JP4623315B2 - 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 high projection lens NA, improved resist performance, and shorter wavelength. With regard to higher resolution and higher sensitivity of resists, 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. (Cited 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 study of the 0.15 micron rule has begun, and the momentum of miniaturization is increasingly accelerated.

  For ArF (193 nm), processing with a design rule of 0.13 μm or less is expected. However, since the conventionally used resins such as novolak resins and polyvinylphenols have very strong absorption around 193 nm, they are used for resists. It cannot be used as a base resin. Therefore, acrylic resins and cycloolefin-based alicyclic resins have been studied in order to ensure transparency and necessary dry etching resistance (cited documents 3 to 6: JP-A-9-73173 and JP-A-10). No. -10739, JP-A-9-230595, pamphlet of International Publication No. 97/33198).

As for F ₂ (157 nm), miniaturization of 0.10 μm or less is expected, but it becomes increasingly difficult to ensure transparency, and acrylic resin that is a base polymer for ArF does not transmit light at all, and cycloolefin 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 near 160 nm and slightly improves the transmittance, but is far from a practical level.

Here, in non-cited document 1: SPIE2001 lecture number 4345-31 Polymer design for 157-nm chemically amplified resists, αCF ₃ t-butyl acrylate and 5- (2-hydroxy-2,2-bistrifluoromethyl) ethyl-2 -Copolymerization with norbornene and copolymerization of αCF ₃ t-butyl acrylate and 3- (hydroxybistrifluoromethyl) methylstyrene were reported to be highly transparent and resist polymers with excellent dry etching resistance. However, even in this case, the absorbance is about 2 to 3. In the above report, only a pattern formation example having a film thickness of about 1000 mm has been reported, and it is necessary to further improve the transmittance. It is said that an absorbance of 2 or less is required to obtain a rectangular pattern of 2000 mm or more. However, a material satisfying all the characteristics such as dry etching resistance, alkali solubility, adhesion, and transparency has not yet been reported.
In addition, in order to process the base with an extremely thin resist pattern having a thickness of 1000 to 1500 mm, a resist material having high etching resistance is required.

  The polymerization method of the polymer of α-trifluoromethylacrylic acid derivative is described in Non-cited Document 2: A. C. S Macromolecules 1982, 15, 915-920, and has been studied as a resist application for main chain decomposition type electron beam exposure.

  Reference 7: Japanese Patent Laid-Open No. 9-43848 proposes α-trifluoromethyl acrylate ester having a cyclic structure. This is also proposed as a non-chemically amplified resist for main chain decomposition.

  By the way, the tertiary ester type has been mainly used as the acid labile group of the acrylic acid ester. The secondary ester has almost no acid detachability and has been used as an acid stabilizing group for improving etching resistance. For example, non-cited document 3: SPIE Vol. 1672 p66 (1992) shows the etching resistance of bicyclo [2.2.1] heptan-2-yl methacrylate polymer, but this group is not used as an acid labile group. In the same report, the etching resistance of 1-adamantane methacrylate polymer is also shown. Although 1-adamantane methacrylate has a tertiary carbon ester moiety, 1-adamantane does not function as an acid leaving group because it cannot produce an internal olefin. Therefore, a positive resist pattern is obtained by copolymerization with t-butyl methacrylate.

  Non-cited document 4: SPIE Vol. In 2724 p334 (1996), isoboronyl methacrylate is shown to undergo acid elimination, and elimination of secondary carbonized esters has been reported.

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 Japanese Patent Laid-Open No. 9-43848 SPIE 2001 Lecture Number 4345-31 Polymer design for 157-nm chemically amplified resists A. C. S Macromolecules 1982, 15, 915-920 SPIE Vol. 1672 p66 (1992) SPIE Vol. 2724 p334 (1996)

  Here, the present inventors paid attention to the acid elimination of the secondary ester-substituted product of 1-alkylbicyclo [2.2.1] heptan-2-yl α-trifluoromethyl acrylic ester. Copolymerization of 1-alkylbicyclo [2.2.1] heptan-2-yl alpha trifluoromethyl acrylic ester and cycloolefin, or hexafluoroalcohol pendant styrene copolymer, the ester moiety is eliminated by acid and alkali We paid attention to the fact that it should be soluble and become a promising material as a positive resist.

The present invention has been made in view of the above circumstances, and is only excellent in transmittance in vacuum ultraviolet light of 300 nm or less, particularly F ₂ (157 nm), Kr ₂ (146 nm), KrAr (134 nm), Ar ₂ (126 nm) and the like. In addition, it is an object of the present invention to provide a novel polymer compound useful as a base polymer of a resist material excellent in etching resistance, particularly a chemically amplified resist material, and a pattern forming method using the resist material containing the same.

  As a result of intensive studies to achieve the above object, the inventors of the present invention have found that a copolymer of 1-alkylbicyclo [2.2.1] heptan-2-yl α-trifluoromethylacrylic ester monomer and hexafluoroisopropanol styrene. It has been found that by using a polymer as a base polymer, a resist material can be obtained in which the transparency is dramatically improved and the dry etching resistance can be secured, and the present invention has been made.

（式中、Ｒ¹はフッ素原子又は少なくとも１個以上のフッ素原子を有する炭素数１〜１５の直鎖状、分岐状又は環状のアルキル基である。Ｒ²は炭素数１〜１５の直鎖状、分岐状又は環状のアルキル基又はフッ素化アルキル基を示す。Ｒ³はメチレン基、エチレン基、酸素原子、又は硫黄原子を示す。ａは０〜２の整数である。Ｒ⁸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されたアルキル基である。Ｒ⁹は単結合、又は炭素数１〜４の２価の炭化水素基、Ｒ¹⁰、Ｒ¹¹は同一もしくは異種で、水素原子、フッ素原子、又は炭素数１〜４のアルキル基又はフッ素化されたアルキル基であり、Ｒ¹⁰、Ｒ¹¹のどちらか一方又は両方に少なくとも１個以上のフッ素原子を含む。Ｒ¹²は水素原子、又は炭素数１〜１０の直鎖状、分岐状もしくは環状のアルキル基であり、又は酸不安定基であってもよい。Ｒ¹³は水素原子、又はメチル基である。ｍ、ｐは各繰り返し単位の存在比を示し、ｍ＋ｐ＝１において、ｍは０．１〜０．９、ｐは０．１〜０．９である。ｄは０〜４の整数であり、ｅは１〜３の整数である。）
請求項２：
Ｒ¹がトリフルオロメチル基であることを特徴とする請求項１記載の高分子化合物。
請求項３：
請求項１又は２記載の高分子化合物を含むことを特徴とするレジスト材料。
請求項４：
（Ａ）請求項１又は２記載の高分子化合物、
（Ｂ）有機溶剤、
（Ｃ）酸発生剤
を含有することを特徴とする化学増幅ポジ型レジスト材料。
請求項５：
更に塩基性化合物を含有する請求項４記載のレジスト材料。
請求項６：
更に溶解阻止剤を含有する請求項４又は５記載のレジスト材料。
請求項７：
（１）請求項３乃至６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８：
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７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 polymer compound having a repeating unit (m unit and p unit) represented by the following general formula (2).

(Wherein R ¹ is a fluorine atom or a linear, branched or cyclic alkyl group having 1 to 15 carbon atoms having at least one fluorine atom. R ² is a linear chain having 1 to 15 carbon atoms. R ³ represents a methylene group, an ethylene group, an oxygen atom, or a sulfur atom, a is an integer of 0 to 2, and R ⁸ is a hydrogen atom. , A fluorine atom, a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms or a fluorinated alkyl group, R ⁹ is a single bond or a divalent hydrocarbon having 1 to 4 carbon atoms. Groups R ¹⁰ and R ¹¹ are the same or different and are a hydrogen atom, a fluorine atom, an alkyl group having 1 to 4 carbon atoms or a fluorinated alkyl group, and one or both of R ¹⁰ and R ¹¹ are comprising at least one fluorine atom .R ¹² are hydrogen atoms , Or a straight, a branched or cyclic alkyl group, or an acid labile group is a good .R ¹³ be a hydrogen atom or a methyl group .m, p is the The abundance ratio of repeating units is shown, and m + p = 1, m is 0.1 to 0.9, p is 0.1 to 0.9, d is an integer of 0 to 4, and e is 1 to 3 Is an integer.)
Claim 2:
The polymer compound according to claim 1, wherein R ¹ is a trifluoromethyl group.
Claim 3:
A resist material comprising the polymer compound according to claim 1.
Claim 4:
(A) The polymer compound according to claim 1 or 2,
(B) an organic solvent,
(C) A chemically amplified positive resist material containing an acid generator.
Claim 5:
The resist material according to claim 4, further comprising a basic compound.
Claim 6:
The resist material according to claim 4 or 5, further comprising a dissolution inhibitor.
Claim 7:
(1) A step of applying the resist material according to any one of claims 3 to 6 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 8:
The pattern forming method according to claim 7, wherein the high energy beam is an F ₂ laser, an Ar ₂ laser, or a soft X-ray.

The resist material of the present invention is sensitive to high energy rays, has excellent sensitivity at a wavelength of 200 nm or less, particularly 170 nm or less, and also has an acrylate monomer containing a fluorinated alkyl group at the α-position and a norbornene derivative or hexagonal derivative. It was found that by using a copolymer of a fluoroisopropanol group-substituted styrene derivative as the base resin, the transparency of the resist was improved and at the same time, it had excellent plasma etching resistance. 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 excimer 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.
According to the study by the present inventors, as a method for improving the transmittance around 157 nm, it is considered that the reduction of the number of carbonyl groups and carbon-carbon double bonds is one method. It has been found that the introduction of fluorine atoms greatly contributes to the improvement of transmittance. In fact, a polymer in which fluorine is introduced into the aromatic ring of polyvinylphenol was able to obtain a transmittance close to practical use. However, it became clear that this base polymer was negatively developed by irradiation with high energy light of an F ₂ laser, and it was found difficult to put it into practical use as a resist. On the other hand, it was found that a polymer in which fluorine was introduced into a polymer compound containing an aliphatic resin derived from an acrylic resin or a norbornene derivative in the main chain can suppress absorption and lower the problem of negativity. .

  In the present invention, a copolymer of an acrylate ester monomer having a fluorinated alkyl group and an alicyclic structure at the α-position as shown by the following general formula (1) or (2), and a norbornene derivative or hexafluoroisopropanol styrene Has been found to have excellent dry etching resistance in addition to ensuring high transparency in the vicinity of 157 nm.

