TWI226509B - Positive resist composition - Google Patents
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- TWI226509B TWI226509B TW090122094A TW90122094A TWI226509B TW I226509 B TWI226509 B TW I226509B TW 090122094 A TW090122094 A TW 090122094A TW 90122094 A TW90122094 A TW 90122094A TW I226509 B TWI226509 B TW I226509B
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/039—Macromolecular compounds which are photodegradable, e.g. positive electron resists
- G03F7/0392—Macromolecular compounds which are photodegradable, e.g. positive electron resists the macromolecular compound being present in a chemically amplified positive photoresist composition
- G03F7/0397—Macromolecular compounds which are photodegradable, e.g. positive electron resists the macromolecular compound being present in a chemically amplified positive photoresist composition the macromolecular compound having an alicyclic moiety in a side chain
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/0045—Photosensitive materials with organic non-macromolecular light-sensitive compounds not otherwise provided for, e.g. dissolution inhibitors
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/0046—Photosensitive materials with perfluoro compounds, e.g. for dry lithography
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/039—Macromolecular compounds which are photodegradable, e.g. positive electron resists
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/039—Macromolecular compounds which are photodegradable, e.g. positive electron resists
- G03F7/0392—Macromolecular compounds which are photodegradable, e.g. positive electron resists the macromolecular compound being present in a chemically amplified positive photoresist composition
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/039—Macromolecular compounds which are photodegradable, e.g. positive electron resists
- G03F7/0392—Macromolecular compounds which are photodegradable, e.g. positive electron resists the macromolecular compound being present in a chemically amplified positive photoresist composition
- G03F7/0395—Macromolecular compounds which are photodegradable, e.g. positive electron resists the macromolecular compound being present in a chemically amplified positive photoresist composition the macromolecular compound having a backbone with alicyclic moieties
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- General Physics & Mathematics (AREA)
- Materials For Photolithography (AREA)
- Exposure And Positioning Against Photoresist Photosensitive Materials (AREA)
Abstract
Description
1226509 五、發明說明(1 ) 【技術領域】 本發明係有關一種使用於平版印刷板或I C等半導體製 造工程、液晶、熱針頭等電路基板的製造、以及其他光阻 應用工程之化學放大系正型光阻組成物,更詳言之,係有 關一種特別適合作爲感應i線等紫外線、準分子雷射光 (F2、XeCl、KrF、ArF)等遠紫外線、電子線、分子線、r 線、冋步加速益放射線寺Is射線的局積體電路製作用光阻 所使用的光阻組成物。 【先前技術】 爲更提局積體電路之集積度,於製造超LSI等之半導體 基板中必須使由半微米以下線寬所成的超微細圖案加工。 爲達成該必要的解像力時,使光刻術中所使用的曝光裝置 之使用波長更爲短波化,且目前亦檢討遠紫外線光或準分 子雷射光(XeCl、KrF、ArF等)。另外,更檢討藉由電子線 直描或經由光罩一起曝光等。 而且,伴隨積體電路之高積體化度、晶圓之蝕刻方式係 自習知晶圓移行至乾式蝕刻,故必須具有耐蝕刻性、耐熱 性。由習知酚醛淸漆樹脂與萘醌二疊氮化合物所成的光阻 劑雖具有良好的耐乾蝕刻性、耐熱性,使其使用紫外線光 或準分子雷射光形成微影術圖案時,由於在酚醛淸漆樹脂 及萘醌二疊氮之紫外線範圍中吸收強,故光不易到達光阻 劑底部、無法以低感度製得錐形圖案。。 爲解決上述問題時,有美國專利第449 1 628號、歐洲專 1226509 五、發明說明(2) 利第249 1 39號、日本特開昭59 - 43439號、P〇lym. Eng. Sci . ’ 23( 18) ’ 1 0 1 2 ( 1 983 )等所記載的化學放大系光阻組 成物。化學放大系正型光阻組成物係藉由遠紫外光等之放 射線照射、在曝光部生成酸、藉由以該酸作爲觸媒反應, 以變化對活性放射線之照射部與非照射部對顯像液而言的 溶解度、在基板上形成圖案之圖案形成材料。 上述正型化學放大系光阻組成物分爲由藉由放射線曝光 產生酸之化合物(光酸發生劑)、及具有酸分解性基之鹼可 溶性樹脂所成的2成分系(美國專利4 4 9 1 6 2 8等)、與由藉 由鹼可溶性樹脂、光酸發生劑及酸之觸媒反應成具鹼可溶 性之溶解阻止化合物(酸分解性溶解阻止劑)所成的3成分 系(歐洲專利249 1 39、特開平2 - 24895 3等)。於此等之中 任一系皆與由酚醛淸漆樹脂與萘醌二疊氮化合物所成的光 阻劑相同,爲達成高解像力時必須增大曝光部與非曝光部 之溶解速度差。另外,可使用在上述2成分系中加入鹼溶 解抑制化合物之多成分系。 伴隨進行微細加工、使用任一曝光光源時,企求具有高 解像力,且企求孤立線之線寬再現性優異的光阻組成物。 孤立線係爲使相鄰線空有廣大空間位置的線,伴隨微細加 工、會有該孤立線自基板界面飛離、消失的問題產生。 該化學放大系光阻組成物中,爲使沒有輝紋情形產生、 提高塗覆性時,一般可配合界面活性劑。一般的界面活性 劑例如有聚環氧乙烷烷醚類、聚環氧乙烷烷基烯丙醚類、 1226509 五、發明說明(3) 聚環氧乙烷•聚環氧丙烷嵌段共聚物類、山梨糖醇脂肪酸 酯類、聚環氧乙烷山梨糖醇脂肪酸酯類等非離子系界面活 性劑、及氟系界面活性劑、有機矽氧烷聚合物或丙烯酸系 或甲基丙烯酸系(共)聚合聚合物等。另外,特公平7-2 1 626中揭示一種半導體微細加工用光阻組成物,其特徵 爲含有鹼可溶性樹脂、至少單氧化單羧酸酯之有機溶劑、 氟系界面活性劑及放射線感應性物質所成。另外,特開平 7 - 24687 3號公報中揭示組合特定構造之溶劑與氟系界面活 性劑及特開2000 - 1 62768公報中揭示使用特定構造之氟系 界面活性劑的化學放大系光阻組成物。 然而,即使使用上述界面活性劑時,仍無法具有改善輝 紋情形等之塗覆性、孤立線飛離的功能,企求孤立線之線 寬再現性。 而且,電子線或X光在下一世代或下下一世代之圖案形 成技術中,企求開發達成高解像度、高感度且爲矩形輪廓 之光阻組成物,惟爲正型電子線或X線光阻劑時容易受到 大氣中鹼性污染物質影響或在照射裝置內外被曝光的影響 、表面難以溶化、且爲線圖案時會形成T - To p形狀(表面 爲T字狀遮篷),爲接觸孔圖案時表面會有凹槽形狀(在接 觸孔表面上形成遮篷)之問題。另外,爲防止凹槽形狀或 T-Top形狀時,黏合劑爲親水性時會有引起膜邊的問題。 【發明之揭示】 因此,本發明之目的係提供一種特別是於製造半導體裝 1226509 五、發明說明(4) 置等具有優異解像力的光阻組成物,以及具有高解力、孤 立線之線寬再線性優異的光阻組成物及具有高解像力、輪 廓形狀佳的電子線或X線用光阻組成物。 本發明人等再三深入硏究的結果,發現藉由在光阻組成 物中添加特定氟系聚合物時,可得高解像力及孤立線之線 寬再線性優異的光阻組成物。本發明爲基於詳細檢討氟化 脂肪族基者之製造工程或構造•組成分佈的見解所發明者 ,著眼於開發共聚合成分、或氟化脂肪族基之取代數,係 爲與習知含有氟系聚合物之感光層技術不同的技術思想。 換言之,本發明下述具有(1)或(2)構成之正型光阻組成物 基於對上述技術課題而言發揮優異效果、具高解像力、不 會降低感度、可抑制孤立線飛離問題之見解者。 本發明係由下述構成所成。 (1) 一種正型光阻組成物,其特徵爲含有 (A )( 1 )藉由酸作用分解、增大在鹼顯像液中之溶解性的 樹脂, (2 )鹼可溶性樹脂及藉由酸作用分解、增大在鹼顯像液 中之溶解性的化合物,或 . (3 )藉由酸作用分解、增大在鹼顯像液中之溶解性的樹 脂及藉由酸作用分解、增大在鹼顯像液中之溶解性的低分 子化合物, (B )藉由活性光線或放射線照射產生酸之化合物’以及 (C )藉由短鏈聚合法或寡聚法所製造的氟脂肪族化合物 1226509 五、發明說明(5) 衍生的在側鏈上具有氟化脂肪族基之高分子化合物。 (2) —種正型光阻組成物,其特徵爲含有 (A )( 1 )藉由酸作用分解、增大在鹼顯像液中之溶解性的 樹脂, (2 )鹼可溶性樹脂及藉由酸作用分解、增大在鹼顯像液 中之溶解性的化合物,或 (3 )藉由酸作用分解、增大在鹼顯像液中之溶解性的樹 脂及藉由酸作用分解、增大在鹼顯像液中之溶解性的低分 子化合物, (B )藉由活性光線或放射線照射產生酸之化合物,以及 (C)在側鏈上具有以下述通式(F 1 )所示氟化脂肪族基之 高分子化合物,且在該高分子化合物中混有通式(F1)中η 爲3,4,5及6之基,此時 η = 4之基的成分對η = 3,4,5及6之成分總而言爲40〜 97莫耳%、或 η = 3之基的成分對η = 3,4,5及6之成分總和而言爲40〜 97莫耳%之高分子化合物|2Υ——X-f-C—)-(CF2CF2)n F (F1)I m r3 1226509 五、發明說明(6) (其中’R2及R3係各表示氫原子、碳數1〜4個之烷基 ’ X係表示單鍵或2價鍵結基,γ係表示高分子主鏈,m係 表不0以上之整數,η係表示1以上之整數)。 作爲(1 )或(2 )之構成成分的在側鏈上具有氟化脂肪族基 之聚合物,與習知物相比時特別優異的原因爲目前所不知 者,係考慮下述之可能性。(1 )藉由短鏈聚合法或寡聚法 製造的氟化烷基之使用效果爲另一典型製造法,具有與電 解氟化法之構造不同的脂肪族烷基,或組成分佈較廣係極 爲有利的作用。例如利用混合碳數不同的氟化烷基、或混 合具有部分支鏈烷基構造之脂肪族氟化烷基的有利作用之 可能性。(2 )之構成要件優異係爲本發明人等之見解的支 持者,通式(1 )之典型氟化脂肪族基中以特定的碳數爲中 心値,且使用組成分佈者,可得優異的效果。 (3 ) —種電子線或X線用化學放大系正型光阻組成物, 其係於含有 (a )藉由電子線或X線照射產生酸之化合物、 (13)重量平均分子量爲3,000〜3000,000、且可滿足下述 條件(1 )及(2 )之鹼可溶性樹脂, (1)至少具有一種碳數6〜20之芳香環及在該芳香環上直 接或經由鍵結基連結有具乙烯性不飽和基之單聚物所衍生 的重複單位’ (b )該芳香環之^電子與芳香環上之取代基的非共有電 子對之間成立下述之關係 12265091226509 V. Description of the Invention (1) [Technical Field] The present invention relates to a chemical amplification system for a semiconductor manufacturing process such as a lithographic printing plate or an IC, a circuit substrate manufacturing such as a liquid crystal, a hot needle, and other photoresist application projects. Type photoresist composition, more specifically, relates to a kind of ultraviolet rays, excimer laser light (F2, XeCl, KrF, ArF) and other extreme ultraviolet rays, electron rays, molecular rays, r rays, ytterbium, etc. Photoresist composition for photoresist for step-by-step accelerating irradiation of Is-rays for localized body circuits. [Prior art] In order to increase the integration degree of local integrated circuits, it is necessary to process ultra-fine patterns with a line width of less than half a micrometer in manufacturing semiconductor substrates such as ultra-LSI. In order to achieve the necessary resolution, the wavelength of the exposure device used in photolithography is shortened, and far-ultraviolet light or excimer laser light (XeCl, KrF, ArF, etc.) is also currently being reviewed. In addition, we also review direct exposure by electron beams or exposure through a photomask. In addition, with the high integration of integrated circuits and the etching method of wafers, since the wafers are moved from dry etching to conventional etching, they must have etching resistance and heat resistance. Although the photoresist formed by the conventional phenolic lacquer resin and naphthoquinonediazide compound has good dry etching resistance and heat resistance, when it uses ultraviolet light or excimer laser light to form a lithography pattern, The phenolic lacquer resin and naphthoquinonediazide have strong absorption in the ultraviolet range, so light does not easily reach the bottom of the photoresist, and it is not possible to obtain a cone pattern with low sensitivity. . To solve the above problems, there are U.S. Patent No. 449 1 628, European Patent No. 1226509 V. Description of Invention (2) Lee No. 249 1 39, Japanese Patent Laid-Open No. 59-43439, Polym. Eng. Sci. 23 (18) '1 0 1 2 (1 983) and other chemically amplified photoresist compositions. The chemical amplification type positive photoresist composition is irradiated with radiation such as far ultraviolet light, generates an acid in the exposed portion, and reacts with the acid as a catalyst to change the irradiation portion of the active radiation to the non-irradiated portion. Pattern-forming material that has solubility in liquids and forms a pattern on a substrate. The positive-type chemically amplified photoresist composition is divided into a two-component system made of a compound (photoacid generator) that generates an acid by radiation exposure and an alkali-soluble resin having an acid-decomposable group (US Patent 4 4 9 1 6 2 8 etc.), 3-component system (Europe patent) which reacts with alkali-soluble resin, photoacid generator and acid catalyst to form alkali-soluble dissolution preventing compound (acid-decomposable dissolution inhibitor). 249 1 39, JP 2-24895 3, etc.). Any of these is the same as a photoresist made of a phenolic resin and a naphthoquinonediazide compound. In order to achieve a high resolution, it is necessary to increase the difference in dissolution rate between the exposed and non-exposed areas. In addition, a multi-component system in which an alkali-solubility-inhibiting compound is added to the two-component system can be used. When microfabrication is used and any exposure light source is used, a photoresist composition having high resolution and excellent line width reproducibility of isolated lines is sought. An isolated line is a line that has a large space in the adjacent line. With fine processing, the isolated line will fly away from the substrate interface and disappear. In the chemically amplified photoresist composition, a surfactant may be blended in general in order to prevent the occurrence of streaks and improve coating properties. General surfactants include, for example, polyethylene oxide alkyl ethers, polyethylene oxide alkyl allyl ethers, 1226509 5. Description of the invention (3) Polyethylene oxide-polypropylene oxide block copolymer Type, sorbitol fatty acid esters, polyethylene oxide sorbitol fatty acid esters and other non-ionic surfactants, and fluorine-based surfactants, organosiloxane polymers or acrylic or methacrylic ( Co-polymeric polymers, etc. In addition, Japanese Patent Publication No. 7-2 1 626 discloses a photoresist composition for semiconductor microfabrication, which is characterized by containing an alkali-soluble resin, an organic solvent of at least a mono-oxidized monocarboxylic acid ester, a fluorine-based surfactant, and a radiation-sensitive substance. Made. In addition, Japanese Patent Application Laid-Open No. 7-24687 discloses a combination of a solvent having a specific structure and a fluorine-based surfactant, and Japanese Patent Application Laid-Open No. 2000-1 62768 discloses a chemically amplified photoresist composition using a fluorine-based surfactant having a specific structure. . However, even when the above-mentioned surfactant is used, it is not possible to improve the coatability of the case such as the appearance of streaks and the function of flying out the isolated lines, and the line width reproducibility of the isolated lines has been sought. Moreover, in the pattern generation technology of the next generation or the next generation of electron beams or X-rays, it is sought to develop a photoresist composition having a high resolution, a high sensitivity, and a rectangular outline, but a positive electron beam or an X-ray photoresist The agent is susceptible to the effects of alkaline pollutants in the atmosphere or exposed to the inside and outside of the irradiation device. The surface is difficult to dissolve and a T-To p shape is formed when the line pattern is formed (the surface is a T-shaped awning). It is a contact hole. When patterning, the surface may have a groove shape (a awning is formed on the surface of the contact hole). In addition, in order to prevent a groove shape or a T-Top shape, the film edge may be caused when the adhesive is hydrophilic. [Disclosure of the invention] Therefore, the object of the present invention is to provide a photoresist composition with excellent resolution, especially for manufacturing semiconductor devices. Excellent photoresist composition and photoresist composition for electronic or X-rays with high resolution and good contour shape. As a result of intensive research, the present inventors have found that by adding a specific fluorine-based polymer to the photoresist composition, a photoresist composition having high resolution and excellent line width of the isolated line and excellent linearity can be obtained. The present inventor is based on the insights on the manufacturing process, structure, and composition distribution of those who have reviewed fluorinated aliphatic groups in detail. The inventors focused on the development of copolymerization components or the substitution numbers of fluorinated aliphatic groups. Different technical ideas of the photosensitive layer technology of the polymer. In other words, the following positive-type photoresist composition of the present invention having the structure (1) or (2) is based on the above-mentioned technical problems that exhibit excellent effects, have high resolution, do not reduce sensitivity, and can suppress the problem of isolated line flying away. Insights. This invention is comprised by the following structures. (1) A positive photoresist composition, characterized by containing (A) (1) a resin which is decomposed by an acid to increase solubility in an alkali developing solution, (2) an alkali-soluble resin and Compounds that decompose and increase the solubility in alkaline imaging solution by acid action, or. (3) Resins that decompose and increase the solubility in alkali imaging solution by acid action and decompose and increase Low-molecular-weight compounds that are soluble in alkaline imaging solutions, (B) compounds that generate acids by irradiation with active light or radiation 'and (C) fluoroaliphatic compounds produced by short-chain polymerization or oligomerization Compound 1226509 5. Description of the invention (5) A polymer compound derived from a fluorinated aliphatic group on a side chain. (2) a type of positive photoresist composition, which is characterized by containing (A) (1) a resin that is decomposed by an acid to increase the solubility in an alkali developing solution, (2) an alkali-soluble resin and a resin Compounds that are decomposed by an acid to increase the solubility in an alkali developer, or (3) resins that decompose by an acid to increase the solubility in an alkali developer, and decomposed and increased by an acid. Low-molecular-weight compounds that are largely soluble in an alkali imaging solution, (B) a compound that generates an acid by irradiation with active light or radiation, and (C) have a fluorine represented by the following general formula (F 1) on the side chain Aliphatic polymer compound, and the polymer compound is mixed with a base of general formula (F1) in which η is 3, 4, 5, and 6; at this time, the component of the base of η = 4 is η = 3, The composition of 4, 5, and 6 is 40 to 97 mol% in total, or the composition of η = 3 is 40 to 97 mol% in total for η = 3, 4, 5, and 6 Molecular compound | 2Υ——XfC —)-(CF2CF2) n F (F1) I m r3 1226509 5. Description of the invention (6) (wherein 'R2 and R3 each represent a hydrogen atom and an alkyl group having 1 to 4 carbon atoms 'X means single bond or 2 valence For bonding groups, γ represents the polymer main chain, m represents an integer of 0 or more, and η represents an integer of 1 or more). As a component of (1) or (2), a polymer having a fluorinated aliphatic group on a side chain is particularly excellent when compared with conventional ones. The reason is currently unknown, and the following possibilities are considered. . (1) The effect of using a fluorinated alkyl group produced by a short-chain polymerization method or an oligomerization method is another typical manufacturing method. It has an aliphatic alkyl group with a structure different from that of the electrolytic fluorination method, or has a broader composition distribution. Very beneficial effect. For example, it is possible to use the advantageous effect of mixing fluorinated alkyl groups having different carbon numbers, or mixing aliphatic fluorinated alkyl groups having a partially branched alkyl structure. The excellent constitutional requirements of (2) are the proponents of the inventors' opinions. The typical fluorinated aliphatic group of the general formula (1) is centered on a specific carbon number, and those who use the composition distribution can obtain excellent results. Effect. (3) A type of positive photoresist composition for chemical amplification of electron rays or X-rays, which is composed of (a) a compound that generates an acid by irradiation with electron rays or X-rays, and (13) a weight average molecular weight of 3,000 to 3,000,000 alkali-soluble resins that can satisfy the following conditions (1) and (2), (1) at least one aromatic ring having 6 to 20 carbon atoms, and the aromatic ring is directly or via a bonding group connected to the aromatic ring A repeating unit derived from a monopolymer having an ethylenically unsaturated group '(b) The following relationship is established between the electron of the aromatic ring and the non-shared electron pair of a substituent on the aromatic ring: 1226509
五、發明說明(7) (式1) + 2 Ni〇ne g 1 〇 (其中,Ν 7Γ係表示V電子總數’ N i。n e係表示作爲取代 基之碳數1〜12之直鏈狀、支鏈狀、或環狀烷氧基、烯氧 基、芳氧基、芳烷氧基、或羥基之非共有電子對的總電子 數,2個以上相鄰的院氧基或羥基互相鍵結以形成5碳數 以上之環構造,惟苯并二噁唑構造除外,且Ν 7Γ =6時該取 代基不含羥基)。 (4 )如上述(3 )之電子線或X光化學放大系正型光阻組成 物,其中(b )鹼可溶性樹脂係爲至少具有一種以下述通式 (1 )〜(5 )所示重複構造單位作爲構成成分,V. Description of the invention (7) (Formula 1) + 2 Ni〇ne g 1 〇 (wherein N 7Γ represents the total number of V electrons' N i. Ne represents a straight chain having 1 to 12 carbon atoms as a substituent, Total number of branched or cyclic alkoxy, alkenyloxy, aryloxy, aralkoxy, or non-shared electron pairs of hydroxy groups. Two or more adjacent oxo groups or hydroxy groups are bonded to each other. In order to form a ring structure with more than 5 carbons, except for the benzodioxazole structure, and the substituent does not contain a hydroxyl group when N 7Γ = 6). (4) The electron beam or X-ray chemical amplification type positive photoresist composition according to the above (3), wherein (b) the alkali-soluble resin has at least one type repeated as shown in the following general formulae (1) to (5) Structural units as constituents,
- (〇Rc)n (ORb)m 1226509 五、發明說明(8)-(〇Rc) n (ORb) m 1226509 V. Description of the invention (8)
Rioi —(-ch2c-)— {Rd〇)p- ,(〇Rg)s ⑵-(〇Rh)t (Re〇)q (Rf〇)r (OR)Rioi — (-ch2c-) — {Rd〇) p-, (〇Rg) s ⑵- (〇Rh) t (Re〇) q (Rf〇) r (OR)
(〇Rf)r (〇Ri)t (RgO) (〇Rh)t (3) {Rd〇)p(ReO)(〇Rf) r (〇Ri) t (RgO) (〇Rh) t (3) (Rd〇) p (ReO)
-fCH2C-fCH2C
(ORk)v (Rt〇)r (Rg〇)s \ (°R^ (ORi) (ORfOt ⑷ -10- 1226509 五、發明說明(9)(ORk) v (Rt〇) r (Rg〇) s \ (° R ^ (ORi) (ORfOt ⑷ -10- 1226509) V. Description of the invention (9)
(其中,R π),係表示氫原子或甲基,L係表示二價鍵結基 ,Ra 、 Rb 、 Rc 、 Rd 、 Re 、 Rf 、 Rg 、 Rh 、 Ri 、 Rj 、 Rk 、 R1 係 -11- 1226509 五、發明說明(1〇) 係各獨立地表示碳數1〜1 2之直鏈狀、支鏈狀、或環狀烷 基、烯基、芳基、芳烷基、或氫原子’而且,此等可相互 連結形成碳數24以下之5碳以上的環,1、m、η、p、q、 r、s、t、u、v、w、x係表不 〇〜3之整數、可滿足 , 3 、 p + cj+r二0,1,2,3 、 s + t + u = 0,l,2,3 、 v + w + x = 0,1,2,3,惟通式(1)中Ra、Rb、Rc不可爲氫原子 且於通式(1 )中除苯并二11惡D坐構造外)。 (5 ) —種電子線或X線用化學放大系正型光阻組成物, 其特徵爲含有 (a )藉由電子線或X線照射產生酸之化合物、 (b’)重量平均分子量爲3,000〜300,000、且可滿足下述 條件(1 )及(2 )之藉由酸作用、分解增大在鹼顯像液中之溶 解性的樹脂, (1)至少具有一種碳數6〜20之芳香環及在該芳香環上直 接或經由鍵結基鍵結有具乙烯性不飽和基之單體所衍生的 重複單位, (2 )該芳香環之7Γ電子與芳香環上之取代基的非共有電 子對之間成立下述之關係,(式υΝ7Γ + Ni〇ne -12- 1226509 五、發明說明(11 ) 爲取代基 、嫌氧基 總電子數 5碳數以 時該取代 正型光阻 種以下述 (其中,Νττ係表示7Γ電子總數,NUne係表示f 之碳數1〜丨2之直鏈狀、支鏈狀、或環狀烷氧連 、芳氧基、芳烷氧基、或羥基之非共有電子對皆 ,2個以上相鄰的烷氧基或羥基互相鍵結以形成 上之環構造,惟苯并二噁唑構造除外,且Ν 7Γ 基不含羥基)。 (6 )如上述(5 )之電子線或X線用化學放大2 組成物,其中(b ’)鹼可溶性樹脂係爲至少具有一 通式(1 )〜(5 )所示重複構造單位作爲構成成分, -13 —--- 1226509 五、發明說明(12) R1(Where, R π) represents a hydrogen atom or a methyl group, and L represents a divalent bonding group. Ra, Rb, Rc, Rd, Re, Rf, Rg, Rh, Ri, Rj, Rk, R1 are -11. -1226509 V. Description of the invention (10) is a linear, branched, or cyclic alkyl, alkenyl, aryl, aralkyl, or hydrogen atom each independently representing a carbon number of 1 to 12 In addition, these can be connected to each other to form a ring of 5 or more carbons with a carbon number of 24 or less. 1, 1, m, η, p, q, r, s, t, u, v, w, and x are integers of 0 to 3. , Satisfiable, 3, p + cj + r two 0, 1, 2, 3, s + t + u = 0, 1, 2, 3, v + w + x = 0, 1, 2, 3, only In the formula (1), Ra, Rb, and Rc cannot be hydrogen atoms and in the general formula (1), except for the benzodioxine structure. (5) A chemically amplified positive photoresist composition for electron or X-rays, characterized in that it contains (a) a compound that generates an acid by irradiation with electrons or X-rays, and (b ') a weight average molecular weight of 3,000 ~ 300,000 Resins which can satisfy the following conditions (1) and (2) to increase the solubility in alkali developing solution by acid action and decomposition, (1) at least one aromatic having 6 to 20 carbon atoms Ring and a repeating unit derived from a monomer having an ethylenically unsaturated group bonded directly or via a bonding group on the aromatic ring, (2) the 7Γ electron of the aromatic ring and the substituent on the aromatic ring are not shared The following relationship is established between the electron pairs: (Formula υΝ7Γ + Ni〇ne -12-1226509 V. Description of the invention (11) is a substituent, and the total number of susceptible oxygen groups is 5 carbons or less. Let the following (where Nττ represents the total number of 7Γ electrons, and NUne represents the linear, branched, or cyclic alkoxy, aryloxy, aralkoxy, or hydroxyl group of carbon number 1 to 2 of f The non-shared electron pairs are all. Two or more adjacent alkoxy groups or hydroxyl groups are bonded to each other to form an upper ring structure. Except for the benzodioxazole structure, and the N 7Γ group does not contain a hydroxyl group.) (6) The chemically amplified 2 composition for electron or X-rays as described in (5) above, wherein (b ′) the alkali-soluble resin is at least A repeating structural unit represented by the general formulae (1) to (5) as a constituent, -13 ----- 1226509 V. Description of the invention (12) R1
⑴ (RaO)l -(〇Rc)n (〇Rb)m⑴ (RaO) l-(〇Rc) n (〇Rb) m
Ri -fCH2i (明 (Re〇)Ri -fCH2i (Ming (Re〇)
{〇Rh)t ⑵ (Rp)r (〇取(〇Rh) t ⑵ (Rp) r (〇 取
?101 CH2c-)-? 101 CH2c-)-
(0Rf)r (ORJu ⑶ 4- 1226509(ORF) r (ORJu ⑶ 4- 1226509
