JP4258645B2 - Polymer compound, resist material, and pattern forming method - Google Patents

Description

  The present invention relates to a high-molecular compound useful as a base polymer of a resist material suitable for microfabrication technology, particularly a chemically amplified resist material, a resist material, and a pattern forming method using the same.

In recent years, with the high integration and high speed of LSI, there is a demand for finer pattern rules.
The background of rapid progress in miniaturization includes higher NA of projection lenses, improved performance of resist materials, and shorter wavelengths. With regard to higher resolution and higher sensitivity of resist materials, chemically amplified positive resist materials catalyzed by acids generated by light irradiation have excellent performance, and have become the mainstream resist materials particularly in deep ultraviolet lithography. (Patent Documents 1 and 2: described in JP-B-2-27660, JP-A-63-27829, etc.).

  In addition, the shortening of the wavelength from i-line (365 nm) to KrF (248 nm) has brought about a major change. Resist materials for KrF excimer lasers started with the 0.30 micron process, passed the 0.25 micron rule, The micron rule is being applied to mass production. Furthermore, the investigation below the 0.10 micron rule has begun, and the momentum of miniaturization is further accelerated.

  In ArF (193 nm), it is expected that the refinement of the design rule will be 0.09 μm or less, but conventionally used resins such as novolak resins and polyvinylphenols have very strong absorption around 193 nm. Therefore, it cannot be used as a base resin for resist. Therefore, acrylic resins and cycloolefin-based alicyclic resins have been studied in order to ensure transparency and necessary dry etching resistance (Patent Documents 3 to 6: JP-A-9-73173 and JP-A-10-10). 10739, JP-A-9-230595, pamphlet of International Publication No. 97/33198).

F ₂ (157 nm) is expected to be as fine as 0.07 μm or less, but it becomes increasingly difficult to ensure transparency, and the acrylic resin, which is a base polymer for ArF, does not transmit light at all. Even in the system, those having a carbonyl bond were found to have strong absorption. Further, it was found that polyvinylphenol, which is a base polymer for KrF, has an absorption window at around 160 nm and slightly improves the transmittance, but is far from a practical level.

In order to improve the transmittance near 157 nm, it is one effective method to reduce the number of carbonyl groups and carbon-carbon double bonds with strong absorption. It has been found that the introduction of fluorine atoms into the substrate is effective in improving the transmittance in the F ₂ region. For example, in “Polymer design for 157 nm chemically amplified resists” (Non-Patent Document 1), tert-butyl α-trifluoromethyl acrylate and 5- (2-hydroxy-2,2-bistrifluoromethyl) ethyl-2-norbornene And a resist material using a copolymer of tert-butyl α-trifluoromethyl acrylate and 4- (2-hydroxy-2,2-bistrifluoromethyl) methylstyrene is a polymer at 157 nm It has been reported that the absorbance of is improved to about 3.

However, in order to obtain a rectangular pattern with a film thickness of 2000 mm or more by F ₂ exposure, it is considered that an absorbance of 2 or less is necessary, so the above resin is still insufficient in transparency. On the other hand, in “Synthesis of novel fluoropolymers for 157 nm photo-sensitives by cyclo-polymerization” (Non-patent Document 2), an extremely highly transparent resin having an absorbance of 1 or less was proposed. This polymer is not only highly transparent, but also excellent in substrate adhesion and affinity with a developer, but its disadvantage is that dry etching resistance is decisively lower than general-purpose polymers for KrF and ArF. Yes.

JP-B-2-27660 JP 63-27829 A JP-A-9-73173 Japanese Patent Laid-Open No. 10-10739 Japanese Patent Laid-Open No. 9-230595 International Publication No. 97/33198 Pamphlet JP 2001-146505 A Proc. SPIE. 4345, pp. 273-284, 2001. Proc. SPIE. 4690, pp. 76-83, 2002.

The present invention has been made in view of the above circumstances, and is useful as a base resin of a chemically amplified resist material having excellent transmittance with respect to a light source such as 300 nm or less, particularly KrF (248 nm), ArF (193 nm), F ₂ (157 nm). It is an object of the present invention to provide a novel polymer compound, a resist material using the same, and a pattern forming method using the resist material.

  As a result of intensive studies in order to overcome the above problems, the present inventors have found that the polymer containing the repeating unit represented by the general formula (1) has excellent resolution while maintaining high transparency of the resin. The present inventors have found that a resist material, particularly a chemically amplified resist material, having high dry etching resistance and excellent in substrate adhesion and affinity with a developer can be obtained.

（式中、Ｒ¹はフッ素原子又は炭素数１〜４のフッ素化されたアルキル基である。Ｒ²は単結合、又は炭素数１〜２０の直鎖状、分岐状もしくは環状のアルキレン基又はフッ素化されたアルキレン基である。Ｒ³及びＲ⁴は水素原子、フッ素原子、又は炭素数１〜２０の直鎖状、分岐状もしくは環状のアルキル基又はフッ素化アルキル基であり、Ｒ³及びＲ⁴の少なくとも一方は一つ以上のフッ素原子を含む。Ｒ⁵は水素原子又は酸不安定基である。Ｒ⁶は酸不安定基、密着性基、又は炭素数１〜２０の直鎖状、分岐状もしくは環状のアルキル基又はフッ素化されたアルキル基である。ａは１又は２である。）
請求項２：
酸不安定基が、下記一般式（ＡＬ−１）〜（ＡＬ−３）で示される基から選ばれる請求項１記載の高分子化合物。

（式中、Ｒ ⁸ 、Ｒ ⁹ 、Ｒ ¹⁰ は同一又は異種の炭素数１〜２０の直鎖状、分岐状又は環状の炭化水素基であり、酸素、硫黄、窒素などのヘテロ原子を含んでもよく、有橋環式炭化水素基であってもよい。又は、Ｒ ⁸ とＲ ⁹ 、Ｒ ⁸ とＲ ¹⁰ 、Ｒ ⁹ とＲ ¹⁰ が互いに結合して、これらが結合する炭素原子と共に炭素数３〜２０の環を形成してもよい。Ｒ ¹¹ 及びＲ ¹⁴ は炭素数１〜２０の直鎖状、分岐状又は環状のアルキル基であり、酸素、硫黄、窒素、フッ素などのヘテロ原子を含んでもよい。Ｒ ¹² 及びＲ ¹³ は水素原子、又は炭素数１〜２０の直鎖状、分岐状又は環状のアルキル基であり、酸素、硫黄、窒素、フッ素などのヘテロ原子を含んでもよい。Ｒ ¹² とＲ ¹³ 、Ｒ ¹² とＲ ¹⁴ 、Ｒ ¹³ とＲ ¹⁴ はそれぞれ結合して、これらが結合する炭素原子と共に炭素数３〜２０の環を形成してもよい。ｃは０〜６の整数である。）
請求項３：
更に、下記式（４ａ）〜（４ｈ）から選ばれる繰り返し単位を含む請求項１又は２記載の高分子化合物。

（式中、Ｒ ²⁹ は水素原子、又は前記と同様の酸不安定基である。Ｒ ³⁰ 〜Ｒ ³⁴ は水素原子、フッ素原子、又は炭素数１〜４のフッ素化されたアルキル基であり、Ｒ ³⁰ 〜Ｒ ³⁴ のうち少なくとも１個以上のフッ素原子を含む。Ｒ ³⁵ 及びＲ ³⁶ は水素原子、メチル基、又はトリフルオロメチル基である。）
請求項４：
請求項１、２又は３記載の高分子化合物を含有することを特徴とするレジスト材料。
請求項５：
請求項１、２又は３記載の高分子化合物と下記一般式（３ａ）〜（３ｃ）で示される繰り返し単位を含む高分子化合物との混合物を含有することを特徴とするレジスト材料。

（式中、Ｒ⁷は水素原子又は酸不安定基である。０＜ｂ１＜１、０＜ｂ２＜１、０≦ｂ３＜１、０＜ｂ１＋ｂ２＋ｂ３≦１である。）
請求項６：
更に、
（Ｂ）有機溶剤、
（Ｃ）酸発生剤
を含有する化学増幅ポジ型であることを特徴とする請求項４又は５記載のポジ型レジスト材料。
請求項７：
更に、（Ｄ）塩基性化合物を含有する請求項６記載のレジスト材料。
請求項８：
更に、（Ｅ）溶解阻止剤を含有する請求項６又は７記載のレジスト材料。
請求項９：
（１）請求項４乃至８のいずれか１項に記載のレジスト材料を基板上に塗布する工程と、
（２）次いで、加熱処理後、フォトマスクを介して波長１００〜１８０ｎｍ帯又は１〜３０ｎｍ帯の高エネルギー線で露光する工程と、
（３）必要に応じて加熱処理した後、現像液を用いて現像する工程と
を含むことを特徴とするパターン形成方法。
請求項１０：
前記高エネルギー線がＦ₂レーザー、Ａｒ₂レーザー、又は軟Ｘ線であることを特徴とする請求項９記載のパターン形成方法。 That is, the present invention provides the following polymer compound, resist material, and pattern forming method.
Claim 1:
A weight average molecular weight of 1,000 to 500, which necessarily contains a repeating unit represented by the following general formula (1) and further contains at least one repeating unit selected from the following general formulas (2a) to (2d): 1,000 polymer compounds.

(In the formula, R ¹ is a fluorine atom or a fluorinated alkyl group having 1 to 4 carbon atoms. R ² is a single bond, a linear, branched or cyclic alkylene group having 1 to 20 carbon atoms, or is a fluorinated alkylene group .R ³ and R ⁴ are a hydrogen atom, a fluorine atom, or a straight, an alkyl group or a fluorinated alkyl group branched or cyclic, R ³ and At least one of R ⁴ contains one or more fluorine atoms, R ⁵ is a hydrogen atom or an acid labile group, R ⁶ is an acid labile group, an adhesive group, or a straight chain having 1 to 20 carbon atoms. A branched or cyclic alkyl group or a fluorinated alkyl group, a is 1 or 2.)
Claim 2:
The polymer compound according to claim 1, wherein the acid labile group is selected from groups represented by the following general formulas (AL-1) to (AL-3).

(In the formula, R ⁸ , R ⁹ and R ¹⁰ are the same or different linear, branched or cyclic hydrocarbon groups having 1 to 20 carbon atoms, and may contain heteroatoms such as oxygen, sulfur and nitrogen. It may be a bridged cyclic hydrocarbon group, or R ⁸ and R ⁹ , R ⁸ and R ¹⁰ , R ⁹ and R ¹⁰ are bonded to each other, and together with the carbon atom to which they are bonded, the number of carbon atoms is 3 R ¹¹ and R ¹⁴ may be a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms and include heteroatoms such as oxygen, sulfur, nitrogen and fluorine. R ¹² and R ¹³ are each a hydrogen atom or a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms, and may contain heteroatoms such as oxygen, sulfur, nitrogen and fluorine. ¹² and R ^13, R ¹² and R ^14, R ¹³ and R ¹⁴ are respectively bonded, carbon together with the carbon atom to which they are attached 3 It may be formed of 20 rings .c is an integer of 0-6.)
Claim 3:
Furthermore, the high molecular compound of Claim 1 or 2 containing the repeating unit chosen from following formula (4a)-(4h).