（式中、Ｒ¹はフッ素原子又は少なくとも１個以上のフッ素原子を有する炭素数１〜１５の直鎖状、分岐状又は環状のアルキル基である。Ｒ²は炭素数１〜１５の直鎖状、分岐状又は環状のアルキル基又はフッ素化アルキル基を示す。Ｒ³はメチレン基、エチレン基、酸素原子、又は硫黄原子を示す。ａは０〜２の整数である。Ｒ^4a、Ｒ^4b、Ｒ^5a及びＲ^5bは水素原子、水酸基、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、（ＣＨ₂）_cＣＯ₂Ｒ⁶、又は（ＣＨ₂）_cＣ（Ｒ⁷）₂（ＯＲ⁶）である。Ｒ⁶は酸不安定基、密着性基、水素原子、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されたアルキル基である。また、Ｒ^4a、Ｒ^4b、Ｒ^5a及びＲ^5bはこれらの２つが結合して環を形成していてもよい。環を形成する場合は、酸素原子又はエステル基を含んでもよい炭素数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る。Ｒ⁷は水素原子、フッ素原子、同一又は異種の炭素数１〜２０の直鎖状、分岐状もしくは環状のアルキル基又はフッ素化されたアルキル基であり、少なくとも１個以上のフッ素原子を含む。０＜ｍ＜１、０＜ｎ＜１であり、０＜ｍ＋ｎ≦１である。ｂは０又は１であり、ｃは０〜６の整数である。）

(Wherein R ¹ is a fluorine atom or a linear, branched or cyclic alkyl group having 1 to 15 carbon atoms having at least one fluorine atom. R ² is a linear chain having 1 to 15 carbon atoms. R ³ represents a methylene group, an ethylene group, an oxygen atom, or a sulfur atom, and a is an integer of 0 to 2. R ^4a , R ^4b , R ^5a and R ^5b are a hydrogen atom, a hydroxyl group, a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms or a fluorinated alkyl group, (CH ₂ ) _c CO ₂ R ⁶ , or (CH ₂ ) _c C (R ⁷ ) ₂ (OR ⁶ ), wherein R ⁶ is an acid labile group, an adhesive group, a hydrogen atom, or a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms, or it is a fluorinated alkyl group. in ^{addition, R 4a, R 4b, R} 5a and R ^5b are of 2 In the case of forming a ring, a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms which may contain an oxygen atom or an ester group, or a fluorinated alkyl group. R ⁷ is a hydrogen atom, a fluorine atom, the same or different linear, branched or cyclic alkyl group having 1 to 20 carbon atoms or a fluorinated alkyl group, and at least one fluorine atom Including atoms. 0 <m <1, 0 <n <1, 0 <m + n ≦ 1, b is 0 or 1, and c is an integer of 0 to 6.)

（式中、Ｒ¹〜Ｒ³、ａは前述の通り、Ｒ⁸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されたアルキル基である。Ｒ⁹は単結合、又は炭素数１〜４の２価の炭化水素基、Ｒ¹⁰、Ｒ¹¹は同一もしくは異種で、水素原子、フッ素原子、又は炭素数１〜４のアルキル基又はフッ素化されたアルキル基であり、Ｒ¹⁰、Ｒ¹¹のどちらか一方又は両方に少なくとも１個以上のフッ素原子を含む。Ｒ¹²は水素原子、又は炭素数１〜１０の直鎖状、分岐状もしくは環状のアルキル基であり、又は酸不安定基であってもよい。Ｒ¹³は水素原子、又はメチル基である。０＜ｍ＜１、０＜ｐ＜１であり、０＜ｍ＋ｐ≦１である。ｄは０〜４の整数であり、ｅは１〜３の整数である。）

(Wherein R ^{1 to} R ³ and a are as described above, R ⁸ is a hydrogen atom, a fluorine atom, a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms, or a fluorinated alkyl group. R ⁹ is a single bond or a divalent hydrocarbon group having 1 to 4 carbon atoms, R ¹⁰ and R ¹¹ are the same or different, and are a hydrogen atom, a fluorine atom, or an alkyl group having 1 to 4 carbon atoms, or A fluorinated alkyl group containing at least one fluorine atom in either or both of R ¹⁰ and R ¹¹ , wherein R ¹² is a hydrogen atom or a straight or branched chain having 1 to 10 carbon atoms Alternatively, it may be a cyclic alkyl group or an acid labile group, and R ¹³ is a hydrogen atom or a methyl group, 0 <m <1, 0 <p <1, and 0 <m + p ≦ 1 D is an integer of 0 to 4, and e is an integer of 1 to 3.)

  Here, as the alkyl group, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, tert-butyl group, pentyl group, cyclopentyl group, hexyl group, cyclohexyl group, octyl group, A decyl group, a dodecyl group, etc. are mentioned. Examples of the alkyl group and fluorinated alkyl group having a fluorine atom include groups in which part or all of the hydrogen atoms of the alkyl group have been substituted with fluorine atoms. Moreover, as an alkylene group, what remove | eliminated one hydrogen atom from the said alkyl group is mentioned.

Various acid labile groups for R ⁶ and R ¹² are selected, and examples thereof include tertiary hydrocarbon groups having 4 to 20 carbon atoms as shown in the following general formula (AL-1).

Here, R ¹⁵ , R ¹⁶ , and R ¹⁷ are the same or different monovalent hydrocarbon groups having 1 to 20 carbon atoms, such as linear, branched, and cyclic alkyl groups and alkenyl groups. It may be a hydrocarbon group. R ¹⁵ and R ¹⁶ , R ¹⁶ and R ¹⁷ , R ¹⁵ and R ¹⁷ may be bonded to each other to form a ring together with the carbon atom to which they are bonded. In the case of forming a ring, one in which one hydrogen atom is eliminated from the hydrocarbon group can be exemplified. Note that the cyclic structure has a higher effect of improving etching resistance, and the cyclic structure may be a monocyclic structure, but the bridged cyclic structure can further improve the etching resistance. In addition, an acid leaving group having a cyclic structure introduced therein has high elimination reactivity and can improve contrast, that is, γ of dissolution. Specifically, what is shown in the following formula can be exemplified.

（式中、Ｒ²¹及びＲ²²は炭素数１〜６のヘテロ原子を含んでもよい１価炭化水素基を示す。この場合、ヘテロ原子としては、酸素原子、硫黄原子、窒素原子を挙げることができ、−ＯＨ、−ＯＲ²⁵、−Ｏ−、−Ｓ−、−Ｓ（＝Ｏ）−、−ＮＨ₂、−ＮＨＲ²⁵、−Ｎ（Ｒ²⁵）₂、−ＮＨ−、−ＮＲ²⁵−などの形態で含有又は介在することができる。Ｒ²⁵は炭素数１〜１０の直鎖状、分岐状又は環状のアルキル基を示す。）

(In the formula, R ²¹ and R ²² each represent a monovalent hydrocarbon group that may contain a hetero atom having 1 to 6 carbon atoms. In this case, examples of the hetero atom include an oxygen atom, a sulfur atom, and a nitrogen atom. ^{can, -OH, -OR 25, -O -} , - S -, - S (= O) -, - NH 2, -NHR 25, -N (R 25) 2, -NH -, - NR 25 - , etc. R ²⁵ represents a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms.)

Specific examples of R ²¹ and R ²² include methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, sec-butyl group, n-pentyl group, n-hexyl group, cyclopropyl group, cyclopropylmethyl. Examples thereof include linear, branched or cyclic alkyl groups such as a group, cyclobutyl group, cyclopentyl group, and cyclohexyl group. Examples of R ²³ and R ²⁴ include a hydrogen atom, a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms, a hydroxyalkyl group, an alkoxyalkyl group, an alkoxy group, an alkoxyalkoxy group, and the like. Examples include methyl, hydroxymethyl, ethyl, hydroxyethyl, propyl, isopropyl, n-butyl, sec-butyl, n-pentyl, n-hexyl, methoxy, methoxymethoxy Ethoxy group, tert-butoxy group and the like.

  Furthermore, acid labile groups represented by the following general formulas (AL-10) and (AL-11) may be used.

In the formulas (AL-10) and (AL-11), R ²⁶ and R ²⁹ are linear, branched or cyclic alkyl groups having 1 to 20 carbon atoms, and heteroatoms such as oxygen, sulfur, nitrogen and fluorine. May be included.

R ²⁷ and R ²⁸ are a hydrogen atom or a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms, and may contain a heteroatom such as oxygen, sulfur, nitrogen, fluorine, and f is 0 to 0. It is an integer of 10. R ²⁷ and R ²⁸ , R ²⁷ and R ²⁹ , and R ²⁸ and R ²⁹ may be bonded to each other to form a ring together with the carbon atom and oxygen atom to which they are bonded. Specific examples of the compound represented by the formula (AL-10) include tert-butoxycarbonyl group, tert-butoxycarbonylmethyl group, tert-amyloxycarbonyl group, tert-amyloxycarbonylmethyl group, 1-ethoxyethoxycarbonyl. Examples thereof include a methyl group, a 2-tetrahydropyranyloxycarbonylmethyl group, a 2-tetrahydrofuranyloxycarbonylmethyl group, and the like, and substituents represented by the following general formulas (AL-10) -1 to (AL-10) -9. .

In formulas (AL-10) -1 to (AL-10) -9, R ³⁰ is the same or different, straight-chain, branched or cyclic alkyl group having 1 to 8 carbon atoms, aryl having 6 to 20 carbon atoms. A group or an aralkyl group; R ³¹ represents a hydrogen atom or a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms. R ³² represents a linear, branched or cyclic alkyl group having 2 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, or an aralkyl group.

  Examples of the acetal compound represented by the formula (AL-11) are (AL-11) -1 to (AL-11) -23.

  In addition, the base resin may be intermolecularly or intramolecularly crosslinked by an acid labile group represented by the general formula (AL-11a) or (AL-11b).

In the formula, R ³³ and R ³⁴ represent a hydrogen atom or a linear, branched or cyclic alkyl group having 1 to 8 carbon atoms. Alternatively, R ³³ and R ³⁴ may be bonded to form a ring, and when forming a ring, R ³³ and R ³⁴ represent a linear or branched alkylene group having 1 to 8 carbon atoms. R ³⁵ is a linear, branched or cyclic alkylene group having 1 to 10 carbon atoms, g and h are 0 or 1 to 10, preferably 0 or an integer of 1 to 5, and i is an integer of 1 to 7. . A represents an (i + 1) -valent aliphatic or alicyclic saturated hydrocarbon group having 1 to 50 carbon atoms, an aromatic hydrocarbon group or a heterocyclic group, and these groups may intervene a hetero atom, Alternatively, a part of hydrogen atoms bonded to the carbon atom may be substituted with a hydroxyl group, a carboxyl group, a carbonyl group, or a fluorine atom. B represents —CO—O—, —NHCO—O— or —NHCONH—.