1226509 五、發明說明(14) 係各獨立地表示碳數1〜12之直鏈狀、支鏈狀、或環狀烷 基、烯基、芳基、芳烷基、氫原子或酸分解性基’而且, 此等可相互連結形成碳數24以下之5碳以上的環,1、m 、n、p、q、r、s、t、u、v、w、X係表不0〜3之整數、可 滿足 1+m+n=2,3 、 p+q+r=0,1,2,3 、 s+t+u=0,1,2,3 、 v + w + x:z〇 ,1,2,3,惟通式(1)中Ra、Rb、Rc不可爲氫原子 且於通式(1 )中除苯并二噁唑構造外)。 (7 )如上述(3 )之電子線或X線用化學放大系正型光阻 組成物,其中(b )驗可溶性樹脂之分子量分佈爲1 . 〇〜1 . 5 〇 (8 )如上述(5 )之電子線或X線用化學放大系正型光阻 組成物,其中(b ’)藉由酸作用、分解增大在鹼顯像液中之 溶解性的樹脂之分子量分佈爲1 . 0〜1 . 5。 (9 )如上述(3 )〜(8 )中任一項之電子線或X線用化學放 大系正型光阻組成物,其中另含有(c )具有藉由酸分解之 基、且藉由酸作用增大在鹼顯像液中之溶解性、分子量 3 0 00以下的低分子溶解阻止化合物。 (1 0 )如上述(3 )〜(9 )中任一之電子線或X線用化學放 大系正型光阻組成物,其中另含有(d )具有陽離子聚合性 機能之化合物。 (1 1 )如上述(3 )〜(1 〇 )中任一項之電子線或X線用化學 放大系正型光阻組成物,其中(d,)爲至少一種選自於乙烯 化合物、環鏈烷化合物、環狀醚化合物、內酯化合物、醛 -16- 1226509 五、發明說明(15) 化合物之化合物。 (1 2 )如上述(1 1 )之電子線或X線用化學放大系正型光 阻組成物,其中(d ’)係爲以通式(A )所示之化合物, 一般式㈧1226509 V. Description of the invention (14) are linear, branched, or cyclic alkyl, alkenyl, aryl, aralkyl, hydrogen atom, or acid decomposable groups each independently representing a carbon number of 1 to 12. 'In addition, these can be connected to each other to form a ring of 5 or more carbons with a carbon number of 24 or less. 1, 1, m, n, p, q, r, s, t, u, v, w, and X are 0 to 3 Integer, can satisfy 1 + m + n = 2,3, p + q + r = 0,1,2,3, s + t + u = 0,1,2,3, v + w + x: z〇 , 1,2,3, except that Ra, Rb, and Rc in the general formula (1) cannot be hydrogen atoms and in the general formula (1) (except for the benzodioxazole structure). (7) The positive-type photoresist composition for chemical amplification of electron rays or X-rays as described in (3) above, wherein (b) the molecular weight distribution of the test-soluble resin is 1.0 to 1.5 as described above (8) 5) The chemical amplification type positive photoresist composition for electron or X-rays, in which (b ′) the molecular weight distribution of the resin which increases the solubility in the alkali developing solution by the action of acid is decomposed to 1.0. ~ 1.5. (9) The chemical amplification type positive photoresist composition for an electron beam or an X-ray according to any one of (3) to (8) above, further containing (c) having a base decomposed by an acid and by Acidic action increases compounds' solubility in alkaline imaging solutions and low molecular weight dissolution preventing compounds with molecular weights below 3,000. (10) The chemical amplification type positive photoresist composition for electron or X-rays according to any one of (3) to (9) above, further containing (d) a compound having a cation polymerizable function. (1 1) The chemical amplification type positive photoresist composition for electron or X-rays according to any one of (3) to (10) above, wherein (d,) is at least one selected from the group consisting of an ethylene compound, a ring Paraffinic compounds, cyclic ether compounds, lactone compounds, aldehydes-16-1226509 5. Compounds of the compound of the invention (15). (1 2) The chemical amplification type positive photoresist composition for electron or X-rays as described in (1 1) above, wherein (d ') is a compound represented by general formula (A), and general formula ㈧
/0-¾ \ R〇 (其中,Ra、Rb、Rc係表示相同或不同的氫原子、可具 取代基之烷基或芳基,且此等之中有2個可鍵結形成飽和 或烯烴系不飽和環,Rd係表示烷基或取代烷基)。 (1 3 )如上述(3 )〜(1 2 )中任一項之電子線或X線用化學 放大系正型光阻組成物,其中(a )藉由電子線或X線照射 產生酸之化合物係爲至少含有一種下述通式(I )〜(I I I )所 示之化合物, -17- 1226509 五、發明說明(16/ 0-¾ \ R〇 (wherein Ra, Rb, and Rc represent the same or different hydrogen atom, an alkyl group or an aryl group which may have a substituent, and 2 of these may be bonded to form a saturated or olefin (Unsaturated ring, Rd means alkyl or substituted alkyl). (1 3) The chemical amplification type positive photoresist composition for electron or X-rays according to any one of (3) to (1 2) above, wherein (a) the acid or The compound system contains at least one compound represented by the following general formulae (I) to (III). -17-1226509 V. Description of the invention (16
RR
29 D29 D
R 35 X (III) (/、中Rl 係表示相同或不同的氫原子、直鏈狀、支 鏈狀或環狀烷基、直鏈狀、支鏈狀或環狀烷氧基、羥基、 鹵素原子、或-s-r38,r38係表示直鏈狀、支鏈狀或環狀烷 基或芳基,R^Rm、Rl6〜R27、R28〜R37中有2個以上鍵結形 成含有單鍵、至少一種或二種以上選自於氧、硫、及氮之R 35 X (III) (/, in which Rl represents the same or different hydrogen atom, linear, branched or cyclic alkyl, linear, branched or cyclic alkoxy, hydroxyl, halogen Atom, or -s-r38, where r38 represents a linear, branched, or cyclic alkyl or aryl group. Two or more of R ^ Rm, R16 ~ R27, and R28 ~ R37 form a single bond, At least one or two or more selected from the group consisting of oxygen, sulfur, and nitrogen
-18- 1226509 五、發明說明(17) X -係表不擴酸之^離子)。 (1 4 )如上述(1 3 )之電子線或X線用化學放大系正型光 阻組成物,其中x _係表示具有至少一種選自於 至少一個氟原子、 至少一個以氟取代的直鏈狀、支鏈狀或環狀烷基、 至少一個以氟取代的直鏈狀、支鏈狀或環狀烷氧基、 至少一'個以氣取代的酿基、 至少一個以氟取代的醯氧基、 至少一個以氟取代的磺醯基、 至少一個以氟取代的磺醯氧基、 至少一個以氟取代的磺醯胺基、 至少一個以氟取代的芳基、 至少一個以氟取代的芳烷基、及 至少一個以氟取代的烷氧基羰基 之苯磺酸、萘磺酸、蒽磺酸的陰離子。 (1 5 )如上述(3 )〜(1 4 )中任一項之電子線或X線用化學 放大系正型光阻組成物,其中溶劑主要含有丙二醇單甲醚 乙酸酯。 (16)如上述(3)〜(15)中任一項之電子線或X線用化學 放大系正型光阻組成物,其中另含有(e )有機鹼性化合物 〇 (1 7 )如上述(3 )〜(1 6 )中任一項之電子線或X線用化學 放大系正型光阻組成物,其中另含有(f )氟系及/或矽系界 -19- 1226509 五、發明說明(18) 面活性劑。 【發明之實施型態】 [I ]首先’詳細說明有關藉由本發明具高解像力、且優 異孤線之線寬再線性的光阻組成物之上述(丨)及(2 )構成 的正型光阻組成物。 首先’說明有關(C)成分之在側鏈上具有氟化脂肪族基 之高分子化合物(簡稱爲「氟系聚合物」)。 本發明所使用的氟系聚合物可以爲滿足(1 )及(2 )構成所 口己載的要件者之大部分聚合物形態。具體的形態可使用丙 烯酸樹脂、甲基丙烯酸樹脂、苯乙烯樹脂、聚酯樹脂、聚 胺基甲酸酯樹脂、聚碳酸酯樹脂、聚醯胺樹脂、聚縮醛樹 脂、苯酚/甲醛縮合樹脂、聚乙烯苯酚樹脂、馬來酸酐/ α -烯烴樹脂、α -雜環取代甲基丙烯酸樹脂等。其中,丙烯 酸樹脂 '甲基丙烯酸樹脂 '苯乙烯樹脂、聚酯樹脂、聚胺 基甲酸酯樹脂較佳,更佳者爲丙烯酸樹脂、甲基丙烯酸樹 月旨、聚胺基甲酸酯樹脂。 本發明側鏈所使用的氟化脂肪族基之一係爲藉由短鏈聚 合法(即短鏈聚合物法)或寡聚法(即寡聚物法)製造的由氟 化脂肪族化合物衍生者。有關此等氟化脂肪族化合物之製 造法’例如「氟化合物之合成與機能」(監修:石川延南 、發行:西耶姆西(譯音)、1 987 )之1 1 7〜1 1 8頁、或「 Chemistry 〇 f Organic Fluorine Compound II 」 (Monograph 187^ Ed by Milos Hudlicky and Attila E. -20- 1226509 五、發明說明(19) Pavlath, American Chemical Society 1995)之 747-752 頁記載。短鏈聚合法係使碘化物等連鏈移動常數大的鹵化 烷基作爲短鏈聚合劑,進行四氟化伸乙基等含氟的乙烯化 合物之游離基聚合以合成短鏈聚合物的方法(S c h e m e - 1例 示)。 Scheme*! R —I + n F2C=CF2 -^ R-^CF2CF^~\ 所得的末端碘化短鏈聚合物通常爲例如施予[Scheme2] 之適當末端化學修飾,導入於氟化脂肪族化合物。此等化 合物視其所需另使用於變換成所企求單體構造的含氟化脂 肪族基之聚合物製造。-18- 1226509 V. Description of the invention (17) X-is an ion which does not extend the acid). (1 4) The chemical amplifying positive photoresist composition for electronic or X-rays as described in (1 3) above, wherein x_ represents a compound having at least one member selected from at least one fluorine atom and at least one fluorine-substituted direct photoresist composition. Chain, branched or cyclic alkyl, at least one linear, branched or cyclic alkoxy substituted with fluorine, at least one alkynyl substituted with gas, at least one substituted with fluorene Oxygen, at least one sulfonyl group substituted with fluorine, at least one sulfonyl group substituted with fluorine, at least one sulfonyl group substituted with fluorine, at least one aryl group substituted with fluorine, at least one substituted with fluorine Anions of aralkyl, and at least one fluorine-substituted alkoxycarbonyl benzenesulfonic acid, naphthalenesulfonic acid, and anthracenesulfonic acid. (1 5) The chemically amplifying positive photoresist composition for electronic or X-rays according to any one of (3) to (1 4) above, wherein the solvent mainly contains propylene glycol monomethyl ether acetate. (16) The chemical amplification type positive photoresist composition for electron rays or X-rays according to any one of the above (3) to (15), which further contains (e) an organic basic compound 〇 (1 7) is as described above (3) ~ (16) The positive amplification composition of the chemical amplification system for electronic or X-rays, further containing (f) a fluorine-based and / or silicon-based boundary-19-1226509 V. Invention Note (18) Surfactants. [Implementation Mode of the Invention] [I] First, the positive-type light composed of the above-mentioned (丨) and (2) regarding the photoresist composition having high resolution and excellent solitary line width and then linearity will be described in detail Resistance composition. First, a polymer compound having a fluorinated aliphatic group on the side chain (referred to as "fluorine polymer") of the component (C) will be described. The fluorine-based polymer used in the present invention can be in the form of most polymers satisfying the requirements contained in (1) and (2). Specific forms include acrylic resin, methacrylic resin, styrene resin, polyester resin, polyurethane resin, polycarbonate resin, polyamide resin, polyacetal resin, phenol / formaldehyde condensation resin, Polyvinylphenol resin, maleic anhydride / α-olefin resin, α-heterocyclic substituted methacrylic resin, and the like. Among them, acrylic resin 'methacrylic resin' styrene resin, polyester resin, and polyurethane resin are preferable, and acrylic resin, methacrylic resin, and polyurethane resin are more preferable. One of the fluorinated aliphatic groups used in the side chain of the present invention is a derivative of a fluorinated aliphatic compound manufactured by a short-chain polymerization method (that is, a short-chain polymer method) or an oligomerization method (that is, an oligomer method). By. For the manufacturing method of these fluorinated aliphatic compounds, for example, "Synthesis and Function of Fluorochemical Compounds" (Supervision: Yannan Ishikawa, Issue: Siemsi (Transliteration), 1 987) Page 1 1 7 ~ 1 1 8 , Or "Chemistry 〇f Organic Fluorine Compound II" (Monograph 187 ^ Ed by Milos Hudlicky and Attila E. -20-1226509 V. Description of the Invention (19) Pavlath, American Chemical Society 1995), pages 747-752. The short-chain polymerization method is a method of synthesizing a short-chain polymer by using a halogenated alkyl group having a large chain shift constant, such as iodide, as a short-chain polymerization agent, and performing radical polymerization of a fluorine-containing ethylene compound such as ethylene tetrafluoride and ethylene. S cheme-1 example). Scheme *! R —I + n F2C = CF2-^ R- ^ CF2CF ^ ~ \ The resulting terminally iodinated short-chain polymer is usually an appropriate terminal chemical modification such as [Scheme2], and is introduced into a fluorinated aliphatic compound . These compounds are used, if necessary, in the manufacture of fluorinated aliphatic group-containing polymers transformed into the desired monomer structure.
Scheme2Scheme2
R-^CF2CF2y-CH2CH2—I R-^CF2CF2^CH2CH—CH2 R-^CF2CF2j-,R- ^ CF2CF2y-CH2CH2—I R- ^ CF2CF2 ^ CH2CH-CH2 R- ^ CF2CF2j-,
CH2CH2—OH R~f-CF2CF2j—CH=CH2 \ / nCH2CH2—OH R ~ f-CF2CF2j—CH = CH2 \ / n
R~^CF2CF2j-C02H 本發明在側鏈上具有氟化脂肪族基之高分子化合物之側 鏈上所導入的化合物之藉由上述短鏈聚合物法製造的適當R ~ ^ CF2CF2j-C02H In the present invention, the compound introduced into the side chain of a polymer compound having a fluorinated aliphatic group on the side chain is suitably produced by the short-chain polymer method described above.
-21 - 1226509 五、發明說明(2〇) 化合物具體例如賴金(譯音)化成品販賣股份有限公司販賣 的氟系化學製品八_111〇、^1210、八-丨310、八-1 420、八-1620、A- 2020、A- 1 260、A- 1 460、A- 1 660、A- 1 860、A- 1435、A-1635、A-1835、A-1473、A-1637、A-1820、請參 照原文P29之第1〜26行、或曰本梅克頓龍(譯音)股份有 限公司製造,DCHEMINOX FA、FA-M、FAAC、FAAC-M、 FAMAC、FAMAC-M等,此等氟系化學製品之主成分構造係爲 以下述通式TM-1所示者(其中,^係表示〇〜20之整數)。 -22- 1226509 五、發明說明(21 t-(cf2)-z —T -CF3 ——CF2CF3 一 cf2cf2cf3 f3c、 CF— / f3c —cf2cf2h ——Z —ch2oh —ch=chch2oh —CH2CH2OH —CH2CHICH2OH 十CH七OH ——OCF2(CF3)CH2OH —co2h —I ——COCI -Br —ch2ch—ch2 V —ch2ch2i —ch2i —ch=ch2 —ch2nh2 \ ch2 o—^ 0 \ ch2—o—^ 0 —ch2ch2~o—/ o —CH2CH2 - o—^ o o —CH2CH(OH)-CH2—〇—/ o 此等氟系化學製品係藉由在該業者間習知的方法,可容 易地在側鏈上導入具有氟化脂肪族基之高分子化合物。上 -23- 1226509 五、發明說明(22) 述通式TM - 1中-Z以下式所示化合物,由於分子末端具有 丙烯醯基或甲基丙烯醯基,故藉由乙烯聚合可更爲簡單地 製得本發明具有氟化脂肪族基之高分子化合物、故爲所企 求。-21-1226509 V. Description of the invention (2) Specific examples of the compounds are fluorine-based chemicals sold by Lai Jin (Transliteration) Chemical Products Sales Co., Ltd. Ya-1620, A-2020, A-1260, A-1460, A-1660, A-1860, A-1435, A-1635, A-1835, A-1473, A-1637, A- 1820, Please refer to lines 1 to 26 of the original P29, or manufactured by Mecton Dragon (Transliteration) Co., Ltd., DCHEMINOX FA, FA-M, FAAC, FAAC-M, FAMAC, FAMAC-M, etc., etc. The main component structure of a fluorine-based chemical is represented by the following general formula TM-1 (where ^ represents an integer from 0 to 20). -22- 1226509 V. Description of the invention (21 t- (cf2) -z —T -CF3 ——CF2CF3 a cf2cf2cf3 f3c, CF— / f3c —cf2cf2h —Z —ch2oh —ch = chch2oh —CH2CH2OH —CH2CHICH2OH Ten CH7 OH ——OCF2 (CF3) CH2OH —co2h —I ——COCI -Br —ch2ch—ch2 V —ch2ch2i —ch2i —ch = ch2 —ch2nh2 \ ch2 o— ^ 0 \ ch2—o— ^ 0 —ch2ch2 ~ o— / o —CH2CH2-o— ^ oo —CH2CH (OH) -CH2—〇— / o These fluorine-based chemicals can be easily introduced into the side chain with fluorination by a method known to those skilled in the art. Aliphatic polymer compound. -23-12126509 V. Description of the invention (22) The compound represented by the formula -Z in the general formula TM-1 below -Z has a propylene fluorenyl group or methacryl fluorene group at the molecular end, so The polymer compound having a fluorinated aliphatic group according to the present invention can be more simply produced by ethylene polymerization, so it is desired.
另外,本發明較佳的使用藉由短鏈聚合法所得氟系化學 製品之在側鏈上具有氟化脂肪族基之高分子化合物本身一 般稱爲「含過氟烷基之寡聚物」,係在商業上可得手者、 予以使用。該化學製品例如藉由大日本油墨化學股份有限 公司製造、販賣的 MEGAFAC F-178K 、 MEGAFAC F-470 、 MEGAFAC F-473 、 MEGAFAC F-475 、 MEGAFAC F-476 、 MEGAFAC F_ 472、MEGAFAC R-08、或由旭玻璃股份有限公 司所製造的 SURFLON SdSl'S-SSS'SdQS'S-lOl'S-iOS 等 。於此 等之中 MEGAFAC F-178K(以 下稱爲 P-1) 、 -24- 1226509 五、發明說明(23) MEGAFAC F- 470 (以下稱爲 P-2)、MEGAFAC F- 47 3 (以下稱爲 P-3) 、 MEGAFAC F-475(以下稱爲 P-4) 、 MEGAFAC F476(以 下稱爲P-5)、MEGAFAC F- 472 (以下稱爲P-6),就不會引 起感度降低問題而言較佳。 於本發明中以藉由募聚法製造的氟化脂肪族化合物較佳 。寡聚法係以氟化鎵或氟化硒作爲觸媒、使四氟化伸乙基 在二氯化物等極性溶劑中游離基聚合以製造寡聚物者 (Scheme3),與上述短鏈聚合物法相同地利用藉由聚合所 得的寡聚物中之反應性基(不飽和鍵),經由適當的化學修 飾、在側鏈上導入具有氟化脂肪族基之高分子化合物。 Scheme3 KF F2C=CF2 _' diglyme CF3CF3 c2f5 C2F5In addition, the present invention preferably uses a polymer compound having a fluorinated aliphatic group on a side chain of a fluorine-based chemical product obtained by a short-chain polymerization method, which is generally referred to as "perfluoroalkyl-containing oligomer", It is commercially available and used. This chemical product is, for example, MEGAFAC F-178K, MEGAFAC F-470, MEGAFAC F-473, MEGAFAC F-475, MEGAFAC F-476, MEGAFAC F_472, MEGAFAC R-08 manufactured and sold by Dainippon Ink Chemical Co., Ltd. Or SURFLON SdSl'S-SSS'SdQS'S-lOl'S-iOS, etc. manufactured by Asahi Glass Co., Ltd. Among them, MEGAFAC F-178K (hereinafter referred to as P-1), -24-1226509 V. Description of the invention (23) MEGAFAC F-470 (hereinafter referred to as P-2), MEGAFAC F- 47 3 (hereinafter referred to as P-3), MEGAFAC F-475 (hereinafter referred to as P-4), MEGAFAC F476 (hereinafter referred to as P-5), and MEGAFAC F-472 (hereinafter referred to as P-6), will not cause the problem of sensitivity reduction It ’s better. In the present invention, a fluorinated aliphatic compound produced by a polymerization method is preferred. The oligomerization method uses gallium fluoride or selenium fluoride as a catalyst to polymerize ethylene tetrafluoride free radical in a polar solvent such as dichloride to produce an oligomer (Scheme3), and the above short-chain polymer In the same manner, a reactive group (unsaturated bond) in the oligomer obtained by polymerization is used to introduce a polymer compound having a fluorinated aliphatic group into a side chain through appropriate chemical modification. Scheme3 KF F2C = CF2 _ 'diglyme CF3CF3 c2f5 C2F5
etc. 除短鏈聚合法、寡聚法外典型氟化脂肪族化合物的製法 係有電解氟化法、及間接氟化法。換言之,藉由電解氟化 法可使過氟化辛基磺酸氟化物(Sc hem e4)以及導入此物之 氟系化學製品於商業上爲非常成功者,係自古以來較常被 使用者。本發明人等發現改換爲此物使用藉由短鏈聚合法 、寡聚法製造的氟系化學製品時可得較佳的結果。etc. Except for short-chain polymerization and oligomerization, typical fluorinated aliphatic compounds are produced by electrolytic fluorination and indirect fluorination. In other words, perfluorinated octyl sulfonate fluoride (Sc hem e4) and the fluorine-based chemicals introduced into it have been commercially very successful by electrolytic fluorination, and they have been more commonly used by users since ancient times. The present inventors have found that a better result can be obtained when a fluorine-based chemical produced by a short-chain polymerization method or an oligomerization method is used instead.
Scheme4Scheme4
C8H17—S02XC8H17—S02X
HF c8f17一so2f e -25- 1226509 五、發明說明(24) 本發明效果之作用原理不爲明確。以電解氟化、或間接 氟化法對應的脂肪族化合物爲製造原料、且使該C-Η鍵氟 化係對照的本發明短鏈聚合法或寡聚法藉由使氟化烯烴聚 合、製得氟化脂肪族化合物者,此係可以任何理由引起較 佳的結果者。例如以短鏈聚合法或寡聚法所得的氟化脂肪 族化合物通常由於產生聚合反應過程之連鏈長分佈,故形 成烷基鏈長不同的化合物之混合物,且視其所需爲具有支 鏈烷基構造者。此可能爲有關本發明之作用原理性。 而且,以往所使用的藉由電解氟化法製造的部分氟化系 化學製品,爲生分解性低、生體蓄積性高的物質,程度雖 輕微、惟恐有生殖毒性、發育毒性的問題。本發明藉由短 鏈聚合法之氟系化學製品爲具有較高環境安全性之物質, 就產業上而言較爲有利。 本發明人等基於該作業之假設、更進一部詳細檢討、發 現爲達成較佳光阻組成物之另一方法係以上述(2 )之構成 較佳。換言之,本發明之側鏈所使用的氟化脂肪族基之另 〜要件係氟系聚合物爲通式(F 1 )所示者,其側鏈部分以通 式(F2)所示、尤以n = 4所示成分對n = 3〜6之成分總和而 ’爲40〜97莫耳%、或n = 3所不成分爲40〜97莫耳%之混 合物具有極佳的性能。 -26- 1226509 五、發明說明(25) ——x+ c—(CF2CF2)n F (F2)| mr3 其中,R2及R3係各表示氫原子、碳數1〜4個(Cl〜C4) 之烷基,烷基之具體例如甲基、乙基、丙基、異丙基、正 丁基、異丁基、第丁基等、較佳者爲氫原子、甲基、更 佳者爲氫原子,X係表示共有鍵、或爲使取代基(F2)與高 分子側鏈鍵結之2價鍵結基(有機基),較佳的X係表示_ 〇-、-S-、-N(R4) -、-C0-、直接或經由2價鍵結基與高分 子主鏈鍵結。此處,R4係表示氫原子、C 1〜’C4之烷基,烷 基之具體例如甲基、乙基、丙基、異丙基、正丁基、異丁 基、第3 -丁基等、較佳者爲氫原子、甲基。X可以爲上述 任一種、惟以-〇 -較佳。Μ係爲0以上之整數、以2〜8之 整數較佳、m = 2時更佳。而且,m爲2以上時互相相鄰的 碳上之官能基鍵結、形成脂肪族環。 η係表示1以上之整數、以1〜1〇之整數較佳。此處,η 以3〜6更佳’另外於高分子化合物中至少混有η爲 3,4,5,6之基較佳。特別是η = 4所示成分(聚合物成分)對 η = 3〜6之成分(η爲3,4,5,6之各成分)總和而言爲40〜97 莫耳%、或η = 3所示成分對η = 3〜6之成分(11爲3,4,5,6之 各成分)總和而言爲40〜97莫耳%較佳。更佳者^ = 4所示 -27- 1226509 五、發明說明(26) 成分對n = 3〜6之成分總和而_爲60〜95莫耳%、最佳者 爲70〜90莫耳%。若小於40莫耳%時孤立線會產生飛離情 形,而若大於97莫耳%時孤立線亦會產生飛離情形,故不 爲企求。 Y之高分子主鏈例如下述所例示之化合物。 其次說明本發明具有氟化脂肪族基之高分子化合物的更 具體製造法。 本發明所使用的氟系聚合物可以爲滿足上述(A )及(B )記 載的要件者全部聚合物形態。具體的形態可使用丙烯酸樹 脂、甲基丙烯酸樹脂、苯乙烯樹脂、聚酯樹脂、聚胺基甲 酸酯樹脂、聚碳酸酯樹脂、聚醯胺樹脂、聚縮醛樹脂、苯 酚/甲醛縮合樹脂、聚乙烯苯酚樹脂、馬來酸酐/ α -烯烴 樹脂、α -雜環取代甲基丙烯酸樹脂等。其中,丙烯酸樹 脂、甲基丙烯酸樹脂、苯乙烯樹脂、聚酯樹脂、聚胺基甲 酸酯樹脂有用,更佳者爲丙烯酸樹脂、甲基丙烯酸樹脂、 聚胺基甲酸酯樹脂。此等樹脂係可使用適當聚合性單體, 且藉由聚縮合或加成聚合、開環聚合等該業者習知的方法 容易製得。爲滿足要件(A )時,此時可適當選擇含氟之單 體原料’而爲滿足要件(B)時可適當選擇單體製造、聚合 時之原料、視其所需予以混合或混合聚合後之聚合物。於 下述中最爲有用的聚合物例如製造適性亦極優異的丙烯酸 樹脂、甲基丙_酸樹脂’特別就有關構成(B)更詳細地說 明。 •28- 1226509 五、發明說明(27) 本發明所使用的丙烯酸樹脂之較佳實施形態例如具有下 述通式(F3)所不構成單位作爲共聚合單位者。HF c8f17-so2f e -25-1226509 V. Description of the invention (24) The working principle of the effect of the present invention is not clear. The short-chain polymerization method or oligomerization method of the present invention, which uses an aliphatic compound corresponding to electrolytic fluorination or an indirect fluorination method as a production raw material, and controls the C-fluorene bond fluorination system by polymerizing and preparing a fluorinated olefin, Those who have obtained fluorinated aliphatic compounds can obtain better results for any reason. For example, a fluorinated aliphatic compound obtained by a short-chain polymerization method or an oligomerization method usually results in a chain length distribution of the polymerization reaction process, so a mixture of compounds having different alkyl chain lengths is formed, and if necessary, it has branched chains. Alkyl constructor. This may be related to the working principle of the present invention. In addition, the partially fluorinated chemical products manufactured by the electrolytic fluorination method used in the past are substances with low biodegradability and high bioaccumulation, although the degree is slight, fearing reproductive toxicity and developmental toxicity. The fluorine-based chemical product of the present invention by the short-chain polymerization method is a substance having high environmental safety, which is advantageous in terms of industry. Based on the hypothesis of this operation, the inventors have carried out a detailed review and found that another method for achieving a better photoresist composition is to use the composition of (2) above. In other words, the other to the fluorinated aliphatic group used in the side chain of the present invention is the one represented by the general formula (F 1), and the side chain portion is represented by the general formula (F2), especially The composition shown by n = 4 is the sum of the components of n = 3 ~ 6 and the mixture of '= 40 ~ 97 mole%, or the composition of n = 3 which has 40 ~ 97 mole% has excellent performance. -26- 1226509 V. Description of the invention (25) ——x + c— (CF2CF2) n F (F2) | mr3 Among them, R2 and R3 each represent a hydrogen atom and 1 to 4 carbon atoms (Cl to C4) Specific examples of the alkyl group include a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a butyl group, and the like, preferably a hydrogen atom, a methyl group, and more preferably a hydrogen atom, X represents a common bond or a divalent bonding group (organic group) that connects a substituent (F2) with a polymer side chain. A preferred X represents _〇-, -S-, -N (R4 )-, -C0-, directly or via a divalent bonding group, are bonded to the polymer main chain. Here, R4 represents a hydrogen atom and an alkyl group having 1 to 4 carbon atoms. Specific examples of the alkyl group include methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, and 3-butyl groups. Preferred are a hydrogen atom and a methyl group. X may be any of the above, but -0-is preferred. M is an integer of 0 or more, an integer of 2 to 8 is preferable, and m is more preferable. When m is 2 or more, functional groups on adjacent carbons are bonded to form an aliphatic ring. η is an integer of 1 or more, and an integer of 1 to 10 is preferable. Here, η is more preferably 3 to 6, and it is preferable that at least η is 3,4,5,6 in the polymer compound. In particular, the component (polymer component) represented by η = 4 is 40 to 97 mol% or η = 3 for the total of the components of η = 3 to 6 (where η is each component of 3, 4, 5, and 6). The components shown are preferably 40 to 97 mole% for the sum of the components of η = 3 to 6 (11 is each component of 3, 4, 5, 6). The better ^ = 4 shows -27-1226509 V. Description of the invention (26) The sum of the components n = 3 to 6 is 60 to 95 mole%, and the best is 70 to 90 mole%. If it is less than 40 mol%, the isolated line will fly away, and if it is greater than 97 mol%, the isolated line will also fly away, so it is not desirable. The polymer main chain of Y is, for example, the compounds exemplified below. Next, a more specific method for producing a polymer compound having a fluorinated aliphatic group according to the present invention will be described. The fluorine-based polymer used in the present invention may be in the form of all polymers satisfying the requirements described in (A) and (B) above. Specific forms include acrylic resin, methacrylic resin, styrene resin, polyester resin, polyurethane resin, polycarbonate resin, polyamide resin, polyacetal resin, phenol / formaldehyde condensation resin, Polyvinylphenol resin, maleic anhydride / α-olefin resin, α-heterocyclic substituted methacrylic resin, and the like. Among them, acrylic resin, methacrylic resin, styrene resin, polyester resin, and polyurethane resin are useful, and acrylic resin, methacrylic resin, and polyurethane resin are more preferable. These resins can be obtained by using a polymerizable monomer, and can be easily produced by methods known to those skilled in the art, such as polycondensation, addition polymerization, and ring-opening polymerization. In order to satisfy the requirement (A), a fluorine-containing monomer raw material can be appropriately selected at this time, and in order to satisfy the requirement (B), a raw material for monomer manufacturing, polymerization can be appropriately selected, and mixed or polymerized as required. Of polymers. The polymers most useful in the following, for example, acrylic resins and methacrylic acid resins, which are also excellent in manufacturing suitability, will be described in more detail with respect to the configuration (B). • 28-1226509 5. Description of the invention (27) A preferred embodiment of the acrylic resin used in the present invention is, for example, a unit having a unit not constituted by the following general formula (F3) as a copolymerization unit.