(Wherein R ²⁹ is a hydrogen atom or an acid labile group as described above. R ^{30 to} R ³⁴ are a hydrogen atom, a fluorine atom, or a fluorinated alkyl group having 1 to 4 carbon atoms, R ^{30 to} R ³⁴ contain at least one fluorine atom, and R ³⁵ and R ³⁶ are a hydrogen atom, a methyl group, or a trifluoromethyl group.)
Claim 4 :
Resist material you characterized by containing the claim 1, 2 or 3 polymer compound according.
Claim 5 :
A resist material comprising a mixture of the polymer compound according to claim 1 , 2 or 3 and a polymer compound containing a repeating unit represented by the following general formulas (3a) to (3c).

(In the formula, R ⁷ is a hydrogen atom or an acid labile group. 0 <b1 <1, 0 <b2 <1, 0 ≦ b3 <1, 0 <b1 + b2 + b3 ≦ 1.)
Claim 6 :
Furthermore,
(B) an organic solvent,
(C) The positive resist material according to claim 4 or 5, wherein it is a chemically amplified positive type containing an acid generator.
Claim 7 :
Furthermore, (D) The resist material of Claim 6 containing a basic compound.
Claim 8 :
The resist material according to claim 6 or 7 , further comprising (E) a dissolution inhibitor.
Claim 9 :
(1) A step of applying the resist material according to any one of claims 4 to 8 on a substrate;
(2) Next, after the heat treatment, a step of exposing with a high energy ray having a wavelength of 100 to 180 nm band or 1 to 30 nm band through a photomask;
(3) A pattern forming method comprising a step of performing heat treatment as necessary and then developing using a developer.
Claim 10 :
The pattern forming method according to claim 9, wherein the high energy beam is an F ₂ laser, an Ar ₂ laser, or a soft X-ray.

The novel fluorine-containing alicyclic polymer compound of the present invention has excellent transparency to radiation having a wavelength of 200 nm or less, particularly 160 nm or less, for example, F ₂ laser light, and is excellent in resin substrate adhesion and dryness. Excellent etching resistance and good resolution. The resist material of the present invention is sensitive to high energy rays, has excellent sensitivity at a wavelength of 300 nm or less, particularly 200 nm or less, particularly 160 nm or less, and has a hydrophilic fluorine-containing alicyclic group in the resin. By introducing it, sufficient dry etching resistance can be ensured without impairing the transparency of the resin, the substrate adhesion, and the developer compatibility. Therefore, the resist material of the present invention can be a resist material having a small absorption particularly at the exposure wavelength of the F ₂ laser due to these characteristics, and can easily form a fine pattern perpendicular to the substrate. Therefore, it is suitable as a fine pattern forming material for VLSI manufacturing.

Hereinafter, the present invention will be described in more detail.
One of the major problems with F ₂ resist is the transmittance of the base resin. As described above, since a resin containing a substituent such as a carbonyl group or an aromatic ring has strong absorption in the F ₂ region, it is difficult to realize the absorbance of 2 or less required for the F ₂ resist. In addition, it is possible to improve the transmittance of the resin by introducing fluorine atoms into the resin. However, increasing the fluorine content to ensure transparency generally increases the water repellency of the resin and makes the resin adherent to the substrate. In addition, the affinity of the developer is lowered, and further, the dry etching resistance of the resin is also lowered.

  On the other hand, since the repeating unit represented by the following general formula (1) includes a hydrophilic fluorine-containing unit in the side chain, it improves the transparency of the resin without impairing the substrate adhesion and developer compatibility. In addition, high resolution and dry etching resistance can be expected. In particular, in the present invention, by combining the repeating unit represented by the general formula (1) and the repeating unit represented by the following general formulas (2a) to (2d), the transparency of the resin, the dry etching resistance, and the substrate adhesion High resolution resist material having excellent properties and developer compatibility.

（式中、Ｒ¹はフッ素原子又は炭素数１〜４のフッ素化されたアルキル基である。Ｒ²は単結合、又は炭素数１〜２０の直鎖状、分岐状もしくは環状のアルキレン基又はフッ素化されたアルキレン基である。Ｒ³及びＲ⁴は水素原子、フッ素原子、又は炭素数１〜２０の直鎖状、分岐状もしくは環状のアルキル基又はフッ素化アルキル基であり、Ｒ³及びＲ⁴の少なくとも一方は一つ以上のフッ素原子を含む。Ｒ⁵は水素原子又は酸不安定基である。Ｒ⁶は酸不安定基、密着性基、又は炭素数１〜２０の直鎖状、分岐状もしくは環状のアルキル基又はフッ素化されたアルキル基である。ａは１又は２である。）

(In the formula, R ¹ is a fluorine atom or a fluorinated alkyl group having 1 to 4 carbon atoms. R ² is a single bond, a linear, branched or cyclic alkylene group having 1 to 20 carbon atoms, or is a fluorinated alkylene group .R ³ and R ⁴ are a hydrogen atom, a fluorine atom, or a straight, an alkyl group or a fluorinated alkyl group branched or cyclic, R ³ and At least one of R ⁴ contains one or more fluorine atoms, R ⁵ is a hydrogen atom or an acid labile group, R ⁶ is an acid labile group, an adhesive group, or a straight chain having 1 to 20 carbon atoms. A branched or cyclic alkyl group or a fluorinated alkyl group, a is 1 or 2.)

  In this case, the linear, branched or cyclic alkyl group having 1 to 20 carbon atoms includes methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl. Group, cyclopentyl group, cyclohexyl group, cyclohexylmethyl group, 2-ethylhexyl group, n-octyl group, 2-adamantyl group, (2-adamantyl) methyl group and the like, and particularly those having 1 to 10 carbon atoms. preferable.

  The fluorinated alkyl group is one in which part or all of the hydrogen atoms of the above alkyl group are substituted with fluorine atoms, and includes a trifluoromethyl group, 2,2,2-trifluoroethyl group, 3, 3, Examples include 3-trifluoropropyl group, 1,1,1,3,3,3-hexafluoroisopropyl group, 1,1,2,2,3,3,3-heptafluoropropyl group, and the like.

  As the linear, branched or cyclic alkylene group having 1 to 20 carbon atoms, those obtained by eliminating one hydrogen atom in the above alkyl group are used, and the fluorinated alkylene group is a part of them or Those in which all are substituted with fluorine atoms are used.

Next, the acid labile group represented by R ⁵ and R ⁶ will be described. Various acid labile groups are selected, and groups represented by the following general formulas (AL-1) to (AL-3) are particularly desirable. The acid labile groups represented by the following general formulas (AL-1) to (AL-3) have a cyclic structure having a higher effect of improving etching resistance, and may be a monocyclic structure. For example, the etching resistance can be further improved. In general, an acid labile group having a cyclic structure has high elimination reactivity, and can improve the γ value of contrast or solubility characteristics.

（式中、Ｒ⁸、Ｒ⁹、Ｒ¹⁰は同一又は異種の炭素数１〜２０の直鎖状、分岐状又は環状の炭化水素基であり、酸素、硫黄、窒素などのヘテロ原子を含んでもよく、有橋環式炭化水素基であってもよい。又は、Ｒ⁸とＲ⁹、Ｒ⁸とＲ¹⁰、Ｒ⁹とＲ¹⁰が互いに結合して、これらが結合する炭素原子と共に炭素数３〜２０、特に５〜１５の環を形成してもよい。Ｒ¹¹及びＲ¹⁴は炭素数１〜２０の直鎖状、分岐状又は環状のアルキル基であり、酸素、硫黄、窒素、フッ素などのヘテロ原子を含んでもよい。Ｒ¹²及びＲ¹³は水素原子、又は炭素数１〜２０の直鎖状、分岐状又は環状のアルキル基であり、酸素、硫黄、窒素、フッ素などのヘテロ原子を含んでもよい。Ｒ¹²とＲ¹³、Ｒ¹²とＲ¹⁴、Ｒ¹³とＲ¹⁴はそれぞれ結合して、これらが結合する炭素原子と共に炭素数３〜２０、特に５〜１５の環を形成してもよい。ｃは０〜６の整数である。）

(In the formula, R ⁸ , R ⁹ and R ¹⁰ are the same or different linear, branched or cyclic hydrocarbon groups having 1 to 20 carbon atoms, and may contain heteroatoms such as oxygen, sulfur and nitrogen. It may be a bridged cyclic hydrocarbon group, or R ⁸ and R ⁹ , R ⁸ and R ¹⁰ , R ⁹ and R ¹⁰ are bonded to each other, and together with the carbon atom to which they are bonded, the number of carbon atoms is 3 May form a ring of ˜20, particularly 5 to 15. R ¹¹ and R ¹⁴ are linear, branched or cyclic alkyl groups having 1 to 20 carbon atoms, such as oxygen, sulfur, nitrogen, fluorine, etc. R ¹² and R ¹³ are each a hydrogen atom or a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms, and includes hetero atoms such as oxygen, sulfur, nitrogen and fluorine. which may contain .R ¹² and R ^13, R ¹² and R ^14, R ¹³ and R ¹⁴ are respectively bonded, the carbon atom to which they are attached Both C3-20, may .c be particularly form a 5-15 ring is an integer of 0-6.)

In the general formula (AL-1), specific examples of R ⁸ , R ⁹ and R ¹⁰ include methyl group, ethyl group, n-propyl group, isopropyl group, tert-butyl group, cyclohexyl group, cyclopentyl group and norbornyl. Group, adamantyl group, menthyl group and the like. Furthermore, specific examples of the acid labile group represented by the general formula (AL-1) include the substituents shown below.

（式中、Ｒ¹⁵及びＲ¹⁶は直鎖状、分岐状又は環状の炭素数１〜２０、特に１〜１５のアルキル基を示す。Ｒ¹⁷及びＲ¹⁸は水素原子、炭素数１〜６のヘテロ原子を含んでもよい１価炭化水素基を示し、これらは直鎖状、分岐状又は環状のいずれでもよい。）

(In the formula, R ¹⁵ and R ¹⁶ represent a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms, particularly 1 to 15 carbon atoms. R ¹⁷ and R ¹⁸ are hydrogen atoms, 1 to 6 carbon atoms. A monovalent hydrocarbon group which may contain a hetero atom is shown, and these may be linear, branched or cyclic.

Specific examples of R ¹⁵ and R ¹⁶ include methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, sec-butyl group, n-pentyl group, n-hexyl group, cyclopropyl group, cyclopropylmethyl. Group, cyclobutyl group, cyclopentyl group, cyclohexyl group and the like. Specific examples of R ¹⁷ and R ¹⁸ include an alkyl group, a hydroxyalkyl group, an alkoxy group, an alkoxyalkoxy group, and the like. A methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, Examples include sec-butyl group, n-pentyl group, n-hexyl group, hydroxymethyl group, hydroxyethyl group, methoxy group, methoxymethoxy group, ethoxy group, and tert-butoxy group. In the case R ¹⁷ and R ¹⁸ contains a hetero atom such as oxygen atom, a sulfur atom, a nitrogen atom, for ^{example, -OH, -OR 19, -O -} , - S -, - S (= O) -, - NH ₂ , —NHR ¹⁹ , —N (R ¹⁹ ) ₂ , —NH—, —NR ¹⁹ — and the like can be contained (R ¹⁹ represents an alkyl group having 1 to 5 carbon atoms).

  Examples of the acid labile group of the general formula (AL-2) include tert-butoxycarbonyl group, tert-butoxycarbonylmethyl group, tert-amyloxycarbonyl group, tert-amyloxycarbonylmethyl group, 1-ethoxyethoxycarbonylmethyl. In addition to the group, 2-tetrahydropyranyloxycarbonylmethyl group, 2-tetrahydrofuranyloxycarbonylmethyl group and the like, the following substituents can be exemplified.