  In this case, preferably, A is a divalent to tetravalent C1-20 linear, branched or cyclic alkylene group, an alkyltriyl group, an alkyltetrayl group, or an arylene group having 6 to 30 carbon atoms. In these groups, a hetero atom may be interposed, and a part of hydrogen atoms bonded to the carbon atom may be substituted with a hydroxyl group, a carboxyl group, an acyl group, or a halogen atom. I is preferably an integer of 1 to 3.

  Specific examples of the cross-linked acetal groups represented by the general formulas (AL-11a) and (AL-11b) include those represented by the following formulas (AL-11) -24 to (AL-11) -31.

  Although the specific example of the repeating unit (m) in General formula (1) or (2) of this invention is shown below, it is not limited to this.

  The elimination mechanism of the secondary carbon ester acid labile group of the present invention is shown below. The elimination mechanism of the tertiary carbon ester acid labile group is shown in the formula 1). It is considered that the following cations 1) -2 and 1) -3 are generated as intermediates in the elimination reaction. The reaction rate of acid elimination is considered to be governed by the stability of the cation intermediate, particularly 1) -3. On the other hand, in the case of the secondary carbon ester shown in 2), the intermediate cation, especially 2) -3, is unstable and returns to the original ester state, so that the elimination reaction does not proceed. However, the intermediate cation 3) -3 with an alkyl group at the 1-position of norbornene has increased stability and accelerated elimination reaction.

  Here, the monomer for superposing | polymerizing the repeating unit (m) in General formula (1) or (2) of this invention can be mentioned below.

  The production of the monomer can be performed, for example, in the following steps, but is not limited thereto.

Here, R ^{1 to} R ³ and a are the same as above. The reaction proceeds easily under known conditions. Preferably, an olefin containing an alicyclic group, acrylic acid having fluorine at the α-position, and a catalytic amount of concentrated sulfuric acid are added sequentially or simultaneously in a solvent such as toluene. The reaction is carried out at room temperature, the usual work-up is followed by distillation and the product is isolated. In this reaction, as shown in formula (i), in addition to the case of using an olefin having an alicyclic group corresponding to the product as a raw material, a synthesis method using a rearrangement reaction as shown in formula (ii) Available.

  In the present invention, the repeating unit (m) has 1-alkylbicyclo [2.2.1] heptan-2-yl α-trifluoromethyl acrylic ester, which is substituted with a conventionally proposed acid labile group. Further, α-trifluoromethyl acrylic ester can be further copolymerized.

  Here, in the general formula (1), specific examples of the repeating unit (n) can be listed below.

  Specific examples of the repeating unit (p) in the general formula (2) include the following.

  The polymer compound of the present invention contains a repeating unit (n) or (p) containing an acid-elimination monomer and an adhesive group of the repeating unit (m) represented by the general formula (1), but further improves the adhesion. The following copolymerization monomer can be added.

In the formula, R ³⁶ , R ³⁷ and R ³⁸ are a hydrogen atom, a fluorine atom, a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms or a fluorinated alkyl group. In particular, R ³⁸ is preferably a trifluoromethyl group.

（式中、Ｒ³⁹は水素原子、ヒドロキシ基、又は炭素数１〜１０の直鎖状、分岐状又は環状のアルキル基を示し、０≦ｈ≦４、０≦ｉ≦４である。Ｒ⁴⁰は水素原子又はメチル基である。）
更に透過率向上のための下記繰り返し単位を共重合させることもできる。 Further, the following adhesive groups can be copolymerized.

(Wherein, R ³⁹ represents a hydrogen atom, hydroxy group, or a straight, branched or cyclic alkyl group, .R ⁴⁰ is 0 ≦ h ≦ 4,0 ≦ i ≦ 4 Is a hydrogen atom or a methyl group.)
Furthermore, the following repeating units for improving the transmittance can be copolymerized.

Here, R ^{36 to} R ³⁸ are the same as described above, R ^{41 to} R ⁴⁴ are a fluorine atom, a hydrogen atom, or a fluorinated alkyl group having 1 to 4 carbon atoms, and at least one of R ^{41 to} R ⁴⁴ is included. Contains one or more fluorine atoms.
R ⁴⁵ and R ⁴⁶ are a hydrogen atom, a methyl group, or a trifluoromethyl group.
R ⁴⁷ is a linear, branched or cyclic fluorinated alkyl group having 1 to 20 carbon atoms, wherein part or all of the hydrogen atoms of the alkyl group are substituted with fluorine atoms, and trifluoro Methyl group, 2,2,2-trifluoroethyl group, 3,3,3-trifluoropropyl group, 1,1,1,3,3,3-hexafluoroisopropyl group, 1,1,2,2, In addition to 3,3,3-heptafluoropropyl group, 2,2,3,3,4,4,5,5-octafluoropentyl group and the like, groups represented by the following formulas are also used.

（式中、Ｒ⁴⁸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されたアルキル基であり、０≦ｆ≦１０である。）

(In the formula, R ⁴⁸ is a hydrogen atom, a fluorine atom, a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms or a fluorinated alkyl group, and 0 ≦ f ≦ 10.)

Cycloolefin or styrene pendant with hexafluoroalcohol may be polymerized while remaining as a hydroxy group, or after substitution with an acetyl group, the acetoxy group may be eliminated with alkaline water after polymerization. An acetoxy group can also be used as an adhesive group. In addition, cycloolefin pendant with hexafluoroalcohol or hydroxy group of styrene may be substituted with acetal such as ethoxyethoxy group to perform polymerization, and after polymerization, ethoxyethoxy group may be eliminated with weak acid. It can also be used as an acid labile group.
In the present invention, a secondary ester repeating unit of 1-alkylbicyclo [2.2.1] heptan-2-yl α-trifluoromethyl acrylic ester is an essential component, and a substituted or unsubstituted hexafluoroalcohol is pendant. It is a binary copolymer with a cycloolefin or a styrene copolymer, but is a ternary copolymer or a quaternary copolymer with a repeating unit containing the adhesive group, a repeating unit for improving transparency. May be. Also, two or more polymers having different molecular weights, dispersities, and copolymerization ratios may be blended. Further, conventionally proposed polymers such as αCF ₃ acrylic acid and norbornene derivative copolymers having tertiary ester acid leaving groups, αCF ₃ acrylic acid and styrene derivative copolymers, polynorbornene, polyacrylic acid, metathesis ring-opening polymers It may be a polymer blend.

  When synthesizing the polymer compound of the present invention, α-trifluoromethyl acrylate monomer, norbornene derivative or hexafluoroisopropanol styrene, and if necessary, an adhesion improving monomer and a transparency improving monomer are dissolved in a solvent, a catalyst is added, In some cases, the polymerization reaction is carried out with heating, cooling or pressurization. The polymerization reaction is also governed by the type of initiator (or catalyst), the starting method (light, heat, radiation, plasma, etc.), the polymerization conditions (temperature, pressure, concentration, solvent, additives), etc. In the polymerization of the polymer compound of the present invention, radical copolymerization in which polymerization is initiated by a radical such as AIBN, ionic polymerization (anionic polymerization) using a catalyst such as alkyllithium, and the like are common. These polymerizations can be carried out according to conventional methods.

  The radical polymerization initiator is not particularly limited, and examples thereof include 2,2′-azobis (4-methoxy-2,4-dimethylvaleronitrile) and 2,2′-azobis (2,4-dimethylvalero). Nitrile), 2,2′-azobisisobutyronitrile, azo compounds such as 2,2′-azobis (2,4,4-trimethylpentane), tert-butyl peroxypivalate, lauroyl peroxide, benzoyl Peroxide compounds such as peroxide, tert-butyl peroxylaurate, and water-soluble initiators such as persulfates such as potassium persulfate, and peroxides such as potassium persulfate and hydrogen peroxide Examples are redox initiators composed of a combination of reducing agents such as sodium sulfite. 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 weight, particularly 0.01 to 2%, based on the total amount of monomers to be polymerized. % By weight is employed.

  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 can be used. These solvents can be used alone or in admixture of two or more. A known molecular weight regulator such as dodecyl mercaptan may be used in combination.

  The reaction temperature of the polymerization reaction is appropriately changed depending on the type of 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 1,000,000, particularly 2,000 to 100,000.

  In the unit (m), unit (n), and unit (p), m / (m + n) is 0.1 to 0.9, preferably 0.2 to 0.8, and n / (m + n) is 0.1 to 0.9. 0.8, preferably 0.2 to 0.7, and p / (m + p) is 0.1 to 0.9, preferably 0.2 to 0.8. Further, m + n is preferably 0.3 to 1.0, particularly 0.4 to 1.0, and m + p is preferably 0.3 to 1.0, particularly 0.4 to 1.0. When m + n <1.0 and m + p <1.0, the other unit can be a repeating unit containing the above-mentioned adhesive group, a repeating unit for improving transparency, or the like.

  The polymer compound of the present invention can be used as a base resin for resist materials, particularly chemically amplified, especially chemically amplified positive resist materials. However, the mechanical properties, thermal properties, alkali solubility, Other polymer compounds can be mixed for the purpose of changing physical properties. 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) It may contain an acid generator.
In this case, these resist materials further include (D) a basic compound,
(E) A dissolution inhibitor may be blended.

  The organic solvent of the component (B) used in the present invention may be any as long as the base resin, acid generator, other additives, etc. can be dissolved. Examples of such an organic solvent include ketones such as cyclohexanone and methyl-2-n-amyl ketone, 3-methoxybutanol, 3-methyl-3-methoxybutanol, 1-methoxy-2-propanol, and 1-ethoxy-2. -Alcohols such as propanol, propylene glycol monomethyl ether, ethylene glycol monomethyl ether, propylene glycol monoethyl ether, ethylene glycol monoethyl ether, propylene glycol dimethyl ether, diethylene glycol dimethyl ether, and other ethers, propylene glycol monomethyl ether acetate, propylene glycol monoethyl Ether acetate, ethyl lactate, ethyl pyruvate, butyl acetate, methyl 3-methoxypropionate, 3-ethoxy Propionate ethyl acetate tert- butyl, tert- butyl propionate, and propylene glycol monobutyl tert- butyl ether acetate.