H2C C /1 、 \ r2 \ C——γ〇- Η —c-‘ I 0 I Ra 一(CF2CF2)nF (F3) 1ΊΊ 其中’ R i係表示氫原子、鹵素原子(例如氟原子、溴原 子)或可具有取代基之甲基,YQ係表示2價有機基,X、r2 、R3、m、η係與通式(F2)者同義,Υ()表示的2價有機基例 如與上述X相同的具體例。 本發明所使用的通式(F3)之含過氟化烷基的單體之具體 構造例如下述。 -29- 1226509 五、發明說明(28H2C C / 1, \ r2 \ C——γ〇- Η —c- 'I 0 I Ra - (CF2CF2) nF (F3) 1ΊΊ where' R i represents hydrogen atom, halogen atom (such as fluorine atom, bromine atom ) Or a methyl group which may have a substituent, YQ represents a divalent organic group, X, r2, R3, m, and η are synonymous with those of the general formula (F2), and the divalent organic group represented by Υ () is, for example, the above-mentioned X The same specific example. The specific structure of the perfluorinated alkyl group-containing monomer of the general formula (F3) used in the present invention is as follows. -29- 1226509 V. Description of the invention (28
0 〇-CH2CHr(CF2CF2)4F(F-1)0 〇-CH2CHr (CF2CF2) 4F (F-1)
0-CH2CH2*(CF2CF2)4F (F-7) ,CH30-CH2CH2 * (CF2CF2) 4F (F-7), CH3
〇-CH2CH2-(CF2CF2)4F 〇〇-CH2CH2- (CF2CF2) 4F 〇
H (F-2) -〇-CH2-(CF2CF2)^F cr (F-8)H (F-2) -〇-CH2- (CF2CF2) ^ F cr (F-8)
H (F-4) -o-ch2ch2ch2-(cf2cf2)4f o OH3 o (F-9) -〇-CH2CH2CH2CH2-(CF2CF2)4F(F-10)H (F-4) -o-ch2ch2ch2- (cf2cf2) 4f o OH3 o (F-9) -〇-CH2CH2CH2CH2- (CF2CF2) 4F (F-10)
HH
H CH3 〇 •N—CH2CH2-(CF2CF2)4F ch3(F-5) -o-c 〇H CH3 〇 • N—CH2CH2- (CF2CF2) 4F ch3 (F-5) -o-c 〇
HCH-(CF2CF2)4F ch3 CF-ll) ΑΗ5 -N—CH2CH2-(CF2CF2)4F ° CaH9HCH- (CF2CF2) 4F ch3 CF-ll) ΑΗ5 -N-CH2CH2- (CF2CF2) 4F ° CaH9
ch3 0-CH-(CF2CF2)4F 〇 (M2) 3之具體例 -30- 1226509 五、發明說明(29) Ηch3 0-CH- (CF2CF2) 4F 〇 (M2) 3 Specific examples -30-1226509 V. Description of the invention (29) Η
Cl 0~CH2CH2**(CF2CF2)3F(F-13)Cl 0 ~ CH2CH2 ** (CF2CF2) 3F (F-13)
-〇-CH2CH2-(CF2CF2)3F o (F-19)-〇-CH2CH2- (CF2CF2) 3F o (F-19)
o-ch2ch2-(cf2cf2)3fo-ch2ch2- (cf2cf2) 3f
H (F-14) -〇-CH2-(CF2CF2)3F 0, (F-20) .CH3H (F-14) -〇-CH2- (CF2CF2) 3F 0, (F-20) .CH3
HH
-S-CH2CH2-(CF2CF2)3F-S-CH2CH2- (CF2CF2) 3F
-〇-CH2CH2CH2-(CF2CF2)3F o o (F-15) (F-21)-〇-CH2CH2CH2- (CF2CF2) 3F o o (F-15) (F-21)
-N—CH2CH2-(CF2CF2)3F o-N—CH2CH2- (CF2CF2) 3F o
HH
0-CH2CH2CH2CHr(CF2CF2)3F (F-16) (F-22)0-CH2CH2CH2CHr (CF2CF2) 3F (F-16) (F-22)
HH
〇 N—CH2CH2-(CF2CF2)3F ch3(F-17)〇 N-CH2CH2- (CF2CF2) 3F ch3 (F-17)
ch3 0-CHCH-(CF2CF2)3F ch3 (P-23) ,C2H5 \—N—CH2CH2-(CF2CF2)3F c4h9ch3 0-CHCH- (CF2CF2) 3F ch3 (P-23), C2H5 \ —N—CH2CH2- (CF2CF2) 3F c4h9
n = 5之具體例 -31 1226509 五、發明說明(30)Specific examples of n = 5 -31 1226509 V. Description of the invention (30)
0-CH2CHr(CF2CF2)5F (F-25)0-CH2CHr (CF2CF2) 5F (F-25)
ClCl
0-CH2CH2-(CF2CF2)5F (F-31) yCH30-CH2CH2- (CF2CF2) 5F (F-31) yCH3
o-ch2ch2-(cf2cf2)5f (F-26) 0-CH2-(CF2CF2)5F 〇 (F-32)o-ch2ch2- (cf2cf2) 5f (F-26) 0-CH2- (CF2CF2) 5F 〇 (F-32)
(F-28)(F-28)
HH
0-CH2CH2CH2-(CF2CF2)5F0-CH2CH2CH2- (CF2CF2) 5F
33
o-ch2ch2ch2ch2-(cf2cf2)5fo-ch2ch2ch2ch2- (cf2cf2) 5f
(F-33) (F-34)(F-33) (F-34)
H ch3 N—CH2CH2-(CF2CF2)5F ch3 〇 -〇-CHCH-(CF2CF2)5F ch3 (F-29) (F-35)H ch3 N-CH2CH2- (CF2CF2) 5F ch3 〇 -〇-CHCH- (CF2CF2) 5F ch3 (F-29) (F-35)
yC2H5 N—CH2CH2-(CF2CF2)5Fy I C4H9yC2H5 N—CH2CH2- (CF2CF2) 5Fy I C4H9
ch3 0-CH-(CF2CF2)5Fch3 0-CH- (CF2CF2) 5F
n二6之具體例 -32- 1226509 五、發明說明(31) ΗSpecific examples of n-2 -32- 1226509 V. Description of the invention (31) Η
Cl 0-CH2CH2-(CF2CF2)6F (F-37)Cl 0-CH2CH2- (CF2CF2) 6F (F-37)
-〇CH2CH2-(CF2CF2)6F 〇 (F-43)-〇CH2CH2- (CF2CF2) 6F 〇 (F-43)
0-CH2CH2-(CF2CF2)6F (F-38)0-CH2CH2- (CF2CF2) 6F (F-38)
o-ch2-(cf2cf2)6fo-ch2- (cf2cf2) 6f
S-CH2CH2-(CF2CF2)6FS-CH2CH2- (CF2CF2) 6F
N—CH2CH2-(CF2CF2)6F H (F〇9) (F-44)N-CH2CH2- (CF2CF2) 6F H (F〇9) (F-44)
(F-46)(F-46)
(F-40)(F-40)
HH
N—CH2CH2-(CF2CF2)6F ch3N-CH2CH2- (CF2CF2) 6F ch3
ch3 0-CHCH-(CF2CF2)6F ch3 (F-41) (F-47) 〇 c2h5ch3 0-CHCH- (CF2CF2) 6F ch3 (F-41) (F-47) 〇 c2h5
N—CH2CH2-(CF2CF2)6F c4h9N-CH2CH2- (CF2CF2) 6F c4h9
ch3 0-CH-(CF2CF2)6F (F-48) 本發明之高分子化合物中以於上述單體中混合有過氟化 烷基不同鏈長者爲較佳的形態。特別是通式(F 1 )及(F3 )中 n = 4所示成分對n = 3〜6之成分(η爲3,4,5,6之各成分)總ch3 0-CH- (CF2CF2) 6F (F-48) In the polymer compound of the present invention, the above monomers are preferably a mixture of different chain lengths of perfluorinated alkyl groups. In particular, in the general formulae (F 1) and (F3), the components represented by n = 4 and the components of n = 3 to 6 (where η is each component of 3, 4, 5, and 6)
-33- 1226509 五、發明說明(32) 和而言爲40〜97莫耳%、或n = 3所示成分對n = 3〜6之成 分(η爲3,4,5,6之各成分)總和而言爲40〜97莫耳%較佳 。更佳者η = 4所示成分對η = 3〜6之成分總和而言爲60〜 93莫耳%、最佳者爲70〜90莫耳%。 該混合物可以混合上述單體(F - 1 )〜(F - 1 2 )所示單體與 η二3、η = 5及η = 6予以調製。而且,使原料之過氟化烷基以 短鏈聚合法合成製得鏈長不同的混合物後,η = 4之成分可 在上述範圍內以蒸餾、柱分離、萃取等方法調製、以製造 單體混合物。 此外,η = 3所示之成分對η = 3〜6之成分(η爲3,4,5及6 之各成分)總和而言爲40〜97莫耳之混合物可混合上述單 體(F-13)〜(F-24)所示單體與η = 4、η = 5及η-6予以調製 。另外’使原料之過氟化烷基以短鏈聚合法合成製得鏈長 不同的混合物後,η = 3之成分可在上述範圍內以蒸餾、柱 分離、萃取等方法調製、製造單體混合物。 #發明所使用的氟系聚合物中使用此等含氟化脂肪族基 之單體量以該氟化聚合物之重量爲基準爲1重量%以上、 較佳者爲3〜70重量%、更佳者爲7〜60重量%。 lit外’本發明由於藉由特定氟系聚合物之氟化脂肪族基 S '構造或組成分佈者,故可任意組合選擇共聚合成 特定氟化脂肪族之取代數等習知技術使用。 例1 $0 ’本發明含過氟化烷基之高分子化合物以使用與具 有聚環氧院基之單體共聚物較佳。聚環氧烷基例如聚環氧 -34- 1226509 五、發明說明(33) 乙院基、聚環氧丙院基、聚環氧丁院基、聚(環氧乙院· 環氧丙烷)無規共聚合基、聚(環氧乙烷•環氧丙烷)嵌段 共聚合基等。此等環氧烷基的具體例如特開昭6 2 - 1 7 0 9 5 0 號公報、特開昭62 - 226 1 43號公報、特開平3_丨72849號 公報、特開平8-15858號公報等記載者。爲充分達成本發 明之目的時,聚環氧烷基的分子量以500〜3000較佳。聚 環氧烷基單位以高分子化合物中之1 〇莫耳%以上較佳。 此外,本發明所使用的聚合物可使具有酸性氫原子之單 體共聚合。具有酸性氫原子之基例如可使用羧基、或苯酚 性羥基之其他文獻中習知酸性基中之任一種。酸性基之習 知文獻例如有 J.A.Dean ed.,Lange’s Handbook of Chemistry 3rd. ed.1985 Mcgraw-Hill Book Co.。而且 ,此等酸性基中酸性氫原子鍵結於氮原子之酸性基的部分 構造具體例如下述(A 1 )〜(A7 )所示者。 一 S02NH2 (A 1) -S02NH - (A 2 ) 一 C0NHS 02- (A3 ) 一CONHCO— (A4) 一 S 〇2ΝΗ— S 〇2— (A 5) 一 C〇NHS〇2NH — (A 6) -NHC0NHS02- (A7), 而且,特開平8 - 1 5 8 5 8號中記載的酸性基極爲有用。包 含特開平7-248628號公報記載的具有偶合構造之含氮原 -35- 1226509 五、發明說明(34) 子的雜環構造。此等含氮的雜環構造例如下述(H )、(1)所 示者。-33- 1226509 V. Description of the invention (32) 40% to 97 mole%, or n = 3 to n = 3 to 6 (n = 3, 4, 5, 6) ) The sum is preferably 40 to 97 mole%. More preferably, the component represented by η = 4 is 60-93 mole% with respect to the sum of the components of η = 3-6, and the most preferable is 70-90 mole%. This mixture can be prepared by mixing the monomers represented by the above monomers (F-1) to (F-1 2) and η2 3, η = 5, and η = 6. In addition, after the perfluorinated alkyl group of the raw material is synthesized by short-chain polymerization to obtain mixtures with different chain lengths, the component of η = 4 can be prepared within the above-mentioned range by distillation, column separation, extraction, etc. to produce monomers. mixture. In addition, a mixture of η = 3 to η = 3 to 6 (where η is 3, 4, 5, and 6) can be mixed with a mixture of 40 to 97 moles of the above monomers (F- 13) The monomers shown in (F-24) are prepared with η = 4, η = 5, and η-6. In addition, after the raw materials of the perfluorinated alkyl group are synthesized by short-chain polymerization to obtain mixtures with different chain lengths, the component of η = 3 can be prepared and manufactured by the methods of distillation, column separation, and extraction within the above-mentioned range to produce monomer mixture . #The amount of these fluorinated aliphatic group-containing monomers used in the fluoropolymer used in the invention is 1% by weight or more, preferably 3 to 70% by weight, more based on the weight of the fluorinated polymer. Preferably, it is 7 to 60% by weight. Since the present invention uses a fluorinated aliphatic group S 'structure or composition distribution of a specific fluorinated polymer, the present invention can be used in any combination of conventional techniques such as copolymerization to a specific fluorinated aliphatic substitution number. Example 1 The polymer compound containing a perfluorinated alkyl group of the present invention is preferably used with a monomer copolymer having a polyepoxy group. Polyalkylene oxides such as polyepoxide-34-1226509 V. Description of the invention (33) Eyuan, Polypropylene oxide, Polybutylene oxide, Poly (Ethylene oxide · propylene oxide) None Regular copolymerization groups, poly (ethylene oxide • propylene oxide) block copolymerization groups, etc. Specific examples of these alkylene oxides are, for example, Japanese Patent Laid-Open No. 6 2-1 7 0 95 0, Japanese Patent Laid-Open No. 62-226 1 43, Japanese Patent Laid-Open No. 3_ 丨 72849, and Japanese Patent Laid-Open No. 8-15858. Gazette and others. In order to sufficiently achieve the purpose of the present invention, the molecular weight of the polyalkylene oxide is preferably 500 to 3000. The polyalkylene oxide unit is preferably at least 10 mol% in the polymer compound. In addition, the polymer used in the present invention can copolymerize a monomer having an acidic hydrogen atom. As the group having an acidic hydrogen atom, for example, any of the conventionally known acidic groups can be used as a carboxyl group or a phenolic hydroxyl group. Examples of known acidic groups include J.A. Dean ed., Lange's Handbook of Chemistry 3rd. Ed. 1985 Mcgraw-Hill Book Co .. In addition, a specific structure of the acidic hydrogen atom of these acidic groups bonded to the acidic group of a nitrogen atom is, for example, the following structures (A 1) to (A7). -S02NH2 (A 1) -S02NH-(A 2)-CONHS 02- (A3)-CONHCO— (A4) —S 〇2ΝΗ— S 〇2— (A 5) —C0NHS〇2NH — (A 6) -NHC0NHS02- (A7), and the acidic group described in Japanese Patent Application Laid-Open No. 8-1 5 8 5 8 is extremely useful. Including the nitrogen-containing proton having a coupling structure described in Japanese Patent Application Laid-Open No. 7-248628 -35-1226509 5. The heterocyclic structure of the invention (34). Examples of such nitrogen-containing heterocyclic structures are shown in (H) and (1) below.
同樣地,特開2000-19724號公報記載的具有鍵結於鄰 接電子吸引性基之碳原子的氫原子之酸性基亦極爲有用。 其他如特開平1 1 - 3 5268 1、特開平1 1 - 327 1 42、特開平 1 1 - 327 1 3 1、特開平 1 1 - 327 1 26、特開平 1 0 - 339948、特開 平 1 0 - 207052、特開平 1 0 - 1 86642、特開平 1 0 - 1 6 1 303 中 記載的共聚物亦極爲適用。 此等具有酸性氫原子之單體係使用具有可游離聚合的不 飽和基之乙烯單體。於此等乙烯單體中較佳者爲丙烯酸酯 、甲基丙烯酸酯、丙烯醯胺、甲基丙烯醯胺、苯乙烯系、 乙烯系。較佳的構造例如特開平104 42778號公報記載的 化合物等。 本發明含氟化脂肪族基之高分子化合物中具有酸性氫原 子之單體含量爲0〜50莫耳%、較佳者爲〇〜40莫耳%、更 佳者爲5〜30莫耳%。 另外’其他共聚合成分有特開平4_ 222805中記載的具 橋狀鍵之單體、或特開平1〇_ 1 42778中記載的在側鏈上具 -36- 1226509 五、發明說明(35) 有9個以上碳原子之脂肪族基或具有2個以上碳原子之脂 肪族基取代的芳香族基之丙烯酸酯、甲基丙烯酸酯、丙烯 醯胺、或甲基丙烯醯胺單體之共聚合。 此外,本發明中可適合使用於特開1 0 - 1 88640、特開平 10-186641、特開平 2000-3032、特開平 2000-304 0 等中記 載的胺基甲酸酯系聚合物之技術、或特開平1 1 - 3 27 1 29中 揭示的、聚縮合、聚合加成系聚合物。而且,特開2000 -1 873 1 8中記載的分子中具有2或3個3〜20之過氟化烷基 的(甲基)丙烯酸酯單體而言亦可適用於本發明。 本發明之氟系聚合物可使用習知慣用方法製造。例如使 具有氟化脂肪族基之(甲基)丙烯酸酯、具有聚環氧烷基之 (甲基)丙烯酸酯及鍵結於酸性氫原子或氮原子之含酸性基 的乙烯單體,在有機溶劑中添加一般的游離基聚合起始劑 、且藉由熱聚合予以製造。或視其所需添加其他加成聚合 性不飽和化合物,以與上述相同的方法製造。 另外,視其所需使用的其他加成聚合不飽和化合物例如 使用 PolymerHandbook 2nd ed· , J. Brandrup , Wiley Interscience( 1 975 ) Chapter 2 Pagel 〜483 記載者。此 等例如(甲基)丙烯酸甲酯、(甲基)丙烯酸乙酯、(甲基)丙 烯酸2 -氯化乙酯、(甲基)丙烯酸2 -羥基乙酯、(甲基)丙 烯酸環氧丙酯、等之(甲基)丙烯酸酯類、(甲基)丙烯醯胺 、N-羥甲基(甲基)丙烯醯胺、n-(對-羥基苯基)_甲基丙烯 醯胺等(甲基)丙烯醯胺類、醋酸烯丙酯、丙酸烯丙酯、烯 -37- 1226509 五、發明說明(36) 丙基氧化乙醇等之烯丙基化合物;乙基以烯醚、丙基乙烯 醚、丁基乙烯醚、辛基乙烯醚、甲氧基乙基乙烯醚、乙氧 基乙基乙烯醚、2 -氯化乙基乙烯醚、羥基乙基乙烯醚、苯 甲基乙烯醚、四氫呋喃基乙烯醚、苯基乙烯醚、甲苯基乙 烯醚、二乙基胺基乙基乙烯醚等之乙烯醚類;乙酸乙烯酯 、丁酸乙烯酯、己酸乙烯酯、氯化乙酸乙烯酯、甲氧基乙 酸乙烯酯、苯基乙酸乙烯酯、乙醯基乙酸乙烯酯、苯甲酸 乙烯酯、氯化苯甲酸乙烯酯等乙烯酯類; 苯乙烯、α -甲基苯乙烯、甲基苯乙烯、二甲基苯乙烯 、氯化甲基苯乙烯、乙氧基甲基苯乙烯、羥基苯乙烯、氯 化苯乙烯、溴化苯乙烯等苯乙烯類;甲基乙烯酮、乙基乙 烯酮、丙基乙烯酮、苯基乙烯酮等乙烯酮類;異丁烯、丁 二烯、異戊烯等之烯烴類;其他有檸檬酸丁酯、衣康酸二 甲酯、衣康酸二乙酯、馬來酸二甲酯、富馬酸二乙酯、Ν -乙烯基吡咯烷酮、Ν -乙烯基吡啶、丙烯腈等。 於下述中爲本發明氟系聚合物之具體構造。而且,式中 之數字係表示各成分之莫耳比例。 -38- 1226509 五、發明說明(37Similarly, an acidic group having a hydrogen atom bonded to a carbon atom adjacent to an electron attracting group described in Japanese Patent Application Laid-Open No. 2000-19724 is extremely useful. Others such as kaiping 1 1-3 5268 1, kaiping 1 1-327 1 42, kaiping 1 1-327 1 3 1, kaiping 1 1-327 1 26, kaiping 1 1-339948, kaiping 1 0 -207052, Japanese Patent Application Laid-open No. 1 0-1 86642, Japanese Patent Application Laid-open No. 1 0-1 6 1 303 are also very suitable. These single systems having an acidic hydrogen atom use ethylene monomers having a freely polymerizable unsaturated group. Preferred among these ethylene monomers are acrylate, methacrylate, acrylamide, methacrylamide, styrene-based, and vinyl-based. A preferred structure is, for example, a compound described in Japanese Patent Application Laid-Open No. 104 42778. The content of the monomer having an acidic hydrogen atom in the fluorinated aliphatic group-containing polymer compound of the present invention is 0 to 50 mole%, preferably 0 to 40 mole%, and more preferably 5 to 30 mole%. . In addition, 'other copolymerization components are monomers having bridge bonds described in Japanese Patent Application Laid-open No. 4_222805, or the side chains of -36-1226509 described in Japanese Patent Application No. 10-1 42778. 5. Description of the invention (35) Yes Copolymerization of acrylate, methacrylate, acrylamide, or methacrylamide monomers with aliphatic groups having 9 or more carbon atoms or aromatic groups substituted with aliphatic groups having 2 or more carbon atoms. In addition, the present invention can be suitably applied to the urethane-based polymers described in JP 10-1088640, JP 10-186641, JP 2000-3032, JP 2000-304 0, and the like, Or the polycondensation and polymer addition system polymers disclosed in Japanese Patent Application Laid-Open Nos. 1 1 to 3 27 1 29. Furthermore, (meth) acrylic acid ester monomers having two or three perfluorinated alkyl groups of 3 to 20 in the molecules described in JP 2000-1 873 1 8 are also applicable to the present invention. The fluorine-based polymer of the present invention can be produced by a conventional method. For example, a (meth) acrylic acid ester having a fluorinated aliphatic group, a (meth) acrylic acid ester having a polyoxyalkylene group, and an acidic group-containing ethylene monomer bonded to an acidic hydrogen atom or a nitrogen atom are used in organic A general radical polymerization initiator is added to the solvent, and it is produced by thermal polymerization. Or, if necessary, another addition polymerizable unsaturated compound is added, and it is produced by the same method as described above. In addition, other addition-polymerized unsaturated compounds that are required to be used are, for example, those described in PolymerHandbook 2nd ed., J. Brandrup, Wiley Interscience (1 975) Chapter 2 Page 1 to 483. These include, for example, methyl (meth) acrylate, ethyl (meth) acrylate, 2-ethyl chloride (meth) acrylate, 2-hydroxyethyl (meth) acrylate, and propylene oxide (meth) acrylate. (Meth) acrylates, (meth) acrylamide, N-methylol (meth) acrylamide, n- (p-hydroxyphenyl) _methacrylamine, etc. ( Meth) acrylamidonium, allyl acetate, allyl propionate, allene-37-1226509 V. Description of the invention (36) Allyl compounds such as propyloxyethanol; ethyl is allyl ether, propyl Vinyl ether, butyl vinyl ether, octyl vinyl ether, methoxyethyl vinyl ether, ethoxyethyl vinyl ether, 2-chloroethyl vinyl ether, hydroxyethyl vinyl ether, benzyl vinyl ether, Tetrahydrofuryl vinyl ether, phenyl vinyl ether, tolyl vinyl ether, diethylamino ethyl vinyl ether, and other vinyl ethers; vinyl acetate, vinyl butyrate, vinyl hexanoate, vinyl chloride acetate, Vinyl methoxyacetate, phenyl vinyl acetate, ethyl vinyl acetate, vinyl benzoate, benzyl chloride Vinyl esters such as vinyl acid esters; styrene, α-methylstyrene, methylstyrene, dimethylstyrene, chloromethylstyrene, ethoxymethylstyrene, hydroxystyrene, chlorinated Styrenes such as styrene and brominated styrene; ketenes such as methylketene, ethylketene, propylketene, and phenylketene; olefins such as isobutene, butadiene, and isopentene; Others include butyl citrate, dimethyl itaconate, diethyl itaconate, dimethyl maleate, diethyl fumarate, N-vinylpyrrolidone, N-vinylpyridine, acrylonitrile, etc. . The specific structure of the fluorine-based polymer of the present invention is described below. In addition, the numbers in the formula represent the mole ratio of each component. -38- 1226509 V. Description of the invention (37
3030
70 C〇2 —CH2CH 十 CF2CF 七 F co2 十 CH2CH2〇)^CH3 (Ρ·7) 师2。 , C02一CH2CH2*(~CF2CF2^-f CO 乂一 ch2ch2o)^ch3 (P-8) 婦- _ C〇2十CH2CH2〇)^CH3 6〇2~fC3H6〇)-7CH3 C02—CH2CH(0H)CH2-^CF2CF2 卜 F (P-9)70 C〇2 —CH2CH Ten CF2CF Seven F co2 Ten CH2CH2〇) ^ CH3 (P · 7) Division 2. , C02-CH2CH2 * (~ CF2CF2 ^ -f CO 乂 一 ch2ch2o) ^ ch3 (P-8) Women-_ C〇2 十 CH2CH2〇) ^ CH3 6〇2 ~ fC3H6〇) -7CH3 C02-CH2CH (0H) CH2- ^ CF2CF2 BU F (P-9)
4040
60 CF3 C02-fcH2CH2c)*^C3H6C^{CH2CH20|-CH3 C〇2 ~CH2CH2^~OF 2CF —CF—CF3 n'1 (P-10) (a+b+c=12) f51 19 26 C02CH3 co2ch2ch2oh C02CH2CH(CH3)2 CF. 3 (P-11) C〇2一CH2CH(OH)CH2-^CF2CF24—CF—cf3 -39- 122650960 CF3 C02-fcH2CH2c) * ^ C3H6C ^ (CH2CH20 | -CH3 C〇2 ~ CH2CH2 ^ ~ OF 2CF —CF—CF3 n'1 (P-10) (a + b + c = 12) f51 19 26 C02CH3 co2ch2ch2oh C02CH2CH (CH3) 2 CF. 3 (P-11) C〇2-CH2CH (OH) CH2- ^ CF2CF24—CF-cf3 -39-1226509
1226509 五、發明說明(39) (P-7)之製法 將藉由短鏈聚合法製造的氟系化學製品(FM - 1,η爲 3,4,5,6之混合物、η = 3之含率41%、η = 4之含率53%)導入 丙烯酸單體(F-48)後,與其他成分藉由共聚合予以聚合物 化。 co2h =\1226509 V. Description of Invention (39) (P-7) The production method will be a fluorine-based chemical product manufactured by short-chain polymerization (FM-1, where η is a mixture of 3, 4, 5, and 6, and η = 3% After the acrylic monomer (F-48) was introduced into the acrylic monomer (F-48) at a rate of 41% and a content ratio of η = 4, it was polymerized by copolymerization with other components. co2h = \
、C02 - CH2CH2^~CF2CF2|^F ho—ch2cfv(-cf2cf2)~f - •H20 F«48 FM-1 (P-8)之製法 使用藉由短鏈聚合法製造的氟系化學製品(FM-2、n = 4、 純度95%)導入甲基丙烯酸單體(F-49)後,與其他成分藉由 共聚合予以聚合物化。 HO—CH,CH十CF〇CFv}-n C02H ‘ -H20 FM-2 co2-ch2ch2-(-cf2cf2)^f F49, C02-CH2CH2 ^ ~ CF2CF2 | ^ F ho_ch2cfv (-cf2cf2) ~ f-• H20 F «48 FM-1 (P-8) is produced using a fluorine-based chemical product (FM -2, n = 4, purity 95%) After introducing a methacrylic acid monomer (F-49), it is polymerized with other components by copolymerization. HO—CH, CH ten CF〇CFv} -n C02H ‘-H20 FM-2 co2-ch2ch2-(-cf2cf2) ^ f F49