（式中、Ｒ²⁰は同一又は異種の炭素数１〜８の直鎖状、分岐状又は環状のアルキル基、又は炭素数６〜２０のアリール基又はアラルキル基を示す。Ｒ²¹は水素原子、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す。Ｒ²²は炭素数２〜２０の直鎖状、分岐状又は環状のアルキル基、又は炭素数６〜２０のアリール基又はアラルキル基を示す。ｃは０〜６の整数である。）

(In the formula, R ²⁰ represents an identical or different linear, branched or cyclic alkyl group having 1 to 8 carbon atoms, or an aryl group or aralkyl group having 6 to 20 carbon atoms. R ²¹ represents a hydrogen atom, Or a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms, wherein R ²² is a linear, branched or cyclic alkyl group having 2 to 20 carbon atoms, or aryl having 6 to 20 carbon atoms. A group or an aralkyl group, c is an integer of 0 to 6)

  Specific examples of the linear or branched acid labile group represented by the general formula (AL-3) include the following groups.

  Among the acid labile groups represented by the above general formula (AL-3), as cyclic ones, tetrahydrofuran-2-yl group, 2-methyltetrahydrofuran-2-yl group, tetrahydropyran-2-yl group, Examples thereof include a 2-methyltetrahydropyran-2-yl group.

  Furthermore, among the acid labile groups represented by the above general formula (AL-3), those having a structure in which the base resin is crosslinked intramolecularly or intermolecularly as exemplified by the following general formula can also be used. .

（式中、Ｒ²³及びＲ²⁴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。Ｒ²³及びＲ²⁴は結合して環を形成してもよく、環を形成する場合にはＲ²³及びＲ²⁴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。Ｒ²⁵は炭素数１〜１０の直鎖状、分岐状又は環状のアルキレン基を示す。Ｒ²⁶は、（ｆ＋１）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す。これらの基はヘテロ原子を介在してもよく、又は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、カルボニル基又はフッ素原子によって置換されていてもよい。Ｒ²⁷は−ＣＯ−Ｏ−、−ＮＨＣＯ−Ｏ−、又は−ＮＨＣＯＮＨ−を示す。ｄ及びｅは０〜１０の整数である。ｆは１〜７の整数である。）

(In the formula, R ²³ and R ²⁴ represent a hydrogen atom or a linear, branched or cyclic alkyl group having 1 to 8 carbon atoms. R ²³ and R ²⁴ may combine to form a ring; When forming a ring, R ²³ and R ²⁴ represent a linear or branched alkylene group having 1 to 8 carbon atoms, and R ²⁵ represents a linear, branched or cyclic alkylene group having 1 to 10 carbon atoms. R ²⁶ represents an (f + 1) -valent aliphatic or alicyclic saturated hydrocarbon group, aromatic hydrocarbon group or heterocyclic group having 1 to 50 carbon atoms, and these groups intervene heteroatoms. Or a part of hydrogen atoms bonded to the carbon atom may be substituted with a hydroxyl group, a carboxyl group, a carbonyl group or a fluorine atom, and R ²⁷ represents —CO—O— or —NHCO—O—. Or -NHCONH-, d and e are integers of 0 to 10. f is 1 to 7 It is an integer.)

In the above-mentioned crosslinked acid labile group, R ²⁶ is preferably a divalent to tetravalent C 1-20 linear, branched or cyclic alkylene group, an alkyltriyl group, an alkyltetrayl group, or a carbon number. 6-30 arylene groups, these groups may have intervening heteroatoms, and some of the hydrogen atoms bonded to the carbon atoms are substituted by hydroxyl groups, carboxyl groups, acyl groups or halogen atoms. May be. d and e are preferably integers of 0 to 5, and f is preferably an integer of 1 to 3. Preferable examples of the crosslinkable acetal group include the following groups.

Next, the adhesive group represented by R ⁶ will be described. Various groups are selected as the adhesive group, and the group represented by the following general formula is particularly preferable.

（式中、Ｒ²⁸はメチレン基、酸素原子、又は硫黄原子であり、Ｍｅはメチル基を示す。）

(In the formula, R ²⁸ represents a methylene group, an oxygen atom, or a sulfur atom, and Me represents a methyl group.)

The monomer corresponding to the repeating unit of the general formula (1) can be synthesized by reacting R ¹ with fluorine-containing acrylic acid and the following chloride in the presence of a base. There is no limitation.

（式中、Ｒ¹はフッ素原子又は炭素数１〜４のフッ素化されたアルキル基である。）

(In the formula, R ¹ is a fluorine atom or a fluorinated alkyl group having 1 to 4 carbon atoms.)

  Examples of bases that can be used in this reaction include sodium hydroxide, sodium carbonate, sodium bicarbonate, potassium hydroxide, potassium carbonate, potassium bicarbonate, sodium hydride, sodium methoxide, sodium ethoxide, sodium tert-butoxide. Potassium tert-butoxide, triethylamine, diethylamine, piperidine, pyrrolidine, 1,8-diazabicyclo [5,4,0] -7-undecene, and the like. The amount of the base used in this case is preferably 1 to 10 times mol, particularly 1 to 5 times mol for acrylic acid.

  Solvents may or may not be used. When used, hydrocarbons such as benzene, toluene and xylene, ethers such as diethyl ether, tetrahydrofuran and dioxane, halogenated hydrocarbons such as dichloromethane and chloroform, acetone and the like And aprotic polar solvents such as N, N-dimethylformamide, dimethyl sulfoxide, hexamethylphosphoric triamide, and the like. Two or more of these may be mixed and used.

  Although reaction temperature is not specifically limited, Usually, reaction is possible in the range of -10 degreeC-200 degreeC, and it is preferably 0 degreeC-50 degreeC in terms of a yield.

  Resins containing repeating units represented by the above general formulas (1) and (2a) to (2d) (hereinafter abbreviated as polymer (I)) are resin substrate adhesion and transparency, and resist dissolution characteristics. The following units can be introduced from the viewpoint of improving.

（式中、Ｒ²⁹は水素原子、又は先述の酸不安定基である。Ｒ³⁰〜Ｒ³⁴は水素原子、フッ素原子、又は炭素数１〜４のフッ素化されたアルキル基であり、Ｒ³⁰〜Ｒ³⁴のうち少なくとも１個以上のフッ素原子を含む。Ｒ³⁵及びＲ³⁶は水素原子、メチル基、又はトリフルオロメチル基である。）

(Wherein, R ²⁹ is a hydrogen atom, or an aforementioned acid labile group .R ³⁰ to R ³⁴ is a hydrogen atom, a fluorine atom, or a fluorinated alkyl group having 1 to 4 carbon atoms, R ³⁰ -At least one fluorine atom is included among R ^34. R ³⁵ and R ³⁶ are a hydrogen atom, a methyl group, or a trifluoromethyl group.)

In the polymer (I), when the unit of the general formula (1) is U1, the unit of the general formulas (2a) to (2d) is U2, and the unit of other units is U3, U1 + U2 + U3 = 1.
0 <U1 ≦ 0.8, more preferably 0.1 ≦ U1 ≦ 0.6,
0 <U2 ≦ 0.8, more preferably 0.1 ≦ U2 ≦ 0.6,
0 ≦ U3 ≦ 0.7, more preferably 0 ≦ U3 ≦ 0.5
It is preferable that

  Although the polymer (I) can exhibit sufficient resist performance by itself, it can be blended with a resin (hereinafter abbreviated as polymer (II)) containing repeating units represented by the following general formulas (3a) to (3c). By using it, the transparency and dissolution characteristics of the resist can be further improved.

（式中、Ｒ⁷は水素原子又は酸不安定基である。０＜ｂ１＜１、０＜ｂ２＜１、０≦ｂ３＜１、０＜ｂ１＋ｂ２＋ｂ３≦１である。）

(In the formula, R ⁷ is a hydrogen atom or an acid labile group. 0 <b1 <1, 0 <b2 <1, 0 ≦ b3 <1, 0 <b1 + b2 + b3 ≦ 1.)

As the acid labile group used for R ⁷ in the polymer (II), those represented by the aforementioned (AL-1) to (AL-3) can be used. As a method of introducing an acid labile group into R ⁷ , there are a method of polymerizing after introducing it in a monomer state in advance, and a method of substituting a hydrogen atom of a hydroxyl group after polymerizing a monomer having R ¹ as a hydrogen atom. In the case of retrofitting, for example, sodium hydride or potassium tert-butoxide can be reacted with a polymer to anionize an acidic hydroxyl group and react with a corresponding halide, but this is not a limitation. . Such as by substitution rate acid labile groups in the polymer (II) is 1 to 50 mol% of the total R ^7, is preferably in the range of 5 to 40 mol%.

  Next, a method for synthesizing the polymer compound of the present invention will be described. When synthesizing the polymer (I), monomers corresponding to the above general formulas (1) and (2a) to (2d) and, if necessary, a transparency improving monomer, and when synthesizing the polymer (II), monomers shown below. Etc. are dissolved in a solvent, a catalyst is added, and the polymerization reaction is carried out with heating or cooling as the case may be.

（式中、Ｒ⁷は水素原子又は酸不安定基である。）

(In the formula, R ⁷ is a hydrogen atom or an acid labile group.)

  The polymerization reaction is also governed by the type of initiator (or catalyst), the starting method (light, heat, radiation, plasma, etc.), the polymerization conditions (temperature, pressure, concentration, solvent, additives), etc. In each of the synthesis reactions of the polymer (I) and the polymer (II), radical copolymerization that is initiated by radicals such as 2,2′-azobisisobutyronitrile (hereinafter abbreviated as AIBN) is used. And the reaction can be carried out according to the conventional method.

  Although it does not specifically limit as an initiator at the time of performing radical polymerization reaction, For example, 2,2'-azobisisobutyronitrile, 2,2'-azobis (4-methoxy-2,4-dimethyl) Valeronitrile), 2,2′-azobis (2,4-dimethylvaleronitrile), azo compounds such as 2,2′-azobis (2,4,4-trimethylpentane), tert-butyl peroxypivalate, Peroxide compounds such as lauroyl peroxide, benzoyl peroxide, tert-butyl peroxylaurate, and water-soluble initiators such as persulfates such as potassium persulfate, and potassium persulfate and hydrogen peroxide A redox initiator composed of a combination of a peroxide and a reducing agent such as sodium sulfite is exemplified. The amount of the polymerization initiator used can be appropriately changed according to the type, polymerization reaction conditions, etc., but is usually 0.001 to 5% by mass, particularly 0.01 to 2%, based on the total amount of monomers to be polymerized. Mass% is adopted.

  In the polymerization reaction, a polymerization solvent may be used. As the polymerization solvent, those that do not inhibit the polymerization reaction are preferable, and typical examples include esters such as ethyl acetate and n-butyl acetate, ketones such as acetone, methyl ethyl ketone, and methyl isobutyl ketone, toluene, xylene, cyclohexane, and the like. Aliphatic or aromatic hydrocarbons, alcohols such as isopropyl alcohol and ethylene glycol monomethyl ether, and ether solvents such as diethyl ether, dioxane and tetrahydrofuran (THF) can be used. These solvents can be used alone or in admixture of two or more. Moreover, you may use together well-known molecular weight regulators, such as dodecyl mercaptan.