  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-trifluoroethyl butyrate, ethyl heptafluorobutyrate, ethyl heptafluorobutyl acetate, ethyl hexafluoroglutaryl methyl, ethyl-3-hydroxy-4,4,4-trifluoro Lobutylate, ethyl-2-methyl-4,4,4-trifluoroacetoacetate, ethylpentafluorobenzoate, ethylpentafluoropropionate, ethylpentafluoropropynylacetate, ethylperfluorooctanoate, ethyl-4,4,4 4-trifluoroacetoacetate, ethyl-4,4,4-trifluorobutyrate, ethyl-4,4,4-trifluorocrotonate, ethyltrifluorosulfonate, ethyl-3- (trifluoromethyl) butyrate, 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-o Tandione, 1,1,1,3,5,5,5-heptafluoropentane-2,4-dione, 3,3,4,4,5,5,5-heptafluoro-2-pentanol, 3, 3,4,4,5,5,5-heptafluoro-2-pentanone, isopropyl 4,4,4-trifluoroacetoacetate, methyl perfluorodenanoate, methyl perfluoro (2-methyl-3-oxahexa Noate), methyl perfluorononanoate, methyl perfluorooctanoate, methyl-2,3,3,3-tetrafluoropropionate, methyl trifluoroacetoacetate, methyltrifluoroacetoacetate, 1,1,1 , 2,2,6,6,6-octafluoro-2,4-hexanedione, 2,2,3,3,4,4,5,5-octafluoro-1-pe Butanol, 1H, 1H, 2H, 2H-perfluoro-1-decanol, perfluoro (2,5-dimethyl-3,6-dioxaneanionic) acid methyl ester, 2H-perfluoro-5-methyl-3,6 -Dioxanonane, 1H, 1H, 2H, 3H, 3H-perfluorononane-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-trioxadodecanoic acid methyl ester, perf Orotripentylamine, perfluorotripropylamine, 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, perfluoro (butyltetrahydrofuran ), Perfluorodecalin, perfluoro (1,2-dimethylcyclohexane), perfluoro (1,3-dimethylcyclohexane), propylene glycol trifluoromethyl ether acetate, propylene glycol methyl ether trifluoromethyl acetate, butyl trifluoromethyl acetate , - trifluoromethoxy acid methyl, perfluoro cyclohexanone, propylene glycol trifluoromethyl ether, butyl trifluoroacetate, 1,1,1-trifluoro-5,5-dimethyl-2,4-hexanedione, and the 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, propylene glycol monomethyl acetate, which is a safety solvent, and mixed solvents thereof, in addition to diethylene glycol dimethyl ether and 1-ethoxy-2-propanol, which have the highest solubility of the acid generator in the resist component Are preferably used.

  The amount of the solvent used may be 300 to 10,000 parts, particularly 500 to 5,000 parts, based on 100 parts of base resin (parts by weight, hereinafter the same).

  (C) Component acid generators include onium salts of the following general formula (3), diazomethane derivatives of formula (4), glyoxime derivatives of formula (5), β-ketosulfonic acid derivatives, disulfone derivatives, nitrobenzyl sulfonate derivatives Sulfonic acid ester derivatives, imidoyl sulfonate derivatives and the like.

The general formula of the onium salt used as the acid generator is represented by the following formula (3).
_{^{(R 51) i M + K}} - (3)
(Wherein R ⁵¹ represents a linear, branched or cyclic alkyl group having 1 to 12 carbon atoms, an aryl group having 6 to 20 carbon atoms, or an aralkyl group having 7 to 12 carbon atoms, and M ⁺ represents Iodonium and sulfonium are represented, K ⁻ represents a non-nucleophilic counter ion, and i is 2 or 3.)

^Examples of the alkyl group for R ⁵¹ include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a 2-oxocyclopentyl group, a norbornyl group, and an adamantyl group. As the aryl group, an alkoxyphenyl group such as a phenyl group, a p-methoxyphenyl group, an m-methoxyphenyl group, an o-methoxyphenyl group, an ethoxyphenyl group, a p-tert-butoxyphenyl group, or an m-tert-butoxyphenyl group. And 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 aralkyl group include a benzyl group and a phenethyl group. Non-nucleophilic counter ions of K ⁻ include halide ions such as chloride ion and bromide ion, fluoroalkyl sulfonates such as triflate, 1,1,1-trifluoroethane sulfonate, and nonafluorobutane sulfonate, tosylate, and benzene sulfonate. And aryl sulfonates such as 4-fluorobenzene sulfonate and 1,2,3,4,5-pentafluorobenzene sulfonate, and alkyl sulfonates such as mesylate and butane sulfonate.

  Specific examples of onium salts include diphenyliodonium trifluoromethanesulfonate, trifluoromethanesulfonic acid (p-tert-butoxyphenyl) phenyliodonium, p-toluenesulfonic acid diphenyliodonium, p-toluenesulfonic acid (p-tert-butoxyphenyl). ) Phenyliodonium, trifluoromethanesulfonic acid triphenylsulfonium, trifluoromethanesulfonic acid (p-tert-butoxyphenyl) diphenylsulfonium, trifluoromethanesulfonic acid bis (p-tert-butoxyphenyl) phenylsulfonium, trifluoromethanesulfonic acid tris (p -Tert-butoxyphenyl) sulfonium, p-toluenesulfonic acid triphenylsulfonium, p-toluenesulfone (P-tert-butoxyphenyl) diphenylsulfonium, p-toluenesulfonic acid bis (p-tert-butoxyphenyl) phenylsulfonium, p-toluenesulfonic acid tris (p-tert-butoxyphenyl) sulfonium, nonafluorobutanesulfonic acid tri Phenylsulfonium, triphenylsulfonium butanesulfonate, trimethylsulfonium trifluoromethanesulfonate, trimethylsulfonium p-toluenesulfonate, cyclohexylmethyl trifluoromethanesulfonate (2-oxocyclohexyl) sulfonium, cyclohexylmethyl p-toluenesulfonate (2-oxo) (Cyclohexyl) sulfonium, dimethylmethanesulfonium trifluoromethanesulfonate, p-toluenesulfonic acid Methylphenylsulfonium, dicyclohexylphenylsulfonium trifluoromethanesulfonate, dicyclohexylphenylsulfonium p-toluenesulfonate, trinaphthylsulfonium trifluoromethanesulfonate, cyclohexylmethyl (2-oxocyclohexyl) sulfonium trifluoromethanesulfonate, trifluoromethanesulfonic acid (2- Norbornyl) methyl (2-oxocyclohexyl) sulfonium, ethylenebis [methyl (2-oxocyclopentyl) sulfonium trifluoromethanesulfonate], 1,2'-naphthylcarbonylmethyltetrahydrothiophenium triflate and the like.

（式中、Ｒ⁵²、Ｒ⁵³は炭素数１〜１２の直鎖状、分岐状又は環状のアルキル基又はハロゲン化アルキル基、炭素数６〜１２のアリール基、又はハロゲン化アリール基又は炭素数７〜１２のアラルキル基を示す。） Next, the diazomethane derivative is represented by the following formula (4).

(In the formula, R ⁵² and R ⁵³ are linear, branched or cyclic alkyl groups or halogenated alkyl groups having 1 to 12 carbon atoms, aryl groups having 6 to 12 carbon atoms, or halogenated aryl groups or carbon atoms. 7 to 12 aralkyl groups are shown.)

^Examples of the alkyl group for R ⁵² and R ⁵³ include a methyl group, an ethyl group, a propyl group, a butyl group, an amyl group, a cyclopentyl group, a cyclohexyl group, a norbornyl group, and an adamantyl group. Examples of the halogenated alkyl group include a trifluoromethyl group, a 2,2,2-trifluoroethyl group, a 2,2,2-trichloroethyl group, and a nonafluorobutyl group. As the aryl group, an alkoxyphenyl group such as a phenyl group, p-methoxyphenyl group, m-methoxyphenyl group, o-methoxyphenyl group, ethoxyphenyl group, p-tert-butoxyphenyl group, m-tert-butoxyphenyl group, Examples thereof include alkylphenyl groups such as 2-methylphenyl group, 3-methylphenyl group, 4-methylphenyl group, ethylphenyl group, 4-tert-butylphenyl group, 4-butylphenyl group, and dimethylphenyl group. Examples of the halogenated aryl group include a fluorophenyl group, a chlorophenyl group, and 1,2,3,4,5-pentafluorophenyl group. Examples of the aralkyl group include a benzyl group and a phenethyl group.

  Specific examples of the diazomethane derivative include bis (benzenesulfonyl) diazomethane, bis (p-toluenesulfonyl) diazomethane, bis (xylenesulfonyl) diazomethane, bis (cyclohexylsulfonyl) diazomethane, bis (cyclopentylsulfonyl) diazomethane, and bis (n-butyl). Sulfonyl) diazomethane, bis (isobutylsulfonyl) diazomethane, bis (sec-butylsulfonyl) diazomethane, bis (n-propylsulfonyl) diazomethane, bis (isopropylsulfonyl) diazomethane, bis (tert-butylsulfonyl) diazomethane, bis (n-amyl) Sulfonyl) diazomethane, bis (isoamylsulfonyl) diazomethane, bis (sec-amylsulfonyl) diazomethane, bis (tert-a) Rusulfonyl) diazomethane, 1-cyclohexylsulfonyl-1- (tert-butylsulfonyl) diazomethane, 1-cyclohexylsulfonyl-1- (tert-amylsulfonyl) diazomethane, 1-tert-amylsulfonyl-1- (tert-butylsulfonyl) And diazomethane.

（式中、Ｒ⁵⁴〜Ｒ⁵⁶は炭素数１〜１２の直鎖状、分岐状又は環状のアルキル基又はハロゲン化アルキル基、炭素数６〜１２のアリール基又はハロゲン化アリール基、又は炭素数７〜１２のアラルキル基を示す。Ｒ⁵⁵、Ｒ⁵⁶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、Ｒ⁵⁵、Ｒ⁵⁶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。） The glyoxime derivative is represented by the following formula (5).

(In the formula, R ^{54 to} R ⁵⁶ are linear, branched or cyclic alkyl groups or halogenated alkyl groups having 1 to 12 carbon atoms, aryl groups or halogenated aryl groups having 6 to 12 carbon atoms, or carbon atoms. 7 to 12 represents an aralkyl group, R ⁵⁵ and R ⁵⁶ may be bonded to each other to form a cyclic structure, and when forming a cyclic structure, R ⁵⁵ and R ⁵⁶ are each a straight chain having 1 to 6 carbon atoms. Represents a branched or branched alkylene group.)

Examples of the alkyl group, halogenated alkyl group, aryl group, halogenated aryl group, and aralkyl group represented by R ^{54 to} R ⁵⁶ include the same groups as those described for R ⁵² and R ⁵³ . ^Examples of the alkylene group for R ⁵⁵ and R ⁵⁶ include a methylene group, an ethylene group, a propylene group, a butylene group, and a hexylene group.