Me (P - 9 )之製法 使用藉由短鏈聚合法製造的氟系化學製品(FM - 3、' 純度95%)導入甲基丙烯酸單體(F-50)後,與其他成分藉由 共聚合予以聚合物化。 H2C-CHCH2-f-CF2CF2)^F ——====^C02-CH2CH(0H)CH2-(-CF2CF2)^F Ο FM-3 F-50 -41 - 1226509 五、發明說明(4〇) (P -1 0 )之製法 使用藉由短鏈聚合法製造的氟系化學製品(FM-3、n = 3、 純度80%)導入甲基丙烯酸單體(F-51)後,與其他成分藉由 共聚合予以聚合物化。 cf3 HO—CH2CH2^~CF2CF2]—CF—CF3 n-1Me (P-9) is produced by using a fluorine-based chemical product (FM-3, 'purity 95%') produced by a short-chain polymerization method. After introducing a methacrylic acid monomer (F-50), it is co-existed with other components. Polymerize to polymerize. H2C-CHCH2-f-CF2CF2) ^ F ---- ==== ^ C02-CH2CH (0H) CH2-(-CF2CF2) ^ F 〇 FM-3 F-50 -41-1226509 V. Description of the invention (4〇) The method of (P -1 0) uses a fluorine-based chemical product (FM-3, n = 3, purity 80%) produced by a short-chain polymerization method, and is introduced into a methacrylic acid monomer (F-51), followed by other components. Polymerization is performed by copolymerization. cf3 HO—CH2CH2 ^ ~ CF2CF2] —CF—CF3 n-1
co2h FM-4 -h2o C02-CH2CH2-f-CF2CF2f-cF—CF3 n-1 F-51 (P - 1 1 )之製法 使用藉由短鏈聚合法製造的氟系化學製品(FM-5、 n = 3,4,5,6之混合物、n = 4之含率60%)導入甲基丙烯酸單 體(F-52)後’與其他成分藉由共聚合予以聚合物化。 CF, H2C-CHCH2^CF2CF2f.cF_cF3 〇 n-1 co2h -h2o FM-5co2h FM-4 -h2o C02-CH2CH2-f-CF2CF2f-cF-CF3 n-1 F-51 (P-1 1) Production method uses a fluorine-based chemical product (FM-5, n = 3,4,5,6 mixture, n = 4 content 60%) After introducing methacrylic acid monomer (F-52), it is polymerized with other ingredients by copolymerization. CF, H2C-CHCH2 ^ CF2CF2f.cF_cF3 〇 n-1 co2h -h2o FM-5
cf3 C〇2^CH2CH(OH)CH2^CF2CF2)—CF- CF——CF3 F-52 (p - l 2 )之製法 使用藉由短鏈聚合法製造的氟系化學製品(FM _ 6、n = 3之 -42- 1226509 五、發明說明(41 ) 含率96%)導入甲基丙烯酸單體(F_53)後,與其他成分藉由 共聚合予以聚合物化。 co2h HOH2C 卜 CF2CF2—h — FM-6 ·Η2〇 SC〇2 - CH2 十 CF2CF2)-h F.53 (P - 1 3 )之製法 使用藉由短鏈聚合法製造的氟系化學製品(FM-7、n = 4之 含率93%)導入二醇(F-54)後,與其他的二醇、二異氰酸酯 成分藉由聚縮合予以胺基甲酸酯聚合物化。 HO、cf3 C〇2 ^ CH2CH (OH) CH2 ^ CF2CF2) —CF- CF——CF3 F-52 (p-l 2) Production method uses a fluorine-based chemical product (FM _ 6, n = 3 of -42-1226509 V. Description of the invention (41) Content 96%) After introducing methacrylic acid monomer (F_53), it is polymerized with other components by copolymerization. co2h HOH2C CF2CF2—h — FM-6 · Η2〇SC〇2-CH2 十 CF2CF2) -h F.53 (P-1 3) Production method uses a fluorine-based chemical product (FM- 7. The content of n = 4 is 93%) After introducing diol (F-54), it is polymerized with other diols and diisocyanate components through polycondensation. HO,
H02C 卜 CF2CF2 卜 FH02C BU CF2 CF2 BU F
N——HN——H
H2ocH FM-7 0 -H2H2ocH FM-7 0 -H2
H2C CH0F2 2N1C—C H2, ‘ C \-H2C CH0F2 2N1C—C H2, ‘C \-
F -5 (P - 1 4 )之製法 使用藉由短鏈聚合法製造的氟系化學製品(FM-3)與甲酣 /福馬林樹脂反應、導入氟化脂肪族側鏈。 (?-16,17,18,19,20)之製法 係爲含有n = 3,4,5,6之混合物,各具有下述組成之 P-16 : n = 4成分對其他成分總和而言爲60% -43~ 1226509 五、發明說明(42) p_17 : n = 4成分對其他成分總和而言爲80% P-18 : n = 4成分對其他成分總和而言爲90% 19 : n = 4成分對其他成分總和而言爲95% P-20 : n = 3成分對其他成分總和而言爲50% 本發明所使用氟系聚合物之分子量範圍以重量平均分子 量通常使用1〇〇〇〜200,000、較佳者爲3,000〜1 00,000者 °此等之分子量例如可藉由使用聚苯乙烯標準物質之GP 法求取。 而且’本發明所使用的氟系聚合物在組成物中的添加量 除溶劑外對全部組成物而言爲〇 . 〇〇 1〜丨〇重量%、較佳者 爲0 · 0 1〜5重量%。此外,本發明之氟系聚合物可2種以 上倂用、大多與界面活性劑倂用。 本發明除所使用的氟系聚合物外之必須成份爲 (A )( 1 )藉由酸作用分解、增大在鹼顯像液中之溶解性的 樹脂,或 (2 )鹼可溶性樹脂、藉由酸作用分解、增大在鹼顯像液 中之溶解性的低分子化合物、或 (3 )藉由酸作用分解、增大在鹼顯像液中之溶解性的樹 脂及藉由酸作用分解、增大在鹼顯像液中之溶解性的低分 子化合物、以及 (B )藉由活性光線或放射線照射、產生酸之化合物。 說明有關(A )成分之藉由酸作用分解、增大在鹼顯像液 中之溶解性的樹脂。 -44- 1226509 五、發明說明(4 3 ) (1 )之藉由酸作用分解、增大在鹼顯像液中之溶解性的 樹脂係藉由使鹼可溶性基以酸分解性基保護達成其目的。 鹼可溶性基以苯酚性羥基、羧酸基較佳。 此等鹼可溶性基之保護基以縮醛基、縮酮基、第3 - 丁酯 基、第3 -丁氧基羰基等較佳、更佳者爲縮醛基、第3 -丁 酯基,尤其是縮醛基就感度、對曝光後放置時間之感度變 動、尺寸變動安定性(PED)而言較佳。而且,曝光光源爲 A rF時由於苯酚架構之吸收高、以第3-丁酯基或羧基之縮 醛酯等較佳。 特別是在KrF準分子雷射光及電子線曝光下導入適當的 酸分解性基之幹聚合物以羥基苯乙烯類較佳,亦可使用該 羥基苯乙烯類與第3 -丁基丙烯酸酯或第3 -丁基甲基丙烯 酸酯等酸分解性之(甲基)丙烯酸酯的共聚物。此外,以調 整幹聚合物之鹼可溶性爲目的時,亦可導入非酸分解性基 。導入的方法以藉由苯乙烯類、(甲基)丙烯酸酯類、(甲 基)丙烯酸醯胺類之共聚合的方法或使羥基苯乙烯類之羥 基以非酸分解性之取代基保護的方法較佳。非酸分解性取 代基以乙醯基、甲磺醯基、甲苯基磺醯基及異丙氧基等較 佳,惟不受此等限制。 另外,具有不同酸分解性之酸分解基例如有在同一主鏈 中使第3-丁氧基、第3 -丁氧基碳氧基、四氫壯喃氧基、 四氫呋喃氧基等共存,就感度、輪廓之調節而言較佳。 較佳的K rF準分子雷射光及電子線曝光之適合酸分解性 -45- 1226509 五、發明說明(44) 基聚合物的通式(E )如下所述。 通式(E) H^c Jr^rd O — CH I o—r4Production method of F -5 (P-1 4) A fluorine-based chemical product (FM-3) produced by a short-chain polymerization method is used to react with formazan / formalin resin to introduce a fluorinated aliphatic side chain. (? -16, 17, 18, 19, 20) The production method is a mixture containing n = 3,4,5,6, each of which has the following composition: P-16: n = 4 60% -43 ~ 1226509 V. Description of the invention (42) p_17: n = 4 is 80% of the sum of other ingredients P-18: n = 4 is 90% of the sum of other ingredients 19: n = 4 component is 95% for the sum of other components P-20: n = 3 component is 50% for the sum of other components The molecular weight range of the fluorine-based polymer used in the present invention is generally 10,000 to the weight average molecular weight The molecular weight of 200,000, more preferably 3,000 to 100,000 ° can be obtained by, for example, the GP method using a polystyrene standard material. Moreover, the addition amount of the fluorine-based polymer used in the present invention to the composition except for the solvent is 0.001 to 1% by weight, and more preferably 0. 0 to 1 to 5 weight%. %. In addition, the fluoropolymer of the present invention can be used in two or more kinds, and most of them can be used with a surfactant. In addition to the fluorine-based polymer used in the present invention, the essential components are (A) (1) a resin that is decomposed by an acid to increase solubility in an alkali developing solution, or (2) an alkali-soluble resin, and Low-molecular compounds that are decomposed by an acid and increase the solubility in an alkali imaging solution, or (3) resins that decompose by an acid, increase the solubility in an alkali imaging solution, and decomposed by an acid. , A low-molecular compound which increases solubility in an alkali imaging solution, and (B) a compound which generates an acid by irradiation with active light or radiation. The resin related to the component (A) which is decomposed by the action of acid to increase the solubility in the alkali developing solution will be explained. -44- 1226509 V. Description of the invention (4 3) (1) The resin which is decomposed by the action of acid and increases the solubility in the alkali imaging solution is achieved by protecting the alkali-soluble group with an acid-decomposable group. purpose. The alkali-soluble group is preferably a phenolic hydroxyl group or a carboxylic acid group. The protective groups of these alkali-soluble groups are acetal group, ketal group, 3-butyl ester group, 3 -butoxycarbonyl group, etc. are preferred, and more preferred are acetal group, 3 -butyl ester group, In particular, the acetal group is preferred in terms of sensitivity, sensitivity change to exposure time after exposure, and dimensional change stability (PED). In addition, when the exposure light source is A rF, the absorption of the phenol structure is high, and the acetal ester having a 3-butyl ester group or a carboxyl group is preferred. In particular, hydroxystyrenes are preferred for dry polymers that introduce appropriate acid-decomposable groups under KrF excimer laser light and electron beam exposure. The hydroxystyrenes and 3-butyl acrylate or Copolymer of acid-decomposable (meth) acrylates such as 3-butyl methacrylate. In addition, for the purpose of adjusting the alkali solubility of the dry polymer, a non-acid-decomposable group may be introduced. The method of introduction is a method of copolymerizing styrenes, (meth) acrylic esters, ammonium (meth) acrylic acid, or a method of protecting hydroxyl groups of hydroxystyrenes with non-acid-degradable substituents. Better. The non-acid-degradable substituents are preferably ethylamyl, mesylsulfonyl, tolylsulfonyl and isopropoxy, but are not limited by these. In addition, acid-decomposing groups having different acid-decomposability include, for example, coexistence of a 3-butoxy group, a 3-butoxycarboxy group, a tetrahydrofuranoxy group, and a tetrahydrofuranoxy group in the same main chain. It is better to adjust the sensitivity and contour. Suitable K rF excimer laser light and electron beam exposure are suitable for acid decomposition -45-1226509 V. Description of the invention (44) The general formula (E) of the polymer is as follows. General formula (E) H ^ c Jr ^ rd O — CH I o—r4
OHOH
ClCl
Rs .c •c、 〇少、〇—ReRs .c • c, 〇 少, 〇-Re
O 、N—R7 I Re (其中,R3’係各獨立地表示氫原子、甲基,數個r3,可爲 相同或各不同。R4係表示直鏈、支鏈、或環狀碳數1〜12 之未經取代或可具取代基之烷基、或碳數6〜1 8之未經取 代或可具取代基之芳香族基、或碳數7〜1 8之未經取代或 可具取代基之芳烷基。直鏈、支鏈或環狀碳數丨〜12個烷 基例如有甲基、乙基、丙基、異丙基、正丁基、異丁基、 第2-丁基、第3-丁基、戊基、己基、庚基、2-乙基己基 、辛基、環丙基、環戊基、1_金剛烷基乙基等之烷基) 此等烷基的另外取代基例如具有羥基、氟、氯、溴、碘 等之_素原子、胺基、硝基、氰基、羰基、酯基、烷氧基 、可含雜原子之環烷基、芳氧基、磺醯基之取代基。此處 ’羯基係以院基取代羯基、芳香族取代羯基較佳,醋基係 以院基取代酯基、芳香族取代酯基較佳,烷氧基係以甲氧 基、乙氧基、丙氧基、第3 - 丁氧基等較佳。環烷基例如有 環己基、金剛垸基、環戊基、環丙基等,含雜原子者例如 嚼哗基等。芳氧基例如苯氧基等,在該芳基上亦可具取代 -46 - 1226509 五、發明說明(45) 基。具有磺醯基之取代基例如有甲基磺醯基、乙基磺醯基 等之院基磺酿基、苯基擴醯基等芳基磺醯基等。 上述芳烷基例如有苯甲基、苯乙基、二苯甲基、萘基甲 基等。此等芳烷基中可具有烷基之取代基所記載者作爲取 代基。 上述芳香族基例如有苯環、萘環、蒽環、菲環等衍生的 基。在此等芳香族基環上可具有上述烷基之取代基所記載 者作爲取代基。 係表示氫原子、直鏈、支鏈碳數1〜4之烷基(例如甲 基、乙基、丙基、丁基、第2-丁基、第3-丁基等)、直鏈 、支鏈碳數1〜4之烷氧基(例如甲氧基、乙氧基、丙氧基 、異丙氧基、正丁氧基、第2-丁氧基、第3-丁氧基等)、 乙醯氧基、甲磺醯氧基、甲苯氧基、第3 -丁氧基羰氧基、 第3 -丁氧基羰基甲氧基、四氫呋喃氧基或四氫吡喃氧基, 惟以第3 -丁基、乙醯基、異丙氧基、四氫氟喃氧基較佳。 R6係爲氫原子、直鏈、支鏈或環狀碳數1〜8之烷基、 可具有碳數6〜12之取代基的芳香族基、或可具有碳數7 〜1 8之取代基的芳烷基,較佳者爲第3 - 丁基、1 -甲氧基 環己基等。 R7、R8係各獨立地表示氫原子、直鏈、支鏈或環狀碳數 1〜8之烷基、可具碳數6〜12之取代基的芳香族基或碳數 7〜1 8之取代基的芳院基。 R0〜R8之烷基、芳香族基、芳烷基的具體例與上述R3’ -47- 1226509 五、發明說明(46) 例中之上述碳數範圍者。 a,b,c,d,e係各表示各單體單位之莫耳%、且 以 OS a/(a + b)S 0.6 較佳、更佳者爲 OS a/(a + b)S 0.5 、最佳者爲 0.05$a/(a + b)S0.5。 以 0Sc/(a + b + c)S0.3 較佳、更佳者爲 0Sc/(a + b + c)S 〇· 2 ° 以 0Sd/(a + b + d)S0.4 較佳、更佳者爲 0Sd/(a + b + d)S 0.3° 以 0Se/(a + b + e)S0.4 較佳、更佳者爲 0Sd/(a + b + d)S 0.3° 於下述中係表示酸分解性聚合物之較佳例。惟「i _ Bu」 係表示異丁基、「n-Bu」係表示正丁基、「Et」係表示乙 基。O, N-R7 I Re (wherein R3 'each independently represents a hydrogen atom, a methyl group, and several r3s may be the same or different. R4 represents a straight chain, a branched chain, or a cyclic carbon number of 1 to 12 unsubstituted or optionally substituted alkyl groups, or 6 to 18 unsubstituted or substituted aromatic groups, or 7 to 18 unsubstituted or substituted carbons Aralkyl group. Linear, branched or cyclic carbon number ~~ 12 alkyl groups such as methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, 2-butyl , 3-butyl, pentyl, hexyl, heptyl, 2-ethylhexyl, octyl, cyclopropyl, cyclopentyl, 1-adamantylethyl, etc.) Substituents have, for example, hydroxyl atoms, fluorine, chlorine, bromine, iodine, etc., amine groups, nitro groups, cyano groups, carbonyl groups, ester groups, alkoxy groups, cycloalkyl groups which may contain hetero atoms, aryloxy groups, Substituent for sulfofluorenyl. Here, the fluorenyl group is preferably substituted with a fluorenyl group and an aromatic substituted fluorenyl group, the acetic acid group is substituted with a sulfonyl group and an aromatic substituted ester group, and the alkoxy group is methoxy and ethoxy A group, a propoxy group, a 3-butoxy group and the like are preferred. Examples of the cycloalkyl group include cyclohexyl, adamantyl, cyclopentyl, and cyclopropyl, and those having a hetero atom include, for example, a chelating group. Aryloxy, such as phenoxy, etc., may have substituents on this aryl group -46-1226509 V. (45) group of the invention description. Examples of the substituent having a sulfofluorenyl group include a methylsulfonyl group such as a methylsulfonyl group and an ethylsulfonyl group, and an arylsulfonyl group such as a phenylsulfonyl group. Examples of the aralkyl group include benzyl, phenethyl, benzhydryl, and naphthylmethyl. Among these aralkyl groups, those described as a substituent having an alkyl group may be used as the substituent. Examples of the aromatic group include a group derived from a benzene ring, a naphthalene ring, an anthracene ring, and a phenanthrene ring. These aromatic group rings may have, as substituents, those described in the substituents having the above-mentioned alkyl group. A hydrogen atom, a straight chain, a branched alkyl group having 1 to 4 carbon atoms (for example, methyl, ethyl, propyl, butyl, 2-butyl, 3-butyl, etc.), straight chain, branch Alkoxy groups with 1 to 4 carbon atoms (such as methoxy, ethoxy, propoxy, isopropoxy, n-butoxy, 2-butoxy, 3-butoxy, etc.), Acetyloxy, methanesulfonyloxy, tolyloxy, 3-butoxycarbonyloxy, 3-butoxycarbonylmethoxy, tetrahydrofuranoxy or tetrahydropyranyloxy. 3-Butyl, ethylfluorenyl, isopropoxy, and tetrahydrofluororanyloxy are preferred. R6 is a hydrogen atom, a linear, branched or cyclic alkyl group having 1 to 8 carbon atoms, an aromatic group having a substituent having 6 to 12 carbon atoms, or a substituent having 7 to 18 carbon atoms The aralkyl group is preferably a 3-butyl group, a 1-methoxycyclohexyl group, or the like. R7 and R8 each independently represent a hydrogen atom, a linear, branched or cyclic alkyl group having 1 to 8 carbon atoms, an aromatic group which may have a substituent having 6 to 12 carbon atoms, or an aromatic group having 7 to 18 carbon atoms Aromatic radicals of substituents. Specific examples of the alkyl group, aromatic group, and aralkyl group of R0 to R8 are those in the above-mentioned carbon number range in the above-mentioned R3'-47-1226509. (46) Examples. a, b, c, d, and e each represent the mole% of each monomer unit, and OS a / (a + b) S 0.6 is better, and more preferably OS a / (a + b) S 0.5 The best is 0.05 $ a / (a + b) S0.5. 0Sc / (a + b + c) S0.3 is preferred, and even more preferred is 0Sc / (a + b + c) S 0.2 ° ° Sd / (a + b + d) S0.4 is preferred, 0Sd / (a + b + d) S 0.3 ° is better, 0Se / (a + b + e) S0.4 is better, and 0Sd / (a + b + d) S 0.3 ° is better than The above description is a preferred example of an acid-decomposable polymer. However, "i_Bu" means isobutyl, "n-Bu" means n-butyl, and "Et" means ethyl.
-48- 1226509-48- 1226509
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(B-22)(B-22)
OH (B-23)OH (B-23)
(B-24)(B-24)
-53- 1226509 五、發明說明(52) 上述聚合物之重量平均分子量可藉由凝膠滲透色層分析 法(GPC)測定聚苯乙烯換算分子量(Mw),較佳者爲2,〇〇〇〜 200,000、更佳者爲4,000〜50,000、最佳者爲7,〇〇〇〜 30, 000。若分子量大於200,000時溶解性不佳、解像力降 低’而若分子量小於2,000時會有引起膜邊之傾向。而且 ’分子量分佈(重量平均分子量/數平均分子量)狹窄(1 . 03 〜1 . 40 )的聚合物就解像力而言較佳。 此外,上述聚合物可以組合2種以上不同者、或組合2 種以上同種、分子量不同者或組成比不同的聚合物,可進 行調整感度、解像力等。 於本發明中(1)之形態中,爲KrF準分子雷射光及電子 線曝光用時,加入於上述酸分解性聚合物、可使用在正型 光阻組成物中不含酸分解性基之鹼可溶性樹脂,藉此可提 局感度。 上述不含酸分解性基之鹼可溶性樹脂(以下簡稱爲鹼可 溶性樹脂)係爲可溶於鹼之樹脂,例如以聚羥基苯乙烯、 酚醛淸漆樹脂及此等之衍生物較佳。而且,只要是含對-羥基苯乙烯單位之共聚合樹脂具鹼可溶性者皆可使用。其 中以使用聚(對-羥基苯乙烯)、聚(對-/間-羥基苯乙烯)共 聚物、聚(對-羥基/鄰-羥基苯乙烯)共聚物、聚(對-羥基 苯乙烯/苯乙烯)共聚物較佳。另外,聚(4 -羥基-3-甲基苯 乙烯)、聚(4 -羥基-3 , 5 -二甲基苯乙烯)之聚(烷基取代羥 基苯乙烯)樹脂、上述樹脂之部分苯酚性羥基經烷基化或 -54- 1226509 五、發明說明(53) 乙醯基化的樹脂只要是具鹼可溶性者皆較佳。 此外,使上述樹脂之部分苯酚核(全部苯酚核之30莫耳 %以下)加氫時,就可提高樹脂之透明性、及感度、解像力 、形成矩形輪廓而言較佳。 於本發明中爲(1 )之形態時,上述不含酸分解性基之鹼 可溶性樹脂在組成物中之添加量,對全部組成物之固成分 全部重量而言以2〜60重量%較佳、更佳者淨5〜30重量% 〇 另外,藉由對應於A rF準分子雷射光曝光之酸作用分解 '增大在鹼顯像液中之溶解性的樹脂,例如在樹脂主鏈及 /或側鏈上具有脂環式構造的樹脂,可使用以習知技術製 得的習知聚合物。 適合使用的樹脂例如含有下述通式(F)所示重複構造單 位及/或下述通式(G )所示重複構造單位之聚合物。-53- 1226509 V. Description of the invention (52) The weight average molecular weight of the above polymer can be determined by gel permeation chromatography (GPC), and the molecular weight (Mw) of polystyrene conversion is preferably 2,000. ~ 200,000, more preferably between 4,000 and 50,000, and the best between 7,000 and 30,000. If the molecular weight is more than 200,000, the solubility is poor and the resolution is lowered. 'If the molecular weight is less than 2,000, the film tends to be edged. A polymer having a narrow molecular weight distribution (weight average molecular weight / number average molecular weight) (1.03 to 1.40) is preferable in terms of resolution. In addition, the above polymers may be combined with two or more different polymers, or polymers of the same kind, different molecular weights, or different composition ratios may be combined, and sensitivity, resolution, etc. may be adjusted. In the aspect (1) of the present invention, when it is used for KrF excimer laser light and electron beam exposure, it can be added to the acid-decomposable polymer described above, and can be used in the positive photoresist composition without acid-decomposable groups. Alkali soluble resin, which can improve local sensitivity. The above-mentioned alkali-soluble resin containing no acid-decomposable group (hereinafter simply referred to as alkali-soluble resin) is a resin that is soluble in alkali, and for example, polyhydroxystyrene, phenolic resin and derivatives thereof are preferred. In addition, any copolymer resin containing para-hydroxystyrene units that has alkali solubility can be used. Among them, poly (p-hydroxystyrene), poly (p- / m-hydroxystyrene) copolymer, poly (p-hydroxy / o-hydroxystyrene) copolymer, poly (p-hydroxystyrene / benzene Ethylene) copolymers are preferred. In addition, poly (4-hydroxy-3-methylstyrene), poly (4-hydroxy-3, 5-dimethylstyrene) poly (alkyl-substituted hydroxystyrene) resins, and partial phenolic properties of the above resins The hydroxyl group is alkylated or -54-1226509 V. Description of the invention (53) Acetyl-based resins are preferred as long as they are alkali-soluble. In addition, when hydrogenating part of the phenol nuclei of the above resin (less than 30 mol% of all phenol nuclei), it is preferable to improve the transparency, sensitivity, resolution, and form a rectangular outline of the resin. In the form of (1) in the present invention, the addition amount of the alkali-soluble resin containing no acid-decomposable group to the composition is preferably 2 to 60% by weight based on the total weight of the solid content of the entire composition. , Better 5 ~ 30% by weight. 〇 In addition, it is decomposed by the acid action corresponding to the exposure of A rF excimer laser light to decompose the resin which increases the solubility in the alkali developing solution, for example, in the resin main chain and / Alternatively, a resin having an alicyclic structure in a side chain may be a conventional polymer prepared by a conventional technique. A suitable resin is, for example, a polymer containing a repeating structural unit represented by the following general formula (F) and / or a repeating structural unit represented by the following general formula (G).
