(Wherein, R ³⁶ , R ³⁷ , and R ^{38 each} represent a linear, branched, or cyclic alkyl group or halogenated alkyl group having 1 to 12 carbon atoms, an aryl group or a halogenated aryl group having 6 to 20 carbon atoms, or And represents an aralkyl group having 7 to 12 carbon atoms, and R ³⁷ and R ³⁸ may be bonded to each other to form a cyclic structure, and when forming a cyclic structure, R ³⁷ and R ³⁸ each have 1 to 1 carbon atoms. 6 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 ³⁶ , R ³⁷ , and R ³⁸ include the same groups as those described for R ³⁴ and R ³⁵ . The alkylene group for R ³⁷ and R ³⁸ includes a methylene group, an ethylene group, a propylene group, a butylene group, a hexylene group, and the like.

（式中、Ｒ^30a、Ｒ^30bは上記と同じである。）

(In the formula, R ^30a and R ^30b are the same as described above.)

（式中、Ｒ³⁹は炭素数６〜１０のアリーレン基、炭素数１〜６のアルキレン基又は炭素数２〜６のアルケニレン基を表し、これらの基の水素原子の一部又は全部は更に炭素数１〜４の直鎖状又は分岐状のアルキル基又はアルコキシ基、ニトロ基、アセチル基、又はフェニル基で置換されていてもよい。Ｒ⁴⁰は炭素数１〜８の直鎖状、分岐状又は置換のアルキル基、アルケニル基又はアルコキシアルキル基、フェニル基、又はナフチル基を表し、これらの基の水素原子の一部又は全部は更に炭素数１〜４のアルキル基又はアルコキシ基；炭素数１〜４のアルキル基、アルコキシ基、ニトロ基又はアセチル基で置換されていてもよいフェニル基；炭素数３〜５のヘテロ芳香族基；又はフッ素原子、塩素原子で置換されていてもよい。）

(In the formula, R ³⁹ represents an arylene group having 6 to 10 carbon atoms, an alkylene group having 1 to 6 carbon atoms or an alkenylene group having 2 to 6 carbon atoms, and a part or all of the hydrogen atoms of these groups further have carbon atoms. R ⁴⁰ may be substituted with a linear or branched alkyl group or alkoxy group, a nitro group, an acetyl group, or a phenyl group having 1 to 4. R ⁴⁰ is a linear or branched C 1 to C 8 group. Or a substituted alkyl group, alkenyl group or alkoxyalkyl group, phenyl group, or naphthyl group, and part or all of the hydrogen atoms of these groups are further an alkyl group or alkoxy group having 1 to 4 carbon atoms; Or a phenyl group which may be substituted by an alkyl group, an alkoxy group, a nitro group or an acetyl group; a heteroaromatic group having 3 to 5 carbon atoms; or a fluorine atom or a chlorine atom.)

Here, as the arylene group for R ³⁹ , a 1,2-phenylene group, 1,8-naphthylene group or the like is used, and as the alkylene group, a methylene group, 1,2-ethylene group, 1,3-propylene group, 1 , 4-butylene group, 1-phenyl-1,2-ethylene group, norbornane-2,3-diyl group and the like, and alkenylene groups include 1,2-vinylene group, 1-phenyl-1,2-vinylene group , 5-norbornene-2,3-diyl group and the like. Examples of the alkyl group for R ⁴⁰ are the same as those for R ^{30a to} R ^30c, and examples of the alkenyl group include a vinyl group, a 1-propenyl group, an allyl group, a 1-butenyl group, a 3-butenyl group, an isoprenyl group, and a 1-alkyl group. Pentenyl group, 3-pentenyl group, 4-pentenyl group, dimethylallyl group, 1-hexenyl group, 3-hexenyl group, 5-hexenyl group, 1-heptenyl group, 3-heptenyl group, 6-heptenyl group, 7-octenyl Groups and the like, as alkoxyalkyl group, methoxymethyl group, ethoxymethyl group, propoxymethyl group, butoxymethyl group, pentoxymethyl group, hexyloxymethyl group, heptyloxymethyl group, methoxyethyl group, ethoxyethyl group, Propoxyethyl group, butoxyethyl group, pentoxyethyl group, hexyloxyethyl group, methoxypropyl group Ethoxypropyl, propoxypropyl group, butoxy propyl group, methoxybutyl group, ethoxybutyl group, propoxybutyl group, a methoxy pentyl group, an ethoxy pentyl group, a methoxy hexyl group, a methoxy heptyl group.

  Examples of the linear or branched alkyl group having 1 to 4 carbon atoms which may be further substituted include a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, an isobutyl group and a tert-butyl group. Groups are alkoxy groups such as methoxy group, ethoxy group, propoxy group, isopropoxy group, n-butoxy group, isobutoxy group, tert-butoxy group, etc. are alkyl groups having 1 to 4 carbon atoms, alkoxy group, nitro group; Examples of the phenyl group which may be substituted with a group or an acetyl group include a phenyl group, a tolyl group, a p-tert-butoxyphenyl group, a p-acetylphenyl group, and a p-nitrophenyl group. Examples include a pyridyl group and a furyl group.

  Specifically, for example, diphenyliodonium trifluoromethanesulfonate, (p-tert-butoxyphenyl) phenyliodonium trifluoromethanesulfonate, diphenyliodonium p-toluenesulfonate, phenyl (p-tert-butoxyphenyl) phenyl p-toluenesulfonate Iodonium, triphenylsulfonium trifluoromethanesulfonate, diphenylsulfonium trifluoromethanesulfonate (p-tert-butoxyphenyl), bis (p-tert-butoxyphenyl) phenylsulfonate trifluoromethanesulfonate, tris (p-tert) trifluoromethanesulfonate -Butoxyphenyl) sulfonium, triphenylsulfonium p-toluenesulfonate, 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, dimethylphenyl p-toluenesulfonate Nylsulfonium, dicyclohexylphenylsulfonium trifluoromethanesulfonate, dicyclohexylphenylsulfonium p-toluenesulfonate, trinaphthylsulfonium trifluoromethanesulfonate, cyclohexylmethyl trifluoromethanesulfonate (2-oxocyclohexyl) sulfonium, trifluoromethanesulfonate (2-norbornyl) Onium salts such as methyl (2-oxocyclohexyl) sulfonium, ethylenebis [methyl (2-oxocyclopentyl) sulfonium trifluoromethanesulfonate], 1,2′-naphthylcarbonylmethyltetrahydrothiophenium triflate, bis (benzenesulfonyl) ) Diazomethane, bis (p-toluenesulfonyl) diazomethane, bis (xylene (Honyl) diazomethane, bis (cyclohexylsulfonyl) diazomethane, bis (cyclopentylsulfonyl) diazomethane, bis (n-butylsulfonyl) diazomethane, bis (isobutylsulfonyl) diazomethane, bis (sec-butylsulfonyl) diazomethane, bis (n-propylsulfonyl) Diazomethane, bis (isopropylsulfonyl) diazomethane, bis (tert-butylsulfonyl) diazomethane, bis (n-amylsulfonyl) diazomethane, bis (isoamylsulfonyl) diazomethane, bis (sec-amylsulfonyl) diazomethane, bis (tert-amylsulfonyl) Diazomethane, 1-cyclohexylsulfonyl-1- (tert-butylsulfonyl) diazomethane, 1-cyclohexylsulfonyl- 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-pentanedione glyoxime , Bis-o- (p-toluenesulfonyl) -2-methyl-3,4-pentanedione glyoxime, bis-o- (n-butanesulfonyl) -α-dimethylglyoxime, bis-o- (n-butane Sulfonyl) -α-diphenylglyoxime, bis-o- (n-butanesulfonyl) -Α-dicyclohexylglyoxime, bis-o- (n-butanesulfonyl) -2,3-pentanedione glyoxime, bis-o- (n-butanesulfonyl) -2-methyl-3,4-pentanedione glyoxime , Bis-o- (methanesulfonyl) -α-dimethylglyoxime, bis-o- (trifluoromethanesulfonyl) -α-dimethylglyoxime, bis-o- (1,1,1-trifluoroethanesulfonyl) -α -Dimethylglyoxime, bis-o- (tert-butanesulfonyl) -α-dimethylglyoxime, bis-o- (perfluorooctanesulfonyl) -α-dimethylglyoxime, bis-o- (cyclohexanesulfonyl) -α- Dimethylglyoxime, bis-o- (benzenesulfonyl) -α-dimethylglyoxime, -O- (p-fluorobenzenesulfonyl) -α-dimethylglyoxime, bis-o- (p-tert-butylbenzenesulfonyl) -α-dimethylglyoxime, bis-o- (xylenesulfonyl) -α-dimethylglyme Glyoxime derivatives such as oxime, bis-o- (camphorsulfonyl) -α-dimethylglyoxime, bisnaphthylsulfonylmethane, bistrifluoromethylsulfonylmethane, bismethylsulfonylmethane, bisethylsulfonylmethane, bispropylsulfonylmethane, bisisopropylsulfonyl Bissulfone derivatives such as methane, bis-p-toluenesulfonylmethane, bisbenzenesulfonylmethane, 2-cyclohexylcarbonyl-2- (p-toluenesulfonyl) propane, 2-isopropylcarbonyl- Β-ketosulfone derivatives such as 2- (p-toluenesulfonyl) propane, disulfone derivatives such as diphenyldisulfone and dicyclohexyldisulfone, 2,6-dinitrobenzyl p-toluenesulfonate, 2,4-dinitrobenzyl p-toluenesulfonate and the like Nitrobenzylsulfonate derivative, 1,2,3-tris (methanesulfonyloxy) benzene, 1,2,3-tris (trifluoromethanesulfonyloxy) benzene, 1,2,3-tris (p-toluenesulfonyloxy) benzene Sulfonic acid ester derivatives, such as N-hydroxysuccinimide methyl sulfonic acid ester, N-hydroxysuccinimide trifluoromethyl sulfonic acid ester, N-hydroxysuccinimide ethyl sulfonic acid ester, N-hydroxys Synimidopropylsulfonic acid ester, N-hydroxysuccinimideisopropylisopropylsulfonic acid ester, N-hydroxysuccinimidepentylsulfonic acid ester, N-hydroxysuccinimideoctylsulfonic acid ester, N-hydroxysuccinimide-p-toluenesulfonic acid ester, N-hydroxysuccinimide -P-anisylsulfonic acid ester, N-hydroxysuccinimide-2-chloroethylsulfonic acid ester, N-hydroxysuccinimidebenzenesulfonic acid ester, N-hydroxysuccinimide-2,4,6-trimethylphenylsulfonic acid ester, N- Hydroxysuccinimide naphthyl sulfonate, N-hydroxy-2-phenylsuccinimide methyl sulfonate, N-hydroxy Droxymaleimidomethylsulfonate, N-hydroxymaleimidoethylsulfonate, N-hydroxy-2-phenylmaleimidomethylsulfonate, N-hydroxyglutarimidemethylsulfonate, N-hydroxyglutarimidephenylsulfonate, N-hydroxyphthalimidomethylsulfonic acid ester, N-hydroxyphthalimidophenylsulfonic acid ester, N-hydroxyphthalimidotrifluoromethanesulfonic acid ester, N-hydroxyphthalimido-p-toluenesulfonic acid ester, N-hydroxy-1,8-naphthalimide Methyl sulfonic acid ester, N-hydroxy-1,8-naphthalimidophenylsulfonic acid ester, N-hydroxy-5-norbornene-2, -Dicarboximide methyl sulfonate, N-hydroxy-5-norbornene-2,3-dicarboximide trifluoromethanesulfonate, N-hydroxy-5-norbornene-2,3-dicarboximide-p-toluenesulfone Sulfonate derivatives of N-hydroxyimide compounds such as acid esters, etc., and the like, such as triphenylsulfonium trifluoromethanesulfonate, trifluoromethanesulfonic acid (p-tert-butoxyphenyl) diphenylsulfonium, and tris (trifluoromethanesulfonic acid) -Tert-butoxyphenyl) sulfonium, triphenylsulfonium p-toluenesulfonate, (p-tert-butoxyphenyl) diphenylsulfonium p-toluenesulfonate, p- Tris (p-tert-butoxyphenyl) sulfonium ruenesulfonate, trinaphthylsulfonium trifluoromethanesulfonate, cyclohexylmethyl trifluoromethanesulfonate (2-oxocyclohexyl) sulfonium, methyl (2-norbornyl) trifluoromethanesulfonate (2-oxo) Onium salts such as cyclohexyl) sulfonium, 1,2′-naphthylcarbonylmethyltetrahydrothiophenium triflate, bis (benzenesulfonyl) diazomethane, bis (p-toluenesulfonyl) diazomethane, bis (cyclohexylsulfonyl) diazomethane, bis (n- Butylsulfonyl) diazomethane, bis (isobutylsulfonyl) diazomethane, bis (sec-butylsulfonyl) diazomethane, bis (n- Diazomethane derivatives such as propylsulfonyl) diazomethane, bis (isopropylsulfonyl) diazomethane, bis (tert-butylsulfonyl) diazomethane, bis-o- (p-toluenesulfonyl) -α-dimethylglyoxime, bis-o- (n-butane Glyoxime derivatives such as sulfonyl) -α-dimethylglyoxime, bissulfone derivatives such as bisnaphthylsulfonylmethane, N-hydroxysuccinimide methylsulfonic acid ester, N-hydroxysuccinimide trifluoromethylsulfonic acid ester, N-hydroxysuccinimidepropyl sulfonic acid ester N-hydroxysuccinimide isopropyl sulfonate, N-hydroxysuccinimide pentyl sulfonate, N-hydroxysuccinimide -P-toluenesulfonic acid ester, N-hydroxy-1,8-naphthalimidomethylsulfonic acid ester, N-hydroxy-1,8-naphthalimidophenylsulfonic acid ester, N-hydroxysuccinimide trifluoromethanesulfonic acid ester, etc. -A sulfonate derivative of a hydroxyimide compound is preferably used. In addition, the said acid generator can be used individually by 1 type or in combination of 2 or more types. The onium salt is excellent in the effect of improving the rectangularity, and the diazomethane derivative and the glyoxime derivative are excellent in the effect of reducing the standing wave. However, by combining the two, fine adjustment of the profile can be performed.