  The reaction temperature of the polymerization reaction is appropriately changed depending on the kind of the polymerization initiator or the boiling point of the solvent, and is usually preferably 20 to 200 ° C, particularly preferably 50 to 140 ° C. The reaction vessel used for such a polymerization reaction is not particularly limited.

  As a method for removing the organic solvent or water as a medium from the polymer solution or dispersion according to the present invention thus obtained, any known method can be used. For example, reprecipitation filtration may be used. Alternatively, there is a method such as heating distillation under reduced pressure.

  The polymer compound preferably has a weight average molecular weight of 1,000 to 500,000, particularly 2,000 to 100,000. In this case, the weight average molecular weight is a value obtained as a weight average molecular weight converted value of polystyrene measured using GPC.

  In the synthesis of the polymer (I), it is possible to arbitrarily change the ratio of repeating units in the resin by changing the monomer charging ratio.

  On the other hand, the composition ratios b1, b2, and b3 of the polymer (II) are changed by changing the polymerization reaction conditions described above, but 0 <b1 <1, 0 <b2 <1, 0 ≦ b3 <1. , B1, b2, and b3 are preferably in the range of 0.1 to 0.8.

  In this case, 0 <b1 + b2 + b3 ≦ 1, but preferably 0.6 ≦ b1 + b2 + b3 ≦ 1. In the case of b1 + b2 + b3 <1, examples of other units include acrylic acid ester derivatives, styrene derivatives, vinyl ether derivatives, norbornene derivatives, and fluoroethylene derivatives, but are not particularly limited. In this case, the transparency of the whole polymer can be increased by introducing a fluorine atom into the unit, and the solubility characteristics of the polymer can be improved by introducing a substituent protecting the fluoroalcohol or its hydroxyl group into the unit. It is also possible to raise.

  The polymer compound of the present invention can be used as a base resin for resist materials, particularly chemically amplified, particularly chemically amplified positive resist materials. However, the polymer physical properties, thermal properties, alkali solubility, and other physical properties of the film can be used. Other polymer compounds can be mixed for the purpose of changing. In this case, the range of the polymer compound to be mixed is not particularly limited, but it can be mixed with a known polymer compound for resist in an arbitrary range.

The resist material of the present invention can be prepared using known components except that the polymer compound of the present invention is used as a base resin.
(A) the polymer compound (base resin),
(B) an organic solvent,
(C) An acid generator is contained. In this case, these resist materials further include (D) a basic compound,
(E) A dissolution inhibitor may be blended.

  The organic solvent of component (B) used in the present invention may be any organic solvent that can dissolve the base resin, acid generator, other additives, and the like. Examples of such organic solvents include ketones such as cyclohexanone and methyl-2-n-amyl ketone, 3-methoxybutanol, 3-methyl-3-methoxybutanol, 1-methoxy-2-propanol, 1-ethoxy- Alcohols such as 2-propanol, ethers such as propylene glycol monomethyl ether, ethylene glycol monomethyl ether, propylene glycol dimethyl ether, diethylene glycol dimethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, ethyl lactate, ethyl pyruvate, acetic acid Butyl, methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, tert-butyl acetate, tert-butyl propionate, pro Esters such as glycol monobutyl tert- butyl ether acetate, lactones such as γ- butyl lactone.

  A fluorinated organic solvent can also be used. Specifically, 2-fluoroanisole, 3-fluoroanisole, 4-fluoroanisole, 2,3-difluoroanisole, 2,4-difluoroanisole, 2,5-difluoroanisole, 5,8-difluoro-1, 4-benzodioxane, 2,3-difluorobenzyl alcohol, 1,3-difluoro-2-propanol, 2 ', 4'-difluoropropiophenone, 2,4-difluorotoluene, trifluoroacetaldehyde ethyl hemiacetal, trifluoro Acetamide, trifluoroethanol, 2,2,2-trifluorobutyrate, ethyl heptafluoroethanol, ethyl heptafluorobutyl acetate, ethyl hexafluoroglutaryl methyl, ethyl-3-hydroxy-4,4,4-trifluoroa Toacetate, ethyl pentafluoropropynyl acetate, ethyl perfluorooctanoate, ethyl-4,4,4-trifluoroacetoacetate, ethyl-4,4,4-trifluorobutyrate, ethyl-4,4,4- Trifluorocrotonate, ethyl trifluoropyruvate, sec-ethyl trifluoroacetate, fluorocyclohexane, 2,2,3,3,4,4,4-heptafluoro-1-butanol, 1,1,1,2, 2,3,3-heptafluoro-7,7-dimethyl-4,6-octanedione, 1,1,1,3,5,5,5-heptafluoropentane-2,4-dione, 3,3,3 4,4,5,5,5-heptafluoro-2-pentanol, 3,3,4,4,5,5,5-heptafluoro-2-pentanone, isop Pill-4,4,4-trifluoroacetoacetate, methyl perfluorodenanoate, methyl perfluoro (2-methyl-3-oxahexanoate), methyl perfluorononanoate, methyl perfluorooctanoate, methyl -2,3,3,3-tetrafluoropropionate, methyl trifluoroacetoacetate, 1,1,1,2,2,6,6,6-octafluoro-2,4-hexanedione, 2,2 3,3,4,4,5,5-octafluoro-1-pentanol, 1H, 1H, 2H, 2H-perfluoro-1-decanol, perfluoro (2,5-dimethyl-3,6-dioxane Anionic) acid methyl ester, 2H-perfluoro-5-methyl-3,6-dioxanonane, 1H, 1H, 2H, 3H, 3H-perfluo Rononane-1,2-diol, 1H, 1H, 9H-perfluoro-1-nonanol, 1H, 1H-perfluorooctanol, 1H, 1H, 2H, 2H-perfluorooctanol, 2H-perfluoro-5,8, 11,14-tetramethyl-3,6,9,12,15-pentaoxaoctadecane, perfluorotributylamine, perfluorotrihexylamine, perfluoro-2,5,8-trimethyl-3,6,9,12 , 15-pentaoxaoctadecane, perfluoro-2,5,8-trimethyl-3,6,9-trioxadodecanoic acid methyl ester, perfluorotripentylamine, perfluorotriisopropylamine, 1H, 1H, 2H, 3H , 3H-perfluoroundecane-1,2-diol, trifluorobutanol 1,1,1-trifluoro-5-methyl-2,4-hexanedione, 1,1,1-trifluoro-2-propanol, 3,3,3-trifluoro-1-propanol, 1,1, 1-trifluoro-2-propyl acetate, perfluorobutyltetrahydrofuran, perfluorodecalin, perfluoro (1,2-dimethylcyclohexane), perfluoro (1,3-dimethylcyclohexane), propylene glycol trifluoromethyl ether acetate, propylene Glycol methyl ether trifluoromethyl acetate, trifluoromethyl butyl acetate, methyl 3-trifluoromethoxypropionate, perfluorocyclohexane, propylene glycol trifluoromethyl ether, butyl trifluoroacetate, 1,1,1- Trifluoroacetic 5,5-dimethyl-2,4-hexanedione like.

  These solvents may be used alone or in combination of two or more, but are not limited thereto. In the present invention, among these organic solvents, in addition to diethylene glycol dimethyl ether and 1-ethoxy-2-propanol, which have the most excellent solubility of acid generators in resist components, propylene glycol monomethyl ether acetate, which is a safety solvent, and mixtures thereof A solvent is preferably used.

  The amount of the solvent used is preferably 300 to 10,000 parts, particularly 500 to 5,000 parts, based on 100 parts of the base resin (parts by mass).

As the acid generator of component (C),
i. An onium salt of the following general formula (P1a-1), (P1a-2) or (P1b),
ii. A diazomethane derivative of the following general formula (P2):
iii. A glyoxime derivative of the following general formula (P3):
iv. A bissulfone derivative of the following general formula (P4):
v. A sulfonic acid ester of an N-hydroxyimide compound of the following general formula (P5),
vi. β-ketosulfonic acid derivatives,
vii. Disulfone derivatives,
viii. Nitrobenzyl sulfonate derivatives,
ix. Examples thereof include sulfonic acid ester derivatives.

（式中、Ｒ^101a、Ｒ^101b、Ｒ^101cはそれぞれ炭素数１〜１２の直鎖状、分岐状又は環状のアルキル基、アルケニル基、オキソアルキル基又はオキソアルケニル基、炭素数６〜２０のアリール基、又は炭素数７〜１２のアラルキル基又はアリールオキソアルキル基を示し、これらの基の水素原子の一部又は全部がアルコキシ基等によって置換されていてもよい。また、Ｒ^101bとＲ^101cとは環を形成してもよく、環を形成する場合には、Ｒ^101b、Ｒ^101cはそれぞれ炭素数１〜６のアルキレン基を示す。Ｋ^-は非求核性対向イオンを表す。）

Wherein R ^101a , R ^101b and R ^101c are each a linear, branched or cyclic alkyl group having 1 to 12 carbon atoms, an alkenyl group, an oxoalkyl group or an oxoalkenyl group, and an aryl having 6 to 20 carbon atoms. Group, an aralkyl group having 7 to 12 carbon atoms or an aryloxoalkyl group, part or all of hydrogen atoms of these groups may be substituted by an alkoxy group, etc. R ^101b and R ^{101c May} form a ring, and in the case of forming a ring, R ^101b and R ^101c each represent an alkylene group having 1 to 6 carbon atoms, and K ⁻ represents a non-nucleophilic counter ion.)

R ^101a , R ^101b and R ^101c may be the same as or different from each other. Specifically, as an alkyl group, methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, sec-butyl Group, tert-butyl group, pentyl group, hexyl group, heptyl group, octyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclopropylmethyl group, 4-methylcyclohexyl group, cyclohexylmethyl group, norbornyl group, adamantyl group, etc. Is mentioned. Examples of the alkenyl group include a vinyl group, an allyl group, a propenyl group, a butenyl group, a hexenyl group, and a cyclohexenyl group. Examples of the oxoalkyl group include 2-oxocyclopentyl group, 2-oxocyclohexyl group, and the like. 2-oxopropyl group, 2-cyclopentyl-2-oxoethyl group, 2-cyclohexyl-2-oxoethyl group, 2- (4 -Methylcyclohexyl) -2-oxoethyl group and the like can be mentioned. Examples of the aryl group include a phenyl group, a naphthyl group, a p-methoxyphenyl group, an m-methoxyphenyl group, an o-methoxyphenyl group, an ethoxyphenyl group, a p-tert-butoxyphenyl group, and an m-tert-butoxyphenyl group. Alkylphenyl groups such as alkoxyphenyl groups, 2-methylphenyl groups, 3-methylphenyl groups, 4-methylphenyl groups, ethylphenyl groups, 4-tert-butylphenyl groups, 4-butylphenyl groups, dimethylphenyl groups, etc. Alkyl naphthyl groups such as methyl naphthyl group and ethyl naphthyl group, alkoxy naphthyl groups such as methoxy naphthyl group and ethoxy naphthyl group, dialkyl naphthyl groups such as dimethyl naphthyl group and diethyl naphthyl group, dimethoxy naphthyl group and diethoxy naphthyl group Dialkoxynaphthyl group And the like. Examples of the aralkyl group include a benzyl group, a phenylethyl group, and a phenethyl group. As the aryloxoalkyl group, 2-aryl-2-oxoethyl group such as 2-phenyl-2-oxoethyl group, 2- (1-naphthyl) -2-oxoethyl group, 2- (2-naphthyl) -2-oxoethyl group and the like Groups and the like. Non-nucleophilic counter ions of K ⁻ include halide ions such as chloride ion and bromide ion, fluoroalkyl sulfonates such as triflate, 1,1,1-trifluoroethane sulfonate, and nonafluorobutane sulfonate, tosylate, and benzene sulfonate. And aryl sulfonates such as 4-fluorobenzene sulfonate and 1,2,3,4,5-pentafluorobenzene sulfonate, and alkyl sulfonates such as mesylate and butane sulfonate.