(其中,RU〜RM係各獨立地表示氫原子或可具取代基之 烷基,a係表示〇或1,R 1!〜R i 4之烷基以碳數1〜1 2者較 佳、更佳者爲1〜1 0者,具體例如有甲基、乙基、丙基、(Among them, RU ~ RM each independently represents a hydrogen atom or an alkyl group which may have a substituent, and a represents a 0 or 1, and an alkyl group of R 1! To R i 4 is preferably one having 1 to 12 carbon atoms. More preferably, it is 1 to 10, and specific examples include methyl, ethyl, propyl,
55- 1226509 五、發明說明(54) 異丙基、正丁基、異丁基、第2_ 丁基、第3_ 丁基、戊基 、己基、庚基、辛基、壬基、癸基較佳。該烷基之取代基 例如有羥基、烷氧基、烷氧基烷氧基等) 通式(G)中R3,係表示氫原子或甲基。a係表示單獨或組 合2種以上選自於單鍵、伸烷基、環伸烷基、醚基、硫化 醚基、羯基、醋基。 W係表示-C(Ra)(Rb)(Rc)所示之基或-CH(Rd)-0-Re所示 之基。此處,Ra、Rb、Rc可各具有鹵素原子、烷氧基、烷 氧基羰基、醯基或醯氧基作爲取代基之碳數1〜20個直鏈 狀或支鏈狀烷基或碳數3〜20個環烷基。惟Ra與Rb可以 互相鍵結形成脂環式單環。Rd係表示氫原子或烷基。Re 係表示具有鹵素原子、烷氧基、烷氧基羰基、醯基或醯氧 基作爲取代基之碳數1〜20個直鏈狀或支鏈狀烷基或碳數 3〜20個環烷基。 上述聚合物亦可另含有下述通式(H)所示重複構造單位55-1226509 V. Description of the invention (54) Isopropyl, n-butyl, isobutyl, 2-butyl, 3-butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl are preferred . Examples of the substituent of the alkyl group include a hydroxyl group, an alkoxy group, and an alkoxyalkoxy group. In the general formula (G), R3 represents a hydrogen atom or a methyl group. The "a" represents two or more kinds selected from a single bond, an alkylene group, a cycloalkylene group, an ether group, a sulfurized ether group, a fluorenyl group, and an acetic acid group, alone or in combination. W represents a group represented by -C (Ra) (Rb) (Rc) or a group represented by -CH (Rd) -0-Re. Here, each of Ra, Rb, and Rc may have a halogen atom, an alkoxy group, an alkoxycarbonyl group, a fluorenyl group, or a fluorenyl group as a substituent. The carbon number is 1 to 20 linear or branched alkyl groups or carbon Number 3 to 20 cycloalkyl. However, Ra and Rb can be bonded to each other to form an alicyclic monocyclic ring. Rd means a hydrogen atom or an alkyl group. The Re system represents a linear or branched alkyl group having 1 to 20 carbon atoms or a cycloalkane having 3 to 20 carbon atoms having a halogen atom, an alkoxy group, an alkoxycarbonyl group, a fluorenyl group, or a fluorenyl group as a substituent. base. The polymer may further include a repeating structural unit represented by the following general formula (H)
(其中,Z2係表示-0-或- N(R3)-,此處R3係表示氫原子 、羥基、烷基、鹵化烷基或- 〇s〇2_R4,L係表示烷基、鹵 化烷基、環烷基或樟腦殘基) 下述係爲通式(F)所示重複構造單位之單體的具體例, -56- 1226509(Where Z2 represents -0- or -N (R3)-, where R3 represents a hydrogen atom, a hydroxyl group, an alkyl group, a halogenated alkyl group, or -0s〇2_R4, and L represents an alkyl group, a halogenated alkyl group, Cycloalkyl or camphor residue) The following are specific examples of monomers having a repeating structural unit represented by the general formula (F), -56-1226509
五、發明說明(55) 惟不受此等所限制。Q ' W HO HO H05. Description of Invention (55) Except for these restrictions. Q 'W HO HO H0
下述係爲通式(G)所示重複構造單位之單體的具體例’ 惟不受此等所限制。 -57- 1226509 五、發明說明(56 )The following are specific examples of monomers having repeating structural units represented by the general formula (G) ', but are not limited thereto. -57- 1226509 V. Description of the invention (56)
58- 122650958- 1226509
1226509 五、發明說明(58)1226509 V. Description of Invention (58)
ΟΟ
刻耐性或標準顯像液適性、基板密接性、阻體輪廓、以及 光阻之一般必要特性的解像力、耐熱性、感度等爲目的時 ,可含有各種重複構造單位。 該重複構造單位例如有下述單體之重複構造單位’惟$ 受此等所限制。 此可微調整酸分解性樹脂所要求的性能,尤其是 (1 )對塗覆溶劑之解性、 -60- 1226509 五、發明說明(59) (2 )製膜性(玻璃轉移溫度)、 (3 )驗顯像性、 (4 )膜邊緣(親疏水性、鹼可溶性基選擇)、 (5 )對未曝光部基板之密接性、 (6 )乾式蝕刻耐性、 等之微調整。 該單體例如有丙烯酸酯類、甲基丙烯酸酯類、丙烯酸醯 胺類、甲基丙醯酸醯胺類、烯丙基化合物、乙烯醚類、乙 烯酯類等具一個選自加成聚合性不飽和鍵之化合物等。 具體而言例如下述之單體。 丙烯酸酯類例如有丙烯酸烷酯類(較佳者爲烷基之碳數 以1〜1 0的丙烯酸烷酯): 丙烯酸甲酯、丙烯酸乙酯、丙烯酸丙酯、丙烯酸戊酯、 丙烯酸環己酯、丙烯酸乙基己酯、丙烯酸辛酯、丙烯酸-第3 -辛酯、丙烯酸氯化乙酯、丙烯酸2 -羥基乙酯、丙烯 酸2,2 -二甲基羥基丙酯、丙烯酸5 -羥基苯甲酯、單丙烯 酸三羥甲基丙烷酯、單丙烯酸季戊四醇酯、丙烯酸苯甲酯 、丙烯酸甲氧基苯甲酯、丙烯酸芴酯、丙烯酸四氫芴酯等 〇 甲基丙烯酸酯類例如有甲基丙烯酸烷酯類(較佳者爲烷 基之碳數1〜10之甲基丙烯酸烷酯): 甲基丙烯酸甲酯、甲基丙烯酸乙酯、甲基丙烯酸丙酯、 甲基丙烯酸異丙酯、甲基丙烯酸醯酯、甲基丙烯酸己酯、 -61 - 1226509 五、發明說明(6〇) 甲基丙烯酸環己酯、甲基丙烯酸苯甲酯、甲基丙烯酸氯化 苯甲酯、甲基丙烯酸辛酯、甲基丙烯酸2 -羥基乙酯、甲基 丙烯酸4 -羥基丁酯、甲基丙烯酸5 -羥基苯甲酯、甲基丙 烯酸2,2 -二甲基-3-羥基丙酯、單甲基丙烯酸三羥甲基丙 烷酯、單甲基丙烯酸季戊四醇酯、甲基丙烯酸芴酯、甲基 丙烯酸四氫芴酯等; 丙烯醯胺類: 丙烯醯胺、N-烷基丙烯醯胺(烷基爲碳數1〜10者,如 甲基、乙基、丙基、丁基、第3-丁基、庚基、辛基、環己 基、羥基乙基等)、N,N -二烷基丙烯醯胺(烷基爲碳數1〜 10者,例如甲基、乙基、丁基、異丁基、乙基己基、環己 基等)、N -羥基乙基-N-甲基丙烯醯胺、N-2 -乙烯基醯胺乙 基-N-乙醯基丙烯醯胺等。 甲基丙烯醯胺類: 甲基丙烯醯胺、N -烷基甲基丙烯醯胺(烷基爲碳數1〜10 者,如甲基、乙基、第3 -丁基、乙基己基、羥基乙基、環 己基等)、N,N -二烷基甲基丙烯醯胺(烷基爲乙基、丙基、 丁基等)、N -羥基乙基-N-甲基甲基丙烯醯胺等。 烯丙基化合物: 烯丙酯類(例如醋酸烯丙酯、己酸烯丙酯、己酸烯丙酯 、月桂酸烯丙酯、棕櫚酸烯丙酯、硬酯酸烯丙酯、苯甲酸 烯丙酯、乙醯醋酸烯丙酯、乳酸烯丙酯等)、烯丙氧基乙 醇等。 -62- 1226509 五、發明說明(61) 乙烯醚類: 烷基乙烯醚(例如己基乙烯醚、辛基乙烯醚、癸基乙烯 醚、乙基己基乙烯醚、甲氧基乙基乙烯醚、乙氧基乙基乙 烯醚、氯化乙基乙烯醚、1-甲基-2,2 -二甲基丙基乙烯醚 、2 -乙基丁基乙烯醚、羥基乙基乙烯醚、二乙二醇乙烯醚 、二甲基胺基乙基乙烯醚、二乙基胺基乙基乙烯醚、丁基 胺基乙基乙烯醚、苯甲基乙烯醚、四氫芴基乙烯醚等。 乙烯酯類: 丁酸乙烯酯、異丁酸乙烯酯、三甲基乙酸乙烯酯、二乙 基乙酸乙烯酯、癸酸乙烯酯、己酸乙烯酯、氯化乙酸乙烯 酯、二氯化乙酸乙烯酯、甲氧基乙酸乙烯酯、丁氧基乙酸 乙烯酯、乙醯基乙酸乙烯酯、乳酸乙烯酯、-苯基丁酸 乙烯酯、環己基羧酸乙烯酯等; 衣康酸二烷酯類: 衣康酸二甲酯、衣康酸二乙酯、衣康酸二丁酯等。 其他有檸檬酸、衣康酸、馬來酸酐、馬來醯胺、丙烯腈 、甲基丙烯腈馬來腈等。 其他如可與上述各種重複構造單位之單體共聚合的加成 聚合性不飽和化合物予以共聚合。 於酸分解性樹脂中,各重複構造單位的含有莫耳比,就 所企求的光阻之乾式蝕刻耐性及標準顯像液適性、基板密 接性、光阻輪廓、以及光阻之一般必要要件的解像力、耐 熱性等而言予以適當地設定。 -63- 1226509 五、發明說明(62) A r F曝光用途中適合的酸分解性樹脂中通式(F )所不重複 構造單位的含量在全部重複構造單位中以25〜70莫耳%較 佳、更佳者爲28〜65莫耳%、最佳者爲30〜60莫耳%。 而且,酸分解性樹脂中通式(G )所示重複構造單位的含 量,在全部重複構造單位中以2〜50莫耳%較佳、更佳者 爲4〜45莫耳%、最佳者爲6〜40莫耳%。 另外,酸分解性樹脂中通式(Η )所示重複構造單位的含 量,在全部重複構造單位中以20〜80莫耳%較佳、更佳者 爲25〜70莫耳%、最佳者爲30〜60莫耳%。 此外,以上述構成共聚合成分之單體爲基準的重複構造 單位在樹脂中之含量可視所企求的光阻性能而定予以適當 設定,一般而言對通式(F )及通式(G )所示的重複構造單位 對合計的總莫耳而言以99莫耳%以下較佳、更佳者爲90 莫耳%以下、最佳者爲80莫耳%以下。 上述酸分解性樹脂之分子量以重量平均(Mw :藉由GPC 法之聚苯乙烯換算値),以1,000〜1,000,000較佳、更佳 者爲1,500〜500,000、尤佳者爲2,000〜200,000、最佳 者爲2,5 00〜1 00,000,愈大時可提高耐熱性等、且可降低 顯像性、藉由此等之平衡可調整爲較佳的範圍。本發明所 使用的酸分解性樹脂可藉由常法(例如游離基聚合)予以合 成 於下述中係爲組合適於A r F曝光用途之酸分解性樹脂的 重複構造單位較佳具體例。 -64- 1226509 五、發明說明(63) —0¾—CH-For the purpose of the resolution, heat resistance, sensitivity, etc. of the resistance to standard or standard imaging solution, substrate adhesion, profile of the resist, and general necessary characteristics of photoresist, various repeating structural units may be included. The repeating structural unit is, for example, the following repeating structural unit of a monomer, but is limited by these. This can finely adjust the properties required for acid-decomposable resins, especially (1) the solubility of the coating solvent, -60-1226509 5. Description of the invention (59) (2) Film-forming properties (glass transition temperature), ( 3) Inspection of imaging, (4) film edges (hydrophilicity, alkali-soluble group selection), (5) adhesion to the substrate of the unexposed part, (6) dry etching resistance, and other fine adjustments. The monomers include, for example, acrylates, methacrylates, ammonium acrylates, ammonium methacrylate, allyl compounds, vinyl ethers, vinyl esters, and the like. Unsaturated compounds, etc. Specifically, the following monomers are mentioned, for example. Examples of the acrylates include alkyl acrylates (preferably alkyl acrylates having 1 to 10 carbon atoms in the alkyl group): methyl acrylate, ethyl acrylate, propyl acrylate, pentyl acrylate, and cyclohexyl acrylate , Ethylhexyl acrylate, octyl acrylate, 3rd-octyl acrylate, ethyl chloride acrylate, 2-hydroxyethyl acrylate, 2,2-dimethylhydroxypropyl acrylate, 5-hydroxybenzoyl acrylate Ethyl esters, trimethylolpropane monoacrylate, pentaerythritol monoacrylate, benzyl acrylate, methoxybenzyl acrylate, methyl acrylate, tetrahydromethyl acrylate and the like. For example, methacrylic acid esters Alkyl esters (preferably alkyl methacrylates having 1 to 10 carbon atoms): methyl methacrylate, ethyl methacrylate, propyl methacrylate, isopropyl methacrylate, methyl ester Methyl acrylate, hexyl methacrylate, -61-1226509 5. Description of the invention (60) Cyclohexyl methacrylate, benzyl methacrylate, benzyl methacrylate chloride, octyl methacrylate Esters, 2-hydroxy methacrylic acid Ethyl ester, 4-hydroxybutyl methacrylate, 5-hydroxybenzyl methacrylate, 2,2-dimethyl-3-hydroxypropyl methacrylate, trimethylolpropane monomethacrylate , Pentaerythritol monomethacrylate, methyl methacrylate, tetrahydromethyl methacrylate, etc .; acrylamides: acrylamide, N-alkylacrylamide (alkyl groups are 1 to 10 carbon atoms, Such as methyl, ethyl, propyl, butyl, 3-butyl, heptyl, octyl, cyclohexyl, hydroxyethyl, etc.), N, N-dialkylpropenamide (alkyl is the number of carbons) 1 to 10, such as methyl, ethyl, butyl, isobutyl, ethylhexyl, cyclohexyl, etc.), N-hydroxyethyl-N-methacrylamide, N-2 -vinylfluorenamine Ethyl-N-ethenylacrylamide and the like. Methacrylamides: Methacrylamides, N-alkylmethacrylamides (alkyl groups are 1 to 10 carbon atoms, such as methyl, ethyl, 3-butyl, ethylhexyl, Hydroxyethyl, cyclohexyl, etc.), N, N-dialkylmethacrylamide (alkyl is ethyl, propyl, butyl, etc.), N-hydroxyethyl-N-methylmethacrylamine Amine, etc. Allyl compounds: Allyl esters (eg allyl acetate, allyl hexanoate, allyl hexanoate, allyl laurate, allyl palmitate, allyl stearate, allyl benzoate Propyl ester, allyl acetate, allyl lactate, etc.), allyloxy ethanol, etc. -62- 1226509 V. Description of the invention (61) Vinyl ethers: Alkyl vinyl ethers (such as hexyl vinyl ether, octyl vinyl ether, decyl vinyl ether, ethylhexyl vinyl ether, methoxyethyl vinyl ether, ethyl Oxyethyl vinyl ether, chlorinated ethyl vinyl ether, 1-methyl-2,2-dimethylpropyl vinyl ether, 2-ethylbutyl vinyl ether, hydroxyethyl vinyl ether, diethylene glycol Vinyl ether, dimethylamino ethyl vinyl ether, diethyl amino ethyl vinyl ether, butyl amino ethyl vinyl ether, benzyl vinyl ether, tetrahydrofluorenyl vinyl ether, etc. Vinyl esters: Vinyl butyrate, vinyl isobutyrate, trimethyl vinyl acetate, diethyl vinyl acetate, vinyl decanoate, vinyl hexanoate, vinyl chloride chloride, vinyl dichloride, methoxy Vinyl Acetate, Butoxy Vinyl Acetate, Ethyl Vinyl Acetate, Vinyl Lactate, Vinyl-Phenyl Butyrate, Vinyl Cyclohexyl Carboxylate, etc .; Dialkyl Itaconates: Itaconic Acid Dimethyl ester, diethyl itaconic acid, dibutyl itaconic acid, etc. Others include citric acid, itaconic acid, maleic anhydride, horse Amidine, acrylonitrile, methacrylonitrile, maleonitrile, etc. Other addition polymerizable unsaturated compounds that can be copolymerized with the monomers of the various repeating structural units described above are copolymerized. In acid-decomposable resins, each repeats The molar ratio of the structural unit is appropriate in terms of the required dry etching resistance of the photoresist, the standard developing solution suitability, the substrate adhesion, the photoresist profile, and the resolution and heat resistance of the general requirements for photoresist. -63- 1226509 V. Description of the invention (62) The content of non-repeating structural units of general formula (F) in acid decomposable resins suitable for A r F exposure applications is 25 to 70 moles in all repetitive structural units. The ear% is preferably, more preferably 28 to 65 mole%, and most preferably 30 to 60 mole%. The content of the repeating structural unit represented by the general formula (G) in the acid-decomposable resin is repeated all over. The structural unit is preferably 2 to 50 mol%, more preferably 4 to 45 mol%, and most preferably 6 to 40 mol%. In addition, the general formula (树脂) in the acid decomposable resin is repeated. Content of tectonic unit 20 to 80 mol% is preferred, 25 to 70 mol% is more preferred, and 30 to 60 mol% is most preferred. The repeating structural unit based on the monomer constituting the copolymerization component described above is The content in the resin can be appropriately set depending on the desired photoresist performance. Generally, the repeating structural unit represented by the general formula (F) and the general formula (G) is 99 mol for the total mol. % Or less is preferred, more preferably 90% or less, and most preferably 80% or less. The molecular weight of the above acid-decomposable resin is weight average (Mw: polystyrene conversion by GPC method), It is preferably 1,000 to 1,000,000, more preferably 1,500 to 500,000, even more preferably 2,000 to 200,000, and the most preferable 2,500 to 1,00,000. The larger the heat resistance is, etc., In addition, the developability can be reduced, and the balance can be adjusted to a better range. The acid-decomposable resin used in the present invention can be synthesized by a conventional method (for example, radical polymerization). The following is a preferred specific example of a repeating structural unit combining an acid-decomposable resin suitable for A F exposure applications. -64- 1226509 V. Description of the invention (63) —0¾—CH-
CH 3 —CH-CH— ο (1) —CH2—CH- CHjCHari0 —CH-CH—〇〜>=〇 C2)CH 3 —CH-CH— ο (1) —CH2—CH- CHjCHari0 —CH-CH—〇 ~ > = 〇 C2)
—CH-CH— 〇 人〇x^〇 ⑶ Ο Ο—CH-CH— 〇 person 〇x ^ 〇 ⑶ Ο Ο
M) (5)M) (5)
-CH2—CH— CH2CH3ViQ 一 CH-CH 一*〇=v=〇 *一CH2一CH一 I c—o II o ⑹ C(CH3)3 -65- 1226509 五、發明說明(64 -CH2—CH— CH3Γ复 一 CH 一 CH—*0=k >〇 (7) 〇 CH厂CH— C—0—CH2CH2OCH3II0 ο —CH2—CH— CH2CH3 c—οIIο-CH2—CH— CH2CH3ViQ—CH—CH— * 〇 = v = 〇 * —CH2—CH—I c—o II o ⑹ C (CH3) 3 -65-1226509 5. Description of the invention (64 -CH2—CH— CH3Γ multiple CH—CH0 ** = k > 〇 (7) 〇CH factory CH— C—0—CH2CH2OCH3II0 ο —CH2—CH— CH2CH3 c—οIIο
—CH—CH—〇〜>=〇 ⑻ *—ch2—ch~° o -CH2—CH— CH3c"°i9 II o 一CHj一CH一 CH3 C—0-CII I o ch3—CH—CH—〇 ~ > = 〇 ⑻ * —ch2—ch ~ ° o -CH2—CH— CH3c " ° i9 II o—CHj—CH—CH3 C—0-CII I o ch3
—CH—CH— 0=k Λ=〇 O —CH—CH——CH—CH— 0 = k Λ = 〇 O —CH—CH—
o -CH5—CH ⑼ CH3 o o (10) *—CH2—CH-r°<500 〇 -66- 1226509 五、發明說明(65) CH3 _ch2 一 C—— c—〇 II 〇 ΙΠ3 一 CH—CH— 〇=^〇^=〇 (11) ch3 •CH2一0"· C 一 0fl 0 ch2ch3i9 —CH—CH—〇〜>=〇 (12) ch3 -ch2—C— CH3ΓΪ0 —CH-CH—Φ 〇<0>〇 (13) *一CHj—CH— f{-〇^2(QH2hCHz 0o -CH5—CH ⑼ CH3 oo (10) * —CH2—CH-r ° <500 〇-66-1226509 V. Description of the invention (65) CH3 _ch2—C—c—〇II 〇ΙΠ3—CH—CH — 〇 = ^ 〇 ^ = 〇 (11) ch3 • CH2—0 " · C—0fl 0 ch2ch3i9 —CH—CH—〇 ~ > = 〇 (12) ch3 -ch2—C— CH3ΓΪ0 —CH-CH—Φ 〇 < 0 > 〇 (13) * _CHj-CH- f {-〇 ^ 2 (QH2hCHz 0
*—CH2—c—— (14) C—〇—CH2CH2〇CH3 o 於本發明正型光阻組成物中,爲(1)之形態時上述酸分 解性樹脂在光阻組成物全體中的配合量爲全部固成分之40 〜99.99重量%較佳、更佳者爲50〜99.97重量%。 其次說明(A )成分之(2 )形態的組合鹼可溶性樹脂與藉由 -67- 1226509 五、發明說明(66) 酸作用分解、增大對顯像液之溶解性的低分子化合物。 鹼可溶性樹脂爲可溶於鹼之樹脂,例如以聚羥基苯乙烯 、酚醛淸漆樹脂及此等之衍生物較佳。而且,只要是含對 -羥基苯乙烯單位之共聚合樹脂具鹼可溶性者皆可使用。 其中以使用聚(對-羥基苯乙烯)、聚(對-/間-羥基苯乙 烯)共聚物、聚(對-羥基/鄰-羥基苯乙烯)共聚物、聚(對_ 羥基苯乙烯/苯乙烯)共聚物較佳。另外,聚(4 -羥基-3 -甲 基苯乙烯)、聚(4 -羥基-3, 5 -二甲基苯乙烯)之聚(烷基取 代羥基苯乙烯)樹脂、上述樹脂之部分苯酚性羥基經烷基 化或乙醯基化的樹脂只要是具鹼可溶性者皆較佳。例如有 苯乙烯-馬來酸酐共聚物或特願平6 - 9867 1號記載的樹脂 或含羧基之甲基丙烯酸系樹脂及其衍生物,惟不受此等所 限制。 本發明之此等鹼可溶性樹脂的重量平均分子量(藉由凝 膠滲透色層分析法測定的聚苯乙烯換算値)以1 , 〇 〇 〇〜 1 00,000較佳。若小於1,〇〇〇時未曝光部於顯像後膜減量 極大,而若大於1 00,〇〇〇時顯像速度會減小。尤以2,000 〜50000更佳。 於本發明正型光阻組成物中,爲(2 )之形態時上述酸分 解性樹脂在光阻組成物全體中的配合量爲全部固成分之40 〜99.99重量%較佳、更佳者爲5〇〜99.97重量%。 其次說明藉由酸作用分解、增大在鹼顯像液中之溶解性 的低分子化合物。 -68- 1226509 五、發明說明(67) 此等以具有分子量3000以下之一定分子量較佳,且在 具有單一構造之化合物中導入以酸分解之基、藉由酸作用 分解、具有鹼可溶性之化合物。 較佳者於其構造中至少具有2個以酸分解之基、且該酸 分解性基間距離最遠的位置上除酸分解性基外、至少具有 8個鍵結原子之化合物。更佳者爲1 0個、最佳者爲1 2個 之化合物,或至少具有3個酸分解性基、且該酸分解性基 間距離最遠的位置上除酸分解性基外、至少具有9個鍵結 原子之化合物、更佳者爲1 0個、最佳者爲1 1個之化合物 。另外,上述鍵結原子之較佳上限爲50個、更佳者爲30 個。 於本發明中酸分解性溶解抑制化合物具有3個以上酸分 解性基、較佳者爲4個以上時、或具有2個酸分解性基時 、該分解性基互相具有一定的距離以上時,可顯著提高對 鹼可溶性樹脂之溶解阻止性。而且,酸分解性基間之距離 除表示酸分解性基外、可表示鍵結原子數。例如爲下述化 合物(1 )、( 2 )時酸分解性基間之距離各爲4個鍵結原子, 爲化合物(3 )時鍵結原子爲1 2個。 2 3 B〇 - 〇 〇‘B〇 ⑴ - 2CH2 - 3CH2 - 4CH2 - COO - A0 (2) -69- 1226509 五、發明說明(68)* —CH2—c—— (14) C—〇—CH2CH2〇CH3 o In the positive photoresist composition of the present invention, when the above-mentioned acid-decomposable resin is in the form of (1), the whole photoresist composition is compounded. The amount is preferably 40 to 99.99% by weight of the total solid content, and more preferably 50 to 99.97% by weight. Next, the combination of (A) component (2) form alkali-soluble resin and -67-1226509 V. Description of the invention (66) Low-molecular-weight compounds that decompose by acid action and increase the solubility in the developing solution. Alkali-soluble resins are alkali-soluble resins, such as polyhydroxystyrene, phenolic lacquer resin, and derivatives thereof. In addition, any copolymer resin having para-hydroxystyrene units having alkali solubility can be used. Among them, poly (p-hydroxystyrene), poly (p- / m-hydroxystyrene) copolymer, poly (p-hydroxy / o-hydroxystyrene) copolymer, and poly (p-hydroxystyrene / benzene Ethylene) copolymers are preferred. In addition, poly (4-hydroxy-3 -methylstyrene), poly (4-hydroxy-3, 5-dimethylstyrene) poly (alkyl-substituted hydroxystyrene) resins, and some of the phenolic properties of the above resins A resin having a hydroxyl group alkylated or acetylated is preferred as long as it is alkali-soluble. For example, a styrene-maleic anhydride copolymer or a resin described in Japanese Patent Application No. 6-9867 1 or a carboxyl group-containing methacrylic resin and derivatives thereof are not limited thereto. The weight-average molecular weight of these alkali-soluble resins according to the present invention (polystyrene equivalent 测定 measured by gel permeation chromatography) is preferably from 1,000 to 100,000. If it is less than 1,000, the unexposed portion will lose a large amount of film after development, and if it is more than 1,000, the development speed will decrease. Especially preferably 2,000 to 50,000. In the positive-type photoresist composition of the present invention, in the form of (2), the compounding amount of the acid-decomposable resin in the entire photoresist composition is 40 to 99.99% by weight of the total solid content. 50 to 99.97% by weight. Next, low-molecular compounds which are decomposed by the action of an acid to increase the solubility in an alkali developing solution will be described. -68- 1226509 V. Description of the invention (67) These compounds with a certain molecular weight of 3,000 or less are preferred, and a compound with a single structure is introduced with a base that decomposes by acid, decomposes by acid action, and has alkali-soluble compounds . A compound having at least two acid-decomposable groups in its structure and having the furthest distance between the acid-decomposable groups in addition to the acid-decomposable group and having at least 8 bonding atoms is preferred. More preferably, 10 or 12 compounds, or at least 3 acid-decomposable groups, and at least the position between the acid-decomposable groups has at least a position other than the acid-decomposable group. Compounds with 9 bonded atoms, more preferably 10 compounds, and most preferably 11 compounds. In addition, the preferable upper limit of the above-mentioned bonding atoms is 50, and the more preferable number is 30. In the present invention, when the acid-decomposable dissolution inhibiting compound has three or more acid-decomposable groups, preferably four or more, or when it has two acid-decomposable groups, the decomposable groups have a certain distance or more from each other, Can significantly improve the solubility of alkali-soluble resins. In addition, the distance between the acid-decomposable groups may indicate the number of bonded atoms in addition to the acid-decomposable group. For example, in the following compounds (1) and (2), the distance between the acid-decomposable groups is 4 bonded atoms each, and in the case of the compound (3), 12 bonded atoms. 2 3 B〇-〇 〇 ‘B〇 ⑴-2CH2-3CH2-4CH2-COO-A0 (2) -69-1226509 V. Description of the invention (68)