  The amount of the acid generator to be added is preferably 0.1 to 15 parts, more preferably 0.5 to 8 parts based on 100 parts of the base resin. If the amount is less than 0.1 part, the sensitivity may be poor. If the amount is more than 15 parts, the resolution of the resist material may be reduced due to a decrease in the alkali dissolution rate. Performance may be reduced.

  The resist composition of the present invention may further contain a dissolution controlling agent as the component (D). As the dissolution controlling agent, the hydrogen atom of the phenolic hydroxyl group of a compound having an average molecular weight of 100 to 1,000, preferably 150 to 800, and having two or more phenolic hydroxyl groups in the molecule is entirely formed by an acid labile group. A compound in which the hydrogen atom of the carboxyl group of the compound having a carboxyl group in the molecule is substituted by an acid labile group at an average rate of 80 to 100 mol%.

  In addition, the substitution rate of the hydrogen atom of the phenolic hydroxyl group or the carboxyl group by the acid labile group is 0 mol% or more, preferably 30 mol% or more of the entire phenolic hydroxyl group or the carboxyl group, and the upper limit thereof is It is 100 mol%, more preferably 80 mol%.

  In this case, as the compound having two or more phenolic hydroxyl groups or the compound having a carboxyl group, those represented by the following formulas (i) to (xiv) are preferable.

（但し、式中Ｒ¹⁵、Ｒ¹⁶はそれぞれ水素原子又は炭素数１〜８の直鎖状又は分岐状のアルキル基又はアルケニル基であり、Ｒ¹⁷は水素原子又は炭素数１〜８の直鎖状又は分岐状のアルキル基又はアルケニル基、あるいは−（Ｒ²¹）_h−ＣＯＯＨであり、Ｒ¹⁸は−（ＣＨ₂）_i−（ｉ＝２〜１０）、炭素数６〜１０のアリーレン基、カルボニル基、スルホニル基、酸素原子又は硫黄原子、Ｒ¹⁹は炭素数１〜１０のアルキレン基、炭素数６〜１０のアリーレン基、カルボニル基、スルホニル基、酸素原子又は硫黄原子、Ｒ²⁰は水素原子又は炭素数１〜８の直鎖状又は分岐状のアルキル基、アルケニル基、それぞれ水酸基で置換されたフェニル基又はナフチル基であり、Ｒ²¹は炭素数１〜１０の直鎖状又は分岐状のアルキレン基、Ｒ²²は水素原子又は水酸基である。また、ｊは０〜５の整数であり、ｕ、ｈは０又は１である。ｓ、ｔ、ｓ’、ｔ’、ｓ’’、ｔ’’はそれぞれｓ＋ｔ＝８、ｓ’＋ｔ’＝５、ｓ’’＋ｔ’’＝４を満足し、かつ各フェニル骨格中に少なくとも１つの水酸基を有するような数である。αは式（ｖｉｉｉ）、（ｉｘ）の化合物の分子量を１００〜１，０００とする数である。）

(Wherein, R ¹⁵ and R ¹⁶ each represent a hydrogen atom or a linear or branched alkyl group or alkenyl group having 1 to 8 carbon atoms, and R ¹⁷ represents a hydrogen atom or a linear chain having 1 to 8 carbon atoms. A branched or branched alkyl or alkenyl group, or-(R ²¹ ) _h -COOH, wherein R ¹⁸ is-(CH ₂ ) _i- (i = 2 to 10), an arylene group having 6 to 10 carbon atoms, A carbonyl group, a sulfonyl group, an oxygen atom or a sulfur atom, R ¹⁹ is an alkylene group having 1 to 10 carbon atoms, an arylene group having 6 to 10 carbon atoms, a carbonyl group, a sulfonyl group, an oxygen atom or a sulfur atom, and R ²⁰ is a hydrogen atom Or a linear or branched alkyl group having 1 to 8 carbon atoms, an alkenyl group, a phenyl group or a naphthyl group each substituted with a hydroxyl group, and R ²¹ has a linear or branched C 1 to 10 carbon atom. alkylene group, R ²² is a hydrogen atom Is a hydroxyl group, j is an integer of 0 to 5, u and h are 0 or 1. s, t, s ′, t ′, s ″, and t ″ are each s + t = 8, s ′ + t ′ = 5, s ″ + t ″ = 4, and a number having at least one hydroxyl group in each phenyl skeleton. α is a number of the compounds of formulas (viii) and (ix) It is a number that makes the molecular weight 100 to 1,000.)

In the above formula, R ¹⁵ and R ¹⁶ are, for example, a hydrogen atom, a methyl group, an ethyl group, a butyl group, a propyl group, an ethynyl group, a cyclohexyl group, and R ¹⁷ are, for example, the same as R ¹⁵ and R ¹⁶ , or -COOH, as the -CH ₂ COOH, R ^18, for example, ethylene group, a phenylene group, a carbonyl group, a sulfonyl group, an oxygen atom, a sulfur atom, etc. Examples of the R ^19, for example, methylene group, or ones similar to R ^18,, Examples of R ²⁰ include a hydrogen atom, a methyl group, an ethyl group, a butyl group, a propyl group, an ethynyl group, a cyclohexyl group, a phenyl group substituted with a hydroxyl group, a naphthyl group, and the like.

  Here, the acid labile group of the dissolution controlling agent includes a group represented by the above general formula (4), a group represented by the above general formula (5), a tertiary alkyl group having 4 to 20 carbon atoms, and each alkyl group. A trialkylsilyl group having 1 to 6 carbon atoms and an oxoalkyl group having 4 to 20 carbon atoms.

  The compounding amount of the dissolution controlling agent is 0 to 50 parts, preferably 5 to 50 parts, more preferably 10 to 30 parts with respect to 100 parts of the base resin, and they can be used alone or in combination of two or more. If the amount is less than 5 parts, the resolution may not be improved. If the amount exceeds 50 parts, the pattern may be reduced in film thickness and the resolution may be reduced.

  The dissolution controlling agent as described above can be synthesized by chemically reacting a compound having a phenolic hydroxyl group or a carboxyl group with an acid labile group in the same manner as in the base resin.

  The resist composition of the present invention may be a compound having a weight average molecular weight of less than 1,000 and having a carboxyl group in the molecule as a dissolution controller instead of or in addition to the dissolution controller. A compound in which atoms are partially substituted by an acid labile group at an average ratio of 0% to 100% as a whole can be blended.

  In this case, the compound in which the hydrogen atom of the carboxyl group is partially substituted with such an acid labile group includes a compound having a repeating unit represented by the following general formula (11) and having a weight average molecular weight of less than 1,000. One or more selected compounds are preferred.

（式中、Ｚ、Ｚ’、Ｒ²、ｐ１、ｐ２、ｐ３、ｐ４、ｘ、ｚは上記と同様の意味を示す。）

(In the formula, Z, Z ′, R ² , p1, p2, p3, p4, x, and z have the same meaning as described above.)

  Here, examples of the acid labile group of the dissolution controlling agent include a group represented by the general formula (4), a group represented by the general formula (5), a tertiary alkyl group having 4 to 20 carbon atoms, and each alkyl. Examples thereof include a trialkylsilyl group having 1 to 6 carbon atoms and an oxoalkyl group having 4 to 20 carbon atoms.

  The compounding amount of the other dissolution controlling agent is 0 to 50 parts, particularly 0 to 30 parts, preferably 0 to 5 parts based on 100 parts of the base resin as a whole of the dissolution controlling agent and the dissolution controlling agent. Preferably, it is within the range.

  In addition, another dissolution controlling agent as described above can be synthesized by chemically reacting an acid labile group with a compound having a carboxyl group in the same manner as in the base resin.

  In addition, a silicone compound can be preferably used as the dissolution controlling agent (D) because the dissolution controlling agent (D) does not deteriorate oxygen plasma etching resistance. As the dissolution controlling agent for the silicone compound, use is made of a silicone compound represented by the following general formulas (12) to (14) in which a carboxyl group or a hydroxyl group is protected with a tert-butyl group or a tert-butoxycarbonylmethyl group. Is preferred.