  Specific examples of glyoxime derivatives include bis-O- (p-toluenesulfonyl) -α-dimethylglyoxime, bis-O- (p-toluenesulfonyl) -α-diphenylglyoxime, bis-O- (p-toluene). Sulfonyl) -α-dicyclohexylglyoxime, bis-O- (p-toluenesulfonyl) -2,3-pentanedione glyoxime, bis-O- (p-toluenesulfonyl) -2-methyl-3,4-pentanediol Lioxime, bis-O- (n-butanesulfonyl) -α-dimethylglyoxime, bis-O- (n-butanesulfonyl) -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-dimethyl Glyoxime, bis-O- (1,1,1-trifluoroethanesulfonyl) -α-dimethylglyoxime, bis-O- (tert-butanesulfonyl) -α-dimethylglyoxime, bis-O- (perfluoro Octanesulfonyl) -α-dimethylglyoxime, bis-O- (cyclohexanesulfonyl) -α-dimethylglyoxime, bis-O- (benzenesulfonyl) -α-dimethylglyoxime, bis-O- (p-fluorobenzenesulfonyl) ) -Α-dimethylglyoxime, bis-O- (p-tert-butylbenzenesulfuryl) Sulfonyl)-.alpha.-dimethylglyoxime, bis -O- (xylene sulfonyl)-.alpha.-dimethylglyoxime, bis -O- (camphorsulfonyl)-.alpha.-dimethylglyoxime, and the like.

  Other examples of the acid generator used include β-ketosulfone derivatives such as 2-cyclohexylcarbonyl-2- (p-toluenesulfonyl) propane, 2-isopropylcarbonyl-2- (p-toluenesulfonyl) propane, and diphenyldisulfone. , Disulfone derivatives such as dicyclohexyldisulfone, nitrobenzyl sulfonate derivatives such as 2,6-dinitrobenzyl p-toluenesulfonate, 2,4-dinitrobenzyl p-toluenesulfonate, 1,2,3-tris (methanesulfonyloxy) Sulfonic acid ester derivatives such as benzene, 1,2,3-tris (trifluoromethanesulfonyloxy) benzene, 1,2,3-tris (p-toluenesulfonyloxy) benzene, phthalimido-yl-triflate, phthalimide- Ru-tosylate, 5-norbornene-2,3-dicarboximido-yl-triflate, 5-norbornene-2,3-dicarboximido-yl-tosylate, 5-norbornene-2,3-dicarboximido-yl -Imidoyl sulfonate derivatives such as -n-butyl triflate sulfonate.

  Among the acid generators described above, triphenylsulfonium trifluoromethanesulfonate, trifluoromethanesulfonic acid (p-tert-butoxyphenyl) diphenylsulfonium, trifluoromethanesulfonic acid tris (p-tert-butoxyphenyl) sulfonium, p-toluene Triphenylsulfonium sulfonate, p-toluenesulfonic acid (p-tert-butoxyphenyl) diphenylsulfonium, p-toluenesulfonic acid tris (p-tert-butoxyphenyl) sulfonium, trifluoromethanesulfonic acid trinaphthylsulfonium, trifluoromethanesulfonic acid Cyclohexylmethyl (2-oxocyclohexyl) sulfonium, trifluoromethanesulfonic acid (2-norbornyl) methyl (2-oxocycle) Hexyl) sulfonium, onium salts such as 1,2'-naphthylcarbonylmethyltetrahydrothiophenium triflate, bis (benzenesulfonyl) diazomethane, bis (p-toluenesulfonyl) diazomethane, bis (cyclohexylsulfonyl) diazomethane, bis (n- Diazomethane derivatives such as butylsulfonyl) diazomethane, bis (isobutylsulfonyl) diazomethane, bis (sec-butylsulfonyl) diazomethane, bis (n-propylsulfonyl) diazomethane, bis (isopropylsulfonyl) diazomethane, bis (tert-butylsulfonyl) diazomethane, Glyoxy such as bis-O- (p-toluenesulfonyl) -α-dimethylglyoxime, bis-O- (n-butanesulfonyl) -α-dimethylglyoxime Beam derivative 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 amount of the acid generator added is preferably 0.2 to 15 parts with respect to 100 parts of the base resin. If the amount is less than 0.2 parts, the amount of acid generated during exposure is small, and the sensitivity and resolution may be poor. If it is more than 15 parts, the transparency may be lowered and the resolution may be lowered.

  As the basic compound (D), a compound that can suppress the diffusion rate when the acid generated from the acid generator diffuses into the resist film is suitable. By blending such a basic compound, the acid diffusion rate in the resist film is suppressed, the resolution is improved, the sensitivity change after exposure is suppressed, the substrate and environment dependency is reduced, and the exposure margin is reduced. And the pattern profile can be improved (Japanese Patent Laid-Open Nos. 5-232706, 5-249683, 5-158239, 5-249626, 5-257282, 5-289322, 5). -289340 etc.).

  Examples of such basic compounds include ammonia, primary, secondary, and tertiary aliphatic amines, hybrid amines, aromatic amines, heterocyclic amines, nitrogen-containing compounds having a carboxyl group, Examples thereof include nitrogen-containing compounds having a sulfonyl group, nitrogen-containing compounds having a hydroxyl group, nitrogen-containing compounds having a hydroxyphenyl group, alcoholic nitrogen-containing compounds, amide derivatives, imide derivatives, and the like.

  Specific examples of primary aliphatic amines include methylamine, ethylamine, n-propylamine, isopropylamine, n-butylamine, isobutylamine, sec-butylamine, tert-butylamine, pentylamine, tert-amylamine, cyclopentyl. Examples include amine, hexylamine, cyclohexylamine, heptylamine, octylamine, nonylamine, decylamine, dodecylamine, cetylamine, methylenediamine, ethylenediamine, tetraethylenepentamine and the like.

Specific examples of secondary aliphatic amines include dimethylamine, diethylamine, di-n-propylamine, diisopropylamine, di-n-butylamine, diisobutylamine, di-sec-butylamine, dipentylamine, dicyclopentylamine. , Dihexylamine, dicyclohexylamine, diheptylamine, dioctylamine, dinonylamine, didecylamine, didodecylamine, dicetylamine, N, N-dimethylmethylenediamine, N, N-dimethylethylenediamine, N, N-dimethyltetraethylenepentamine, etc. Illustrated.
Specific examples of tertiary aliphatic amines include trimethylamine, triethylamine, tri-n-propylamine, triisopropylamine, tri-n-butylamine, triisobutylamine, tri-sec-butylamine, tripentylamine, tripentylamine, Cyclopentylamine, trihexylamine, tricyclohexylamine, triheptylamine, trioctylamine, trinonylamine, tridecylamine, tridodecylamine, tricetylamine, N, N, N ′, N′-tetramethylmethylenediamine, Examples thereof include N, N, N ′, N′-tetramethylethylenediamine, N, N, N ′, N′-tetramethyltetraethylenepentamine and the like.

  Specific examples of the hybrid amines include dimethylethylamine, methylethylpropylamine, benzylamine, phenethylamine, benzyldimethylamine and the like.

  Specific examples of aromatic amines include aniline, N-methylaniline, N-ethylaniline, N-propylaniline, N, N-dimethylaniline, 2-methylaniline, 3-methylaniline, 4-methylaniline and ethyl. Aniline, propylaniline, trimethylaniline, 2-nitroaniline, 3-nitroaniline, 4-nitroaniline, 2,4-dinitroaniline, 2,6-dinitroaniline, 3,5-dinitroaniline, N, N-dimethyltoluidine And aniline derivatives such as diphenyl (p-tolyl) amine, methyldiphenylamine, triphenylamine, phenylenediamine, naphthylamine, and diaminonaphthalene.

  Specific examples of the heterocyclic amines include pyrrole derivatives such as pyrrole, 2H-pyrrole, 1-methylpyrrole, 2,4-dimethylpyrrole, 2,5-dimethylpyrrole, N-methylpyrrole, oxazole, isoxazole and the like. Oxazole derivatives, thiazole derivatives such as thiazole, isothiazole, imidazole derivatives such as imidazole, 4-methylimidazole, 4-methyl-2-phenylimidazole, pyrazole derivatives, furazane derivatives, pyrroline, pyrroline such as 2-methyl-1-pyrroline Derivatives, pyrrolidine derivatives such as pyrrolidine, N-methylpyrrolidine, pyrrolidinone, N-methylpyrrolidone, imidazoline derivatives, imidazolidine derivatives, pyridine, methylpyridine, ethylpyridine, propylpyridine, butylpyridine, 4 (1-butylpentyl) pyridine, dimethylpyridine, trimethylpyridine, triethylpyridine, phenylpyridine, 3-methyl-2-phenylpyridine, 4-tert-butylpyridine, diphenylpyridine, benzylpyridine, methoxypyridine, butoxypyridine, dimethoxypyridine Pyridine derivatives such as 1-methyl-2-pyridine, 4-pyrrolidinopyridine, 1-methyl-4-phenylpyridine, 2- (1-ethylpropyl) pyridine, aminopyridine, dimethylaminopyridine, pyridazine derivatives, pyrimidine derivatives , Pyrazine derivatives, pyrazoline derivatives, pyrazolidine derivatives, piperidine derivatives, piperazine derivatives, morpholine derivatives, indole derivatives, isoindole derivatives, 1H-indazole derivatives, indoline Conductors, quinoline, quinoline derivatives such as 3-quinolinecarbonitrile, 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 derivative, adenine derivative, adenosine derivative, guanine derivative, guanosine derivative, uracil derivative, uridine derivative and the like.

  Specific examples of nitrogen-containing compounds having a carboxyl group include aminobenzoic acid, indolecarboxylic acid, nicotinic acid, alanine, arginine, aspartic acid, glutamic acid, glycine, histidine, isoleucine, glycylleucine, leucine, methionine, phenylalanine. And amino acid derivatives such as threonine, lysine, 3-aminopyrazine-2-carboxylic acid and methoxyalanine.

  Specific examples of the nitrogen-containing compound having a sulfonyl group include 3-pyridinesulfonic acid and pyridinium p-toluenesulfonate.

  Specific examples of the nitrogen-containing compound and alcoholic nitrogen-containing compound containing a hydroxyl group and a hydroxyphenyl group include 2-hydroxypyridine, aminocresol, 2,4-quinolinediol, 3-indolemethanol hydrate, monoethanolamine, diethanolamine , Triethanolamine, N-ethyldiethanolamine, N, N-diethylethanolamine, triisopropanolamine, 2,2′-iminodiethanol, 2-aminoethanol, 3-amino-1-propanol, 4-amino-1-butanol 4- (2-hydroxyethyl) morpholine, 2- (2-hydroxyethyl) pyridine, 1- (2-hydroxyethyl) piperazine, 1- [2- (2-hydroxyethoxy) ethyl] piperazine, piperidine ethanol, 1 − 2-hydroxyethyl) pyrrolidine, 1- (2-hydroxyethyl) -2-pyrrolidinone, 3-piperidino-1,2-propanediol, 3-pyrrolidino-1,2-propanediol, 8-hydroxyeurolidine, 3- Examples include quinuclidinol, 3-tropanol, 1-methyl-2-pyrrolidine ethanol, 1-aziridine ethanol, N- (2-hydroxyethyl) phthalimide, N- (2-hydroxyethyl) isonicotinamide.