酸分解性基:―COO-A0、一0-B0 此外’本發明之溶解阻止化合物可以在1個苯環上具有 數個酸分解性基、較佳者爲在1個苯環上具有1個酸分解 性基之架構所成的化合物。另外,本發明溶解阻止化合物 之分子量以3000以下較佳、更佳者爲500〜3000、最佳者 爲 1000〜2500 。 本發明之較佳實施形態中,藉由酸分解之基、即含有-COO-A()、-0-BG 基、例如有-a()、-R2G()-COOA()或-ArOB° 所示 之基。 其中,A° 係表示- C(R(n ) (R〇2) (R〇3)、-Si (R()I ) (R〇2) (R03) 、R〇3、R()4、RQ5係各表示相同或不同的氫原子、 直鏈狀院基、支鏈狀烷基、環狀烷基、烯基或芳基,R〇6 係表示直鏈狀烷基、支鏈狀烷基或芳基,惟R01〜中任 意2個,或Ι?ϋ1〜、R(m〜R〇6中任意2個可互相鍵結形成 環。R()係表示可具取代基之2價脂肪族或芳香族烴基,-Ar -係表示單環或多環之可具取代基的2價芳香族基。 -70- 1226509 五、發明說明(69) 此處,烷基以甲基、乙基、丙基、正丁基、第2 -丁基、 第3 -丁基之碳數1〜4個者較佳,環狀烷基以環丙基、環 丁基、環己基、金剛烷基之碳數3〜1 0個者較佳,烯基以 乙烯基、丙烯基、烯丙基、丁烯基之碳數2〜4個者較佳 ,芳基以苯基、甲苯基、甲苯醯基、枯烯基、萘基、蒽基 之碳數6〜14個者。 而且,取代基例如有羥基、鹵素原子(氟、氯、溴、碘) 、硝基、氰基、上述烷基、甲氧基·乙氧基•羥基乙氧基 •丙氧基•羥基丙氧基•正丁氧基•異丁氧基•第2 -丁氧 基•第3 -丁氧基等烷氧基、甲氧基羰基•乙氧基羰基等烷 氧基羰基、苯甲基·苯乙基•枯基等芳烷基、 芳烷氧基 、甲醯基•乙醯基· 丁醯基•苯甲醯基•氰醯基·戊醯基 等醯基、丁醯氧基之醯氧基、上述烯基、乙烯氧基•丙烯 氧基•烯丙氧基•丁烯氧基3之烯氧基、上述芳基、苯氧 基等之芳氧基、苯甲醯氧基等之芳氧基羰基等。 藉由酸分解之基以矽烷醚基、枯酯基、縮醛基、四氫吡 喃醚基、乙醇醚基、乙醇酯基、3級烷醚基、3級烷酯基 、:3級烷基碳酸酯基較佳。更佳者爲3級烷酯基、3級烷 基碳酸酯基、枯酯基、四氫吡喃醚基較佳。 較佳的化合物架構之具體例如下所述。 1226509 五、發明說明(7〇)Acid-decomposable group: "COO-A0, -0-B0" In addition, the "dissolution preventing compound of the present invention may have several acid-decomposable groups on one benzene ring, preferably one on one benzene ring A compound formed by the structure of an acid-decomposable group. In addition, the molecular weight of the dissolution preventing compound of the present invention is preferably 3,000 or less, more preferably 500 to 3,000, and most preferably 1,000 to 2500. In a preferred embodiment of the present invention, a group decomposed by an acid, that is, a group containing -COO-A (), -0-BG, for example, -a (), -R2G ()-COOA (), or -ArOB ° The base shown. Among them, A ° represents-C (R (n) (R〇2) (R〇3), -Si (R () I) (R〇2) (R03), R03, R () 4, RQ5 represents each the same or different hydrogen atom, straight chain radical, branched alkyl, cyclic alkyl, alkenyl or aryl, and R06 represents straight linear or branched alkyl. Or aryl groups, but any two of R01 ~, or any two of ?? 1 ~, R (m ~ R06) can be bonded to each other to form a ring. R () represents a divalent aliphatic group which may have a substituent. Or aromatic hydrocarbon group, -Ar- represents a monocyclic or polycyclic divalent aromatic group which may have a substituent. -70-1226509 V. Description of the Invention (69) Here, the alkyl group is methyl, ethyl, or Propyl, n-butyl, 2-butyl, and 3-butyl have 1 to 4 carbon atoms. Cycloalkyl is cyclopropyl, cyclobutyl, cyclohexyl, and adamantyl. Numbers 3 to 10 are preferred. Alkenyl is preferably vinyl, propenyl, allyl, butenyl. Numbers 2 to 4 are preferred. Aryl is phenyl, tolyl, tolyl, Cumene, naphthyl, and anthracenyl have 6 to 14 carbon atoms. Examples of the substituent include a hydroxyl group, a halogen atom (fluorine, chlorine, bromine, and iodine). , Nitro, cyano, the above-mentioned alkyl, methoxy · ethoxy · hydroxyethoxy · propoxy · hydroxypropoxy · n-butoxy · isobutoxy • 2nd-butoxy • 3rd-Alkoxy groups such as butoxy, methoxycarbonyl and ethoxycarbonyl groups, alkoxycarbonyl groups such as benzyl, phenethyl, and cumyl groups, aralkyloxy groups, and methylamino groups Fluorenyl groups such as ethenyl, butyryl, benzyl, cyano and pentamyl, ethoxy of butyryl, the alkenyl, vinyloxy, allyloxy, allyloxy, and butene Alkenyloxy group of oxy group 3, aryloxy group such as aryl group, phenoxy group, aryloxycarbonyl group such as benzamyloxy group, etc. The groups decomposed by acid are silyl ether group, cumyl group, condensation Aldehyde group, tetrahydropyranyl ether group, ethanol ether group, ethanol ester group, tertiary alkyl ether group, tertiary alkyl ester group, tertiary alkyl carbonate group are preferred. Tertiary alkyl ester group is more preferred A tertiary alkyl carbonate group, a cumyl ester group, and a tetrahydropyranyl ether group are preferred. Specific examples of preferred compound structures are described below. 1226509 V. Description of the invention (70)
-72- 1226509 五、發明說明(71)-72- 1226509 V. Description of the invention (71)
-73- 1226509 五、發明說明(72)-73- 1226509 V. Description of the Invention (72)
(11)(11)
-74- 1226509 五、發明說明(73)-74- 1226509 V. Description of the Invention (73)
-75- 1226509 五、發明說明(74)-75- 1226509 V. Description of the invention (74)
OR OROR OR
(16)(16)
OROR
-16- 1226509 五、發明說明(75)-16- 1226509 V. Description of the Invention (75)
(19)(19)
-77- 1226509 五、發明說明(76)-77- 1226509 V. Description of the invention (76)
OR OR OROR OR OR
(22)(twenty two)
OR OR OROR OR OR
(23)(twenty three)
OR OR OROR OR OR
(24) -78- 1226509 五、發明說明(77)(24) -78- 1226509 V. Description of the invention (77)
OR OR OROR OR OR
-79- 1226509 五、發明說明(78)-79- 1226509 V. Description of the Invention (78)
OROR
OROR
-80- 1226509-80- 1226509
1226509 五、發明說明(80)1226509 V. Description of Invention (80)
OROR
RORO
CH 3 CH. -82- 1226509 五、發明說明(81)CH 3 CH. -82- 1226509 V. Description of the invention (81)
OR OROR OR
-83- 1226509 五、發明說明(82)-83- 1226509 V. Description of the invention (82)
-84- 1226509 五、發明說明(83)-84- 1226509 V. Description of the Invention (83)
OR OROR OR
於上述化合物(1)〜(43)中R係表示氫原子及下述之基 -85- 1226509 五、發明說明(84) 一 ch2- coo-c(ch3)2c6h5 , 一 CH2 - COO—C4H9(t) ·、 一 co〇 一 C4H9 ⑴, 惟至少2個或視其構造而定3個爲除氫原子外之基,各 取代基R亦可以爲相同的基。 適合作爲Ai:F準分子雷射光阻用途者例如特願2000 -248658號記載的[3 ](C)所示之溶解阻止化合物,惟不受此 等所限制。 本發明中爲(2 )之形態時,該溶解阻止化合物之含量以 組成物全部重量(除溶劑外)爲基準爲3〜45重量%、較佳 者爲5〜30重量%、更佳者爲10〜20重量%。 (3 )所示形態係爲含有上述(1 )所示藉由酸作用分解、增 大在鹼顯像液中之溶解性的樹脂,與上述(2 )所示藉由酸 作用分解、增大在鹼顯像液中之溶解性的化合物兩者。另 外,爲調節感度或固定波之影響等時,可添加鹼可溶性樹 脂。 爲(3 )之形態時各成分之含量係可與上述(2 )之形態時藉 由酸作用分解、增大在鹼顯像液中之溶解性的樹脂、藉由 酸作用分解、增大在鹼顯像液中之溶解性的低分子化合物 、爲調節感度或固定波之影響等之鹼可溶性樹脂的各含量 具有相同的範圍。 本發明所使用的藉由活性光線或放射線照射產生酸之化 合物(光酸發生劑:包含以電子線產生酸之化合物),係可 -86- 1226509 五、發明說明(85) 使用光陽離子聚合之光起始劑、光游離基聚合之光起始劑 、色素類之光消色劑、光變色劑、或微光阻等所使用的習 知光(400〜200nm之紫外線、尤以g線、h線、i線、KrF 準分子雷射光)、ArF準分子雷射光、F2準分子雷射光、 電子線、X線、分子線或離子束以產生酸之化合物及適當 地選擇此等混合物。 而且,倂用其他所得的光酸發生劑例如重氮 鹽、銨鹽 、磷 鹽、碘 鹽、毓鹽、硒 鹽、砷 鹽、有機鹵素化 合物、有機金屬/有機鹵化物、具有鄰-硝基苯甲基型保護 基之光發生劑、胺基磺酸酯等典型的光分解而產生磺酸之 化合物、重氮酮、重氮二 化合物等。 此外,可使用此等藉由光產生酸之基、或使化合物導入 聚合物之主鏈或側鏈之化合物。 另外,亦可使用 V.N.R.Pillai,Synthesis,(1), 1 ( 1 9 80 ) 、 A . Abad e t a 1 , Tetrahedron Lett., (47)4555( 1971 )、D.H.R. Barton e t al,J. Chem.Soc. ,(C),329 ( 1 970 )、美國專利第3,799,778號、歐洲專利 第1 26,7 1 2號所記載的藉由光產生酸之化合物。 於下述中說明有關上述藉由電子線或X光照射產生酸之 化合物中尤爲有效的可倂用者。 (1)三鹵素甲基取代的下述通式(PAG 1 )所示之噁唑衍生 物或通式(PAG2)所示之S-三畊衍生物。 -87- 1226509 五、發明說明(86) N-N〆、〇’、_ (PAG1)In the above compounds (1) to (43), R represents a hydrogen atom and the following group: -85-1226509 V. Description of the invention (84) a ch2- coo-c (ch3) 2c6h5, a CH2-COO-C4H9 ( t) ·, one co0-C4H9 ⑴, but at least two or three depending on its structure are groups other than hydrogen atoms, and each substituent R may be the same group. Those suitable for use as the Ai: F excimer laser photoresist are, for example, a dissolution preventing compound shown in [3] (C) described in Japanese Patent Application No. 2000-248658, but are not limited thereto. In the case of the form (2) in the present invention, the content of the dissolution preventing compound is 3 to 45% by weight based on the total weight of the composition (excluding the solvent), preferably 5 to 30% by weight, and more preferably 10 to 20% by weight. The morphology shown in (3) is a resin containing an acid that is decomposed by the action of (1) as described above and has increased solubility in an alkali developing solution, and a resin that is decomposed and increased by the action of acid as shown in (2) above. Both soluble compounds in alkaline imaging solution. In addition, in order to adjust the sensitivity or the influence of a fixed wave, an alkali-soluble resin can be added. When in the form of (3), the content of each component is a resin that can be decomposed by the action of acid in the form of (2) above to increase the solubility in the alkali developing solution, and decomposed by the action of acid to increase the Each content of the soluble low-molecular-weight compound in the alkali imaging solution and the alkali-soluble resin for adjusting sensitivity or the influence of a fixed wave has the same range. The compounds used in the present invention to generate acids by irradiation with active light or radiation (photoacid generators: compounds containing acids generated by electron rays) are -86-1226509 V. Description of the invention (85) Photocationic polymerization Photo-initiator, photo-radical polymerization photo-initiator, photochromic agent for pigments, photochromic agent, or microphotoresist used in conventional light (ultraviolet light of 400 ~ 200nm, especially g-line, h-line , I-line, KrF excimer laser light), ArF excimer laser light, F2 excimer laser light, electron rays, X-rays, molecular rays or ion beams to generate acid compounds and appropriately select these mixtures. In addition, other photoacid generators such as diazonium salts, ammonium salts, phosphorus salts, iodide salts, selenium salts, selenium salts, arsenic salts, organic halogen compounds, organic metal / organic halides, ortho-nitro groups are used. The benzyl-type protective group photo-generating agent, sulfamate and other typical photo-decompositions produce sulfonic acid compounds, diazones, diazo compounds, and the like. In addition, compounds which generate an acid group by light or introduce a compound into the main or side chain of a polymer can be used. Alternatively, VNRPillai, Synthesis, (1), 1 (19080), A. Abad eta1, Tetrahedron Lett., (47) 4555 (1971), DHR Barton et al, J. Chem. Soc. (C), 329 (1970), US Pat. No. 3,799,778, and European Patent No. 1 26,7 1 2 are compounds which generate acid by light. The following is a description of those who are particularly effective among the compounds which generate an acid by electron beam or X-ray irradiation. (1) A trihalomethyl substituted oxazole derivative represented by the following general formula (PAG 1) or an S-Sanken derivative represented by the general formula (PAG2). -87- 1226509 V. Description of the invention (86) N-N〆, 〇 ′, _ (PAG1)
C(Y)3 (PAG2) (其中,係表示經取代或未經取代的芳基、烯基, R2()2係表示經取代或未經取代的芳基、烯基、烷基、-C(Y)3。Y係表示氯原子或溴原子。 具體而言例如有下述之化合物,惟本發明不受此等所限 制0 -88- 1226509 五、發明說明(87) (M1-1) Λ=ν N CH.CH- 0, ^'c CH-CH-C^^C-CO, CHi-C (Y) 3 (PAG2) (wherein represents a substituted or unsubstituted aryl, alkenyl, R2 () 2 represents a substituted or unsubstituted aryl, alkenyl, alkyl, -C (Y) 3. Y represents a chlorine atom or a bromine atom. Specifically, for example, there are the following compounds, but the present invention is not limited by these. 0 -88-1226509 V. Description of the invention (87) (M1-1) Λ = ν N CH.CH- 0, ^ 'c CH-CH-C ^^ C-CO, CHi-
H-H U 1« _C、#CH-H U 1 «_C, #C
HftCO- CB#,响叫―^ CH^CH - C:〇:C_ C〇3 (WC1-3)〔^^CHeCH 一之。二 (PACl-δ) (P/Cl-4) co- m〇aa CHmCH^^ CC,a CC^ CH-l ⑽H) <PACl-7) a P·1 n (⑽·” 〇3〇^Ν^( (FAC2-2)HftCO- CB #, ringing-^ CH ^ CH-C: 〇: C_ C〇3 (WC1-3) [^^ CHeCH one of them. (PACl-δ) (P / Cl-4) co- m〇aa CHmCH ^^ CC, a CC ^ CH-l ⑽H) < PACl-7) a P · 1 n (⑽ · "〇3〇 ^ Ν ^ ((FAC2-2)
aa
C^CC ^ C
l CH»CH Λ N Λ Al CH »CH Λ N Λ A
CH-CCH-C
scW j A CPAC2-9) CCJ, (PAC2-10) (2)下述通式(PAG3)所示之碘 鹽、或通式(PAG4)所示 之毓鹽。 、 、 a/ :ιΘ ζΘ r2〇3 R^-^S®scW j A CPAC2-9) CCJ, (PAC2-10) (2) An iodized salt represented by the following general formula (PAG3), or a green salt represented by the general formula (PAG4). ,, A /: ιΘ ζΘ r2〇3 R ^-^ S®
Z Θ (PAG3) R205 (PAG4) -89- 1226509 五、發明說明(88) (其中,A r 1、A r 2係表示各爲獨立的經取代或未終取代 的芳基,R203、R204、R205係各獨立地表示經取仵十| μ代莰未經 取代的烷基、芳基。 Ζ-係表示對陰離子,例如BF4-、AsF6-、PF6-、、Z Θ (PAG3) R205 (PAG4) -89- 1226509 V. Description of the invention (88) (wherein A r 1 and A r 2 each represent an independently substituted or unsubstituted aryl group, R203, R204, The R205 series each independently represents an unsubstituted alkyl group or aryl group, which is substituted by 仵 | | substituting μ. The Z- series represents a counter anion, such as BF4-, AsF6-, PF6-,,,
SiF6-、C104-、CF3S03-等過氟鏈烷基磺酸陰離子、五氣 苯磺酸陰離子、萘-1 -磺酸陰離子等縮合多核芳香族磺酸 陰離子、蒽酿磺酸陰離子、含磺酸基之染料等,惟本發明 不受此等所限制。 而且,R203、R204、R2 05中至少2個可各爲單鍵或經由 取代基鍵結。 具體例如下述所示之化合物,惟本發明不受此等所限制 -90- 1226509 五、發明說明(89)Condensed polynuclear aromatic sulfonic acid anions such as perfluoroalkanesulfonic acid anions, pentafluorobenzenesulfonic acid anions, naphthalene-1 -sulfonic acid anions, such as SiF6-, C104-, CF3S03-, etc. Dyes and the like, but the present invention is not limited by them. In addition, at least two of R203, R204, and R205 may each be a single bond or bonded through a substituent. Specific examples are the compounds shown below, but the present invention is not limited by these -90-1226509 V. Description of the invention (89)
CiiH,5 (PAG3-1) 〇-·Θ-〇 C4HgCiiH, 5 (PAG3-1) 〇- · Θ-〇 C4Hg
ΟτΆ CfsS0p 1 -sof (PA63-2) (PAC3-3) (ms-4) :©ΟτΆ CfsS0p 1 -sof (PA63-2) (PAC3-3) (ms-4): ©
-91 - 1226509 五、發明說明(9〇)(PACW2) iCHjCHiCHa-91-1226509 V. Description of the Invention (90) (PACW2) iCHjCHiCHa
H3COOCH3COOC
ac^xy 外"Ο (PAC3-13) sop (PAG3-14) \}~或Q^O ^^^-8°30 < (PAC3-15) •1E)ac ^ xy 外 " Ο (PAC3-13) sop (PAG3-14) \} ~ or Q ^ O ^^^-8 ° 30 < (PAC3-15) • 1E)
(PAC3-18)(PAC3-18)
(FAC3-19) \jj \_) ο-·^α Θ C4F9S〇3 (PAG3-21) -92- 1226509 五、發明說明(91)(FAC3-19) \ jj \ _) ο- · ^ α Θ C4F9S〇3 (PAG3-21) -92-1226509 V. Description of the invention (91)
F F F (PAG3-22) CF3S03 ΘF F F (PAG3-22) CF3S03 Θ
OfO·—Qr邊 ©OfO · —Qr side ©
nh-so3 θ (PAG3-23) (PAG3-24) (PAG3-25) -93- 1226509 五、發明說明(92)nh-so3 θ (PAG3-23) (PAG3-24) (PAG3-25) -93- 1226509 V. Description of the invention (92)
5^ (PA04-1)L/)~s0 ^ PAW-3)5 ^ (PA04-1) L /) ~ s0 ^ PAW-3)
CFjSpj® °12Ημ / /_y \ _* (Qj-S® (PAG4-i) -1) (PAG4-2) CH3CFjSpj® ° 12Ημ / / _y \ _ * (Qj-S® (PAG4-i) -1) (PAG4-2) CH3
(PAG4-6) sc>3G HgC A rr# CtF17SP3e (〇Vs0 f(PAG4-6) sc > 3G HgC A rr # CtF17SP3e (〇Vs0 f
F FF F
F F hQ-I^oc,^ (PAG4-7) cf3so3©F F hQ-I ^ oc, ^ (PAG4-7) cf3so3 ©
HiC HO (PAG4-9)HiC HO (PAG4-9)
Θ Γ㈣SbF斤 CH,Θ Γ㈣SbF kg CH,
CFaSO^ (PAG4-8) Θ -S-CHb CHa (PAG4-10) CM Θ (PAG4-11) (PAG4-12) c4ivCFaSO ^ (PAG4-8) Θ -S-CHb CHa (PAG4-10) CM Θ (PAG4-11) (PAG4-12) c4iv
Kicq HO H^CO -94- 1226509 五、發明說明(93 (ηϊΟ,Ηο HO (η)04Ηα (PAG4-14) e ,\w/ ▼、/ BF‘e ch, (FAG4-15)Kicq HO H ^ CO -94- 1226509 V. Description of the invention (93 (ηϊΟ, Ηο HO (η) 04Ηα (PAG4-14) e, \ w / ▼, / BF‘e ch, (FAG4-15)
sw Οsw Ο
H3C CH^Qg (PAC4-16) 〇 0 Θ o~s 0 (PAM-17) 〇 了一CHj sbFee /==^ 汗CH, ^J^c^-seJ pFee (PAC4-1S) CQiCHjCHjCHjCH. 音吧)2 (PAM-20) Q^Lch,-^) pp. e ^Q-sofH3C CH ^ Qg (PAC4-16) 〇0 Θ o ~ s 0 (PAM-17) 〇 一 CHj sbFee / == ^ Khan CH, ^ J ^ c ^ -seJ pFee (PAC4-1S) CQiCHjCHjCHjCH. Sound bar ) 2 (PAM-20) Q ^ Lch,-^) pp. E ^ Q-sof
Cf-^CHaCI^Cf^O- 〇 (PAG4‘21) (PAG4-22) :户 (PAW-23) (FA64-24) ^2η,5 (PAG4-25) -95- 1226509 五、發明說明(94)Cf- ^ CHaCI ^ Cf ^ O- 〇 (PAG4'21) (PAG4-22): household (PAW-23) (FA64-24) ^ 2η, 5 (PAG4-25) -95-122526 5. Description of the invention ( 94)
-96- 1226509 五、發明說明(95 -Ph2 eo3s - cf3 (PAG4-38) MeO —^^-1 一 Ph2 0o3s-c4f9 (PA64-39) e〇3S-CF3 (PA64-40) Ph2 θ〇3δ—C4F9 (PAG4-41) —^^-S~Ph2 e〇3S--Q^CH3 (PAG4 - 42) ! - Ph2 %ShQ)-CH3 (PA64-43) S-Ph2 e〇3S—CF3 (PA64-44) e〇3S-C4F« (PAG4-45) -97- 1226509 五、發明說明(96)-96- 1226509 V. Description of the invention (95 -Ph2 eo3s-cf3 (PAG4-38) MeO — ^^-1-Ph2 0o3s-c4f9 (PA64-39) e〇3S-CF3 (PA64-40) Ph2 θ〇3δ —C4F9 (PAG4-41) — ^^-S ~ Ph2 e〇3S--Q ^ CH3 (PAG4-42)!-Ph2% ShQ) -CH3 (PA64-43) S-Ph2 e〇3S—CF3 (PA64 -44) e〇3S-C4F «(PAG4-45) -97-1226509 V. Description of the invention (96)
〇3s-〇~ CH3 (PAG4-46) —0~S-Ph2(-+Ois(-Wi? -+〇-*s"ph2 %S - CF3 圆-47) eo3s - c4fs (pa_ e〇3S - CF3 (PAG4- 49) e〇zS-CAf% (PA64-50) 0〇3S-CF3 (PAG4-51) e〇3S - C4F9 (PA64-52) (其中,Ph係表示苯基) 通式(PAG3)、(PAG4)所示之上述鐵鹽係爲習知物 有美國專利第2,807,648號及同4,247,473號、 53 - 1 0 1,33 1號等所記載的方法所合成。 (3)下述通式(PAG5)所示之二碾衍生物、或通式 所示之亞胺基磺酸酯衍生物。 Ar3—S02-S02—Ar4 R206—s〇2—〇—N (PAG5) (PAG6)〇3s-〇 ~ CH3 (PAG4-46) —0 ~ S-Ph2 (-+ Ois (-Wi?-+ 〇- * s " ph2% S-CF3 circle-47) eo3s-c4fs (pa_ e〇3S- CF3 (PAG4- 49) e〇zS-CAf% (PA64-50) 0〇3S-CF3 (PAG4-51) e〇3S-C4F9 (PA64-52) (where Ph is phenyl) General formula (PAG3 ) And (PAG4) are synthesized by the methods described in US Pat. Nos. 2,807,648 and 4,247,473, 53-10, 1,33 1, etc. (3) The second mill derivative represented by the formula (PAG5), or the iminosulfonate derivative represented by the general formula: Ar3—S02-S02—Ar4 R206—s〇2—〇—N (PAG5) (PAG6)
(其中,A1·3、A r4係表示各爲獨立的經取代或未 的芳基。 ,例如 特開昭 (PAG6) 經取代 -98- 1226509 五、發明說明(97)R2Q6係各獨立地表示經取代或未經取代的烷基、芳基。A 係表示經取代或未經取代的伸烷基、伸烯基、伸芳基) 具體例如下述所示之化合物,惟本發明不受此等所限制 -SOf (PAG5-1)(Among them, A1 · 3 and A4 represent independent substituted or unsubstituted aryl groups. For example, JP-A (PAG6) is substituted-98-1226509. V. Description of the invention (97) R2Q6 are each independently represented A substituted or unsubstituted alkyl group and aryl group. A represents a substituted or unsubstituted alkylene group, an alkenyl group, and an arylene group. Specific examples include the compounds shown below, but the present invention is not limited thereto. Waiting Limit-SOf (PAG5-1)
CHa (PAC5-2)CHa (PAC5-2)
HjCHjC
CJ (ΡΑβδ-4) (PA6S-3)CJ (ΡΑβδ-4) (PA6S-3)
Qj〇a5 HC HaC F f F F (PAG5-13)Qj〇a5 HC HaC F f F F (PAG5-13)
caJ (PACS-6) (PAG6-i) acaJ (PACS-6) (PAG6-i) a
(PAC5-1D)(PAC5-1D)
(PAB5-12) (PAG5-M) a(PAB5-12) (PAG5-M) a
^^SO^SOj— SOj- (PAG5-15) -99- 1226509 五、發明說明(⑽) 〇^^ SO ^ SOj— SOj- (PAG5-15) -99- 1226509 V. Description of the invention (⑽) 〇
° (PAG6-3) (PAG6-S) ° (PAG6-2) Ο Ο (PAG6-4) ° (ΡΑΒδ-ε)° (PAG6-3) (PAG6-S) ° (PAG6-2) Ο Ο (PAG6-4) ° (ΡΑΒδ-ε)
fi M-O-SC^-CjHs ° <PA«-7) Οfi M-O-SC ^ -CjHs ° < PA «-7) Ο
_·1Ζ) •100- 1226509_ · 1Z) • 100- 1226509
1226509 五、發明說明(100 P 0 ^Jn-〇-ShQhcH3 (PA66-21) 飞 Ο Ο Ο N—Ο 一 S一 CF3 II 〇 ° (PAG6-22) Ο i? N一Ο一S一 CHj*〇艺1226509 V. Description of the invention (100 P 0 ^ Jn-〇-ShQhcH3 (PA66-21) Fly 〇 〇 〇 N—〇 One S—CF3 II 〇 ° (PAG6-22) 〇 i? N—O—S—CHj * 〇Art
(PAG6-23) Ο Ο ? (PAG6-24) CH3 (PAG6-25)(PAG6-23) Ο Ο? (PAG6-24) CH3 (PAG6-25)
(PAG6-26) (PAG6-27) -102- 1226509 五、發明說明((PAG6-26) (PAG6-27) -102- 1226509 5. Description of the invention (
(PA66-2B)(PA66-2B)
N一〇—S一C3H7 (PAG6-29) N—〇—S一C4H9N-〇-S-C3H7 (PAG6-29) N-〇-S-C4H9
(PAG6 - 30) (PAG6 - 32) (PAG6-33) (PAG6 - 34) f u N-〇-S-^^-CH3 (PAG6-31) (4 )下述通式(PAG7 )所示之重氮二楓衍生物化合物 -103- 1226509 五、發明說明(1〇2 )(PAG6-30) (PAG6-32) (PAG6-33) (PAG6-34) fu N-〇-S-^^-CH3 (PAG6-31) (4) The weight shown by the following general formula (PAG7) Azadiapine derivative compound -103-1226509 V. Description of the invention (102)
Ο Ο (PAG7) (其中,R係各表示直鏈、支鏈或環狀烷基、或可具取代 基之芳基) 具體例如下述化合物,惟不受此等所限制。Ο Ο (PAG7) (wherein R is each a linear, branched or cyclic alkyl group, or an aryl group which may have a substituent) Specific examples include the following compounds, but are not limited thereto.