（式中、Ｒ¹⁰はメチル基又はフェニル基を示し、Ｒ¹¹はカルボキシエチル基又はｐ−ヒドロキシフェニルアルキル基（但し、アルキル基は炭素数１〜８の直鎖状、分岐状又は環状のアルキル基）を示す。Ｅはトリメチルシリル基、トリフェニルシリル基又は−ＳｉＲ¹⁰Ｒ¹¹（Ｒ¹⁰、Ｒ¹¹は上記と同様の意味を示す）基を示す。γは０〜５０の整数、δは１〜５０の整数、εは３〜１０の整数を示す。）

(Wherein, R ¹⁰ represents a methyl group or a phenyl group, and R ¹¹ represents a carboxyethyl group or a p-hydroxyphenylalkyl group (provided that the alkyl group is a linear, branched or cyclic alkyl having 1 to 8 carbon atoms) a group) .E trimethylsilyl group, a triphenylsilyl group or a ^{-SiR 10 R 11 (R 10,} R 11 are as defined above) .Ganma showing a group 0-50 integers, [delta] is 1 Is an integer of ５０50, and 示 す is an integer of 3 to 10.)

  Here, as the silicone compounds in which the carboxyl group or hydroxyl group of the silicone compounds of the above formulas (12) to (14) are protected with an alkali-soluble group (tert-butyl group or tert-butoxycarbonylmethyl group), Compounds of the C group are exemplified. Note that Me represents a methyl group, and t-Bu represents a tert-butyl group.

  The content of the dissolution controlling agent is preferably 40% by weight or less based on the whole base resin, and particularly preferably 10 to 30% by weight. If it exceeds 40% by weight, the resistance of the resist film to oxygen plasma etching is remarkably reduced, so that the resist film may not be usable as a two-layer resist.

  Furthermore, the resist composition of the present invention may contain a basic compound as the component (E).

  As the basic compound to be added as the (E) additive, a compound capable of suppressing the diffusion rate when the acid generated from the acid generator diffuses into the resist film is suitable. By compounding the compound, the diffusion rate of acid in the resist film is suppressed and the resolution is improved, the sensitivity change after exposure is suppressed, the dependence on the substrate and the environment is reduced, and the exposure margin and pattern profile are improved. Can be improved.

  Examples of such basic compounds include primary, secondary, and tertiary aliphatic amines, mixed amines, aromatic amines, heterocyclic amines, nitrogen-containing compounds having a carboxy group, and sulfonyl 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.

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

  Examples of the hybrid amines include dimethylethylamine, methylethylpropylamine, benzylamine, phenethylamine, and benzyldimethylamine. Specific examples of the aromatic amines and heterocyclic amines include aniline derivatives (for example, aniline, N-methylaniline, N-ethylaniline, N-propylaniline, N, N-dimethylaniline, 2-methylaniline, 3-methylaniline, 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 (for example, pyrrole, 2H-pyrrole, 1-methylpyrrole, 2,4-dimension 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, -Methyl-2-phenylimidazole, etc.), pyrazole derivatives, furazane derivatives, pyrroline derivatives (eg, pyrroline, 2-methyl-1-pyrroline, etc.), pyrrolidine derivatives (eg, pyrrolidine, N-methylpyrrolidine, pyrrolidinone, N-methylpyrrolidone, etc.) ), Imidazoline derivatives, imidazolidine derivatives, pyridine derivatives (eg, pyridine, methylpyridine, ethylpyridine, propylpyridine, butylpyridine, 4- (1-butylpentyl) pyridine, dimethyl) Lysine, trimethylpyridine, triethylpyridine, phenylpyridine, 3-methyl-2-phenylpyridine, 4-tert-butylpyridine, diphenylpyridine, benzylpyridine, methoxypyridine, butoxypyridine, dimethoxypyridine, 1-methyl-2-pyridone, 4-pyrrolidinopyridine, 1-methyl-4-phenylpyridine, 2- (1-ethylpropyl) pyridine, aminopyridine, dimethylaminopyridine, etc.), pyridazine derivative, pyrimidine derivative, pyrazine derivative, pyrazoline derivative, pyrazolidine derivative, piperidine Derivatives, piperazine derivatives, morpholine derivatives, indole derivatives, isoindole derivatives, 1H-indazole derivatives, indoline derivatives, quinoline derivatives (e.g., quinoline, 3-quinolinecarbo) Nitrile, etc.), 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 Derivatives, guanine derivatives, guanosine derivatives, uracil derivatives, uridine derivatives and the like are exemplified.

  Further, examples of the nitrogen-containing compound having a carboxy group include aminobenzoic acid, indolecarboxylic acid, and amino acid derivatives (eg, 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. Examples of the nitrogen-containing compound having a hydroxy group, the nitrogen-containing compound having a hydroxyphenyl group, and the alcoholic nitrogen-containing compound include 2-hydroxypyridine, aminocresol, 2,4-quinolinediol, and 3-indolemeta. Ethyl 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-hydroxyethoxy) Ethyl] piperazine, piperidineethanol, 1- (2-hydroxyethyl) pyrrolidine, 1- (2-hydroxyethyl) -2-pyrrolidinone, 3-piperidino-1,2-propanediol, 3-pyrrolidino-1,2-propane Diol, 8-hydroxy Loridine, 3-quinuclidinol, 3-tropanol, 1-methyl-2-pyrrolidineethanol, 1-aziridineethanol, N- (2-hydroxyethyl) phthalimide, N- (2-hydroxyethyl) isonicotinamide and the like. Is exemplified. Examples of the amide derivative include formamide, N-methylformamide, N, N-dimethylformamide, acetamide, N-methylacetamide, N, N-dimethylacetamide, propionamide, benzamide and the like. Examples of the imide derivative include phthalimide, succinimide, and maleimide.

  Further, basic compounds represented by the following general formulas (15) and (16) can be blended.

（式中、Ｒ⁴¹、Ｒ⁴²、Ｒ⁴³、Ｒ⁴⁷、Ｒ⁴⁸はそれぞれ独立して直鎖状、分岐鎖状又は環状の炭素数１〜２０のアルキレン基、Ｒ⁴⁴、Ｒ⁴⁵、Ｒ⁴⁶、Ｒ⁴⁹、Ｒ⁵⁰は水素原子、炭素数１〜２０のアルキル基又はアミノ基を示し、Ｒ⁴⁴とＲ⁴⁵、Ｒ⁴⁵とＲ⁴⁶、Ｒ⁴⁴とＲ⁴⁶、Ｒ⁴⁴とＲ⁴⁵とＲ⁴⁶、Ｒ⁴⁹とＲ⁵⁰はそれぞれ結合して環を形成してもよい。Ｓ、Ｔ、Ｕはそれぞれ０〜２０の整数を示す。但し、Ｓ、Ｔ、Ｕ＝０のとき、Ｒ⁴⁴、Ｒ⁴⁵、Ｒ⁴⁶、Ｒ⁴⁹、Ｒ⁵⁰は水素原子を含まない。）

(Wherein, R ⁴¹ , R ⁴² , R ⁴³ , R ⁴⁷ and R ⁴⁸ are each independently a linear, branched or cyclic alkylene group having 1 to 20 carbon atoms, R ⁴⁴ , R ⁴⁵ , R ⁴⁶ , R ⁴⁹ and R ⁵⁰ represent a hydrogen atom, an alkyl group having 1 to 20 carbon atoms or an amino group, and R ⁴⁴ and R ⁴⁵ , R ⁴⁵ and R ⁴⁶ , R ⁴⁴ and R ⁴⁶ , R ⁴⁴ and R ⁴⁵ and R ⁴⁶ , may be R ⁴⁹ and R ⁵⁰ is bonded to each other to form a ring .S, T, U each represent an integer of 0 to 20. However, S, T, when U = 0, R ^44, R ⁴⁵ , R ⁴⁶ , R ⁴⁹ and R ⁵⁰ do not contain a hydrogen atom.)

Here, the alkylene group of R ⁴¹ , R ⁴² , R ⁴³ , R ⁴⁷ , and R ⁴⁸ has 1 to 20, preferably 1 to 10, and more preferably 1 to 8 carbon atoms. , Methylene group, ethylene group, n-propylene group, isopropylene group, n-butylene group, isobutylene group, n-pentylene group, isopentylene group, hexylene group, nonylene group, decylene group, cyclopentylene group, cyclohexylene group And the like.

The alkyl group of R ⁴⁴ , R ⁴⁵ , R ⁴⁶ , R ⁴⁹ , and R ⁵⁰ has 1 to 20, preferably 1 to 8, and more preferably 1 to 6 carbon atoms. , Branched or cyclic. Specifically, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, isopentyl, hexyl, nonyl, decyl, dodecyl Group, tridecyl group, cyclopentyl group, cyclohexyl group and the like.

Further, when R ⁴⁴ and R ⁴⁵ , R ⁴⁵ and R ⁴⁶ , R ⁴⁴ and R ⁴⁶ , R ⁴⁴ and R ⁴⁵ and R ⁴⁶ , and R ⁴⁹ and R ⁵⁰ form a ring, R ⁴⁴ , R ⁴⁵ , R ⁴⁶ , R ⁴⁹ and R ⁵⁰ are each an alkylene group having 1 to 20, more preferably 1 to 8, and still more preferably 1 to 6 carbon atoms, and these rings are alkyl having 1 to 6 carbon atoms, particularly 1 to 4 carbon atoms. The groups may be branched.

  S, T and U are each an integer of 0 to 20, more preferably 1 to 10, and still more preferably 1 to 8.

  Specific examples of the compounds of the above (15) and (16) include tris {2- (methoxymethoxy) ethyl} amine, tris {2- (methoxyethoxy) ethyl} amine, and tris [2-{(2-methoxyethoxy) amine. ) Methoxy {ethyl] amine, tris {2- (2-methoxyethoxy) ethyl} amine, tris {2- (1-methoxyethoxy) ethyl} amine, tris {2- (1-ethoxyethoxy) ethyl} amine, tris {2- (1-ethoxypropoxy) ethyl} amine, tris [2-{(2-hydroxyethoxy) ethoxy} ethyl] amine, 4,7,13,16,21,24-hexaoxa-1,10-diazabicyclo [ 8.8.8] hexacosan, 4,7,13,18-tetraoxa-1,10-diazabicyclo [8.5.5] eicosan, , 4,10,13-Tetraoxa-7,16-diazabicyclooctadecane, 1-aza-12-crown-4, 1-aza-15-crown-5, 1-aza-18-crown-6 and the like. Can be In particular, tertiary amines, aniline derivatives, pyrrolidine derivatives, pyridine derivatives, quinoline derivatives, amino acid derivatives, nitrogen-containing compounds having a hydroxy group, nitrogen-containing compounds having a hydroxyphenyl group, alcoholic nitrogen-containing compounds, amide derivatives, imide derivatives, Tris {2- (methoxymethoxy) ethyl} amine, tris {(2- (2-methoxyethoxy) methyl} amine, tris [2-{(2-methoxyethoxy) methyl} ethyl] amine, 1-aza-15- Crown-5 and the like are preferred.