（式中、Ｒ^102a、Ｒ^102bはそれぞれ炭素数１〜８の直鎖状、分岐状又は環状のアルキル基を示す。Ｒ¹⁰³は炭素数１〜１０の直鎖状、分岐状又は環状のアルキレン基を示す。Ｒ^104a、Ｒ^104bはそれぞれ炭素数３〜７の２−オキソアルキル基を示す。Ｋ^-は非求核性対向イオンを表す。）

(In the formula, R ^102a and R ^102b each represent a linear, branched or cyclic alkyl group having 1 to 8 carbon atoms. R ¹⁰³ is a linear, branched or cyclic alkylene having 1 to 10 carbon atoms. R ^104a and R ^104b each represent a 2-oxoalkyl group having 3 to 7 carbon atoms, and K ⁻ represents a non-nucleophilic counter ion.)

Specific examples of R ^102a and R ^102b include a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, a tert-butyl group, a pentyl group, a hexyl group, a heptyl group, and an octyl group. , Cyclopentyl group, cyclohexyl group, cyclopropylmethyl group, 4-methylcyclohexyl group, cyclohexylmethyl group and the like. R ¹⁰³ is methylene group, ethylene group, propylene group, butylene group, pentylene group, hexylene group, heptylene group, octylene group, nonylene group, 1,4-cyclohexylene group, 1,2-cyclohexylene. Group, 1,3-cyclopentylene group, 1,4-cyclooctylene group, 1,4-cyclohexanedimethylene group and the like. ^{Examples of} R ^104a and R ^104b include a 2-oxopropyl group, a 2-oxocyclopentyl group, a 2-oxocyclohexyl group, and a 2-oxocycloheptyl group. K ^- is can be exemplified the same ones as described in the formulas (P1a-1) and (P1a-2).

（式中、Ｒ¹⁰⁵、Ｒ¹⁰⁶は炭素数１〜１２の直鎖状、分岐状又は環状のアルキル基又はハロゲン化アルキル基、炭素数６〜２０のアリール基又はハロゲン化アリール基、又は炭素数７〜１２のアラルキル基を示す。）

(In the formula, R ¹⁰⁵ and R ¹⁰⁶ are linear, branched or cyclic alkyl groups or halogenated alkyl groups having 1 to 12 carbon atoms, aryl groups or halogenated aryl groups having 6 to 20 carbon atoms, or carbon atoms. 7 to 12 aralkyl groups are shown.)

^Examples of the alkyl group of R ¹⁰⁵ and R ¹⁰⁶ include methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, sec-butyl group, tert-butyl group, pentyl group, hexyl group, heptyl group, octyl group, amyl Group, cyclopentyl group, cyclohexyl group, cycloheptyl group, norbornyl group, adamantyl group and the like. Examples of the halogenated alkyl group include a trifluoromethyl group, a 1,1,1-trifluoroethyl group, a 1,1,1-trichloroethyl group, and a nonafluorobutyl group. As the aryl group, an alkoxyphenyl group such as a phenyl group, p-methoxyphenyl group, m-methoxyphenyl group, o-methoxyphenyl group, ethoxyphenyl group, p-tert-butoxyphenyl group, m-tert-butoxyphenyl group, Examples thereof include alkylphenyl groups such as 2-methylphenyl group, 3-methylphenyl group, 4-methylphenyl group, ethylphenyl group, 4-tert-butylphenyl group, 4-butylphenyl group, and dimethylphenyl group. Examples of the halogenated aryl group include a fluorophenyl group, a chlorophenyl group, and 1,2,3,4,5-pentafluorophenyl group. Examples of the aralkyl group include a benzyl group and a phenethyl group.

（式中、Ｒ¹⁰⁷、Ｒ¹⁰⁸、Ｒ¹⁰⁹は炭素数１〜１２の直鎖状、分岐状又は環状のアルキル基又はハロゲン化アルキル基、炭素数６〜２０のアリール基又はハロゲン化アリール基、又は炭素数７〜１２のアラルキル基を示す。Ｒ¹⁰⁸、Ｒ¹⁰⁹は互いに結合して環状構造を形成してもよく、環状構造を形成する場合、Ｒ¹⁰⁸、Ｒ¹⁰⁹はそれぞれ炭素数１〜６の直鎖状、分岐状のアルキレン基を示す。）

(Wherein R ¹⁰⁷ , R ¹⁰⁸ and R ¹⁰⁹ are each a linear, branched or cyclic alkyl group or halogenated alkyl group having 1 to 12 carbon atoms, an aryl group or halogenated aryl group having 6 to 20 carbon atoms, Or an aralkyl group having 7 to 12 carbon atoms, R ¹⁰⁸ and R ¹⁰⁹ may be bonded to each other to form a cyclic structure, and in the case of forming a cyclic structure, R ¹⁰⁸ and R ¹⁰⁹ each have 1 to 6 carbon atoms. A linear or branched alkylene group.)

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

（式中、Ｒ^101a、Ｒ^101bは上記と同様である。）

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

（式中、Ｒ¹¹⁰は炭素数６〜１０のアリーレン基、炭素数１〜６のアルキレン基又は炭素数２〜６のアルケニレン基を示し、これらの基の水素原子の一部又は全部は更に炭素数１〜４の直鎖状又は分岐状のアルキル基又はアルコキシ基、ニトロ基、アセチル基、又はフェニル基で置換されていてもよい。Ｒ¹¹¹は炭素数１〜８の直鎖状、分岐状又は置換のアルキル基、アルケニル基又はアルコキシアルキル基、フェニル基、又はナフチル基を示し、これらの基の水素原子の一部又は全部は更に炭素数１〜４のアルキル基又はアルコキシ基；炭素数１〜４のアルキル基、アルコキシ基、ニトロ基又はアセチル基で置換されていてもよいフェニル基；炭素数３〜５のヘテロ芳香族基；又は塩素原子、フッ素原子で置換されていてもよい。）

(In the formula, R ¹¹⁰ represents an arylene group having 6 to 10 carbon atoms, an alkylene group having 1 to 6 carbon atoms, or an alkenylene group having 2 to 6 carbon atoms, and some or all of the hydrogen atoms of these groups are further carbon atoms. It may be substituted with a linear or branched alkyl group or alkoxy group having 1 to 4 carbon atoms, a nitro group, an acetyl group, or a phenyl group, and R ¹¹¹ is a linear or branched chain having 1 to 8 carbon atoms. Or a substituted alkyl group, an alkenyl group or an alkoxyalkyl group, a phenyl group, or a naphthyl group, and part or all of the hydrogen atoms of these groups are further an alkyl group or alkoxy group having 1 to 4 carbon atoms; A phenyl group which may be substituted with an alkyl group of 4 to 4, an alkoxy group, a nitro group or an acetyl group; a heteroaromatic group having 3 to 5 carbon atoms; or a phenyl group which may be substituted with a chlorine atom or a fluorine atom.

Here, as the arylene group of R ¹¹⁰ , 1,2-phenylene group, 1,8-naphthylene group, etc., and as the alkylene group, methylene group, ethylene group, trimethylene group, tetramethylene group, phenylethylene group, norbornane Examples of the alkenylene group such as -2,3-diyl group include 1,2-vinylene group, 1-phenyl-1,2-vinylene group, 5-norbornene-2,3-diyl group and the like. The alkyl group for R ¹¹¹ is the same as R ^{101a to} R ^101c, and the alkenyl group is a vinyl group, 1-propenyl group, allyl group, 1-butenyl group, 3-butenyl group, isoprenyl group, 1- Pentenyl group, 3-pentenyl group, 4-pentenyl group, dimethylallyl group, 1-hexenyl group, 3-hexenyl group, 5-hexenyl group, 1-heptenyl group, 3-heptenyl group, 6-heptenyl group, 7-octenyl Groups such as alkoxyalkyl groups include methoxymethyl, ethoxymethyl, propoxymethyl, butoxymethyl, pentyloxymethyl, hexyloxymethyl, heptyloxymethyl, methoxyethyl, ethoxyethyl, Propoxyethyl, butoxyethyl, pentyloxyethyl, hexyloxyethyl, methoxypro Group, ethoxypropyl group, propoxypropyl group, butoxy propyl group, methoxybutyl group, ethoxybutyl group, propoxybutyl group, a methoxy pentyl group, an ethoxy pentyl group, a methoxy hexyl group, a methoxy heptyl group.

  In addition, examples of the optionally substituted alkyl group having 1 to 4 carbon atoms include a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, an isobutyl group, and a tert-butyl group. As the alkoxy group of ˜4, a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, an n-butoxy group, an isobutoxy group, a tert-butoxy group and the like are an alkyl group having 1 to 4 carbon atoms, an alkoxy group, and a nitro group. As the phenyl group which may be substituted with an acetyl group, a phenyl group, a tolyl group, a p-tert-butoxyphenyl group, a p-acetylphenyl group, a p-nitrophenyl group, etc. are heterocycles having 3 to 5 carbon atoms. Examples of the aromatic group include a pyridyl group and a furyl group.