  Specific examples of the amide derivative include formamide, N-methylformamide, N, N-dimethylformamide, acetamide, N-methylacetamide, N, N-dimethylacetamide, propionamide, benzamide and the like.

  Specific examples of the imide derivative 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.
N (X) _n (Y) _3-n (B) -1
In the formula, n = 1, 2 or 3. The side chains 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 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. Xs may be bonded to form a ring.

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 or 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, and a hydroxy group , An ether group, an ester group, or a lactone ring may be contained.

Specific examples of the compound represented by 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-formyloxyethyl) amine, tris (2-acetoxyethyl) amine, Tris (2-propionyloxyethyl) amine, tris (2-butyryloxyethyl) amine, tris (2-isobutyryloxyethyl) amine, tris (2-valeryloxyethyl) amine, tris (2-pivalloy) Ruoxyxyethyl) 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] amine, tris [2- (tert-butoxycarbonylmethyloxy) ethyl] amine, tris [2- (cyclohexyloxycarbonylmethyloxy) ethyl] amine, tris (2-methoxycarbonylethyl) amine, tris (2-ethoxycarbonylethyl) amine, N, N-bis (2-hydroxyethyl) 2- (methoxycarbonyl) ethylamine, N, N-bis (2-acetoxyethyl) 2- (methoxycarbonyl) ethylamine, N, N -Bis (2-hydroxyethyl) 2- (ethoxycarbonyl) ethylamine, N, N-bis (2-acetoxyethyl) 2- (ethoxycarbonyl) ethylamine, N, N-bis (2-hydroxyethyl) 2- (2 -Methoxyethoxycarbonyl) Tylamine, N, N-bis (2-acetoxyethyl) 2- (2-methoxyethoxycarbonyl) ethylamine, N, N-bis (2-hydroxyethyl) 2- (2-hydroxyethoxycarbonyl) ethylamine, N, N- Bis (2-acetoxyethyl) 2- (2-acetoxyethoxycarbonyl) ethylamine, N, N-bis (2-hydroxyethyl) 2-[(methoxycarbonyl) methoxycarbonyl] ethylamine, N, N-bis (2-acetoxy) Ethyl) 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 ( -Hydroxyethyl) 2- (tetrahydrofurfuryloxycarbonyl) 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-formyl) Oxyethyl) 2- (2-formyloxyate) Sicarbonyl) ethylamine, N, N-bis (2-methoxyethyl) 2- (methoxycarbonyl) ethylamine, N- (2-hydroxyethyl) bis [2- (methoxycarbonyl) ethyl] amine, N- (2-acetoxy) Ethyl) bis [2- (methoxycarbonyl) ethyl] amine, N- (2-hydroxyethyl) bis [2- (ethoxycarbonyl) ethyl] amine, N- (2-acetoxyethyl) bis [2- (ethoxycarbonyl) Ethyl] amine, N- (3-hydroxy-1-propyl) bis [2- (methoxycarbonyl) ethyl] amine, N- (3-acetoxy-1-propyl) bis [2- (methoxycarbonyl) ethyl] amine, N- (2-methoxyethyl) bis [2- (methoxycarbonyl) ethyl] amine, N-butylbis [2 -(Methoxycarbonyl) ethyl] amine, N-butylbis [2- (2-methoxyethoxycarbonyl) ethyl] amine, N-methylbis (2-acetoxyethyl) amine, N-ethylbis (2-acetoxyethyl) amine, N- Methylbis (2-pivaloyloxyoxyethyl) amine, N-ethylbis [2- (methoxycarbonyloxy) ethyl] amine, N-ethylbis [2- (tert-butoxycarbonyloxy) ethyl] amine, tris (methoxycarbonylmethyl) Examples include, but are not limited to, amine, tris (ethoxycarbonylmethyl) amine, N-butylbis (methoxycarbonylmethyl) amine, N-hexylbis (methoxycarbonylmethyl) amine, and β- (diethylamino) -δ-valerolactone.

（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、スルフィドを１個あるいは複数個含んでいてもよい。） Furthermore, 1 type, or 2 or more types of the basic compound which has the cyclic structure shown by the following general formula (B) -2 can also be added.

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

  Formula (B) -2 specifically includes 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, methoxy 2- (1-pyrrolidinyl) ethyl acetate, 4- [2- (methoxycarbonyloxy) ethyl] morpholine 1- [2- (t-butoxycarbonyloxy) ethyl] piperidine, 4- [2- (2-methoxyethoxycarbonyloxy) ethyl] morpholine, methyl 3- (1-pyrrolidinyl) propionate, 3-piperidino Methyl propionate, methyl 3-morpholinopropionate, methyl 3- (thiomorpholino) propionate, methyl 2-methyl-3- (1-pyrrolidinyl) propionate, ethyl 3-morpholinopropionate, 3-piperidinopropionic acid Methoxycarbonylmethyl, 2-hydroxyethyl 3- (1-pyrrolidinyl) propionate, 2-acetoxyethyl 3-morpholinopropionate, 2-oxotetrahydrofuran-3-yl 3- (1-pyrrolidinyl) propionate, 3-morpholinopropion Tetrahydrofurfuryl acid, 3 Glycidyl piperidinopropionate, 2-methoxyethyl 3-morpholinopropionate, 2- (2-methoxyethoxy) ethyl 3- (1-pyrrolidinyl) propionate, butyl 3-morpholinopropionate, 3-piperidinopropionic acid Cyclohexyl, α- (1-pyrrolidinyl) methyl-γ-butyrolactone, β-piperidino-γ-butyrolactone, β-morpholino-δ-valerolactone, methyl 1-pyrrolidinyl acetate, methyl piperidinoacetate, methyl morpholinoacetate, methyl thiomorpholinoacetate , Ethyl 1-pyrrolidinyl acetate, 2-methoxyethyl morpholinoacetate.

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

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

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

  The (E) component dissolution inhibitor is a compound having a molecular weight of 3,000 or less whose solubility in an alkaline developer is changed by the action of an acid, in particular, a part of the hydroxyl group of a phenol or carboxylic acid derivative having a molecular weight of 2,500 or less. Compounds in which all are substituted with acid labile groups are suitable. The acid labile group may contain fluorine mentioned in the present invention, but may not contain conventional fluorine.

  Examples of phenol or carboxylic acid derivatives having a molecular weight of 2,500 or less include 4,4 ′-(1-methylethylidene) bisphenol, [1,1′-biphenyl-4,4′-diol] -2,2′-methylenebis [ 4-methylphenol], 4,4-bis (4′-hydroxyphenyl) valeric acid, tris (4-hydroxyphenyl) methane, 1,1,1-tris (4′-hydroxyphenyl) ethane, 1,1, 2-tris (4′-hydroxyphenyl) ethane, phenolphthalein, thymolphthalein, 3,3′-difluoro [(1,1′-biphenyl) -4,4′-diol], 3,3 ′, 5 , 5′-tetrafluoro [(1,1′-biphenyl-4,4′-diol], 4,4 ′-[2,2,2-trifluoro-1- (trifluoromethyl) ester Ridene] bisphenol, 4,4′-methylenebis [2-fluorophenol], 2,2′-methylenebis [4-fluorophenol], 4,4′-isopropylidenebis [2-fluorophenol], cyclohexylidenebis [ 2-fluorophenol], 4,4 ′-[(4-fluorophenyl) methylene] bis [2-fluorophenol], 4,4′-methylenebis [2,6-difluorophenol], 4,4 ′-(4 -Fluorophenyl) methylenebis [2,6-difluorophenol], 2,6-bis [(2-hydroxy-5-fluorophenyl) methyl] -4-fluorophenol, 2,6-bis [(4-hydroxy-3 -Fluorophenyl) methyl] -4-fluorophenol, 2,4-bis [(3-hydroxy-4-hydro Shifeniru) methyl] -6-methylphenol and the like, as The acid labile substituents are the same as those described above.

  Specific examples of the dissolution inhibitor suitably used include 3,3 ′, 5,5′-tetrafluoro [(1,1′-biphenyl) -4,4′-di-tert-butoxycarbonyl], 4, 4 ′-[2,2,2-trifluoro-1- (trifluoromethyl) ethylidene] bisphenol-4,4′-di-tert-butoxycarbonyl, bis (4- (2′-tetrahydropyranyloxy) phenyl ) Methane, bis (4- (2′-tetrahydrofuranyloxy) phenyl) methane, bis (4-tert-butoxyphenyl) methane, bis (4-tert-butoxycarbonyloxyphenyl) methane, bis (4-tert-butoxy) Carbonylmethyloxyphenyl) methane, bis (4- (1′-ethoxyethoxy) phenyl) methane, bis (4- (1′-e Xypropyloxy) phenyl) methane, 2,2-bis (4 ′-(2 ″ -tetrahydropyranyloxy)) propane, 2,2-bis (4 ′-(2 ″ -tetrahydrofuranyloxy) phenyl) Propane, 2,2-bis (4′-tert-butoxyphenyl) propane, 2,2-bis (4′-tert-butoxycarbonyloxyphenyl) propane, 2,2-bis (4-tert-butoxycarbonylmethyloxy) Phenyl) 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 4,4-bis (4 ′-(2 ″ -teto) Hydrofuranyloxy) phenyl) tert-butyl valerate, 4,4-bis (4′-tert-butoxyphenyl) tert-butyl valerate, 4,4-bis (4-tert-butoxycarbonyloxyphenyl) valeric acid tert-butyl 4,4-bis (4′-tert-butoxycarbonylmethyloxyphenyl) valerate tert-butyl 4,4-bis (4 ′-(1 ″ -ethoxyethoxy) phenyl) valerate tert-butyl Butyl, 4,4-bis (4 ′-(1 ″ -ethoxypropyloxy) phenyl) tert-butyl valerate, tris (4- (2′-tetrahydropyranyloxy) phenyl) methane, tris (4- ( 2'-tetrahydrofuranyloxy) phenyl) methane, tris (4-tert-butoxyphenyl) methane, tris ( 4-tert-butoxycarbonyloxyphenyl) methane, tris (4-tert-butoxycarbonyloxymethylphenyl) methane, tris (4- (1′-ethoxyethoxy) phenyl) methane, tris (4- (1′-ethoxypropyl) Oxy) phenyl) methane, 1,1,2-tris (4 ′-(2 ″ -tetrahydropyranyloxy) phenyl) ethane, 1,1,2-tris (4 ′-(2 ″ -tetrahydrofuranyloxy) ) Phenyl) ethane, 1,1,2-tris (4′-tert-butoxyphenyl) ethane, 1,1,2-tris (4′-tert-butoxycarbonyloxyphenyl) ethane, 1,1,2-tris (4′-tert-butoxycarbonylmethyloxyphenyl) ethane, 1,1,2-tris (4 ′-(1′- Toxiethoxy) phenyl) ethane, 1,1,2-tris (4 ′-(1′-ethoxypropyloxy) phenyl) ethane, 1,1-tert-butyl 2-trifluoromethylbenzenecarboxylate, 2-trifluoro Tert-butyl methylcyclohexanecarboxylate, tert-butyl decahydronaphthalene-2,6-dicarboxylate, tert-butyl cholate, tert-butyl deoxycholate, tert-butyl adamantanecarboxylate, tert-butyl adamantane acetate, 1, Examples thereof include tetra-tert-butyl 1′-bicyclohexyl-3,3 ′, 4,4′-tetracarboxylate.