  The compounding amount of the basic compound is 0.001 to 10 parts, preferably 0.01 to 1 part, per part of the acid generator. If the amount is less than 0.001 part, the effect as an additive may not be sufficiently obtained, and if it exceeds 10 parts, the resolution and sensitivity may be reduced.

  Further, a compound having a group represented by ΔC-COOH in the molecule can be blended as the component (F) in the resist composition of the present invention.

As the compound having a group represented by ≡C-COOH in the molecule blended as the component (F), for example, one or more compounds selected from the following groups I and II can be used. However, the present invention is not limited to these. By blending the component (F), the PED stability of the resist can be improved, and the edge roughness on the nitride film substrate can be improved.
[Group I]
Following general formula ^{(17) ~ -R 51 -COOH (} R 51 a part or all of the hydrogen atoms of the phenolic hydroxyl group of the compound represented by (26) is a straight or branched alkylene And the molar ratio of the phenolic hydroxyl group (C) in the molecule to the group (D) represented by ΔC-COOH is C / (C + D) = 0.1 to 1.0. Compound.
[Group II]
Compounds represented by the following general formulas (27) to (31).

（但し、式中Ｒ¹は水素原子又はメチル基であり、Ｒ⁵²、Ｒ⁵³はそれぞれ水素原子又は炭素数１〜８の直鎖状又は分岐状のアルキル基又はアルケニル基であり、Ｒ⁵⁴は水素原子又は炭素数１〜８の直鎖状又は分岐状のアルキル基又はアルケニル基、或いは−（Ｒ⁵⁹）_h−ＣＯＯＲ’基（Ｒ’は水素原子又は−Ｒ⁵⁹−ＣＯＯＨ）であり、Ｒ⁵⁵は−（ＣＨ₂）_i−（ｉ＝２〜１０）、炭素数６〜１０のアリーレン基、カルボニル基、スルホニル基、酸素原子又は硫黄原子、Ｒ⁵⁶は炭素数１〜１０のアルキレン基、炭素数６〜１０のアリーレン基、カルボニル基、スルホニル基、酸素原子又は硫黄原子、Ｒ⁵⁷は水素原子又は炭素数１〜８の直鎖状又は分岐状のアルキル基、アルケニル基、それぞれ水酸基で置換されたフェニル基又はナフチル基であり、Ｒ⁵⁸は水素原子又は炭素数１〜８の直鎖状又は分岐状のアルキル基又はアルケニル基又は−Ｒ⁵⁹−ＣＯＯＨ基である。Ｒ⁵⁹は炭素数１〜１０の直鎖状又は分岐状のアルキレン基である。ｊは０〜５の整数であり、ｕ、ｈは０又は１である。ｓ１、ｔ１、ｓ２、ｔ２、ｓ３、ｔ３、ｓ４、ｔ４はそれぞれｓ１＋ｔ１＝８、ｓ２＋ｔ２＝５、ｓ３＋ｔ３＝４、ｓ４＋ｔ４＝６を満足し、かつ各フェニル骨格中に少なくとも１つの水酸基を有するような数である。κは式（２３）の化合物を重量平均分子量１，０００〜５，０００とする数、λは式（２４）の化合物を重量平均分子量１，０００〜１０，０００とする数である。）

Wherein R ¹ is a hydrogen atom or a methyl group, R ⁵² and R ⁵³ are a hydrogen atom or a linear or branched alkyl or alkenyl group having 1 to 8 carbon atoms, respectively, and R ⁵⁴ is A hydrogen atom, a linear or branched alkyl or alkenyl group having 1 to 8 carbon atoms, or a — (R ⁵⁹ ) _h —COOR ′ group (R ′ is a hydrogen atom or —R ⁵⁹ —COOH); ⁵⁵ is-(CH ₂ ) _i- (i = 2 to 10), an arylene group having 6 to 10 carbon atoms, a carbonyl group, a sulfonyl group, an oxygen atom or a sulfur atom, R ⁵⁶ is an alkylene group having 1 to 10 carbon atoms, An arylene group having 6 to 10 carbon atoms, a carbonyl group, a sulfonyl group, an oxygen atom or a sulfur atom, and R ⁵⁷ is a hydrogen atom or a linear or branched alkyl group or alkenyl group having 1 to 8 carbon atoms, each of which is substituted with a hydroxyl group. Phenyl or naphthyl group , R ⁵⁸ is .R ⁵⁹ is straight or branched having 1 to 10 carbon atoms is a linear or branched alkyl or alkenyl group, or -R ⁵⁹ -COOH group having 1 to 8 carbon hydrogen or C J is an integer of 0 to 5, and u and h are 0 or 1. s1, t1, s2, t2, s3, t3, s4, and t4 are s1 + t1 = 8 and s2 + t2 = 5, respectively. , S3 + t3 = 4, s4 + t4 = 6, and has at least one hydroxyl group in each phenyl skeleton, and κ is a compound having a weight average molecular weight of from 1,000 to 5,000. Λ is a number that makes the compound of formula (24) have a weight average molecular weight of 1,000 to 10,000.)

（Ｒ⁵²、Ｒ⁵³、Ｒ⁵⁹は上記と同様の意味を示す。ｓ５、ｔ５は、ｓ５≧０、ｔ５≧０で、ｓ５＋ｔ５＝５を満足する数である。また、Ｒ⁶⁰は水素原子又は水酸基、ｈ’は０又は１である。）

(R ⁵² , R ⁵³ and R ⁵⁹ have the same meaning as described above. S5 and t5 are s5 ≧ 0 and t5 ≧ 0 and are numbers satisfying s5 + t5 = 5. Further, R ⁶⁰ is a hydrogen atom or The hydroxyl group and h 'are 0 or 1.)

  Specific examples of the component (F) include, but are not limited to, compounds represented by the following formulas VIII-1 to VIII-14 and IX-1-10.

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

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

  The compound having a group represented by 示 C-COOH in the molecule can be used alone or in combination of two or more.

  The amount of the compound having a group represented by ≡C-COOH in the molecule is 0 to 5 parts, preferably 0.1 to 5 parts, more preferably 0.1 to 3 parts based on 100 parts of the base resin. And more preferably 0.1 to 2 parts. If the amount is more than 5 parts, the resolution of the resist material may decrease.

  Further, an acetylene alcohol derivative can be added to the resist composition of the present invention as the component (G), whereby the storage stability can be improved.

  As the acetylene alcohol derivative, those represented by the following general formulas (32) and (33) can be suitably used.

（式中、Ｒ⁷¹、Ｒ⁷²、Ｒ⁷³、Ｒ⁷⁴、Ｒ⁷⁵はそれぞれ水素原子、又は炭素数１〜８の直鎖状、分岐状又は環状のアルキル基であり、Ｘ、Ｙは０又は正数を示し、下記値を満足する。０≦Ｘ≦３０、０≦Ｙ≦３０、０≦Ｘ＋Ｙ≦４０である。）

(Wherein, R ⁷¹ , R ⁷² , R ⁷³ , R ⁷⁴ , and R ⁷⁵ are each a hydrogen atom or a linear, branched, or cyclic alkyl group having 1 to 8 carbon atoms, and X and Y are 0 or It indicates a positive number and satisfies the following values: 0 ≦ X ≦ 30, 0 ≦ Y ≦ 30, and 0 ≦ X + Y ≦ 40.)

  As the acetylene alcohol derivative, Surfynol 61, Surfynol 82, Surfynol 104, Surfynol 104E, Surfynol 104H, Surfynol 104A, Surfynol TG, Surfynol PC, Surfynol 440, Surfynol 465, Surfynol 485 (Made by Air Products and Chemicals Inc.), Surfynol E1004 (made by Nissin Chemical Industry Co., Ltd.) and the like.

  The amount of the acetylene alcohol derivative to be added is 0.01 to 2% by weight, more preferably 0.02 to 1% by weight, based on 100% by weight of the resist composition. When the amount is less than 0.01% by weight, the effect of improving coating properties and storage stability may not be sufficiently obtained, and when the amount is more than 2% by weight, the resolution of the resist material may decrease.

Further, in the present invention, as a resist material different from the resist material containing the components (A) to (G),
(A) the organic solvent described above,
(B) the high molecular silicone compound described above,
(C) In addition to the above-mentioned acid generator, there is provided a resist material containing a compound (H) which is crosslinked by the action of the following acid.

  Here, examples of the compound (H) that is crosslinked by the action of an acid include the following epoxy compounds and urea compounds.

  The compounding amount of the compound which is crosslinked by the action of an acid is preferably 5 to 95 parts, particularly preferably 15 to 85 parts, and more preferably 20 to 75 parts based on 100 parts of the base resin. If the amount is less than 5 parts, it is difficult to cause a sufficient cross-linking reaction, which tends to cause a decrease in the residual film ratio, meandering of the pattern, and swelling. On the other hand, if it exceeds 95 parts, scum tends to be large and developability tends to deteriorate.

  In addition to the above components, a surfactant which is commonly used for improving coating properties can be added to the resist composition of the present invention. In addition, the addition amount of the optional component can be a normal amount as long as the effect of the present invention is not hindered.

  Here, nonionic surfactants are preferable, and perfluoroalkylpolyoxyethylene ethanol, fluorinated alkyl esters, perfluoroalkylamine oxides, perfluoroalkyl EO adducts, fluorinated organosiloxane compounds, etc. No. For example, Florad “FC-430” and “FC-431” (all manufactured by Sumitomo 3M Limited), Surflon “S-141” and “S-145” (all manufactured by Asahi Glass Co., Ltd.), Unidyne “DS- 401 "," DS-403 "," DS-451 "(all manufactured by Daikin Industries, Ltd.), Megafac" F-8151 "(manufactured by Dainippon Ink Industries, Ltd.)," X-70-092 " And "X-70-093" (all manufactured by Shin-Etsu Chemical Co., Ltd.). Preferably, Florard "FC-430" (manufactured by Sumitomo 3M Limited) and "X-70-093" (manufactured by Shin-Etsu Chemical Co., Ltd.) are exemplified.

To form a pattern using the resist material of the present invention, a known lithography technique can be employed.For example, a film having a thickness of 0.5 to 0.5 on a substrate such as a silicon wafer by a method such as spin coating. It is applied to 2.0 μm and prebaked on a hot plate at 60 to 150 ° C. for 1 to 10 minutes, preferably at 80 to 120 ° C. for 1 to 5 minutes. Next, a mask for forming a target pattern is held over the resist film, and a deep ultraviolet ray having a wavelength of 300 nm or less, an excimer laser, a high energy ray such as an X-ray or an electron beam is exposed at a dose of about 1 to 200 mJ / cm ² . After irradiating to preferably about 10 to 100 mJ / cm ² , post-exposure bake (PEB) is performed on a hot plate at 60 to 150 ° C. for 1 to 5 minutes, preferably 80 to 120 ° C. for 1 to 3 minutes. . Further, using a developer of an aqueous alkali solution such as 0.1-5%, preferably 2-3% tetramethylammonium hydroxide (TMAH), immersion for 0.1-3 minutes, preferably 0.5-2 minutes. A target pattern is formed on the substrate by developing by a conventional method such as a (dip) method, a paddle method, a spray method, or the like. The material of the present invention is particularly suitable for fine patterning with 254 to 193 nm far ultraviolet rays or excimer lasers, X-rays and electron beams among high energy rays. If the above range is outside the upper and lower limits, the desired pattern may not be obtained.