(PAG7-5)(PAG7-5)
另外可使用特願2000 - 24 1 45 7號、特願2000 - 240060號 、特願 2000 - 23473 3 號、特願 2000 - 1 502 1 7 號、特願 2000 - 1 88077號、特願2000 - 62 3 78號記載的光酸發生劑。 此等光酸發生劑之添加量以組成物中之固成分爲基準, 通常爲0.1〜30重量%、較佳者爲0.3〜20重量%、更佳者 爲0 . 5〜1 0重量%。 -104- 1226509 五、發明說明(1〇3 ) 光酸發生劑之添加量若小於0.1重量%時會有感度降低 的傾向,而若大於3 0重量%時光阻之光吸收過高、輪廓惡 化、工程(特別是燒成過程)範圍狹窄,故爲不企求。 本發明之組成物中另可添加鹼性化合物。 本發明可使用的較佳鹼性化合物物係爲比苯酚具較強鹼 性的有機鹼性化合物。其中,以含氮有機鹼性化合物較佳 。藉由加入有機鹼性化合物,可改良經時之感度變動情形 。有機鹼性化合物例如具有下述所示構造之化合物。 R251 R250—N一r252 —(A) (其中’ R25()、R251、R252係爲獨立的氫原子、碳數1〜6 之烷基、碳數1〜6之醯基烷基、碳數丨〜6之羥基烷基或 碳數6〜20之經取代或未經取代之芳基,其中,R2”與 R 2 5 2.可互相鍵結以形成環。) -N-0=4^1 — …(B) 1 | …(c) -C-N~ …(D) r253 γ, r …(E) R —C~N—C—R256 (其中,R253、R254、R255及R256係表示相同或不同的碳 數1〜6之烷基) -105- 1226509 五、發明說明(1〇4 更ί土的化合物係爲在一分中 ~ 中〃、有2個不同化學環境之 忍原子的含氮鹼性化合物,尤佳者爲 ‘一 否爲曰有兩方含經取代或 未經取代的胺基龃氮厣子夕擐燼处的IA# 代2 基之H 的化合_具有院基胺 基之化曰物。較佳的具體例如經取代或未經取代的胍、經 取代:未經取代的胺基吡啶、經取代或未經取代的胺㈣ 基吡啶、經取代或未經取代的胺基壯咯烷、經取代或未: 取代的咪唑、經取代或未經取代的吡唑、經取代或未經: 代的吡哄、經取代或未經取代的嘧啶、經取代或未經: 的嘌呤、經取代或未經取代的咪唑啉、經取代或未經取、 的吡唑啉、經取代或未經取代的哌啶、經取代或未妒取弋 的嗎啉、經取代或未經取代的胺基嗎啉等。 2又代 干义1土 e取代某 有胺基、胺基烷基、烷基胺基、胺基芳基、芳 一 乃鸯妝基、烷 基、烷氧基、醯基、醯氧基、芳基、芳氧基、 俯基、羥基 、氰基。 运 更佳的化合物例如有胍、丨,丨-二甲基胍、1 ,1 ’ 3,3 -四甲 基胍、2 -胺基吡啶、3 -胺基吡啶、4 ·胺基吡啶、。一 2 - —甲基 胺基吡啶、4 -二甲基胺基吡啶、2 -二乙基胺基啦〇定 月女基甲基)tt B定、2 - fl女基-3 -甲基口比Π定、2 -胺基」 4'甲基吡 B定、2 -月女基-5 -甲基口比π定、2 -胺基-6 -甲基口比D定、q ^ J 一月女基乙 基吡B定、4 -胺基乙基吡D定、3 -胺基吡略院、哌口肚 汁、N - ( 2 · 胺基乙基)哌哄、N - ( 2 -胺基乙基)哌啶、4 -胺基、9 ,2,6,6 -Additionally, No. 2000-24 1 45 7, No. 2000-240060, No. 2000-23473 No. 3, No. 2000-1 502 1 No. 7, No. 2000-1 88077, No. 2000- 62 3 78 Photoacid generator. The addition amount of these photoacid generators is based on the solid content in the composition, and is usually 0.1 to 30% by weight, preferably 0.3 to 20% by weight, and more preferably 0.5 to 10% by weight. -104- 1226509 5. Description of the invention (103) If the amount of photoacid generator is less than 0.1% by weight, the sensitivity will tend to decrease, and if it exceeds 30% by weight, the light absorption of the photoresist will be too high and the profile will deteriorate. 2. The scope of the project (especially the firing process) is narrow, so it is not desired. A basic compound may be added to the composition of the present invention. The preferred basic compound system usable in the present invention is an organic basic compound having a stronger basicity than phenol. Among them, nitrogen-containing organic basic compounds are preferred. By adding organic basic compounds, the sensitivity change over time can be improved. The organic basic compound is, for example, a compound having a structure shown below. R251 R250—N—r252 — (A) (wherein 'R25 (), R251, and R252 are independent hydrogen atoms, alkyl groups having 1 to 6 carbon atoms, fluorenyl alkyl groups having 1 to 6 carbon atoms, and carbon number 丨A hydroxyalkyl group of ~ 6 or a substituted or unsubstituted aryl group having 6 to 20 carbon atoms, in which R2 "and R 2 5 can be bonded to each other to form a ring.) -N-0 = 4 ^ 1 —… (B) 1 |… (c) -CN ~… (D) r253 γ, r… (E) R —C ~ N—C—R256 (where R253, R254, R255, and R256 are the same or different Alkyl group of 1 to 6 carbon atoms) -105-1226509 V. Description of the invention (10) The compound of the more soil is a nitrogen-containing alkali with one to two points in the middle to the middle, and has two different chemical environments. The most preferred compound is 'one or not', which means that there are two groups containing a substituted or unsubstituted amine group. Chemical compounds. Preferred examples are substituted or unsubstituted guanidine, substituted: unsubstituted aminopyridine, substituted or unsubstituted aminopyridine, substituted or unsubstituted amino Zyrrolidine, substituted or unsubstituted: Azole, substituted or unsubstituted pyrazole, substituted or unsubstituted pyridine, substituted or unsubstituted pyrimidine, substituted or unsubstituted: purine, substituted or unsubstituted imidazoline , Substituted or unsubstituted, pyrazoline, substituted or unsubstituted piperidine, substituted or unenacted morpholine, substituted or unsubstituted aminomorpholine, etc. 2 Generation In the sense of the meaning, the substitution of an amino group, an amino alkyl group, an alkylamino group, an amine aryl group, an aryl group is an alkyl group, an alkyl group, an alkoxy group, a fluorenyl group, an alkoxy group, an aryl group, Aryloxy, peptyl, hydroxy, cyano. Compounds that are more preferred include guanidine, 丨, dimethyl guanidine, 1, 1 '3,3-tetramethylguanidine, 2-aminopyridine, 3 -Aminopyridine, 4-Aminopyridine, 2-methylaminopyridine, 4-dimethylaminopyridine, 2-diethylaminopyridine methyl) , 2-fl female group-3-methyl group ratio, 2-amino group "4 'methylpyridine B, 2-month female group-5-methyl group ratio π group, 2-amino group-6 -Methyl hydrazine D, q ^ J January feminine ethylpyridine, 4-amine Ethylpyridine, 3-aminopyridine, piper belly, N- (2-aminoethyl) piperidine, N- (2-aminoethyl) piperidine, 4-amino, 9, 2, 6, 6-
四甲基哌啶、4 -吡喃基哌啶、2 -亞胺基哌啶、。D 1 · ( 2 -胺基 乙基)吡咯烷、吡唑、3 -胺基-5 -甲基吡唑、5_ 3 _ -10 6- 1226509 五、發明說明(1〇5) 基-1 -對-三吡唑、吡畊、2 胺基甲基I 5 _甲基吡畊、嘧 D定、2,4 - 一胺基嘧啶、4,6 -二羥基嘧啶、2 -吡唑啉、3 -吡 口坐啉、N -胺基嗎啉、N _ ( 2 _胺基乙基)嗎啉、丨,5 _二偶氮二 環[4.3·0]-5 -壬烯、1,8 -二偶氮二環[5·4·0]-7 -十一烯、 1,4-二偶氮二環[2.2·2]辛烷、2,4,5-三苯基咪唑啉、Ν-甲基嗎啉、Ν -乙基嗎啉、ν -羥基乙基嗎啉、Ν -苯甲基嗎啉 、環己基嗎啉基乙基硫尿素(CHMETU)等3級嗎啉衍生物、 特開平1 1 - 52 57 5號公報所記載.的受阻胺類(該公報中 [ 0005 ]所記載者)等,惟不受此等所限制。 更佳的具體例如1 , 5 -二偶氮二環[4 . 3 . 0 ] - 5 ·壬烯、1 , 8 -一偶氣一 [5.4·0]-7 -十一儲(DBU)、1,4 -二偶氮二環 [2.2.2]辛烷、4 -二甲基胺基吡啶、六亞甲基四胺、4,4-二甲基咪唑啉、吡咯類、吡唑類、咪唑類、噠嗪類、嘧啶 類、CHMETU等3級嗎啉類、雙(1,2 , 2,6,6 -五甲基-4 -哌啶 基)癸酸酯等受阻胺類等。 其中以1,5 -二偶氮二環[4·3.0]-5 -壬烯、1,8 -二偶氮二 環[5·4·0]-7-十一烯、1,4 -二偶氮二環[2.2.2]辛烷、4-二甲基胺基吡啶、六亞甲基四胺、4,4 -二甲基咪唑啉、 CHMETU、雙(1,2,2,6,6-五甲基-4-哌啶基)癸酸酯、二環 己基甲胺較佳。 此等之有機鹼性化合物可單獨使用或2種以上組合使用 。有機鹼性化合物之使用量對1 00重量份光阻組成物之全 部固成分而言通常爲0.001〜10重量份、較佳者爲0.01〜 -107· 1226509 五、發明說明(1〇6) 5重量份。若小於0 . 00 1重量份時無法得到有機鹼性化合 物之添加效果。 另外,大於1 0重量份時會有感度降低且非曝光部之顯 像性惡化的傾向。 本發明之正型光阻組成物中除添加本發明之氟系聚合物 外,亦可另含有其他氟系及/或矽系界面活性劑。 本發明之正型光阻組成物中可含有氟系界面活性劑、矽 系界面活性劑、含有氟原子與矽原子兩者之界面活性劑中 任一種、或含有2種以上。 此等之界面活性劑例如有特開昭62 - 3 6663號、特開昭 6 1 - 226746 號、特開昭 6 1 - 226745 號、特開昭 62 - 1 70950 號、特開昭63-34540號、特開平7 - 230 1 65號、特開平8-62834號、特開平9 - 5988號所記載的界面活性劑,亦可直 接使用下述市售的界面活性劑。 可使用的市售界面活性劑例如有耶部頓普(譯音)EF30 1 、EF3 03 (新秋田化成(股)製)、夫羅拉頓FC430、FC431 (住 友史理耶姆(譯音)(股)製)、梅卡法克F 1 7 1、F 1 7 3、F 1 7 6 、F189、R08(大日本油墨(股)製)、紗夫龍S-382、SC101 、SCI 02、SCI 03、SCI 04、SCI 05、SCI 06(旭硝子(股)製) 等之氟系界面活性劑或矽系界面活性劑。而且,聚矽氧烷 聚合物KP-34 1(信越化學工業(股)製)亦可作爲矽系界面活 性劑使用。 此等界面活性劑的配合量以本發明之組成物中全部組成 -108 - 1226509 五、發明說明(107) 物之固成分爲基準通常爲0.001〜2重量%、較佳者爲0·01 〜1重量%。此等界面活性劑可單獨使用或幾種組合使用。 其他的界面活性劑之具體例如聚環氧乙烷月桂醚、聚環 氧乙烷硬脂醚、聚環氧乙烷十六烷醚、聚環氧乙烷油醚等 之聚環氧乙烷烷醚類,聚環氧乙烷辛基苯酚醚、聚環氧乙 烷壬基苯酚醚等之聚環氧乙烷烷基芳醚類、聚環氧乙烷· 聚環氧丙醚嵌段共聚物類,山梨糖醇單月桂酸酯、山梨糖 醇單棕櫚酸酯、山梨糖醇單硬脂酸酯、山梨糖醇單油酸酯 、山梨糖醇三油酸酯、山梨糖醇單硬脂酸酯等之山梨糖醇 脂肪酸酯類、聚環氧乙烷山梨糖醇單月桂酸酯、聚環氧乙 烷山梨糖醇單棕櫚酸酯、聚環氧乙烷山梨糖醇單硬脂酸酯 、聚環氧乙烷山梨糖醇三油酸酯、聚環氧乙烷山梨糖醇三 硬脂酸酯等之聚環氧基山梨糖醇脂肪酸酯類等之非離子系 界面活性劑’丙烯酸系或甲基丙烯酸系(共)聚合聚弗龍( 譯音)No . 75 ’ No· 95(共榮公司油脂化學工業(股)製)等。 此等其他界面活性劑的配合量以1 〇〇重量份本發明之組 成物中的固成分爲基準通常爲2重量份以下、較佳者爲i 重量%以下。 促進對顯像液之溶解性的具有2個以上苯酚性0H基之 化合物例如聚經基化合物、較佳者爲聚羥基化合物中以苯 酌類、間苯二酚、氟化糖精、2,3,4 _三羥基二苯甲酮、 2,3,4,4’-四羥基二苯甲酮、^,61:,,^'參(4-羥基苯基)-1,3,5-三異丙基苯、參(4_羥基苯基)甲烷、參(4_羥基苯 -109- 1226509 五、發明說明(1〇8) 基)乙烷、1,1 ’ -雙(4 -羥基苯基)環己烷。 本發明之化學放大型光阻組成物係使上述各成分溶解於 溶劑中,塗覆於載體上,此處所使用的溶劑以二氯乙烯、 環己酮、環戊酮、2 -庚酮、7-丁內酯、甲基乙酮、乙二 醇單甲醚、乙二醇單乙醚、2 -甲氧基乙基乙酸酯、乙二醇 單乙醚乙酸酯、丙二醇單甲醚、丙二醇單甲醚乙酸酯、甲 苯、醋酸乙酯、乳酸甲酯、乳酸乙酯、甲氧基丙酸甲酯、 乙氧基丙酸乙酯、丙酮酸甲酯、丙酮酸乙酯、丙酮酸丙酯 、N,N -二甲基甲醯胺、二甲基亞礪、N -甲基吡咯烷酮、四 氫 喃等較佳,此等可單獨使用或混合使用。 另外,可混合N-甲基甲醯胺、Ν,Ν-二甲基甲醯胺、N -甲 基乙醯胺、Ν,Ν-二甲基乙醯胺、Ν -甲基吡咯烷酮、二甲基 亞碾、苯甲基乙醚等高沸點溶劑使用。 上述化學放大型光阻組成物可使製造精密積體電路構件 時所使用的基板(例如矽/二氧化矽被覆)上藉由旋轉器、 滾筒等適當塗覆方法予以塗覆後,通過所定的遮光罩予以 曝光,藉由進行燒成、顯像製得良好光阻圖案。 本發明化學放大型光阻組成物之顯像液可使用例如氫氧 化鈉、氫氧化鉀、碳酸鈉、矽酸鈉、甲基矽酸鈉、銨水等 無機鹼類,乙胺、正丙胺等一級胺,二乙胺、二正丙胺等 二級胺,三乙胺、甲基二乙胺等三級胺,二甲基乙醇胺、 三乙醇胺等醇胺類,甲基甲醯胺或乙醯胺等醯胺類、四曱 銨氫氧化物、四乙銨氫氧化物、三甲基(2 -羥基乙基)銨氫 -110- 1226509 五、發明說明(109 ) 氧化物、四乙銨氫氧化物、三丁基甲銨氫氧化物、四乙醇 銨氫氧化物、甲基三乙醇銨氫氧化物、苯甲基二乙醇銨氫 氧化物、苯甲基二甲基乙醇銨氫氧化物、苯甲基三乙醇銨 氫氧化物、四丙銨氫氧化物、四丁銨氫氧化物等四級銨鹽 ,吡咯、哌啶等環狀胺類等之鹼類水溶液。 將本發明之正型光阻組成物塗覆於基板上,以形成薄膜 。該塗膜之膜厚以0 · 2〜1 . 2 // m較佳。於本發明中視其所 需可使用市售的無機或有機反射防止膜。 反射防止膜可使用鈦、二氧化鈦、氮化鈦、氧化鉻、碳 、α -二氧化矽等之無機膜型、與由吸光劑與聚合物材料 所成的有機膜型。前者必須使用膜形成之真空蒸熔裝置、 CVD裝置、濺射裝置等之設備。有機反射防止膜例如有特 公平7- 6 96 1 1號記載的由二苯胺衍生物與甲醛改性蜜胺樹 脂之縮合物、鹼可溶性樹脂、吸光劑所成者,或美國專利 5294680號記載的馬來酸酐共聚物與二胺型吸光劑之反應 物,特開平6 - 1 1 863 1號記載的含有樹脂黏合劑與羥甲基 蜜胺系熱交聯劑者,特開平6 - 1 1 86 56號公報中記載的在 同一分子中具有羧酸基與環氧基與吸光基之丙烯酸樹脂型 反射防止膜,特開平8-871 15號公報中記載的由羥甲基蜜 胺與二苯甲酮系吸光劑所成者,特開平8 - 1 79509號公報 中記載的聚乙二醇樹脂中添加低分子吸光劑者等。 有機反射防止膜亦可使用部紐瓦塞恩斯(譯音)公司製 DUV30系列、或DUV-40系列、西部雷(譯音)公司製AC_2 -111- 1226509 五、發明說明(110) 、AC-3 等。 使上述光阻液於製造精密積體電路構件時所使用的基板 (例如矽/二氧化矽被覆)上(視其所需在設置有上述反射防 止膜之基板上)藉由旋轉器、滾筒等之適當塗覆方法予以 塗覆後,通過所定的遮光罩予以曝光,藉由進行燒成、顯 像製得良好光阻圖案。. 此處,曝光光或放射線以150nm〜250nm之波長的光或X 線、電子線較佳。具體而言,例如有KrF準分子雷射 (248nm)、ArF準分子雷射(193nm)、F2準分子雷射(157nm) 、X光線、電子線等。 [Π ]其次,說明有關本發明之具高解像力、高感度、輪 廓形狀佳的電子線或X線用光阻組成物。 上述(3 )〜(1 4 )構成之典型本發明電子線或X線用光阻 組成物含有成分(a )的藉由電子線或X線照射產生酸之化 合物。該成分(a )可使用任一藉由電子線或X光照射產生 酸之化合物,惟以通式(I )〜(I Π )所示化合物較佳。 -112- 1226509Tetramethylpiperidine, 4-pyranylpiperidine, 2-iminopiperidine,. D 1 · (2-Aminoethyl) pyrrolidine, pyrazole, 3-amino-5-methylpyrazole, 5-3_-10 6-1226509 5. Description of the invention (105) P-Tripyrazole, Pycnogenol, 2 aminomethyl I 5 _methylpyridine, pyrimidine, 2,4-monoaminopyrimidine, 4,6-dihydroxypyrimidine, 2-pyrazoline, 3 -Pyridinoline, N-aminomorpholine, N_ (2-aminoamino) morpholine, 丨, 5_diazobicyclo [4.3 · 0] -5 -nonene, 1,8- Diazobicyclo [5 · 4 · 0] -7-undecene, 1,4-diazobicyclo [2.2 · 2] octane, 2,4,5-triphenylimidazoline, N- Tertiary morpholine derivatives such as methylmorpholine, N-ethylmorpholine, ν-hydroxyethylmorpholine, N-benzylmorpholine, cyclohexylmorpholinylethylthiourea (CHMETU), Tokaihei 1 1-52 57 Hindered amines described in Gazette No. 5 (as described in [0005] in the Gazette), etc. are not limited by these. More specific examples include 1, 5 -diazobicyclo [4.3.0]-5 · nonene, 1, 8 -a diazo- [5.4 · 0] -7 -undiple storage (DBU), 1,4-diazobicyclo [2.2.2] octane, 4-dimethylaminopyridine, hexamethylenetetramine, 4,4-dimethylimidazoline, pyrrole, pyrazole, Tertiary morpholines such as imidazoles, pyridazines, pyrimidines, CHMETU, and hindered amines such as bis (1,2,2,6,6-pentamethyl-4-piperidinyl) decanoate and the like. Among them, 1,5-diazobicyclo [4 · 3.0] -5-nonene, 1,8-diazobicyclo [5 · 4 · 0] -7-undecene, 1,4-diene Azobicyclo [2.2.2] octane, 4-dimethylaminopyridine, hexamethylenetetramine, 4,4-dimethylimidazoline, CHMETU, bis (1,2,2,6, 6-pentamethyl-4-piperidinyl) decanoate and dicyclohexylmethylamine are preferred. These organic basic compounds can be used alone or in combination of two or more. The amount of the organic basic compound used is generally 0.001 to 10 parts by weight, preferably 0.01 to -107 · 1226509 for 100 parts by weight of the total solid content of the photoresist composition. 5. Description of the invention (106) 5 Parts by weight. If it is less than 0.001 part by weight, the effect of adding an organic basic compound cannot be obtained. Further, if it is more than 10 parts by weight, the sensitivity tends to decrease and the developability of the non-exposed portion tends to deteriorate. The positive-type photoresist composition of the present invention may contain other fluorine-based and / or silicon-based surfactants in addition to the fluorine-based polymer of the present invention. The positive-type photoresist composition of the present invention may contain any one of a fluorine-based surfactant, a silicon-based surfactant, a surfactant containing both a fluorine atom and a silicon atom, or two or more kinds thereof. Such surfactants include, for example, JP-A-Sho 62-3 6663, JP-A-Sho 6 1-226746, JP-A-Sho 6 1-226745, JP-A-Sho 62-1 70950, and JP-A-Sho 63-34540. The surfactants described in Japanese Patent Application Laid-Open No. 7-230 1 65, Japanese Patent Application Laid-Open No. 8-62834, Japanese Patent Application Laid-Open No. 9-5988 can also be used directly as described below. Commercially available surfactants include, for example, Yebei Dunpu (transliteration) EF30 1, EF3 03 (produced by Shin Akita Kasei Co., Ltd.), Floraton FC430, FC431 (Sumitomo Shriyem (transliteration) (stock) System), Mercat F1 7 1, F 1 7 3, F 1 7 6, F189, R08 (made by Dainippon Ink Co., Ltd.), Safron S-382, SC101, SCI 02, SCI 03, SCI 04, SCI 05, SCI 06 (made by Asahi Glass Co., Ltd.) and other fluorine-based surfactants or silicon-based surfactants. In addition, polysiloxane polymer KP-34 1 (manufactured by Shin-Etsu Chemical Co., Ltd.) can also be used as a silicon-based surfactant. The compounding amount of these surfactants is based on the total composition of the composition of the present invention -108-1226509 V. Description of the solid component of the invention (107) The standard is usually 0.001 ~ 2% by weight, preferably 0 · 01 ~ 1% by weight. These surfactants may be used singly or in combination. Specific examples of other surfactants include polyethylene oxide lauryl ether, polyethylene oxide stearyl ether, polyethylene oxide hexadecyl ether, polyethylene oxide oleyl ether and the like. Ethers, polyethylene oxide alkyl aryl ethers such as polyethylene oxide octyl phenol ether, polyethylene oxide nonyl phenol ether, polyethylene oxide · polypropylene oxide block copolymers Class, sorbitol monolaurate, sorbitol monopalmitate, sorbitol monostearate, sorbitol monooleate, sorbitol trioleate, sorbitol monostearate Esters such as sorbitol fatty acid esters, polyethylene oxide sorbitol monolaurate, polyethylene oxide sorbitol monopalmitate, polyethylene oxide sorbitol monostearate, Non-ionic surfactants such as polyethylene oxide sorbitol trioleate, polyepoxide sorbitol fatty acid esters, etc. Methacrylic (co) polymerized polyfuron (transliteration) No. 75 'No. 95 (Gongrong Company Fat Chemical Industry Co., Ltd.) and so on. The compounding amount of these other surfactants is usually 2 parts by weight or less, preferably i% by weight or less, based on 100 parts by weight of the solid content in the composition of the present invention. Compounds having two or more phenolic OH groups that promote solubility in a developing solution, such as polyacryl compounds, preferably polyhydroxy compounds, among which are benzene, resorcinol, fluorinated saccharin, 2, 3 4,4-trihydroxybenzophenone, 2,3,4,4'-tetrahydroxybenzophenone, ^, 61: ,, ^ '(4-hydroxyphenyl) -1,3,5-tris Cumene, 4- (4-hydroxyphenyl) methane, 4- (4-hydroxyphenyl) -109-1226509 5. Description of the invention (1 08) yl) ethane, 1,1'-bis (4-hydroxybenzene) Group) cyclohexane. In the chemically amplified photoresist composition of the present invention, the above components are dissolved in a solvent and coated on a carrier. The solvent used here is dichloroethylene, cyclohexanone, cyclopentanone, 2-heptanone, 7 -Butyrolactone, methyl ethyl ketone, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, 2-methoxyethyl acetate, ethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether, propylene glycol monomethyl ether Methyl ether acetate, toluene, ethyl acetate, methyl lactate, ethyl lactate, methyl methoxypropionate, ethyl ethoxypropionate, methyl pyruvate, ethyl pyruvate, propyl pyruvate , N, N-dimethylformamide, dimethylarylene, N-methylpyrrolidone, tetrahydrofuran and the like are preferred, and these can be used alone or in combination. In addition, N-methylformamide, N, N-dimethylformamide, N-methylacetamide, N, N-dimethylacetamide, N-methylpyrrolidone, dimethyl It is used for high boiling point solvents such as kiln and benzyl ether. The above-mentioned chemically amplified photoresist composition can be coated on a substrate (such as silicon / silicon dioxide coating) used in manufacturing precision integrated circuit components by a suitable coating method such as a spinner, a roller, etc. The hood is exposed, and a good photoresist pattern is obtained by firing and developing. The developing solution of the chemically amplified photoresist composition of the present invention can use, for example, inorganic bases such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium methylsilicate, ammonium water, ethylamine, n-propylamine, etc. Primary amines, secondary amines such as diethylamine, di-n-propylamine, tertiary amines such as triethylamine, methyldiethylamine, alcohol amines such as dimethylethanolamine, triethanolamine, methylformamide or acetamidine Isoamidine, tetraammonium hydroxide, tetraethylammonium hydroxide, trimethyl (2-hydroxyethyl) ammonium hydrogen-110-1226509 V. Description of the invention (109) oxide, tetraethylammonium hydroxide Compounds, tributylmethylammonium hydroxide, tetraethanolammonium hydroxide, methyltriethanolammonium hydroxide, benzyldiethanolammonium hydroxide, benzyldimethylethanolammonium hydroxide, benzyl Aqueous solutions of quaternary ammonium such as triethanolammonium hydroxide, tetrapropylammonium hydroxide, and tetrabutylammonium hydroxide, and cyclic amines such as pyrrole and piperidine. The positive photoresist composition of the present invention is coated on a substrate to form a thin film. The film thickness of the coating film is preferably from 0.2 · 1.2 to 1.2 // m. In the present invention, a commercially available inorganic or organic antireflection film may be used as necessary. As the anti-reflection film, an inorganic film type such as titanium, titanium dioxide, titanium nitride, chromium oxide, carbon, α-silicon dioxide, or an organic film type made of a light absorbing agent and a polymer material can be used. The former must use equipment such as a vacuum evaporation apparatus, a CVD apparatus, and a sputtering apparatus for film formation. The organic antireflection film is, for example, a product formed from a condensate of a diphenylamine derivative and a formaldehyde-modified melamine resin, an alkali-soluble resin, and a light-absorbing agent described in Japanese Patent No. 7-6 96 1 1 or US Patent No. 5,294,680. Reactant of maleic anhydride copolymer and diamine-type light absorbing agent, Japanese Patent Application Laid-open No. 6-1 1 863 No. 1 containing resin binder and methylolmelamine-based thermal crosslinking agent, Japanese Patent Application Laid-open No. 6-1 1 86 An acrylic resin-type antireflection film having a carboxylic acid group, an epoxy group, and a light-absorbing group in the same molecule described in Japanese Patent Publication No. 56, which is described in Japanese Patent Application Laid-Open No. 8-871 15 by methylolmelamine and dibenzoyl A ketone-based light absorbing agent is prepared by adding a low-molecular-weight light absorbing agent to a polyethylene glycol resin described in JP-A No. 8-1 79509. The organic anti-reflection film can also use the DUV30 series or DUV-40 series made by Newark Sainz (Transliteration), AC_2 -111-1226509 made by Western Ray (Transliteration). 5. Description of the invention (110), AC-3 Wait. The above photoresist liquid is applied to a substrate (such as a silicon / silicon dioxide coating) used in manufacturing precision integrated circuit components (on a substrate provided with the antireflection film as required) by a spinner, a roller, etc. After being coated by an appropriate coating method, it is exposed through a predetermined hood, and a good photoresist pattern is obtained by firing and developing. Here, light, X-rays, and electron rays having a wavelength of 150 nm to 250 nm of exposure light or radiation are preferred. Specifically, there are, for example, KrF excimer laser (248 nm), ArF excimer laser (193 nm), F2 excimer laser (157 nm), X-rays, and electron rays. [Π] Next, a photoresist composition for an electron or X-ray with high resolution, high sensitivity, and good contour shape according to the present invention will be described. The typical photoresist for electron or X-rays of the present invention constituted by the above (3) to (1 4) is a compound containing a component (a) which generates an acid when irradiated with electrons or X-rays. As the component (a), any compound that generates an acid by electron beam or X-ray irradiation can be used, but compounds represented by the general formulae (I) to (I Π) are preferred. -112- 1226509