  Specifically, for example, trifluoromethanesulfonic acid diphenyliodonium, trifluoromethanesulfonic acid (p-tert-butoxyphenyl) phenyliodonium, p-toluenesulfonic acid diphenyliodonium, p-toluenesulfonic acid (p-tert-butoxyphenyl) phenyl Iodonium, triphenylsulfonium trifluoromethanesulfonate, trifluoromethanesulfonate (p-tert-butoxyphenyl) diphenylsulfonium, bis (p-tert-butoxyphenyl) phenylsulfonium trifluoromethanesulfonate, tris (p-tert) trifluoromethanesulfonate -Butoxyphenyl) sulfonium, p-toluenesulfonic acid triphenylsulfonium, p-toluenesulfonic acid (pt rt-butoxyphenyl) diphenylsulfonium, bis (p-tert-butoxyphenyl) phenylsulfonium p-toluenesulfonate, tris (p-tert-butoxyphenyl) sulfonium p-toluenesulfonate, triphenylsulfonium nonafluorobutanesulfonate, Triphenylsulfonium butanesulfonate, trimethylsulfonium trifluoromethanesulfonate, trimethylsulfonium p-toluenesulfonate, cyclohexylmethyl (2-oxocyclohexyl) sulfonium trifluoromethanesulfonate, cyclohexylmethyl (2-oxocyclohexyl) sulfonium p-toluenesulfonate , Dimethylphenylsulfonium trifluoromethanesulfonate, dimethylphenol p-toluenesulfonate Nylsulfonium, dicyclohexylphenylsulfonium trifluoromethanesulfonate, dicyclohexylphenylsulfonium p-toluenesulfonate, trinaphthylsulfonium trifluoromethanesulfonate, cyclohexylmethyl (2-oxocyclohexyl) sulfonium trifluoromethanesulfonate, trifluoromethanesulfonic acid (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 (xylenesulfur) Phonyl) 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, bi -O- (p-fluorobenzenesulfonyl) -α-dimethylglyoxime, bis-O- (p-tert-butylbenzenesulfonyl) -α-dimethylglyoxime, bis-O- (xylenesulfonyl) -α-dimethylglyoxime 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, nitrobenzyl sulfonate derivatives such as 2,6-dinitrobenzyl p-toluenesulfonate, 2,4-dinitrobenzyl p-toluenesulfonate, 1,2, Sulfonic acid ester derivatives such as 3-tris (methanesulfonyloxy) benzene, 1,2,3-tris (trifluoromethanesulfonyloxy) benzene, 1,2,3-tris (p-toluenesulfonyloxy) benzene, N-hydroxy Succinimide methanesulfonate, N-hydroxysuccinimide trifluoromethanesulfonate, N-hydroxysuccinimide ethanesulfonate, N-hydroxysuccinimide 1-propanesulfonate, N-hydroxysuccinimid 2-propanesulfonic acid ester, N-hydroxysuccinimide 1-pentanesulfonic acid ester, N-hydroxysuccinimide 1-octanesulfonic acid ester, N-hydroxysuccinimide p-toluenesulfonic acid ester, N-hydroxysuccinimide p-methoxybenzenesulfonic acid Ester, N-hydroxysuccinimide 2-chloroethanesulfonic acid ester, N-hydroxysuccinimide benzenesulfonic acid ester, N-hydroxysuccinimide-2,4,6-trimethylbenzenesulfonic acid ester, N-hydroxysuccinimide 1-naphthalenesulfonic acid ester, N-hydroxysuccinimide 2-naphthalenesulfonic acid ester, N-hydroxy-2-phenylsuccinimide methanesulfonic acid ester Ter, N-hydroxymaleimide methanesulfonate, N-hydroxymaleimide ethanesulfonate, N-hydroxy-2-phenylmaleimide methanesulfonate, N-hydroxyglutarimide methanesulfonate, N-hydroxyglutarimide benzenesulfone Acid ester, N-hydroxyphthalimide methanesulfonic acid ester, N-hydroxyphthalimide benzenesulfonic acid ester, N-hydroxyphthalimide trifluoromethanesulfonic acid ester, N-hydroxyphthalimide p-toluenesulfonic acid ester, N-hydroxynaphthalimide methanesulfonic acid Ester, N-hydroxynaphthalimide benzene sulfonate, N-hydroxy-5-norbornene-2,3-dicar Ximidomethanesulfonic acid ester, N-hydroxy-5-norbornene-2,3-dicarboximide trifluoromethanesulfonic acid ester, N-hydroxy-5-norbornene-2,3-dicarboximide p-toluenesulfonic acid ester, etc. Sulfonic acid ester derivatives of N-hydroxyimide compounds, and the like, but include trifluoromethanesulfonic acid triphenylsulfonium, trifluoromethanesulfonic acid (p-tert-butoxyphenyl) diphenylsulfonium, trifluoromethanesulfonic acid tris (p-tert- Butoxyphenyl) sulfonium, p-toluenesulfonic acid triphenylsulfonium, p-toluenesulfonic acid (p-tert-butoxyphenyl) diphenylsulfonium, p-toluenesulfuric acid Tris (p-tert-butoxyphenyl) sulfonium acid, trinaphthylsulfonium trifluoromethanesulfonate, cyclohexylmethyl trifluoromethanesulfonate (2-oxocyclohexyl) sulfonium, trifluoromethanesulfonic acid (2-norbornyl) methyl (2-oxocyclohexyl) ) Sulfonium, onium salts such as 1,2'-naphthylcarbonylmethyltetrahydrothiophenium triflate, bis (benzenesulfonyl) diazomethane, bis (p-toluenesulfonyl) diazomethane, bis (cyclohexylsulfonyl) diazomethane, bis (n-butyl) Sulfonyl) diazomethane, bis (isobutylsulfonyl) diazomethane, bis (sec-butylsulfonyl) diazomethane, bis (n-propylsulfone) Diazomethane derivatives such as phonyl) diazomethane, bis (isopropylsulfonyl) diazomethane, bis (tert-butylsulfonyl) diazomethane, bis-O- (p-toluenesulfonyl) -α-dimethylglyoxime, bis-O- (n-butanesulfonyl) ) Glyoxime derivatives such as -α-dimethylglyoxime, bissulfone derivatives such as bisnaphthylsulfonylmethane, N-hydroxysuccinimide methanesulfonate, N-hydroxysuccinimide trifluoromethanesulfonate, N-hydroxysuccinimide 1-propanesulfonate N-hydroxysuccinimide 2-propanesulfonic acid ester, N-hydroxysuccinimide 1-pentanesulfonic acid ester, N-hydroxysuccinimide p- A sulfonic acid ester derivative of an N-hydroxyimide compound such as toluenesulfonic acid ester, N-hydroxynaphthalimide methanesulfonic acid ester, or N-hydroxynaphthalimide benzenesulfonic acid ester is preferably used.

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

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

  As the basic compound of component (D), a compound capable of suppressing the diffusion rate when the acid generated from the acid generator diffuses into the resist film is suitable. By adding a basic compound, the acid diffusion rate in the resist film is suppressed and resolution is improved, sensitivity change after exposure is suppressed, and substrate and environment dependency is reduced, and exposure margin and pattern profile are reduced. Etc. can be improved.

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

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

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

  Furthermore, examples of the nitrogen-containing compound having a carboxy group include aminobenzoic acid, indolecarboxylic acid, amino acid derivatives (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 examples of the nitrogen-containing compound having a sulfonyl group include 3-pyridinesulfonic acid, pyridinium p-toluenesulfonate, and the like. Nitrogen-containing compounds having a hydroxyl group, nitrogen-containing compounds having a hydroxyphenyl group, and alcoholic nitrogen-containing compounds include 2-hydroxypyridine, aminocresol, 2,4-quinolinediol, and 3-indolemethanol. Drate, monoethanolamine, diethanolamine, triethanolamine, N-ethyldiethanolamine, N, N-diethylethanolamine, triisopropanolamine, 2,2′-iminodiethanol, 2-aminoethanol, 3-amino-1-propanol, 4-amino-1-butanol, 4- (2-hydroxyethyl) morpholine, 2- (2-hydroxyethyl) pyridine, 1- (2-hydroxyethyl) piperazine, 1- [2- (2-hydroxyethoxy) ethyl Piperazine, piperidine ethanol, 1- (2-hydroxyethyl) pyrrolidine, 1- (2-hydroxyethyl) -2-pyrrolidinone, 3-piperidino-1,2-propanediol, 3-pyrrolidino-1,2-propanediol , 8-hydroxyuroli , 3-cuincridinol, 3-tropanol, 1-methyl-2-pyrrolidineethanol, 1-aziridineethanol, N- (2-hydroxyethyl) phthalimide, N- (2-hydroxyethyl) isonicotinamide, etc. Illustrated. Examples of amide derivatives include formamide, N-methylformamide, N, N-dimethylformamide, acetamide, N-methylacetamide, N, N-dimethylacetamide, propionamide, benzamide and the like. Examples of imide derivatives include phthalimide, succinimide, maleimide and the like.

  Furthermore, 1 type, or 2 or more types chosen from the basic compound shown by the following general formula (B) -1 can also be added.

（式中、ｎは１、２又は３である。側鎖Ｘは同一でも異なっていてもよく、下記一般式（Ｘ）−１〜（Ｘ）−３で表すことができる。側鎖Ｙは同一又は異種の、水素原子もしくは直鎖状、分岐状又は環状の炭素数１〜２０のアルキル基を示し、エーテル基もしくはヒドロキシル基を含んでもよい。また、Ｘ同士が結合して環を形成してもよい。）

(In the formula, n is 1, 2 or 3. The side chain X may be the same or different and can be represented by the following general formulas (X) -1 to (X) -3. The side chain Y is It represents the same or different hydrogen atom or linear, branched or cyclic alkyl group having 1 to 20 carbon atoms, and may contain an ether group or a hydroxyl group, and Xs may combine to form a ring. May be.)

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

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

  Furthermore, 1 type, or 2 or more types of the basic compound which has the cyclic structure shown by the following general formula (B) -2 can also be added.

（式中、Ｘは前述の通り、Ｒ³⁰⁷は炭素数２〜２０の直鎖状又は分岐状のアルキレン基であり、カルボニル基、エーテル基、エステル基又はスルフィドを１個あるいは複数個含んでいてもよい。）

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

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

  Furthermore, a basic compound containing a cyano group represented by the following general formulas (B) -3 to (B) -6 can be added.

（式中、Ｘ、Ｒ³⁰⁷、ｎは前述の通り、Ｒ³⁰⁸、Ｒ³⁰⁹は同一又は異種の炭素数１〜４の直鎖状又は分岐状のアルキレン基である。）

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

  Specific examples of the basic compound containing a cyano group include 3- (diethylamino) propiononitrile, N, N-bis (2-hydroxyethyl) -3-aminopropiononitrile, N, N-bis (2-acetoxy). Ethyl) -3-aminopropiononitrile, N, N-bis (2-formyloxyethyl) -3-aminopropiononitrile, N, N-bis (2-methoxyethyl) -3-aminopropiononitrile, N , N-bis [2- (methoxymethoxy) ethyl] -3-aminopropiononitrile, methyl N- (2-cyanoethyl) -N- (2-methoxyethyl) -3-aminopropionate, N- (2- Cyanoethyl) -N- (2-hydroxyethyl) -3-aminopropionic acid methyl, N- (2-acetoxyethyl) -N- (2-cyanoethyl) -3-a Methyl nopropionate, N- (2-cyanoethyl) -N-ethyl-3-aminopropiononitrile, N- (2-cyanoethyl) -N- (2-hydroxyethyl) -3-aminopropiononitrile, N- (2-acetoxyethyl) -N- (2-cyanoethyl) -3-aminopropiononitrile, N- (2-cyanoethyl) -N- (2-formyloxyethyl) -3-aminopropiononitrile, N- ( 2-cyanoethyl) -N- (2-methoxyethyl) -3-aminopropiononitrile, N- (2-cyanoethyl) -N- [2- (methoxymethoxy) ethyl] -3-aminopropiononitrile, N- (2-cyanoethyl) -N- (3-hydroxy-1-propyl) -3-aminopropiononitrile, N- (3-acetoxy-1-propyl)- -(2-cyanoethyl) -3-aminopropiononitrile, N- (2-cyanoethyl) -N- (3-formyloxy-1-propyl) -3-aminopropiononitrile, N- (2-cyanoethyl)- N-tetrahydrofurfuryl-3-aminopropiononitrile, N, N-bis (2-cyanoethyl) -3-aminopropiononitrile, diethylaminoacetonitrile, N, N-bis (2-hydroxyethyl) aminoacetonitrile, N, N-bis (2-acetoxyethyl) aminoacetonitrile, N, N-bis (2-formyloxyethyl) aminoacetonitrile, N, N-bis (2-methoxyethyl) aminoacetonitrile, N, N-bis [2- ( Methoxymethoxy) ethyl] aminoacetonitrile, N-cyanomethyl-N- (2-methoxy Methyl) -3-ethylpropionate, methyl N-cyanomethyl-N- (2-hydroxyethyl) -3-aminopropionate, methyl N- (2-acetoxyethyl) -N-cyanomethyl-3-aminopropionate, N-cyanomethyl-N- (2-hydroxyethyl) aminoacetonitrile, N- (2-acetoxyethyl) -N- (cyanomethyl) aminoacetonitrile, N-cyanomethyl-N- (2-formyloxyethyl) aminoacetonitrile, N- Cyanomethyl-N- (2-methoxyethyl) aminoacetonitrile, N-cyanomethyl-N- [2- (methoxymethoxy) ethyl] aminoacetonitrile, N- (cyanomethyl) -N- (3-hydroxy-1-propyl) aminoacetonitrile N- (3-acetoxy-1-propi ) -N- (cyanomethyl) aminoacetonitrile, N-cyanomethyl-N- (3-formyloxy-1-propyl) aminoacetonitrile, N, N-bis (cyanomethyl) aminoacetonitrile, 1-pyrrolidinepropiononitrile, 1-piperidine Propiononitrile, 4-morpholinepropiononitrile, 1-pyrrolidineacetonitrile, 1-piperidineacetonitrile, 4-morpholineacetonitrile, cyanomethyl 3-diethylaminopropionate, N, N-bis (2-hydroxyethyl) -3-aminopropionic acid Cyanomethyl, cyanomethyl N, N-bis (2-acetoxyethyl) -3-aminopropionate, cyanomethyl N, N-bis (2-formyloxyethyl) -3-aminopropionate, N, N-bis (2-methoxy) Til) -3-aminopropionic acid cyanomethyl, N, N-bis [2- (methoxymethoxy) ethyl] -3-aminopropionic acid cyanomethyl, 3-diethylaminopropionic acid (2-cyanoethyl), N, N-bis (2 -Hydroxyethyl) -3-aminopropionic acid (2-cyanoethyl), N, N-bis (2-acetoxyethyl) -3-aminopropionic acid (2-cyanoethyl), N, N-bis (2-formyloxyethyl) ) -3-Aminopropionic acid (2-cyanoethyl), N, N-bis (2-methoxyethyl) -3-aminopropionic acid (2-cyanoethyl), N, N-bis [2- (methoxymethoxy) ethyl] -3-aminopropionic acid (2-cyanoethyl), cyanomethyl 1-pyrrolidinepropionate, 1-piperidinepropion Examples thereof include cyanomethyl acid, cyanomethyl 4-morpholine propionate, 1-pyrrolidinepropionic acid (2-cyanoethyl), 1-piperidinepropionic acid (2-cyanoethyl), and 4-morpholine propionic acid (2-cyanoethyl).