  The resist material of the present invention is also useful as a two-layer resist material because it has excellent resistance to oxygen plasma etching by using a polymer silicone compound as a base resin.

  That is, after forming a thick organic polymer layer as a lower resist on a substrate according to a conventional method, the resist solution of the present invention is spin-coated thereon. The upper resist layer of the present invention is patterned by the same method as described above, and then the lower resist is selectively etched by etching, so that the upper resist pattern can be formed in the lower layer.

  As the lower layer resist, a novolak resin-based positive resist can be used, and after coating on a substrate, hard-baking at 200 ° C. for 1 hour can prevent intermixing with the silicone-based resist. .

  Hereinafter, the present invention will be described specifically with reference to Synthesis Examples and Examples, but the present invention is not limited to the following Examples.

[Synthesis Example 1]
Synthesis of poly (3-carboxycyclohexylsilsesquioxane) 150.0 g (0.544 mol) of 3-trichlorosilyl-1-cyclohexylcarboxylic acid methyl ester was dissolved in 150 g of toluene and added dropwise to 300 g of water with stirring at room temperature. Was added. After completion of the dropwise addition, an acidic aqueous layer was separated from the reaction mixture, and then the organic layer was washed with 1 L of water, and further washed twice after the aqueous layer became neutral. The solvent was distilled off from the organic layer using an evaporator. The concentrate was heated at 200 ° C. for 2 hours to polymerize. A solution obtained by adding 800 g of tetrahydrofuran to the polymer and dissolving the solution was dropped into 1,000 g of a 10% sodium hydroxide solution, and heated at 40 ° C. for 3 hours to hydrolyze a methyl ester group. The polymer was crystallized by acidification with hydrochloric acid, filtered and dried to obtain 83.4 g of poly (3-carboxycyclohexylsilsesquioxane). The weight average molecular weight of the obtained polymer was 3,000.

[Synthesis Example 2]
Synthesis of poly [(3-carboxycyclohexylsilsesquioxane)-(cyclohexylsilsesquioxane)] 3-trichlorosilyl-1-cyclohexylcarboxylic acid methyl ester 75.0 g (0.272 mol) and cyclohexyltrichlorosilane 59.2 g (0.272 mol) was dissolved in 150 g of toluene, and added dropwise to 300 g of water while stirring at room temperature. After completion of the dropwise addition, an acidic aqueous layer was separated from the reaction mixture, and then the organic layer was washed with 1 L of water, and further washed twice after the aqueous layer became neutral. The solvent was distilled off from the organic layer using an evaporator. The concentrate was heated at 200 ° C. for 2 hours to polymerize. A solution obtained by adding 800 g of tetrahydrofuran to the polymer and dissolving the solution was dropped into 1,000 g of a 10% sodium hydroxide solution, and heated at 40 ° C. for 3 hours to hydrolyze a methyl ester group. The polymer was crystallized by acidification with hydrochloric acid, filtered and dried to obtain 82.0 g of poly [(3-carboxycyclohexylsilsesquioxane)-(cyclohexylsilsesquioxane)]. The weight average molecular weight of the obtained polymer was 3,500. In ¹ H-NMR analysis, the composition ratio of 3-carboxycyclohexylsilsesquioxane / cyclohexylsilsesquioxane was 50/50 (molar ratio).

[Synthesis Examples 3 to 8]
Silicone polymers shown in Table 1 were obtained in the same manner as in Synthesis Examples 1 and 2.
Table 1 shows the weight average molecular weights and ratios of the polymers obtained in Synthesis Examples 1 to 8 above.

[Synthesis Example 9]
50 g of the polymer obtained in Synthesis Example 1 was dissolved in 450 ml of tetrahydrofuran, and after adding a catalytic amount of p-toluenesulfonic acid, 15.0 g of ethyl vinyl ether was added while stirring at 20 ° C. After reacting for 1 hour, the mixture was neutralized with concentrated aqueous ammonia and the neutralized reaction solution was added dropwise to 5 L of water to obtain a white solid. After filtration, this was dissolved in 100 ml of acetone, dropped into 5 L of water, filtered, and dried under vacuum. 60 g of the obtained polymer was dissolved in 560 ml of tetrahydrofuran, and after adding 34.0 g of 1-hydrobenzotriazole and 31.6 g of diisopropylcarbodiimide, 7.7 g of ethanolamine was added. After reacting at 30 ° C. for 5 hours, the mixture was concentrated and dropped into 3 L of water to obtain a white solid. After filtration, this was dissolved in 50 ml of acetone, dropped into 3 L of water, filtered, and dried under vacuum to obtain a polymer. The obtained polymer has a structure represented by the following descriptive formula (Polym. 1). In the analysis by ¹ H-NMR, 50% of the hydrogen atoms of the carboxyl group of the polymer compound are ethoxyethylated, and % it was confirmed substituted with -NHCH ₂ CH ₂ OH.

[Synthesis Example 10]
After dissolving 50 g of the polymer obtained in Synthesis Example 1 in 450 ml of tetrahydrofuran and adding a catalytic amount of p-toluenesulfonic acid, 12.0 g of ethylene-1-propenyl ether was added dropwise with stirring at 20 ° C., and after 2 hours, Then, 8.7 g of 1,4-butanediol divinyl ether was added dropwise, reacted for 30 minutes, neutralized with concentrated aqueous ammonia, and the neutralized reaction solution was added dropwise to 5 L of water to obtain a white solid. After filtration, this was dissolved in 100 ml of acetone, dropped into 5 L of water, filtered, and dried under vacuum. Dissolve 60 g of the obtained polymer in 560 ml of tetrahydrofuran, add 34.0 g of 1-hydrobenzotriazole and 31.6 g of diisopropylcarbondiimide, and then add 26.3 g of 2-amino-2-methyl-1,3-propanediol. did. After reacting at 30 ° C. for 5 hours, the mixture was concentrated and dropped into 3 L of water to obtain a white solid. After filtration, this was dissolved in 50 ml of acetone, dropped into 3 L of water, filtered, and dried under vacuum to obtain a polymer. The obtained polymer has a structure represented by the following descriptive formula (Polym. 2). In the analysis by ¹ H-NMR, 40% of the hydrogen atoms of the carboxyl group of the polymer compound are ethoxypropylated, and % Had a crosslinked structure, and it was confirmed that 40% was substituted with NHC (CH ₃ ) (CH ₂ OH) ₂ .

[Synthesis Examples 11 to 18]
In Synthesis Examples 9 and 10, the polymer of any of Synthesis Examples 1 to 8 was used, and instead of ethyl vinyl ether and ethanolamine, Polym. Except that a compound capable of introducing an acid labile group represented by 3 to 10 and a group represented by formula (2b) is used, and instead of 1,4-butanediol divinyl ether, 1,4-bis [(vinyloxy) methyl A silicone polymer represented by the following formula (Polym. 3 to 10) was obtained in the same manner except that cyclohexane was used.

[Synthesis Example 19]
50 g of the polymer obtained in Synthesis Example 1 was dissolved in 450 ml of tetrahydrofuran, 69.7 g of trifluoroacetic anhydride was added, and 17.2 g of t-butyl alcohol was added with stirring at 20 ° C. After reacting for 5 hours, the mixture was neutralized with concentrated aqueous ammonia, and the neutralized reaction solution was added dropwise to 5 L of water to obtain a white solid. After filtration, this was dissolved in 100 ml of acetone, dropped into 5 L of water, filtered, and dried under vacuum. 60 g of the obtained polymer was dissolved in 560 ml of tetrahydrofuran, 34.0 g of 1-hydrobenzotriazole and 31.6 g of diisopropylcarbondiimide were added, and 19.5 g of 4-aminomethyl-1-cyclohexanol was added. After reacting at 30 ° C. for 5 hours, the mixture was concentrated and dropped into 3 L of water to obtain a white solid. After filtration, this was dissolved in 50 ml of acetone, dropped into 3 L of water, filtered, and dried under vacuum to obtain a polymer. The obtained polymer has a structure represented by the following descriptive formula (Polym. 11). In ¹ H-NMR analysis, 40% of the hydrogen atoms of the carboxyl group of the polymer compound are tert-butylated, It was confirmed that 60% was substituted by the following formula.

[Synthesis Example 20]
In Synthesis Example 19, the following descriptive formula (Polym.) Was used in the same manner as in Synthesis Example 2 except that the polymer of Synthesis Example 2 was used and 3-amino-1,2-propanediol was used instead of 4-aminomethyl-1-cyclohexanol. A silicone polymer represented by 12) was obtained.

[Synthesis Example 21]
In Synthesis Example 19, the following descriptive formula (Polym. 13) was used in the same manner as in Synthesis Example 6 except that the polymer of Synthesis Example 6 was used and 2- (2-aminoethoxy) ethanol was used instead of 1-aminomethyl-1-cyclohexanol. ) Was obtained.

[Synthesis Example 22]
50 g of the polymer obtained in Synthesis Example 1 was dissolved in 450 ml of tetrahydrofuran, and after adding a catalytic amount of p-toluenesulfonic acid, 21.5 g of ethyl-1-propenyl ether was added while stirring at 20 ° C. After reacting for 2 hours, the mixture was neutralized with concentrated aqueous ammonia, and the neutralized reaction solution was added dropwise to 5 L of water, whereby a white solid was obtained. After filtration, this was dissolved in 100 ml of acetone, dropped into 5 L of water, filtered, and dried under vacuum. 60 g of the obtained polymer is dissolved in tetrahydrofuran, potassium carbonate is added as a solid, 27.8 g of bromoethanol is added with stirring, and the mixture is reacted at 60 ° C. for 6 hours. Was filtered off. The solvent and unreacted bromoethanol were distilled off from the filtrate under reduced pressure. When the residue was dissolved in acetone and added dropwise to 5 L of water, a white solid was obtained. This was filtered, dissolved in 200 ml of acetone, dropped into 3 L of water, filtered, and dried under vacuum to obtain a polymer. The obtained polymer has a structure represented by the following descriptive formula (Polym. 14). In the analysis by ¹ H-NMR, 60% of the hydrogen atoms of the carboxyl group of the polymer compound are ethoxypropylated, and % it was confirmed substituted with -OCH ₂ CH ₂ OH.

[Synthesis Example 23]
Except for using the polymer of Synthesis Example 6, the same procedure as in Synthesis Example 20 was carried out to obtain a silicone polymer represented by the following formula (Polym. 15).