Furthermore, the dissolution inhibitor shown below can also be added.
Wherein, R ⁵ is R ⁵ the same or different acid labile group units (n).

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

The resist for F ₂ lithography has poor developer permeability because fluorine is introduced into the base polymer. In order to improve the wettability of the developer, a method of adding a compound containing a water-soluble group such as phenol, carboxyl group, sulfonamide, carbonamide, etc. has been proposed for resist materials for KrF and ArF exposure. For example, carboxylic acid anhydrides described in JP-A Nos. 2000-47385 and 2000-275840, phosphine compounds described in JP-A No. 2000-275438, thiocarbonyl group-containing compounds described in JP-A No. 2000-275841, Examples thereof include a carboxyl group-containing compound described in Kaihei 11-338150 and a sulfonamide compound described in JP-A-11-327145. However, all of the above substances have strong absorption at 157 nm, and there is a defect that the transmittance of the resist is lowered, and a material in which hexafluoroalcohol pendant without penetrating the transmittance has been proposed.

  This is obtained by replacing the acid labile group of the dissolution inhibitor with a hydrogen atom, and can be specifically shown below. The amount added is in the range of 5 to 40 parts, preferably 8 to 30 parts, per 100 parts of polymer. If the addition amount is less than this range, the original effect cannot be exhibited, and if it is too much, the film of the unexposed part after development is dissolved, or the film after spin coating becomes a mottled pattern due to phase separation with the polymer. To do.

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

  Here, the surfactant is preferably nonionic, such as perfluoroalkyl polyoxyethylene ethanol, fluorinated alkyl ester, perfluoroalkylamine oxide, perfluoroalkyl EO adduct, fluorine-containing organosiloxane compound, and the like. Can be mentioned. For example, Florard “FC-430”, “FC-431” (both manufactured by Sumitomo 3M), Surflon “S-141”, “S-145” (both manufactured by Asahi Glass Co., Ltd.), Unidyne “DS-” 401 "," DS-403 "," DS-451 "(manufactured by Daikin Industries, Ltd.), MegaFuck" F-8151 "(manufactured by Dainippon Ink Industries, Ltd.)," X-70-092 " , “X-70-093” (all manufactured by Shin-Etsu Chemical Co., Ltd.) and the like. Preferably, Florard “FC-430” (manufactured by Sumitomo 3M Co., Ltd.), “X-70-093” (manufactured by Shin-Etsu Chemical Co., Ltd.) can be used.

In order to form a pattern using the resist material of the present invention, a known lithography technique can be employed. For example, 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 in an exposure amount of about 1 to 200 mJ / cm ² , preferably 10 to After irradiation so as to be about 100 mJ / cm ^2, post-exposure baking (PEB) is performed on a hot plate at 60 to 180 ° C. for 10 seconds to 5 minutes, preferably 80 to 150 ° C. for 30 seconds to 3 minutes. Further, a developer of an alkaline aqueous solution such as 0.1 to 5%, preferably 2 to 3% tetramethylammonium hydroxide (TMAH) is used for 10 seconds to 3 minutes, preferably 30 seconds to 2 minutes. ) Method, paddle method, spray method and the like, and a desired pattern is formed on the substrate. In addition, an antireflection film may be created between the substrate and the resist to suppress the generation of standing waves by the narrow band excimer laser, and an antireflection film may be created on the resist. Also good. The material of the present invention is an excimer laser such as a deep ultraviolet ray of 254 to 120 nm or an excimer laser, particularly 193 nm of ArF, 157 nm of F ₂ , 146 nm of Kr ₂ , 134 nm of KrAr, 126 nm of Ar ₂ among high energy rays. It is most suitable for fine patterning by X-ray and electron beam. 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.
[Synthesis Example 1]
In polymerizing the polymer compound of the present invention, ester compound monomer 1 was synthesized with the following formulation.
30.0 g of the following olefin 1, 34.4 g of α-trifluoromethylacrylic acid and 0.3 g of concentrated sulfuric acid were dissolved in 60 g of toluene together with a polymerization stabilizer and reacted at room temperature for 24 hours. After cooling to room temperature, normal reaction post-treatment was performed, and purification by distillation (boiling point 74 ° C./0.9 mmHg) yielded 36.0 g of the following monomer 1. The yield was 56%.

¹Ｈ−ＮＭＲ（ＣＤＣｌ₃、２７０ＭＨｚ）：δ０．８６（ｔ、３Ｈ、Ｊ＝７．６Ｈｚ）、１．１３〜２．２４（ｍ、１１Ｈ）、４．７８（ｍ、１Ｈ）、６．３８（ｍ、１Ｈ）、６．６９（ｍ、１Ｈ）
ＦＴ−ＩＲ（ＮａＣｌ）：２９６２、２８７３、１７３３、１４６４、１４５４、１４０６、１３８１、１３４０、１２５４、１１４９、１１１７、１０９７、１０５７、９９５ｃｍ^-1

¹ H-NMR (CDCl ₃ , 270 MHz): δ 0.86 (t, 3H, J = 7.6 Hz), 1.13 to 2.24 (m, 11H), 4.78 (m, 1H), 6. 38 (m, 1H), 6.69 (m, 1H)
FT-IR (NaCl): 2962, 2873, 1733, 1464, 1454, 1406, 1381, 1340, 1254, 1149, 1117, 1097, 1057, 995 cm ⁻¹

[Synthesis Example 2] Copolymerization of the following monomer 1 and monomer 2 (0.7: 0.3), polymer 1 (Reference Example 1)
In a 500 mL flask, 26.3 g of the following monomer 1 and 27.4 g of monomer 2 were dissolved in 100 mL of toluene, and after sufficiently removing oxygen in the system, 0.33 g of initiator AIBN was charged and the temperature was raised to 60 ° C. The polymerization reaction was carried out 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 tetrahydrofuran and pouring it into 10 L of hexane to precipitate the polymer was repeated twice, and then the polymer was separated and dried. The 44.9 g of the white polymer thus obtained has a weight average molecular weight of 9,500 g / mol by a light scattering method, and a polymer having a dispersity (= Mw / Mn) of 1.66 from the GPC elution curve. It was confirmed that. From the measurement result of ¹ H-NMR, the obtained polymer was found to contain monomer 1 and monomer 2 in a content ratio of 72:28.

[Synthesis Example 3] Copolymerization of the following monomer 3 and monomer 2 (0.7: 0.3), polymer 2 (Reference Example 2)
In a 500 mL flask, 32.8 g of the following monomer 3 and 27.4 g of monomer 2 were dissolved in 100 mL of toluene, and after sufficiently removing oxygen in the system, 0.33 g of initiator AIBN was charged and the temperature was raised to 60 ° C. The polymerization reaction was carried out 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 tetrahydrofuran and pouring it into 10 L of hexane to precipitate the polymer was repeated twice, and then the polymer was separated and dried. The thus obtained 38.2 g of white polymer has a weight average molecular weight of 9,300 g / mol by light scattering method, and has a dispersity (= Mw / Mn) of 1.65 from the GPC elution curve. It was confirmed that. From the measurement result of ¹ H-NMR, it was found that the obtained polymer contained monomer 3 and monomer 2 in a content ratio of 71:29.

[Synthesis Example 4] Copolymerization of monomer 1 and monomer 4 below (0.2: 0.8), polymer 3 (Example)
In a 500 mL flask, 10.5 g of the following monomer 1 and 43.2 g of monomer 4 were dissolved in 100 mL of toluene, and after sufficiently removing oxygen in the system, 0.33 g of initiator AIBN was charged and the temperature was raised to 60 ° C. The polymerization reaction was carried out 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 tetrahydrofuran and pouring it into 10 L of hexane to precipitate the polymer was repeated twice, and then the polymer was separated and dried. The thus obtained 35.2 g of the white polymer has a weight average molecular weight of 11,600 g / mol by light scattering method, and a polymer having a dispersity (= Mw / Mn) of 1.85 from the GPC elution curve. It was confirmed that. From the measurement result of ¹ H-NMR, it was found that the obtained polymer contained monomer 1 and monomer 4 in a content ratio of 22:78.

[Synthesis Example 5] Copolymerization of monomer 1, monomer 2 and monomer 5 (0.4: 0.3: 0.3), polymer 4 (Reference Example 3)
In a 500 mL flask, 15.0 g of the following monomer 1, 27.4 g of monomer 2 and 11.9 g of monomer 5 were dissolved in 100 mL of toluene to sufficiently remove oxygen in the system. 33 g was charged, 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 tetrahydrofuran and pouring it into 10 L of hexane to precipitate the polymer was repeated twice, and then the polymer was separated and dried. The 35.1 g of the white polymer thus obtained has a weight average molecular weight of 8,600 g / mol by light scattering method, and has a dispersity (= Mw / Mn) of 1.66 from the GPC elution curve. It was confirmed that. From the measurement result of ¹ H-NMR, the obtained polymer was found to contain monomer 1, monomer 2 and monomer 5 in a content ratio of 41:28:31.