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

  (E) As a dissolution inhibitor for the component, the hydrogen atom of the phenolic hydroxyl group of the compound having a weight average molecular weight of 100 to 1,000 and having two or more phenolic hydroxyl groups in the molecule is formed entirely by an acid labile group. Are preferably substituted at an average ratio of 10 to 100 mol%.

  Examples of such suitably used dissolution inhibitors include bis (4- (2′-tetrahydropyranyloxy) phenyl) methane, bis (4- (2′-tetrahydrofuranyloxy) phenyl) methane, bis ( 4-tert-butoxyphenyl) methane, bis (4-tert-butoxycarbonyloxyphenyl) methane, bis (4-tert-butoxycarbonylmethyloxyphenyl) methane, bis (4- (1′-ethoxyethoxy) phenyl) methane Bis (4- (1′-ethoxypropyloxy) phenyl) methane, 2,2-bis (4 ′-(2 ″ -tetrahydropyranyloxy)) propane, 2,2-bis (4 ′-(2 '' -Tetrahydrofuranyloxy) phenyl) propane, 2,2-bis (4′-tert-butoxyphenyl) propyl Bread, 2,2-bis (4′-tert-butoxycarbonyloxyphenyl) propane, 2,2-bis (4-tert-butoxycarbonylmethyloxyphenyl) propane, 2,2-bis (4 ′-(1 ′) '-Ethoxyethoxy) phenyl) propane, 2,2-bis (4'-(1 ''-ethoxypropyloxy) phenyl) propane, 4,4-bis (4 '-(2' '-tetrahydropyranyloxy) Phenyl) tert-butyl valerate, 4,4-bis (4 ′-(2 ″ -tetrahydrofuranyloxy) phenyl) tert-butyl valerate, 4,4-bis (4′-tert-butoxyphenyl) valeric acid tert-butyl 4,4-bis (4-tert-butoxycarbonyloxyphenyl) valerate tert-butyl 4,4-bis (4′-t rt-butoxycarbonylmethyloxyphenyl) tert-butyl valerate, 4,4-bis (4 ′-(1 ″ -ethoxyethoxy) phenyl) tert-butyl valerate, 4,4-bis (4 ′-(1 '' -Ethoxypropyloxy) phenyl) tert-butyl valerate, tris (4- (2′-tetrahydropyranyloxy) phenyl) methane, tris (4- (2′-tetrahydrofuranyloxy) phenylmethane, tris (4 -Tert-butoxyphenyl) methane, tris (4-tert-butoxycarbonyloxyphenyl) methane, tris (4-tert-butoxycarbonyloxymethylphenyl) methane, tris (4- (1'-ethoxyethoxy) phenyl) methane, Tris (4- (1′-ethoxypropyloxy) phenyl) meta 1,1,2-tris (4 ′-(2 ″ -tetrahydropyranyloxy) phenyl) ethane, 1,1,2-tris (4 ′-(2 ″ -tetrahydrofuranyloxy) phenyl) ethane 1,1,2-tris (4′-tert-butoxyphenyl) ethane, 1,1,2-tris (4′-tert-butoxycarbonyloxyphenyl) ethane, 1,1,2-tris (4′- tert-butoxycarbonylmethyloxyphenyl) ethane, 1,1,2-tris (4 ′-(1′-ethoxyethoxy) phenyl) ethane, 1,1,2-tris (4 ′-(1′-ethoxypropyloxy) ) Phenyl) ethane and the like.

  In addition, the weight average molecular weight of the said compound is 100-1,000, Preferably it is 150-800. The compounding quantity of a dissolution inhibitor is 0-50 parts with respect to 100 parts of base resins, Preferably it is 5-50 parts, More preferably, it is 10-30 parts, It can use individually or in mixture of 2 or more types. If the blending amount is small, the resolution may not be improved. If the blending amount is too large, the pattern film is reduced and the resolution tends to decrease.

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

  Examples of the surfactant include, but are not limited to, polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether, polyethylene stearyl ether, polyoxyethylene cetyl ether, polyoxyethylene olein ether, and polyoxyethylene Polyoxyethylene alkyl allyl ethers such as octylphenol ether and polyoxyethylene nonylphenol, polyoxyethylene polyoxypropylene block copolymers, sorbitan fatty acid esters such as sorbitan monolaurate, sorbitan monopalmitate, sorbitan monostearate, polyoxy Ethylene sorbitan monolaurate, polyoxyethylene sorbitan monopalmitate, polyoxyethylene sorbitan monostearate Nonionic surfactants of polyoxyethylene sorbitan fatty acid esters such as polyoxyethylene sorbitan trioleate and polyoxyethylene sorbitan tristearate, F-top EF301, EF303, EF352 (Tochemputtoc), MegaFuck F171, F172, F173 (Dainippon Ink Chemical Co., Ltd.), Fluorard FC430, FC431 (Sumitomo 3M), Asahi Guard AG710, Surflon S-381, S-382, SC101, SC102, SC103, SC104, SC105, SC106, Surfinol E1004, KH-10, Fluorosurfactants such as KH-20, KH-30, KH-40 (Asahi Glass), organosiloxane polymers KP-341, X-70-092, X-70-093 (Shin-Etsu Chemical) Work), acrylic acid-based or methacrylic acid-based Polyflow No. 75, no. 95 (Kyoeisha Yushi Chemical Industry Co., Ltd.), among which FC430, Surflon S-381, Surfynol E1004, KH-20, KH-30 are preferred. These can be used alone or in combination of two or more.

In order to form a pattern using the resist material of the present invention, a known lithography technique can be employed. For example, it is applied onto a substrate such as a silicon wafer by spin coating or the like so that the film thickness becomes 0.1 to 1.0 μm, and this is applied on a hot plate at 60 to 200 ° C. for 10 seconds to 10 minutes, preferably Pre-bake at 80 to 150 ° C. for 30 seconds to 5 minutes. Next, a mask for forming a target pattern is placed over the resist film, and a high energy beam such as deep ultraviolet light, excimer laser, or X-ray, or an electron beam is applied to an exposure dose of about 1 to 200 mJ / cm ² , preferably 10 After irradiation so as to be about ˜100 mJ / cm ^2, post exposure baking (PEB) is performed on a hot plate at 60 to 150 ° C. for 10 seconds to 5 minutes, preferably 80 to 130 ° C. for 30 seconds to 3 minutes. Furthermore, 0.1 to 5% by mass, preferably 2 to 3% by mass of an aqueous developer solution such as tetramethylammonium hydroxide (TMAH) is used for 10 seconds to 3 minutes, preferably 30 seconds to 2 minutes. A target pattern is formed on the substrate by developing by a conventional method such as a dip method, a paddle method, or a spray method. The material of the present invention is a deep ultraviolet ray or excimer laser of 254 to 120 nm, especially 248 nm of KrF, 193 nm of ArF, 157 nm of F ₂ , 146 nm of Kr ₂ , 134 nm of KrAr, 126 nm of Ar _2. Although it is optimal for fine patterning using a laser such as X-rays and electron beams, exposure with high energy rays having a wavelength of 100 to 180 nm or 1 to 30 nm is particularly preferable. In addition, when deviating from the upper limit and the lower limit of the above range, the target pattern may not be obtained.

  EXAMPLES Hereinafter, although a synthesis example and an Example are shown and this invention is demonstrated concretely, this invention is not restrict | limited to the following Example. In addition, about any polymer, the measurement of the weight average molecular weight (= Mw) and the number average molecular weight (= Mn) was performed using GPC (HLC-8120 and HLC-8220, all manufactured by Tosoh Corporation).

[Synthesis Example 1] Copolymerization of the following monomer 1, monomer 2, and monomer 3 (0.4 / 0.3 / 0.3)
Into a 500 mL flask was charged 8.00 g of the following monomer 1, 5.58 g of the following monomer 2, and 6.42 g of the following monomer 3, dissolved in 6.67 g of ethyl acetate, and sufficiently removing oxygen in the system. 0.230 g of initiator AIBN was added, the temperature was raised to 60 ° C., and a polymerization reaction was performed for 24 hours. In order to purify the polymer obtained, the reaction mixture was poured into hexane to precipitate the polymer obtained. Furthermore, after the obtained polymer was dissolved in tetrahydrofuran (hereinafter abbreviated as THF) and poured into hexane to precipitate the polymer twice, the polymer was separated and dried. The 14.0 g of the white polymer thus obtained (hereinafter abbreviated as polymer 1) has a weight average molecular weight (= Mw) of 9,800 and a dispersity (= Mw / Mn) of 1.7 by GPC. It was confirmed that the polymer was. ^From the measurement results of ¹ H-NMR and ¹⁹ F-NMR, it was found that the abundance ratio of monomer 1, monomer 2 and monomer 3 in polymer 1 was a molar ratio of 0.36: 0.31: 0.33. .