[Synthesis Example 24]
Synthesis of poly [(3-carboxycyclohexylsilsesquioxane)-(8-hydroxy-4-tricyclo [5,2,1,0 ^2,6 ] decanylsilsesquioxane)] 3-trichlorosilyl-1- 75.0 g (0.272 mol) of cyclohexylcarboxylic acid methyl ester and 89.1 g (0.272 mol) of 8-acetoxy-4-trichlorosilyltricyclo [5,2,1,0 ^2,6 ] decane are dissolved in 150 g of toluene. Then, it was added dropwise to 300 g of water at room temperature with stirring. After completion of the dropwise addition, an acidic aqueous layer was separated from the reaction mixture, and then the organic layer was washed with 1 L of water, and further washed twice after the aqueous layer became neutral. The solvent was distilled off from the organic layer using an evaporator. The concentrate was heated at 200 ° C. for 2 hours to polymerize. A solution obtained by adding 800 g of tetrahydrofuran to the polymer and dissolving the solution was dropped into 1,000 g of a 10% sodium hydroxide solution, and heated at 40 ° C. for 3 hours to hydrolyze a methyl ester group and an acetoxy group. The polymer was crystallized by acidification with hydrochloric acid, filtered, and dried. Poly [(3-carboxycyclohexylsilsesquioxane)-(8-hydroxy-4-tricyclo [5,2,1,0 ^2,6 ] de Canyl silsesquioxane] in a yield of 98.6 g. The obtained polymer had a weight average molecular weight of 4,000. In ¹ H-NMR analysis, 3-carboxycyclohexyl silsesquioxane / The composition ratio of 8-hydroxy-4-tricyclo [5,2,1,0 ^2,6 ] decanylsilsesquioxane was 50/50 (molar ratio).

[Synthesis Example 25]
Poly [(3-carboxycyclohexylsilsesquioxane)-(8-hydroxy-4-tricyclo [5,2,1,0 ^2,6 ] decanylsilsesquioxane)-(cyclohexylsilsesquioxane)] Synthesis 30.1 g (0.218 mol) of 3-trichlorosilyl-1-cyclohexylcarboxylic acid methyl ester and 71.4 g of 8-acetoxy-4-trichlorosilyltricyclo [5,2,1,0 ^2,6 ] decane (0 .218 mol) and 23.7 g (0.109 mol) of cyclohexyltrichlorosilane were dissolved in 150 g of toluene, and added dropwise to 300 g of water with stirring at room temperature. After completion of the dropwise addition, an acidic aqueous layer was separated from the reaction mixture, and then the organic layer was washed with 1 L of water, and further washed twice after the aqueous layer became neutral. The solvent was distilled off from the organic layer using an evaporator. The concentrate was heated at 200 ° C. for 2 hours to polymerize. A solution obtained by adding 800 g of tetrahydrofuran to the polymer and dissolving the solution was dropped into 1,000 g of a 10% sodium hydroxide solution, and heated at 40 ° C. for 3 hours to hydrolyze a methyl ester group and an acetoxy group. The polymer was crystallized by acidification with hydrochloric acid, filtered, and dried. Poly [(3-carboxycyclohexylsilsesquioxane)-(8-hydroxy-4-tricyclo [5,2,1,0 ^2,6 ] de Canylsilsesquioxane)-(cyclohexylsilsesquioxane)] in a yield of 83.4 g. The weight average molecular weight of the obtained polymer was 5,000. In ¹ H-NMR analysis, 3-carboxycyclohexylsilsesquioxane / 8-hydroxy-4-tricyclo [5,2,1,0 ^2,6 ] decanylsilsesquioxane / cyclohexylsilsesquioxane Was 40/40/20 (molar ratio).

[Synthesis Examples 26 to 31]
Silicone polymers shown in Table 2 were obtained in the same manner as in Synthesis Examples 24 and 25. Table 2 shows the weight average molecular weight and composition ratio of the obtained polymer.

[Synthesis Example 32]
50 g of the polymer obtained in Synthesis Example 24 was dissolved in 450 ml of tetrahydrofuran, and after adding a catalytic amount of p-toluenesulfonic acid, 10.8 g of ethyl vinyl ether was added while stirring at 20 ° C. After reacting for 1 hour, the mixture was neutralized with concentrated aqueous ammonia and the neutralized reaction solution was added dropwise to 5 L of water to obtain a white solid. After filtration, this was dissolved in 100 ml of acetone, dropped into 5 L of water, filtered, and dried under vacuum. The obtained polymer had a structure represented by the following descriptive formula (Polym. 16). According to analysis by ¹ H-NMR, 90% of the hydrogen atoms of the carboxyl group of the polymer compound were ethoxyethylated. Was confirmed.

[Synthesis Example 33]
50 g of the polymer obtained in Synthesis Example 31 was dissolved in 450 ml of tetrahydrofuran, a catalytic amount of p-toluenesulfonic acid was added, and then 8.7 g of ethyl vinyl ether was added while stirring at 20 ° C. After reacting for 1 hour, the mixture was neutralized with concentrated aqueous ammonia and the neutralized reaction solution was added dropwise to 5 L of water to obtain a white solid. After filtration, this was dissolved in 100 ml of acetone, dropped into 5 L of water, filtered, and dried under vacuum. 60 g of the obtained polymer was dissolved in 540 ml of tetrahydrofuran, 27.0 g of 1-hydroxybenzotriazole and 12.6 g of N, N'-diisopropylcarbodiimide were added, and then 6.1 g of ethanolamine was added. After reacting at 30 ° C. for 5 hours, the mixture was concentrated and dropped into 3 L of water to obtain a white solid. After filtration, this was dissolved in 50 ml of acetone, dropped into 3 L of water, filtered, and dried under vacuum to obtain a polymer. The obtained polymer has a structure represented by the following descriptive formula (Polym. 17), and when analyzed by ¹ H-NMR, 60% of the hydrogen atoms of the carboxyl group of the polymer compound are ethoxyethylated to give 30%. % it was confirmed substituted with -NHCH ₂ CH ₂ OH.

[Synthesis Example 34]
After dissolving 50 g of the polymer obtained in Synthesis Example 31 in 450 ml of tetrahydrofuran and adding a catalytic amount of p-toluenesulfonic acid, 6.9 g of ethylene-1-propenyl ether was added dropwise with stirring at 20 ° C., and after 2 hours, After dropping 5.7 g of 1,4-butanediol divinyl ether and reacting for 30 minutes, the mixture was neutralized with concentrated aqueous ammonia and the neutralized reaction solution was dropped into 5 L of water to obtain a white solid. After filtration, this was dissolved in 100 ml of acetone, dropped into 5 L of water, filtered, and dried under vacuum. 60 g of the obtained polymer was dissolved in 540 ml of tetrahydrofuran, 27.0 g of 1-hydroxybenzotriazole and 12.6 g of N, N'-diisopropylcarbodiimide were added, and then 2-amino-2-methyl-1,3-propanediol 10 0.5 g was added. After reacting at 30 ° C. for 5 hours, the mixture was concentrated and dropped into 3 L of water to obtain a white solid. After filtration, this was dissolved in 50 ml of acetone, dropped into 3 L of water, filtered, and dried under vacuum to obtain a polymer. The obtained polymer has a structure represented by the following descriptive formula (Polym. 18). In the analysis by ¹ H-NMR, 40% of the hydrogen atoms of the carboxyl group of the polymer compound are ethoxypropylated, and % Had a crosslinked structure, and 30% was substituted with NHC (CH ₃ ) (CH ₂ OH) ₂ .

[Synthesis Examples 35 to 41]
In Synthesis Examples 32, 33 and 34, the polymer of any of Synthesis Examples 24 to 31 was used, and instead of ethyl vinyl ether and ethanolamine, Polym. Except for using a compound capable of introducing an acid labile group represented by 19 to 25 and a group represented by the general formula (2a) or (2b), and instead of 1,4-butanediol divinyl ether, 1,4-bis [ By the same method except that (vinyloxy) methyl] cyclohexane was used, a silicone polymer represented by the following descriptive formula (Polym. 19 to 25) was obtained.

[Synthesis Example 42]
20 g of the polymer obtained in Synthesis Example 24 was dissolved in 200 ml of dimethylformamide, potassium carbonate was added as it was, 15.1 g of chloroacetic acid-tert-butyl ester was added with stirring, and the mixture was reacted at 60 ° C. for 6 hours. After that, solid potassium carbonate was filtered off from the reaction solution, and 10 L of water was added dropwise, whereby a white solid was obtained. After filtration, this was dissolved in 100 ml of acetone, dropped into 5 L of water, filtered, and dried in vacuo to obtain a polymer. The obtained polymer has a structure represented by the following descriptive formula (Polym. 26), and the analysis by ¹ H-NMR shows that the tert-butoxycarbonyl methylation rate of the hydrogen atom of the carboxyl group of the polymer compound is 60. %.

[Synthesis Example 43]
50 g of the polymer obtained in Synthesis Example 24 was dissolved in 180 ml of tetrahydrofuran, 52.5 g of trifluoroacetic anhydride was added, and then 18.5 g of t-butyl alcohol was added while stirring at 5 ° C. or lower. After reacting for 2 hours, the mixture was neutralized with concentrated aqueous ammonia, and the neutralized reaction solution was added dropwise to 5 L of water, whereby a white solid was obtained. After filtration, this was dissolved in 100 ml of acetone, dropped into 5 L of water, filtered, and dried under vacuum. The obtained polymer has a structure represented by the following descriptive formula (Polym. 27), and when analyzed by ¹ H-NMR, 80% of the hydrogen atoms of the carboxyl groups of the polymer compound are tert-butylated. It was confirmed that.

[Examples 1 to 28]
Using the polymer (Polym. 1 to 15) obtained in the above synthesis example as a base resin, an acid generator represented by the following formula (PAG. 1 to 5), represented by the following formula (DRR. 1, 2) A dissolution controlling agent, a basic compound, and an aromatic compound having a group represented by ≡C-COOH in a molecule represented by the following formula (ACC.1) are mixed with propylene glycol monoethyl acetate (PGMEA) in the composition shown in Tables 3 and 4. ), Ethyl lactate (EL) or diethylene glycol monomethyl ether (DGLYME) to prepare a resist material, and each composition was filtered through a 0.2 μm Teflon filter to prepare a resist solution.

The obtained resist solution was spin-coated on a silicon wafer and applied to a thickness of 0.3 μm. Next, the silicon wafer was baked at 100 ° C. for 90 seconds using a hot plate. This was exposed using an ArF excimer laser stepper (Nikon Corporation, NA = 0.55), baked at 110 ° C. for 90 seconds, and developed with an aqueous solution of 2.38% by weight of tetramethylammonium hydroxide. I got a pattern. The obtained resist pattern was evaluated as follows. The results are shown in Tables 3 and 4.
Evaluation method: First, the sensitivity was determined. Next, an exposure amount at which a 0.20 μm line and space is resolved at 1: 1 is defined as an optimum exposure amount (Eop), and a minimum line width of a separated line and space at this exposure amount is defined as a resolution of an evaluation resist. . The shape of the resolved resist pattern was observed using a scanning electron microscope. The unevenness (edge roughness) of the 0.18 μm line and space was measured by a scanning electron microscope with a length measuring function (S7280, manufactured by Hitachi, Ltd.).

  From the results of Tables 3 and 4, it was confirmed that the resist material of the present invention had a pattern with high resolution and no irregularities (small edge roughness).