[Synthesis Example 6] Copolymerization of monomer 1, monomer 2, monomer 5, and monomer 6 (0.2: 0.3: 0.3: 0.2), polymer 5 (Reference Example 4)
In a 500 mL flask, 7.5 g of the following monomer 1, 27.4 g of monomer 2, 11.9 g of monomer 5 and 8.3 g of monomer 6 were dissolved in 100 mL of toluene, and oxygen in the system was sufficiently removed. Then, 0.33 g of initiator AIBN was charged, 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 tetrahydrofuran and pouring it into 10 L of hexane to precipitate the polymer was repeated twice, and then the polymer was separated and dried. The thus obtained 35.1 g of white polymer has a weight average molecular weight of 7,600 g / mol by light scattering method, and a polymer having a dispersity (= Mw / Mn) of 1.62 from the GPC elution curve. It was confirmed that. From the measurement result of ¹ H-NMR, the obtained polymer was found to contain monomer 1, monomer 2, monomer 5, and monomer 6 in a content ratio of 19: 32: 28: 21.

[Synthesis Example 7] Copolymerization of monomer 1, monomer 2, monomer 5, and monomer 7 (0.3: 0.3: 0.3: 0.1), polymer 6 (Reference Example 5)
After dissolving 7.5 g of the following monomer 1, 27.4 g of monomer 2, 11.9 g of monomer 5 and 8.3 g of monomer 7 in 100 mL of toluene in a 500 mL flask, and sufficiently removing oxygen in the system Then, 0.33 g of initiator AIBN was charged, 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 tetrahydrofuran and pouring it into 10 L of hexane to precipitate the polymer was repeated twice, and then the polymer was separated and dried. The thus obtained 35.1 g of white polymer has a weight average molecular weight of 7,600 g / mol by light scattering method, and a polymer having a dispersity (= Mw / Mn) of 1.62 from the GPC elution curve. It was confirmed that. From the measurement result of ¹ H-NMR, the obtained polymer was found to contain monomer 1, monomer 2, monomer 5, and monomer 7 in a content ratio of 19: 32: 28: 21.

[Comparative Synthesis Example 1] Copolymerization of the following monomer 8 and monomer 2 (0.7: 0.3), comparative polymer 1
In a 500 mL flask, 19.6 g of the following monomer 8 and 27.2 g of monomer 2 were dissolved in 100 mL of toluene, and after sufficiently removing oxygen in the system, 0.33 g of initiator AIBN was charged and the temperature was raised to 60 ° C. The polymerization reaction was carried out 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 tetrahydrofuran and pouring it into 10 L of hexane to precipitate the polymer was repeated twice, and then the polymer was separated and dried. The thus obtained 32.2 g of white polymer has a weight average molecular weight of 9,500 g / mol by light scattering method, and a polymer having a dispersity (= Mw / Mn) of 1.78 from the GPC elution curve. It was confirmed that. From the measurement result of ¹ H-NMR, it was found that the obtained polymer contained monomer 8 and monomer 2 in a content ratio of 71:29.

[Comparative Synthesis Example 2] Copolymerization (0.4: 0.6) of the following monomer 8 and monomer 4, comparative polymer 2
In a 500 mL flask, 15.4 g of the following monomer 8 and 32.4 g of monomer 4 were dissolved in 100 mL of toluene, and after sufficiently removing oxygen in the system, 0.33 g of initiator AIBN was charged and the temperature was raised to 60 ° C. The polymerization reaction was carried out 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 tetrahydrofuran and pouring it into 10 L of hexane to precipitate the polymer was repeated twice, and then the polymer was separated and dried. The 30.2 g of the white polymer thus obtained has a weight average molecular weight of 12,800 g / mol according to the light scattering method, and has a dispersity (= Mw / Mn) of 1.73 from the GPC elution curve. It was confirmed that. From the measurement result of ¹ H-NMR, the obtained polymer was found to contain monomer 8 and monomer 4 in a content ratio of 42:58.

[Comparative Synthesis Example 3] Copolymerization of the following monomer 9 and monomer 2 (0.7: 0.3), comparative polymer 3
In a 500 mL flask, 23.4 g of the following monomer 9 and 27.2 g of monomer 2 were dissolved in 100 mL of toluene, and after sufficiently removing oxygen in the system, 0.33 g of initiator AIBN was charged and the temperature was raised to 60 ° C. The polymerization reaction was carried out 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 tetrahydrofuran and pouring it into 10 L of hexane to precipitate the polymer was repeated twice, and then the polymer was separated and dried. The thus obtained 30.2 g of white polymer has a weight average molecular weight of 9,200 g / mol by light scattering method, and a polymer having a dispersity (= Mw / Mn) of 1.75 from the GPC elution curve. It was confirmed that. From the measurement result of ¹ H-NMR, the obtained polymer was found to contain monomer 9 and monomer 2 in a content ratio of 71:29.

[Comparative Synthesis Example 4] Copolymerization of monomer 10 and monomer 2 below (0.7: 0.3), comparative polymer 4
In a 500 mL flask, 27.6 g of the following monomer 10 and 27.2 g of monomer 2 were dissolved in 100 mL of toluene, and after sufficiently removing oxygen in the system, 0.33 g of initiator AIBN was charged and the temperature was raised to 60 ° C. The polymerization reaction was carried out 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 tetrahydrofuran and pouring it into 10 L of hexane to precipitate the polymer was repeated twice, and then the polymer was separated and dried. The thus obtained 36.2 g of the white polymer has a weight average molecular weight of 7,500 g / mol by light scattering method, and a polymer having a dispersity (= Mw / Mn) of 1.68 from the GPC elution curve. It was confirmed that. From the measurement result of ¹ H-NMR, the obtained polymer was found to contain monomer 10 and monomer 2 in a content ratio of 70:30.

[Comparative Synthesis Example 5] Copolymerization of the following monomer 11 and monomer 2 (0.7: 0.3), comparative polymer 5
In a 500 mL flask, 27.4 g of the following monomer 11 and 27.2 g of monomer 2 were dissolved in 100 mL of toluene, and after sufficiently removing oxygen in the system, 0.33 g of initiator AIBN was charged and the temperature was raised to 60 ° C. The polymerization reaction was carried out 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 tetrahydrofuran and pouring it into 10 L of hexane to precipitate the polymer was repeated twice, and then the polymer was separated and dried. The 31.2 g of the white polymer thus obtained has a weight average molecular weight of 6,500 g / mol according to the light scattering method, and has a dispersity (= Mw / Mn) of 1.58 from the GPC elution curve. It was confirmed that. From the measurement result of ¹ H-NMR, it was found that the obtained polymer contained monomer 11 and monomer 2 in a content ratio of 73:27.

[Evaluation example]
Measurement of polymer permeability 1 g of the polymer obtained was sufficiently dissolved in 20 g of propylene glycol monomethyl ether acetate (PGMEA) and filtered through a 0.2 μm filter to prepare a polymer solution.
The polymer solution was spin-coated on an 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.

＊本発明例

* Example of the present invention

Resist Preparation and Exposure A resist solution was prepared by a conventional method using the above polymers and the components shown below in the amounts shown in Table 2. Next, after spin-coating a resist solution obtained on a silicon wafer on which DUV-30 (manufactured by Brewer Science) was formed to a film thickness of 55 nm, the resist solution was baked at 100 ° C. for 90 seconds using a hot plate. The thickness was 200 nm. This was exposed with an F ₂ excimer laser (Risotech Japan, VUVES-4500) while changing the exposure amount, and immediately after exposure, baked at 120 ° C. for 90 seconds, and with an aqueous solution of 2.38% tetramethylammonium hydroxide. Development was performed for 60 seconds to determine the relationship between the exposure amount and the remaining film ratio. The exposure amount at which the film thickness became 0 was determined as Eth, and the sensitivity of the resist and the tan θ of the gradient at that time were determined as γ.

＊本発明例（実施例）

* Example of the present invention (Example)

In the dry etching resistance test, a polymer solution obtained by dissolving 2 g of polymer in 10 g of PGMEA and filtered through a 0.2 μm size filter was formed on a Si substrate by spin coating to form a film having a thickness of 300 nm. It was evaluated with.
(1) Etching test with CHF ₃ / CF ₄ gas Using a dry etching apparatus TE-8500P manufactured by Tokyo Electron Co., Ltd., the difference in film thickness of the polymer film before and after etching was determined.
Etching conditions are as shown below.
Chamber pressure 40.0Pa
RF power 1,300W
Gap 9mm
CHF ₃ gas flow rate 30ml / min
CF ₄ gas flow rate 30ml / min
Ar gas flow rate 100ml / min
60 sec
₍₂₎ Cl ₂ / BCl ₃ system using an etching test Nichiden Anelva Co., Ltd. dry etching apparatus L-507D-L Gas was calculated the difference between the film thickness of before and after etching of the polymer film.
Etching conditions are as shown below.
Chamber pressure 40.0Pa
RF power 300W
Gap 9mm
Cl ₂ gas flow rate 30ml / min
BCl ₃ gas flow rate 30ml / min
CHF ₃ gas flow rate 100ml / min
O ₂ gas flow rate 2ml / min
60 sec

From Table 2, it was found 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). Further, as a result of VUVES exposure, it was found that the film thickness decreased as the exposure amount increased, showed the characteristics of a positive resist, and was excellent in etching resistance.

Claims (8)

A polymer compound having a repeating unit (m unit and p unit) represented by the following general formula (2).

(Wherein R ¹ is a fluorine atom or a linear, branched or cyclic alkyl group having 1 to 15 carbon atoms having at least one fluorine atom. R ² is a linear chain having 1 to 15 carbon atoms. R ³ represents a methylene group, an ethylene group, an oxygen atom, or a sulfur atom, a is an integer of 0 to 2, and R ⁸ is a hydrogen atom. , A fluorine atom, a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms or a fluorinated alkyl group, R ⁹ is a single bond or a divalent hydrocarbon having 1 to 4 carbon atoms. Groups R ¹⁰ and R ¹¹ are the same or different and are a hydrogen atom, a fluorine atom, an alkyl group having 1 to 4 carbon atoms or a fluorinated alkyl group, and one or both of R ¹⁰ and R ¹¹ are comprising at least one fluorine atom .R ¹² are hydrogen atoms , Or a straight, a branched or cyclic alkyl group, or an acid labile group is a good .R ¹³ be a hydrogen atom or a methyl group .m, p is the The abundance ratio of repeating units is shown, and m + p = 1, m is 0.1 to 0.9, p is 0.1 to 0.9, d is an integer of 0 to 4, and e is 1 to 3 Is an integer.) The polymer compound according to claim 1, wherein R ¹ is a trifluoromethyl group.   A resist material comprising the polymer compound according to claim 1. (A) The polymer compound according to claim 1 or 2,
(B) an organic solvent,
(C) A chemically amplified positive resist material containing an acid generator.   The resist material according to claim 4, further comprising a basic compound.   The resist material according to claim 4 or 5, further comprising a dissolution inhibitor. (1) A step of applying the resist material according to any one of claims 3 to 6 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 7, wherein the high energy beam is an F ₂ laser, an Ar ₂ laser, or a soft X-ray.