[Synthesis Example 2] Copolymerization of monomer 1, monomer 3, and the following monomer 4 (0.4 / 0.3 / 0.3)
Into a 500 mL flask was charged 7.21 g of monomer 1, 5.79 g of monomer 3, 7.00 g of monomer 4 below, dissolved in 6.67 g of ethyl acetate, and after sufficiently removing oxygen in the system, the initiator 0.207 g of AIBN was added, the temperature was raised to 60 ° C., and a polymerization reaction was performed for 24 hours. In order to purify the polymer obtained, the reaction mixture was poured into hexane to precipitate the polymer obtained. Further, the operation of dissolving the obtained polymer in THF and pouring it into hexane to precipitate the polymer was repeated twice, and then the polymer was separated and dried. The thus obtained 13.7 g of white polymer (hereinafter abbreviated as polymer 2) has a weight average molecular weight (= Mw) of 11,000 and a dispersity (= Mw / Mn) of 1.7 by GPC. It was confirmed that the polymer was. ^From the measurement results of ¹ H-NMR and ¹⁹ F-NMR, it was found that the abundance ratio of monomer 1, monomer 3 and monomer 4 in polymer 2 was a molar ratio of 0.38: 0.31: 0.31. .

[Synthesis Example 3] Copolymerization of monomer 1, monomer 2, and monomer 5 below (0.4 / 0.3 / 0.3)
Into a 500 mL flask was charged 9.18 g of monomer 1, 6.41 g of monomer 2, 4.41 g of monomer 5 below, dissolved in 6.67 g of ethyl acetate, and after sufficiently removing oxygen in the system, the initiator 0.264 g of AIBN was added, the temperature was raised to 60 ° C., and a polymerization reaction was performed for 24 hours. In order to purify the polymer obtained, the reaction mixture was poured into hexane to precipitate the polymer obtained. Further, the operation of dissolving the obtained polymer in THF and pouring it into hexane to precipitate the polymer was repeated twice, and then the polymer was separated and dried. The 12.7 g of the white polymer thus obtained (hereinafter abbreviated as polymer 3) has a weight average molecular weight (= Mw) of 10,500 and a dispersity (= Mw / Mn) of 1.7 by GPC. It was confirmed that the polymer was. ^From the measurement results of ¹ H-NMR and ¹⁹ F-NMR, it was found that the abundance ratio of monomer 1, monomer 2 and monomer 5 in polymer 3 was a molar ratio of 0.35: 0.30: 0.35. .

[Synthesis Example 4] Copolymerization of monomer 1, monomer 4, monomer 5, and the following monomer 6 (0.3 / 0.3 / 0.3 / 0.1)
In a 500 mL flask, 6.38 g of monomer 1, 8.26 g of monomer 4, 4.08 g of monomer 5, and 1.28 g of the following monomer 6 were charged and dissolved in 6.67 g of ethyl acetate. Then, 0.245 g of initiator AIBN was added, the temperature was raised to 60 ° C., and a polymerization reaction was performed for 24 hours. In order to purify the polymer obtained, the reaction mixture was poured into hexane to precipitate the polymer obtained. Further, the operation of dissolving the obtained polymer in THF and pouring it into hexane to precipitate the polymer was repeated twice, and then the polymer was separated and dried. The 13.3 g of the white polymer thus obtained (hereinafter abbreviated as polymer 4) has a weight average molecular weight (= Mw) of 9,500 and a dispersity (= Mw / Mn) of 1.7 by GPC. It was confirmed that the polymer was. ^From the measurement results of ¹ H-NMR and ¹⁹ F-NMR, the abundance ratio of monomer 1, monomer 4, monomer 5, monomer 6 in polymer 4 was 0.31: 0.28: 0.33: 0.08 mole. It turned out to be a ratio.

[Synthesis Example 5] Copolymerization of monomer 1, monomer 4, and the following monomer 7 (0.4 / 0.3 / 0.3)
A 500 mL flask was charged with 8.00 g of monomer 1, 7.77 g of monomer 4, and 4.23 g of monomer 7 below, dissolved in 6.67 g of ethyl acetate, and after sufficiently removing oxygen in the system, an initiator 0.230 g of AIBN was added, the temperature was raised to 60 ° C., and a polymerization reaction was performed for 24 hours. In order to purify the polymer obtained, the reaction mixture was poured into hexane to precipitate the polymer obtained. Further, the operation of dissolving the obtained polymer in THF and pouring it into hexane to precipitate the polymer was repeated twice, and then the polymer was separated and dried. The thus obtained 12.9 g of a white polymer (hereinafter abbreviated as polymer 5) has a weight average molecular weight (= Mw) of 12,500 and a dispersity (= Mw / Mn) of 1.7 by GPC. It was confirmed that the polymer was. ^From the measurement results of ¹ H-NMR and ¹⁹ F-NMR, it was found that the abundance ratio of monomer 1, monomer 4 and monomer 7 in polymer 5 was a molar ratio of 0.37: 0.30: 0.33. .

[Evaluation example]
Measurement of polymer permeability 1 g of the above-described polymers 1 to 5 and the following polymer 6 (FPR-200 manufactured by Asahi Glass Co., Ltd .: weight average molecular weight (= Mw) 14,000, dispersity (= Mw / Mn) 2.5) are propylene. A polymer solution was prepared by sufficiently dissolving in 20 g of glycol monomethyl ether acetate (hereinafter abbreviated as PGMEA) and filtering through a 0.2 μm filter.

As a polymer for a comparative example, a polymer was prepared in which 30 mol% of the hydroxyl group of monodisperse polyhydroxystyrene having a molecular weight (= Mw) of 10,000 and a dispersity (= Mw / Mn) of 1.1 was substituted with a tetrahydropyranyl group. This was designated as Comparative Example Polymer 1. Similarly, a polymethyl methacrylate having a molecular weight (= Mw) of 15,000 and a dispersity (= Mw / Mn) of 1.7 is used as a polymer for comparative example 2, with a meta / para ratio of 40/60 and a molecular weight (= Mw) of 9,000. A polymer solution was prepared in the same manner as described above using a novolak polymer having a dispersity (= Mw / Mn) of 2.5 as a comparative polymer 3.
The polymer solution was spin-coated on the MgF ₂ substrate and applied, and then baked at 100 ° C. for 90 seconds using a hot plate to form a polymer film having a thickness of 100 nm on the MgF ₂ substrate. This substrate was placed in a vacuum ultraviolet photometer (manufactured by JASCO Corporation, VUV-200S), and transmittances at 248 nm, 193 nm, and 157 nm were measured. The measurement results are shown in Table 1. Table 1 shows that the resist material using the polymer compound of the present invention can ensure sufficient transparency even at a wavelength of F ₂ (157 nm).

Resist preparation and exposure liquids 1 to 6 and the components shown below were used in the amounts shown in Table 2 to prepare resist solutions by conventional methods.
Next, after spin-coating the resist solution obtained on a silicon wafer on which DUV-30 (manufactured by Brewer Science) was formed to a film thickness of 85 nm, the resist solution was baked at 120 ° C. for 90 seconds using a hot plate. The thickness was 200 nm. This was exposed with an F ₂ laser (VUVES, manufactured by RISOTEC Co., Ltd.) while changing the exposure amount, immediately after exposure, baked at 120 ° C. for 90 seconds, and developed with an aqueous solution of 2.38% by mass of tetramethylammonium hydroxide for 60 seconds. The relationship between the exposure amount and the remaining film rate was determined. Further, the exposure amount at which the film thickness became 0 was determined as E _th , and the tan θ of the inclination at that time was determined as γ. Furthermore, exposure is performed using a KrF scanner (S203B, manufactured by Nikon, NA 0.68, σ0.75, 2/3 annular illumination, Cr mask), and the minimum resolution is 150 nm line and space 1: 1. The pattern of the mask dimension was obtained and used as the limit resolution. These data are summarized in Table 2.
As a result of VUVES exposure, it was found that the film thickness decreased as the exposure amount increased and exhibited the characteristics of a positive resist.

Claims (10)

A weight average molecular weight of 1,000 to 500, which necessarily contains a repeating unit represented by the following general formula (1) and further contains at least one repeating unit selected from the following general formulas (2a) to (2d): 1,000 polymer compounds.

(In the formula, R ¹ is a fluorine atom or a fluorinated alkyl group having 1 to 4 carbon atoms. R ² is a single bond, a linear, branched or cyclic alkylene group having 1 to 20 carbon atoms, or is a fluorinated alkylene group .R ³ and R ⁴ are a hydrogen atom, a fluorine atom, or a straight, an alkyl group or a fluorinated alkyl group branched or cyclic, R ³ and At least one of R ⁴ contains one or more fluorine atoms, R ⁵ is a hydrogen atom or an acid labile group, R ⁶ is an acid labile group, an adhesive group, or a straight chain having 1 to 20 carbon atoms. A branched or cyclic alkyl group or a fluorinated alkyl group, a is 1 or 2.)   The polymer compound according to claim 1, wherein the acid labile group is selected from groups represented by the following general formulas (AL-1) to (AL-3).

(Wherein R ⁸ , R ⁹ , R ^Ten Are the same or different linear, branched or cyclic hydrocarbon groups having 1 to 20 carbon atoms, which may contain heteroatoms such as oxygen, sulfur and nitrogen, and are bridged cyclic hydrocarbon groups. Also good. Or R ⁸ And R ⁹ , R ⁸ And R ^Ten , R ⁹ And R ^Ten May be bonded to each other to form a ring having 3 to 20 carbon atoms together with the carbon atom to which they are bonded. R ¹¹ And R ¹⁴ Is a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms and may contain heteroatoms such as oxygen, sulfur, nitrogen and fluorine. R ¹² And R ¹³ Is a hydrogen atom or a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms, and may contain heteroatoms such as oxygen, sulfur, nitrogen and fluorine. R ¹² And R ¹³ , R ¹² And R ¹⁴ , R ¹³ And R ¹⁴ May be bonded to each other to form a ring having 3 to 20 carbon atoms together with the carbon atom to which they are bonded. c is an integer of 0-6. )   Furthermore, the high molecular compound of Claim 1 or 2 containing the repeating unit chosen from following formula (4a)-(4h).

(Wherein R ²⁹ Is a hydrogen atom or an acid labile group as described above. R ³⁰ ~ R ³⁴ Is a hydrogen atom, a fluorine atom, or a fluorinated alkyl group having 1 to 4 carbon atoms, and R ³⁰ ~ R ³⁴ Of which contains at least one fluorine atom. R ³⁵ And R ³⁶ Is a hydrogen atom, a methyl group, or a trifluoromethyl group. ) Resist material you characterized by containing the claim 1, 2 or 3 polymer compound according. A resist material comprising a mixture of the polymer compound according to claim 1 , 2 or 3 and a polymer compound containing a repeating unit represented by the following general formulas (3a) to (3c).

(In the formula, R ⁷ is a hydrogen atom or an acid labile group. 0 <b1 <1, 0 <b2 <1, 0 ≦ b3 <1, 0 <b1 + b2 + b3 ≦ 1.) Furthermore,
(B) an organic solvent,
(C) The positive resist material according to claim 4 or 5, wherein it is a chemically amplified positive type containing an acid generator. Furthermore, (D) The resist material of Claim 6 containing a basic compound. The resist material according to claim 6 or 7 , further comprising (E) a dissolution inhibitor. (1) A step of applying the resist material according to any one of claims 4 to 8 on a substrate;
(2) Next, after the heat treatment, a step of exposing with a high energy ray having a wavelength of 100 to 180 nm band or 1 to 30 nm band through a photomask;
(3) A pattern forming method comprising a step of performing heat treatment as necessary and then developing using a developer. The pattern forming method according to claim 9, wherein the high energy beam is an F ₂ laser, an Ar ₂ laser, or a soft X-ray.