[Example 29]
OFPR800 (manufactured by Tokyo Ohka Co., Ltd.) as a lower layer resist material was applied to a silicon wafer to a thickness of 2.0 μm, and heated at 200 ° C. for 5 minutes to be cured. The resist material used in Example 1 was applied on the lower resist film to a thickness of about 0.35 μm in the same manner as described above, and prebaked. Next, KrF excimer laser exposure and development were performed to form a pattern on the lower resist film. At this time, a pattern perpendicular to the lower resist film could be obtained, and the occurrence of footing was not recognized.

Thereafter, etching was performed with a parallel plate type sputter etching apparatus using oxygen gas as an etchant gas. While the etching rate of the lower resist film was 150 nm / min, this resist film was 15 nm / min or less. By etching for 15 minutes, the lower layer resist film not covered with the present resist film completely disappeared, and a two-layer resist pattern having a thickness of 1 μm or more was formed. The etching conditions are shown below.
Gas flow rate: 50 sccm, gas pressure: 1.3 Pa,
rf power: 50 W, dc bias: 450 V

[Examples 30 to 64]
Using the polymer (Polym. 16 to 28) obtained in the above synthesis example as a base resin, an acid generator represented by the following formula (PAG. 1 to 8), and an acid generator represented by the following formula (DRR. 1 to 4) Table 5 shows a dissolution controlling agent, a basic compound, a compound having a group represented by ＣＣC-COOH in a molecule represented by the following formula (ACC.1), and a compound (Crosslinker 1, 2) which is crosslinked by the action of an acid. A resist material was prepared by dissolving in a solvent containing 0.05% by weight of FC-430 (manufactured by Sumitomo 3M) with the composition shown in No. 7 to prepare a resist material, and further filtering each composition with a 0.2 μm Teflon filter. Each resist solution was prepared.

The obtained resist solution was spin-coated on a silicon wafer and applied to a thickness of 0.3 μm. Next, the silicon wafer was baked at 100 ° C. for 90 seconds using a hot plate. This is exposed using an ArF excimer laser stepper (Nikon Corporation, NA = 0.55), baked at 110 ° C. for 90 seconds (PEB), and developed with a 2.38% aqueous solution of tetramethylammonium hydroxide. And I was able to get a pattern. The obtained resist pattern was evaluated as follows. The results are shown in Tables 5 to 7.
Evaluation method:
First, the sensitivity was determined. Next, an exposure amount at which a 0.20 μm line and space is resolved at 1: 1 is defined as an optimum exposure amount (Eop), and a minimum line width of a separated line and space at this exposure amount is defined as a resolution of an evaluation resist. . The shape of the resolved resist pattern was observed using a scanning electron microscope. The unevenness (edge roughness) of 0.20 μm line and space was measured by a scanning electron microscope with a length measuring function (S7280, Hitachi, Ltd.).

  From the results of Tables 5 to 7, it was confirmed that the resist material of the present invention had a pattern with high resolution and no irregularities (small edge roughness).

ＰＧＭＥＡ：プロピレングリコールメチルエーテルアセテート
ＥＬ：乳酸エチル
ＥＩＰＡ：１−エトキシ−２−プロパノール

PGMEA: Propylene glycol methyl ether acetate EL: Ethyl lactate EIPA: 1-ethoxy-2-propanol

[Example 65]
OFPR800 (manufactured by Tokyo Ohka Co., Ltd.) as a lower layer resist material was applied to a silicon wafer to a thickness of 1.0 μm, and heated at 300 ° C. for 5 minutes to be cured. The resist material used in Example 30 was applied on the lower resist film to a thickness of 0.3 μm in the same manner as described above, and prebaked. Next, KrF excimer laser exposure and development were performed to form a pattern on the lower resist film. At this time, a pattern perpendicular to the lower resist film could be obtained, and the occurrence of footing was not recognized.

Thereafter, etching was performed with a parallel plate type sputter etching apparatus using oxygen gas as an etchant gas. While the etching rate of the lower resist film was 150 nm / min, this resist film was 15 nm / min or less. By etching for 15 minutes, the lower layer resist film not covered with the present resist film completely disappeared, and a two-layer resist pattern having a thickness of 1 μm or more was formed. The etching conditions are shown below.
Gas flow rate: 50 sccm, gas pressure: 1.3 Pa,
rf power: 50 W, dc bias: 450 V

Claims (15)

A polymeric silicone compound comprising a repeating unit represented by the following general formula (1) and having a weight average molecular weight of 1,000 to 50,000.

[In the formula, Z is a divalent to hexavalent non-aromatic monocyclic or polycyclic hydrocarbon group having 5 to 12 carbon atoms or a bridged cyclic hydrocarbon group, and Z ′ is a divalent to hexavalent hydrocarbon group. A linear or branched hydrocarbon group having 1 to 20 carbon atoms or a non-aromatic monocyclic or polycyclic hydrocarbon group or a bridged cyclic hydrocarbon group having 3 to 20 carbon atoms, In these groups, a nitrogen atom, an oxygen atom or a sulfur atom may be interposed between carbon-carbon bonds, and a hydrogen atom on the carbon atom is substituted with a halogen atom, an alkoxy group, a nitro group, a cyano group or an acetyl group. And the methylene group in the carbon skeleton may be substituted with a carbonyl group.
x, y, and z each represent an integer of 1 to 5, depending on the valence of Z and Z '.
R ¹ is a group represented by the following general formula (2a) or (2b); R ² is a linear, branched or cyclic unsubstituted or substituted alkyl or alkenyl group having 1 to 8 carbon atoms, or carbon number 5 to 12 non-aromatic monovalent polycyclic hydrocarbon groups or bridged cyclic hydrocarbon groups.

(In the formula, R represents a hydrogen atom, a hydroxyl group or a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms, and R ′ represents a linear, branched or cyclic alkylene having 1 to 20 carbon atoms. These alkyl groups and alkylene groups may have an oxygen atom interposed in the carbon-carbon bond, or a part of the carbon-bonded hydrogen atom may be substituted with a hydroxyl group. 'May form a ring with each other, and when forming a ring, R and R' each represent a linear or branched alkylene group having 1 to 8 carbon atoms.)
In the formula (1), p1, p2, p3, and p4 are p1 + p2 + p3 + p4 = 1, p1 and p2 are positive numbers, p3 is 0 or a positive number, and p4 is 0,
0 <p1 / (p1 + p2 + p3) ≦ 0.9
0 <p2 / (p1 + p2 + p3) ≦ 0.8
0 ≦ p3 / (p1 + p2 + p3) ≦ 0.7
Or p1 and p4 are positive numbers, p3 is 0 or a positive number, p2 is 0,
0 <p1 / (p1 + p3 + p4) ≦ 0.9
0 ≦ p3 / (p1 + p3 + p4) ≦ 0.7
0 <p4 / (p1 + p3 + p4) ≦ 0.9
Is a number that satisfies. ]   A carboxyl group or a part or all of hydrogen atoms of a carboxyl group and a hydroxyl group of the high molecular silicone compound comprising a repeating unit represented by the general formula (1) according to claim 1 is one or more acid labile groups. A substituted high-molecular silicone compound having a weight average molecular weight of 1,000 to 50,000. The remaining carboxyl groups and / or the remaining carboxyl groups of the high molecular silicone compound represented by the above general formula (1) in which a part of the hydrogen atoms of the carboxyl group or the carboxyl group and the hydroxyl group are partially substituted by one or more acid labile groups. Alternatively, the hydrogen atom of the hydroxyl group is represented by the following general formula (3a) or (3b) at a ratio of more than 0 mol% and 50 mol% or less of the hydrogen atom of the carboxyl group and the hydroxyl group of the whole polymer silicone compound of the formula (1). The polymer silicone compound according to claim 2, wherein the polymer silicone compound is crosslinked intra- and / or intermolecularly by being substituted with a group having a C-O-C group.

(Wherein, R ³ and R ⁴ represent a hydrogen atom or a linear, branched or cyclic alkyl group having 1 to 8 carbon atoms. Alternatively, R ³ and R ⁴ may form a ring, When a ring is formed, R ³ and R ⁴ represent a linear or branched alkylene group having 1 to 8 carbon atoms, and R ⁵ represents a linear, branched or cyclic alkylene group having 1 to 10 carbon atoms. And d is an integer of 0 or 1 to 10. A represents a c-valent aliphatic or alicyclic saturated hydrocarbon group having 1 to 50 carbon atoms, an aromatic hydrocarbon group or a heterocyclic group, May have a hetero atom interposed, and a part of the hydrogen atom bonded to the carbon atom may be substituted by a hydroxyl group, a carboxyl group, an acyl group or a fluorine atom. -, -NHCO-O- or -NHCONH-, where c is an integer of 2 to 8 and c 'is an integer of 1 to 7.) The polymer according to claim 3, wherein the crosslinking group having a C-O-C group represented by the general formula (3a) or (3b) is represented by the following general formula (3a "") or (3b ""). Silicone compounds.

(Wherein, R ³ and R ⁴ represent a hydrogen atom or a linear, branched or cyclic alkyl group having 1 to 8 carbon atoms. Alternatively, R ³ and R ⁴ may form a ring, When a ring is formed, R ³ and R ⁴ represent a linear or branched alkylene group having 1 to 8 carbon atoms, and R ⁵ represents a linear, branched or cyclic alkylene group having 1 to 10 carbon atoms. And d is an integer of 0 or 1 to 5. A ′ is a linear, branched or cyclic alkylene group having 1 to 20 carbon atoms, an alkyltriyl group or an alkyltetrayl group having a c ″ valency. Or an arylene group having 6 to 30 carbon atoms, and these groups may have a hetero atom interposed, and a part of the hydrogen atoms bonded to the carbon atom is a hydroxyl group, a carboxyl group, an acyl group or a fluorine atom. B represents -CO-O-, -NHCO-O- or -NHCONH- C ″ is an integer of 2 to 4 and c ″ ′ is an integer of 1 to 3.) The acid labile group is a group represented by the following general formula (4), a group represented by the following general formula (5), a tertiary alkyl group having 4 to 20 carbon atoms, and a tertiary alkyl group having 1 to 6 carbon atoms in each alkyl group. The polymer silicone compound according to claim 2, which is one or more groups selected from a trialkylsilyl group and an oxoalkyl group having 4 to 20 carbon atoms.

(R ⁶ and R ^{7 each} represent a hydrogen atom or a linear, branched or cyclic alkyl group having 1 to 18 carbon atoms, and R ⁸ represents a monovalent group which may have a hetero atom having 1 to 18 carbon atoms. R ⁶ and R ⁷ , R ⁶ and R ⁸ or R ⁷ and R ⁸ may form a ring, and when forming a ring, R ⁶ , R ⁷ and R ⁸ each represent a hydrocarbon group; A linear or branched alkylene group having 1 to 18 carbon atoms, R ⁹ represents a tertiary alkyl group having 4 to 20 carbon atoms, a trialkylsilyl group having 1 to 6 carbon atoms in each alkyl group, And represents an oxoalkyl group of 4 to 20 or a group represented by the general formula (4), and a is an integer of 0 to 6.)   A resist material comprising the polymer silicone compound according to claim 1. (A) an organic solvent (B) a polymer silicone compound having a repeating unit represented by the following general formula (1), or a carboxyl group of the polymer silicone compound or part or all of a hydrogen atom of a carboxyl group and a hydroxyl group is one kind Or a high molecular weight silicone compound having a weight average molecular weight of 1,000 to 50,000 substituted by two or more acid labile groups,

[In the formula, Z is a divalent to hexavalent non-aromatic monocyclic or polycyclic hydrocarbon group having 5 to 12 carbon atoms or a bridged cyclic hydrocarbon group, and Z ′ is a divalent to hexavalent hydrocarbon group. A linear or branched hydrocarbon group having 1 to 20 carbon atoms or a non-aromatic monocyclic or polycyclic hydrocarbon group or a bridged cyclic hydrocarbon group having 3 to 20 carbon atoms, In these groups, a nitrogen atom, an oxygen atom or a sulfur atom may be interposed between carbon-carbon bonds, and a hydrogen atom on the carbon atom is substituted with a halogen atom, an alkoxy group, a nitro group, a cyano group or an acetyl group. And the methylene group in the carbon skeleton may be substituted with a carbonyl group.
x, y, and z each represent an integer of 1 to 5, depending on the valence of Z and Z '.
R ¹ is a group represented by the following general formula (2a) or (2b); R ² is a linear, branched or cyclic unsubstituted or substituted alkyl or alkenyl group having 1 to 8 carbon atoms, or carbon number 5 to 12 non-aromatic monovalent polycyclic hydrocarbon groups or bridged cyclic hydrocarbon groups.

(In the formula, R represents a hydrogen atom, a hydroxyl group or a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms, and R ′ represents a linear, branched or cyclic alkylene having 1 to 20 carbon atoms. These alkyl groups and alkylene groups may have an oxygen atom interposed in the carbon-carbon bond, or a part of the carbon-bonded hydrogen atom may be substituted with a hydroxyl group. 'May form a ring with each other, and when forming a ring, R and R' each represent a linear or branched alkylene group having 1 to 8 carbon atoms.)
In the formula (1), p1, p2, p3, and p4 are p1 + p2 + p3 + p4 = 1, p1 and p2 are positive numbers, p3 is 0 or a positive number, and p4 is 0,
0 <p1 / (p1 + p2 + p3) ≦ 0.9
0 <p2 / (p1 + p2 + p3) ≦ 0.8
0 ≦ p3 / (p1 + p2 + p3) ≦ 0.7
Or p1 and p4 are positive numbers, p3 is 0 or a positive number, p2 is 0,
0 <p1 / (p1 + p3 + p4) ≦ 0.9
0 ≦ p3 / (p1 + p3 + p4) ≦ 0.7
0 <p4 / (p1 + p3 + p4) ≦ 0.9
Is a number that satisfies.
Further, the carboxyl group or the remaining carboxyl group of the high molecular silicone compound represented by the general formula (1) in which a part of the hydrogen atom of the carboxyl group and the hydroxyl group is partially substituted with one or more acid labile groups. And / or substitution by a group having a C—O—C group represented by the following general formula (3a) or (3b) at a ratio of more than 0 mol% and not more than 50 mol% of all hydrogen atoms of a hydroxyl group. And / or may be cross-linked between molecules.

(Wherein, R ³ and R ⁴ represent a hydrogen atom or a linear, branched or cyclic alkyl group having 1 to 8 carbon atoms. Alternatively, R ³ and R ⁴ may form a ring, When a ring is formed, R ³ and R ⁴ represent a linear or branched alkylene group having 1 to 8 carbon atoms, and R ⁵ represents a linear, branched or cyclic alkylene group having 1 to 10 carbon atoms. And d is an integer of 0 or 1 to 10. A represents a c-valent aliphatic or alicyclic saturated hydrocarbon group having 1 to 50 carbon atoms, an aromatic hydrocarbon group or a heterocyclic group, May have a hetero atom interposed, and a part of the hydrogen atom bonded to the carbon atom may be substituted by a hydroxyl group, a carboxyl group, an acyl group or a fluorine atom. -, -NHCO-O- or -NHCONH-, where c is an integer of 2 to 8 and c 'is an integer of 1 to 7.)
(C) A resist material comprising an acid generator. The acid labile group is a group represented by the following general formula (4), a group represented by the following general formula (5), a tertiary alkyl group having 4 to 20 carbon atoms, and a tertiary alkyl group having 1 to 6 carbon atoms in each alkyl group. The resist material according to claim 7, which is one or more groups selected from a trialkylsilyl group and an oxoalkyl group having 4 to 20 carbon atoms.

(R ⁶ and R ^{7 each} represent a hydrogen atom or a linear, branched or cyclic alkyl group having 1 to 18 carbon atoms, and R ⁸ represents a monovalent group which may have a hetero atom having 1 to 18 carbon atoms. R ⁶ and R ⁷ , R ⁶ and R ⁸ or R ⁷ and R ⁸ may form a ring, and when forming a ring, R ⁶ , R ⁷ and R ⁸ each represent a hydrocarbon group; A linear or branched alkylene group having 1 to 18 carbon atoms, R ⁹ represents a tertiary alkyl group having 4 to 20 carbon atoms, a trialkylsilyl group having 1 to 6 carbon atoms in each alkyl group, And represents an oxoalkyl group of 4 to 20 or a group represented by the general formula (4), and a is an integer of 0 to 6.)   9. The resist material according to claim 7, further comprising (D) a dissolution controlling agent.   10. The resist material according to claim 7, further comprising (E) a basic compound.   The resist material according to any one of claims 7 to 10, further comprising (F): a compound having a group represented by ≡C-COOH in the molecule.   The resist material according to any one of claims 7 to 11, further comprising (G): an acetylene alcohol derivative. (A) an organic solvent (B) a polymer silicone compound having a repeating unit represented by the following general formula (1), or one or two of a carboxyl group or a hydrogen atom of a carboxyl group and a hydroxyl group of the polymer silicone compound are A high molecular weight silicone compound having a weight average molecular weight of 1,000 to 50,000 substituted by at least one kind of acid labile group,

[In the formula, Z is a divalent to hexavalent non-aromatic monocyclic or polycyclic hydrocarbon group having 5 to 12 carbon atoms or a bridged cyclic hydrocarbon group, and Z ′ is a divalent to hexavalent hydrocarbon group. A linear or branched hydrocarbon group having 1 to 20 carbon atoms or a non-aromatic monocyclic or polycyclic hydrocarbon group or a bridged cyclic hydrocarbon group having 3 to 20 carbon atoms, In these groups, a nitrogen atom, an oxygen atom or a sulfur atom may be interposed between carbon-carbon bonds, and a hydrogen atom on the carbon atom is substituted with a halogen atom, an alkoxy group, a nitro group, a cyano group or an acetyl group. And the methylene group in the carbon skeleton may be substituted with a carbonyl group.
x, y, and z each represent an integer of 1 to 5, depending on the valence of Z and Z '.
R ¹ is a group represented by the following general formula (2a) or (2b); R ² is a linear, branched or cyclic unsubstituted or substituted alkyl or alkenyl group having 1 to 8 carbon atoms, or carbon number 5 to 12 non-aromatic monovalent polycyclic hydrocarbon groups or bridged cyclic hydrocarbon groups.

(In the formula, R represents a hydrogen atom, a hydroxyl group or a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms, and R ′ represents a linear, branched or cyclic alkylene having 1 to 20 carbon atoms. These alkyl groups and alkylene groups may have an oxygen atom interposed in the carbon-carbon bond, or a part of the carbon-bonded hydrogen atom may be substituted with a hydroxyl group. 'May form a ring with each other, and when forming a ring, R and R' each represent a linear or branched alkylene group having 1 to 8 carbon atoms.)
In the formula (1), p1, p2, p3, and p4 are p1 + p2 + p3 + p4 = 1, p1 and p2 are positive numbers, p3 is 0 or a positive number, and p4 is 0,
0 <p1 / (p1 + p2 + p3) ≦ 0.9
0 <p2 / (p1 + p2 + p3) ≦ 0.8
0 ≦ p3 / (p1 + p2 + p3) ≦ 0.7
Or p1 and p4 are positive numbers, p3 is 0 or a positive number, p2 is 0,
0 <p1 / (p1 + p3 + p4) ≦ 0.9
0 ≦ p3 / (p1 + p3 + p4) ≦ 0.7
0 <p4 / (p1 + p3 + p4) ≦ 0.9
Is a number that satisfies.
Further, the carboxyl group or the remaining carboxyl group of the high molecular silicone compound represented by the general formula (1) in which a part of the hydrogen atom of the carboxyl group and the hydroxyl group is partially substituted with one or more acid labile groups. And / or substitution by a group having a C—O—C group represented by the following general formula (3a) or (3b) at a ratio of more than 0 mol% and not more than 50 mol% of all hydrogen atoms of a hydroxyl group. And / or may be cross-linked between molecules.

(Wherein, R ³ and R ⁴ represent a hydrogen atom or a linear, branched or cyclic alkyl group having 1 to 8 carbon atoms. Alternatively, R ³ and R ⁴ may form a ring, When a ring is formed, R ³ and R ⁴ represent a linear or branched alkylene group having 1 to 8 carbon atoms, and R ⁵ represents a linear, branched or cyclic alkylene group having 1 to 10 carbon atoms. And d is an integer of 0 or 1 to 10. A represents a c-valent aliphatic or alicyclic saturated hydrocarbon group having 1 to 50 carbon atoms, an aromatic hydrocarbon group or a heterocyclic group, May have a hetero atom interposed, and a part of the hydrogen atom bonded to the carbon atom may be substituted by a hydroxyl group, a carboxyl group, an acyl group or a fluorine atom. -, -NHCO-O- or -NHCONH-, where c is an integer of 2 to 8 and c 'is an integer of 1 to 7.)
(C) an acid generator,
(H) A resist material comprising a compound which is crosslinked by the action of an acid. The acid labile group is a group represented by the following general formula (4), a group represented by the following general formula (5), a tertiary alkyl group having 4 to 20 carbon atoms, and a tertiary alkyl group having 1 to 6 carbon atoms in each alkyl group. 14. The resist material according to claim 13, which is one or more groups selected from a trialkylsilyl group and an oxoalkyl group having 4 to 20 carbon atoms.

(R ⁶ and R ^{7 each} represent a hydrogen atom or a linear, branched or cyclic alkyl group having 1 to 18 carbon atoms, and R ⁸ represents a monovalent group which may have a hetero atom having 1 to 18 carbon atoms. R ⁶ and R ⁷ , R ⁶ and R ⁸ or R ⁷ and R ⁸ may form a ring, and when forming a ring, R ⁶ , R ⁷ and R ⁸ each represent a hydrocarbon group; A linear or branched alkylene group having 1 to 18 carbon atoms, R ⁹ represents a tertiary alkyl group having 4 to 20 carbon atoms, a trialkylsilyl group having 1 to 6 carbon atoms in each alkyl group, And represents an oxoalkyl group of 4 to 20 or a group represented by the general formula (4), and a is an integer of 0 to 6.) (I) applying the resist material according to any one of claims 6 to 14 onto a substrate;
(Ii) then, after the heat treatment, exposing with a high energy beam or an electron beam having a wavelength of 300 nm or less through a photomask;
(Iii) performing a heat treatment as necessary, and then developing using a developer.