R3I ^32 卩37 尺36 X- 通式(I)〜(III)中,之直鏈狀、支鏈狀烷基例如 具有取代基之甲基、乙基、丙基、異丁基、第2 -丁基、第 3 - 丁基之碳數1〜4個者。環狀烷基例如有可具取代基之環 丙基、環戊基、環己基之碳數3〜8個者。 R,〜R37之直鏈狀、支鏈狀烷氧基例如有甲氧基、乙氧基 、羥基乙氧基、丙氧基、正丁氧基、異丁氧基、第2 -丁氧 -113- 1226509 五、發明說明(112 ) 基、第3 -丁氧基等碳數1〜4個者。 環狀院氧基係爲環戊氧基、例如有環戊氧基、環己氧基 〇 R!〜R37之鹵素原子例如有氟原子、氯原子、溴原子、碘 原子等。 尺38之芳基例如苯基、甲苯基、甲氧基苯基、萘基之可 具取代基的碳數6〜1 4個者。 此#之取代基以碳數1〜4個院氧基、鹵素原子(氟原子 、氯原子、碘原子)、碳數6〜1 0個芳基、碳數2〜6個烯基 、氰基、羥基、羧基、羧基羰基、硝基等。 而且’ R】〜R】5、R】6〜R27或R28〜R37中可2個以上鍵結形成 含有1種或2種以上選自單鍵、碳、氧、硫、及氮之環, 例如有吡喃環、二氫吡喃環、吡喃環、三氫吡喃環、噻吩 環、吡咯環等。 於通式(I )〜(I I I )中X -爲磺酸之陰離子。 另外’例如CF3S03-等過氟化鏈烷磺酸陰離子、五氟苯 磺酸陰離子、萘-1 _磺酸陰離子等縮合多核芳香族陰離子 ' i醌磺酸陰離子、含磺酸基之染料等,惟不受此等所限 制。 其中’ X -係以具有至少一種選自下述基之苯磺酸、萘磺 酸 '或醌磺酸之陰離子更佳。 至少一個氟原子、 至少一個以氟取代的直鏈狀、支鏈狀或環狀烷基、 -114- 1226509 五、發明說明(113) 至少一個以氟取代的直鏈狀、支鏈狀或環狀烷氧基、 至少一個以氟取代的醯基、 至少一個以氟取代的醯氧基、 至少一個以氟取代的磺醯基、 至少一個以氟取代的磺醯氧基、 至少一個以氟取代的磺醯基胺基、 至少一個以氟取代的芳基、 至少一個以氟取代的芳烷基、及 至少一個以氟取代的烷氧羰基 上述直鏈狀、支鏈狀或環狀烷基係爲碳數1〜1 2、以 1〜25個氟原子取代者較佳。具體例如三氟甲基、五氟乙基 、2,2, 2-三氟乙基、五氟丙基、七氟異丙基、過氟丁基、 過氟辛基、過氟十二烷基、過氟環己基等。其中,以全部 以氟取代的碳數1〜4之過氟烷基較佳。 上述直鏈狀、支鏈狀或環狀烷氧基係爲碳數1〜1 2、以 1〜25個氟原子取代者較佳。具體例如三氟甲氧基、五氟乙 氧基、五氟異丙氧基、過氟丁氧基、過氟辛氧基、過氟十 二烷氧基、過氟環己氧基等。其中,以全部以氟取代的碳 數1〜4之過氟烷氧基較佳。 上述醯基係爲碳數2〜12、以1〜23個氟原子取代者較佳 。具體例如三氟乙醯基、氟化乙醯基、五氟丙醯基、五氟 苯甲醯基等。 上述醯氧基爲碳數2〜12、以1〜23個氟原子取代者較佳 -115- 1226509 五、發明說明(114) 。具體例如三氟乙醯氧基、氟化乙醯氧基、五氟丙醯氧基 、五氟苯甲醯氧基等。 上述磺醯基係爲碳數1〜1 2、以1〜2 5個氟原子取代者較 佳。具體例如三氟甲烷磺醯基、五氟乙院磺基、過氟丁 烷磺醯基、過氟辛烷磺醯基、過氟苯磺醯基、4 -三氟甲基 苯磺醯基等。 上述磺醯氧基係爲碳數1〜12、以1〜25個氟原子取代者 較佳。具體例如三氟甲烷磺醯氧基、過氟丁烷磺醯氧基、 4 -三氟甲基苯磺醯氧基等。 上述磺醯胺基係爲碳數1〜12、以1〜25個氟原子取代者 較佳。具體例如三氟甲烷磺醯胺基、過氟丁烷磺醯胺基、 過氟辛烷磺醯胺基、五氟苯磺醯胺基等。 上述之芳基係爲碳數6〜1 4、以1〜9個氟原子取代者較佳 。具體例如五氟苯基、4 -三氟甲基苯基、五氟葱基、九氟 基、4-氯苯基、2,4-二氯苯基等。 上述之芳烷基係爲碳數7〜10、以1〜15個氟原子取代者 較佳。具體例如五氟苯基甲基、五氟苯基乙基、過氟苯甲 基、過氟苯乙基等。 上述烷氧基羰基係爲碳數2〜13、以1〜25個氟原子取代 者較佳。具體例如二氟/甲氧基鐵基、五截乙氧基幾基、五 氟苯氧基羰基、過氟丁氧基羰基、過氟辛氧基羰基等。 最佳的X -係爲氟取代的苯磺酸陰離子,其中,以五氟苯 磺酸陰離子更佳。 -1 16- 1226509 五、發明說明(115) 另外,上述具有含氟取代基之苯磺酸、萘擴酸、或蒽磺 酸亦可以直鏈狀、支鏈狀或環狀烷氧基、醯基、醯氧基、 磺醯基、磺醯氧基、磺醯胺基、芳基、芳烷基、烷氧基羰 基(此等之碳數係與上述相同者)、鹵素(除氟外)、羥基、 硝基等取代。 下述爲通式(I )所示化合物之具體例。R3I ^ 32 卩 37 feet 36 X- In the general formulae (I) to (III), the linear or branched alkyl group is, for example, a methyl group, an ethyl group, a propyl group, an isobutyl group, a second group -Butyl and 3 -butyl have 1 to 4 carbon atoms. Examples of the cyclic alkyl group include a cyclopropyl group, a cyclopentyl group, and a cyclohexyl group having 3 to 8 carbon atoms which may have a substituent. Examples of linear and branched alkoxy groups of R and R37 include methoxy, ethoxy, hydroxyethoxy, propoxy, n-butoxy, isobutoxy, and 2-butoxy- 113-1226509 V. Description of the invention (112) group, 1-but 4-carbon number such as 3-butoxy. The cyclic alkoxy group is a cyclopentyloxy group, and examples thereof include a cyclopentyloxy group and a cyclohexyloxy group. The halogen atom of R! To R37 includes, for example, a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. The aryl group having a size of 38, for example, a phenyl group, a tolyl group, a methoxyphenyl group, or a naphthyl group may have 6 to 14 carbon atoms. The substituents of this # are 1 to 4 carbon atoms, halogen atoms (fluorine atom, chlorine atom, iodine atom), 6 to 10 carbon atoms, 2 to 6 alkenyl groups, and cyano groups. , Hydroxyl, carboxyl, carboxycarbonyl, nitro, etc. In addition, 'R] ~ R] 5, R] 6 ~ R27 or R28 ~ R37 may form a ring containing one or two or more kinds selected from single bonds, carbon, oxygen, sulfur, and nitrogen. There are pyran ring, dihydropyran ring, pyran ring, trihydropyran ring, thiophene ring, pyrrole ring and the like. In the general formulae (I) to (I I I), X-is an anion of a sulfonic acid. In addition, 'such as condensation polynuclear aromatic anions such as perfluorinated alkane sulfonic acid anions such as CF3S03-, pentafluorobenzenesulfonic acid anions, naphthalene-1 sulfonic acid anions', i. But not limited by these. Among them, X 'is more preferably an anion having benzenesulfonic acid, naphthalenesulfonic acid' or quinonesulfonic acid having at least one selected from the following groups. At least one fluorine atom, at least one linear, branched or cyclic alkyl substituted with fluorine, -114-1226509 V. Description of the invention (113) At least one linear, branched or cyclic substituted with fluorine Alkoxy, at least one fluorenyl substituted with fluorine, at least one fluorenyl substituted with fluorine, at least one sulfonyl substituted with fluorine, at least one sulfonyl substituted with fluorine, at least one substituted with fluorine Sulfonylamino, at least one aryl substituted with fluorine, at least one arylalkyl substituted with fluorine, and at least one alkoxycarbonyl substituted with fluorine The number of carbon atoms is 1 to 1, and 2. 1 to 25 fluorine atoms are preferred. Specific examples include trifluoromethyl, pentafluoroethyl, 2,2,2-trifluoroethyl, pentafluoropropyl, heptafluoroisopropyl, perfluorobutyl, perfluorooctyl, perfluorododecyl , Perfluorocyclohexyl and so on. Among them, perfluoroalkyl groups having 1 to 4 carbon atoms which are all substituted with fluorine are preferred. The linear, branched, or cyclic alkoxy group is preferably 1 to 12 carbon atoms, and is preferably substituted with 1 to 25 fluorine atoms. Specific examples include trifluoromethoxy, pentafluoroethoxy, pentafluoroisopropoxy, perfluorobutoxy, perfluorooctyloxy, perfluorododecyloxy, perfluorocyclohexyloxy and the like. Among them, perfluoroalkoxy groups having 1 to 4 carbon atoms which are all substituted with fluorine are preferred. The above fluorenyl group is preferably those having 2 to 12 carbon atoms and being substituted with 1 to 23 fluorine atoms. Specific examples include trifluoroacetamido, fluorinated ethidium, pentafluoropropionyl, pentafluorobenzyl, and the like. The above fluorenyloxy group is preferably those having 2 to 12 carbon atoms and substituted with 1 to 23 fluorine atoms. -115-1226509 V. Description of the invention (114). Specific examples include trifluoroacetamyloxy, fluorinated acetamyloxy, pentafluoropropamyloxy, pentafluorobenzyloxy and the like. The sulfofluorenyl group is preferably one having 1 to 12 carbon atoms and one having 2 to 5 fluorine atoms substituted. Specific examples include trifluoromethanesulfonyl, pentafluoroethanesulfonyl, perfluorobutanesulfonyl, perfluorooctanesulfonyl, perfluorobenzenesulfonyl, 4-trifluoromethylbenzenesulfonyl, etc. . The sulfonyloxy group is preferably one having 1 to 12 carbon atoms and substituted with 1 to 25 fluorine atoms. Specific examples include trifluoromethanesulfonyloxy, perfluorobutanesulfonyloxy, and 4-trifluoromethylbenzenesulfonyloxy. The sulfonamide group is preferably one having 1 to 12 carbon atoms and substituted with 1 to 25 fluorine atoms. Specific examples include trifluoromethanesulfonamido, perfluorobutanesulfonamido, perfluorooctanesulfonamido, and pentafluorobenzenesulfonamido. The above-mentioned aryl group is preferably 6 to 14 carbon atoms and substituted with 1 to 9 fluorine atoms. Specific examples include pentafluorophenyl, 4-trifluoromethylphenyl, pentafluoroallyl, nonafluoro, 4-chlorophenyl, 2,4-dichlorophenyl, and the like. The above aralkyl system is preferably one having 7 to 10 carbon atoms and substituted with 1 to 15 fluorine atoms. Specific examples include pentafluorophenylmethyl, pentafluorophenylethyl, perfluorobenzyl, perfluorophenethyl and the like. The alkoxycarbonyl group is preferably one having 2 to 13 carbon atoms and substituted with 1 to 25 fluorine atoms. Specific examples thereof include a difluoro / methoxy iron group, a pentaethoxyloxy group, a pentafluorophenoxycarbonyl group, a perfluorobutoxycarbonyl group, a perfluorooctyloxycarbonyl group, and the like. The most preferred X-series is a fluorine-substituted benzenesulfonic acid anion, of which pentafluorobenzenesulfonic acid anion is more preferred. -1 16-1226509 5. Explanation of the invention (115) In addition, the benzenesulfonic acid, naphthalene acid, or anthracenesulfonic acid having a fluorine-containing substituent may be linear, branched, or cyclic alkoxy, and fluorene. Group, fluorenyl group, sulfonyl group, sulfonyl group, sulfonyl group, aryl group, aralkyl group, alkoxycarbonyl group (these carbon numbers are the same as above), halogen (except fluorine) , Hydroxyl, nitro, etc. The following are specific examples of the compound represented by the general formula (I).
-117- 1226509 五、發明說明(116)-117- 1226509 V. Description of the Invention (116)
〇 丨+cf3 0 -118- 1226509 五、發明說明(117)〇 丨 + cf3 0 -118-1226509 V. Description of the invention (117)
cf3so3' α -15)cf3so3 'α -15)
C4F9S03C4F9S03
CgF^SOsCgF ^ SOs
C11F23SO3C11F23SO3
(I-20) CH3(I-20) CH3
-119- 1226509 五、發明說明(118)-119- 1226509 V. Description of the invention (118)
(I-23) 〇C4H9(I-23) 〇C4H9
(卜 27)(Bu 27)
C4F9SO3 -120- 1226509 五、發明說明(彳19) h3cC4F9SO3 -120- 1226509 V. Description of the invention (彳 19) h3c
COOCH2CH2CH2CH3 (卜 30)COOCH2CH2CH2CH3 (Bu 30)
(卜 32) 下述爲通式(I I )所示化合物之具體例 -121 - 1226509 五、發明說明(12〇 )(Bu 32) The following are specific examples of compounds represented by the general formula (I I) -121-1226509 V. Description of the invention (12)
-122- 1226509 五、發明說明(121)-122- 1226509 V. Description of the Invention (121)
ch3 下述爲通式(I I I )所示化合物之具體例。 -123- 1226509 五、發明說明(122 /Οη_ηΟ"4ά ^ (ΠΜ)ch3 The following are specific examples of the compound represented by the general formula (I I I). -123- 1226509 V. Description of the Invention (122 / Οη_ηΟ " 4ά ^ (ΠΜ)
F CF3F CF3
(ΙΙΙ-3)(ΙΙΙ-3)
OzSOzS
〇ρ〇ρ
•〇3S •CF3 (III-5)• 〇3S • CF3 (III-5)
jF=^\ H 〇 NHCOCbH17 卞 C4F9 •ojF = ^ \ H 〇 NHCOCbH17 卞 C4F9 • o
MeOMeO
-o3s-o3s
Br F -124- 1226509 五、發明說明(123 Οκ_ι+·ηΟ cp3S〇3"㈣0’^ ^—1+~^ ^ c8f17so3 〈》—丨+-^ ^ C11F23S03Q_r^ fs〇3- 〈〉—1+~^ ^~〇CH3 CF3SO3 〈^ ^~〇CH3 C4F9SO3 N5->+-q N[}~|+0^02 cf3so3_ H3C-~^ ^—1+-^ ^~~CH3 CF3SO3 H3c--^ ^—Γ~^~CH3 CF3SO3 o2n NO, CF3S03 (III-9) M-10) 11-11) I M2) I M3) 11-14) I 卜15) 11-16) 11-17) 11-18) (111-19) h3c C7H15(n) Cl CH3 ~广~~(π)〇7Η15 CF3SO3 (Ml一20) CF3SCV (IN-21) -125- 1226509 五、發明說明(124) f3c—^ ^—丨+~^~^~CF3 cf3so3 cf3so3 一Br F -124- 1226509 5. Description of the invention (123 Οκ_ι + · ηΟ cp3S〇3 " ㈣0 '^ ^ —1 + ~ ^ ^ c8f17so3 〈〉 —— 丨 +-^ ^ C11F23S03Q_r ^ fs〇3- <〉-1+ ~ ^ ^ ~ 〇CH3 CF3SO3 <^ ^ ~ 〇CH3 C4F9SO3 N5- > +-q N [} ~ | + 0 ^ 02 cf3so3_ H3C- ~ ^ ^ -1 +-^ ^ ~~ CH3 CF3SO3 H3c-^ ^ —Γ ~ ^ ~ CH3 CF3SO3 o2n NO, CF3S03 (III-9) M-10) 11-11) I M2) I M3) 11-14) I BU 15) 11-16) 11-17) 11-18 ) (111-19) h3c C7H15 (n) Cl CH3 ~ Guang ~~ (π) 〇7Η15 CF3SO3 (Ml-20) CF3SCV (IN-21) -125- 1226509 V. Description of the invention (124) f3c— ^ ^ —丨 + ~ ^ ~ ^ ~ CF3 cf3so3 cf3so3 1
h3co〇c cooch3h3co〇c cooch3
ClCl
CF3S03 tBu CF3SO3 tBu C4F9SO3CF3S03 tBu CF3SO3 tBu C4F9SO3
CF3SO3 (111-22) (111-23) (111-24) (I I 卜25) (111-26) (111-27) (111-28) (111-29) -126- 1226509 五、發明說明(125 一 〇3s ^δΗιι(η)CF3SO3 (111-22) (111-23) (111-24) (II Bu 25) (111-26) (111-27) (111-28) (111-29) -126- 1226509 V. Description of the invention ( 125 〇3s ^ δΗιι (η)
H^co- —OCH3 (MI-30) 0~r_0 (111-31) dll-32) (MI-33)H ^ co- —OCH3 (MI-30) 0 ~ r_0 (111-31) dll-32) (MI-33)
Cl (MI-34)Cl (MI-34)
0~,+_{D0 ~, + _ {D
03S—4 A—OC2H5 NH'〇3δΌ0 (n)C5H103S—4 A—OC2H5 NH'〇3δΌ0 (n) C5H1
(111-35)下述爲除通式(I )〜(I I I )所示化合物外之酸發生劑 -127- 1226509 五、發明說明(126)(111-35) The following are acid generators other than the compounds represented by the general formulae (I) to (I I I) -127-1226509 V. Description of the invention (126)
(n)C4H9 CF3SO3(n) C4H9 CF3SO3
(n)C4H9 cf3so3~(n) C4H9 cf3so3 ~
ch3ch3
C02Me -128- 1226509 五、發明說明(127)C02Me -128- 1226509 V. Description of the invention (127)
-129- 1226509 五、發明說明(128) —〇 ;0^—CHrf—⑼W CF3S03- (n)C4H9 •〇3S s+—ch2ci ch3 通式(I )、通式(in )之化合物可單獨一種使用或二種以 上倂用。 通式(I )及通式(II )之化合物例如藉由使用芳基鎂溴化 物等之芳基格利雅試劑與經取代或未取代的苯基亞颯反應 、使所得的三芳基磺醯基鹵化物與對應的磺酸鹽交換的方 法,或使經取代或未取代的苯基亞碾與對應的芳香族化合 物使用甲烷磺酸/五氧二磷或氯化鋁等之酸觸媒予以縮合 、鹽交換的方法,使用二芳基碘鏺鹽與二芳基磺化物使用 醋酸酮等之觸媒予以縮合、鹽交換的方法等予以合成。 通式(I I I )之化合物可藉由使用過碘酸鹽使芳香族化合 物反應予以合成。 而且,鹽交換所使用的磺酸或磺酸鹽可藉由使用市售的 氯化磺酸加水分解的方法、使芳香族化合物與氯磺酸反應 的方法、使芳香族化合物與胺基磺酸反應的方法等製得。 於下述中具體而言爲通式(I)〜(III)之具體化合物的合 成方法。 -1 30--129- 1226509 V. Description of the invention (128) —〇; 0 ^ —CHrf—⑼W CF3S03- (n) C4H9 • 〇3S s + —ch2ci ch3 Compounds of general formula (I) and general formula (in) can be used alone Or two or more kinds. The compounds of the general formula (I) and the general formula (II) are reacted with a substituted or unsubstituted phenylsulfenyl group, for example, by using an aryl Grignard reagent such as an arylmagnesium bromide, and the obtained triarylsulfonyl group is reacted. Method for exchanging halide with corresponding sulfonate, or condensing substituted or unsubstituted phenylimine with corresponding aromatic compound using acid catalyst such as methanesulfonic acid / pentaoxophosphate or aluminum chloride The method of salt exchange is synthesized by using a diaryl iodonium salt and a diaryl sulfonate to condense using a catalyst such as ketone acetate, or a salt exchange method. The compound of the general formula (I I I) can be synthesized by reacting an aromatic compound with a periodate. The sulfonic acid or sulfonate used in the salt exchange can be prepared by hydrolyzing a commercially available chlorinated sulfonic acid, a method of reacting an aromatic compound with chlorosulfonic acid, and an aromatic compound with an aminosulfonic acid. Prepared by reaction methods and the like. A method for synthesizing a specific compound of the general formulae (I) to (III) will be specifically described below. -1 30-
1226509 五、發明說明(129) (五氟苯磺酸四甲銨鹽之合成) 在冰冷下1 00ml甲醇中溶解於25g五氟苯磺醯基氯化物 ,於其中徐徐地加入1 0 0 g之2 5 %四甲銨氫氧化物水溶液中 。在室溫下攪拌3小時,製得五氟苯磺酸四甲銨鹽之溶液 。使該溶液使用與毓鹽、碘鏺鹽之鹽交換。 (三苯基毓基五氟苯磺酸酯之合成:具體例(〗_丨)之合成) 使50g二苯基亞楓溶解於800ml苯,於其中加入200g 氯化鋁、回流24小時。使反應液慢慢地注入2L冰中,於 其中加入400ml濃鹽酸、在7(TC下加熱1〇分鐘。使該水 溶液以5 00ml醋酸乙酯洗淨、過濾後加入400ml溶解有 2 0 0 g砩:化錢者。 使析出的粉體過濾、水洗後以醋酸乙酯洗淨、乾燥,製 得70g三苯基毓碘化物。 使3 0 . 5 g三苯基毓碘化物溶解於1 0 〇 〇 m 1甲醇中,在該 溶液中加入1 9 . 1 g氧化銀,在室溫下攪拌4小時。使溶液 過濾、且於其中加入過量的五氟苯磺酸四甲銨鹽之溶液, 使反應液濃縮、且使其溶解於500ml二氯甲烷,且使該溶 液以5%四甲銨氫氧化物水溶液、及水洗淨。使有機相以無 水硫酸鈉乾燥後、予以濃縮,製得三苯基銳五氟苯磺酸酯 (I - 1 ) ° (三芳基毓五氟苯磺酸鹽之合成:具體例(I - 9 )與(I I - 1 )之 混合物的合成) 將50g三芳基毓氯化物(Fluka製、三苯基毓氯化物50% • 131 - 1226509 五、發明說明(13〇) 水溶液)溶解於500m 1水中,於其中加入過量的五氟苯磺 酸四甲胺鹽之溶液,可析出油狀物質。以癸烷除去上層澄 淸液,使所得的油狀物質水洗、乾燥,製得三芳基毓五氟 苯磺酸酯(具體例(I - 9 )、( I I - 1 )作爲主成分)。 (二(4 -第3 -戊基苯基)碘鐵五氟苯磺酸酯之合成:具體例 (III-1)之合成) 使60g第3-戊基苯、39.5g碘酸鉀、81g醋酸酐、170ml 二氯甲烷混合,且在冰冷下於其中慢慢地滴入66 . 8g濃硫 酸。在冰冷下攪拌2小時後,在室溫下攪拌1 〇小時。在 反應液中、冰冷下加入500ιώ1水,使其以二氯甲烷萃取、 使有機相以碳酸氫鈉、水洗淨後予以濃縮,製得二(4 -第 3 -醯基苯基)碘鐵硫酸鹽。使該硫酸鹽加入過量的五氟苯 磺酸四甲銨溶液中。在該溶液中加入500m水,使其以二 氯甲烷萃取、使有機相以5%四甲銨氫氧化物水溶液、吸水 洗淨後予以濃縮,製得二(4 -第3 -戊基苯基)碘五氟苯磺 酸酯。 其他化合物亦可使用相同的方法合成。 可作爲成分(a )之其他酸發生劑 於本發明之電子線或X線用光阻組成物中,作爲成分(a ) 除上述較佳的酸發生劑外,可適當地選擇使用光陽離子聚 合之光起始劑、光游離基聚合之光起始劑、色素類之光消 色劑、光變色劑、或微光阻等所使用的習知光以產生酸之 化合物及此等混合物’較具體例如上述說明的光阻組成物 -132- 1226509 五、發明說明(131 ) 中作爲光酸發生劑所例示者。 而且,成分(a)之上述通式(I)〜通式(ΠΙ)所示化合物 可倂用其他光酸發生劑。 與本發明上述通式(I )〜(I I I )所示之化合物倂用的酸發 生劑之使用量’以臭耳比(通式(I)〜(III)所示化合物/其 他酸發生劑)通常爲100/0〜20 / 80、較佳者爲100/0〜40/60 、更佳者爲100/0〜50 / 50。 成分(a )之總含量對本發明正型電子線或X線光阻組成 物的全部組成物固成分而言,通常爲0.1〜20重量%、較佳 者爲0.5〜10重量%、更佳者爲1〜7重量%。 本發明電子線或X線用光阻組成物含有作爲(b )或(b,) 成分之鹼可溶性樹脂或酸分解性樹脂。 鹼可溶性樹脂係不溶於水、可溶於鹼水溶液的水溶液樹 脂(稱爲鹼可溶性樹脂)。 此等鹼可溶性樹脂之鹼溶解速度係在0 · 26 1 N四甲銨氫 氧化物(TMAH)測定(23°C )下以20A/秒以上者較佳。更佳 者爲200A/秒以上(A爲埃)。 酸分解性樹脂具有藉由酸分解之基、且藉由酸作用成鹼 可溶性樹脂。 本發明電子線或X線用光阻組成物中所使用的鹼可溶性 樹脂及酸分解性樹脂,另可滿足下述條件(1 )及(2 )。 (1)至少具有一種碳數6〜20之芳香環及在該芳香環上直 接或經由鍵結基鍵結有具乙烯性不飽和基之單體所衍生的 -133- 1226509 五、發明說明(132) 重複單位, (2 )該芳香環之7^電子與芳香環上之取代基的非共有電 子對之間成立式(1 )之關係。 (式1) Ν7Γ + Ni〇ne =1〇 此處,Ν 7Γ係表示π電子總數,Nl()ne係表示作爲取代基 之碳數1〜1 2之直鏈狀、支鏈狀、或環狀烷氧基、烯氧基 、芳氧基、芳烷氧基、或羥基之非共有電子對的總電子數 ,2個以上相鄰的烷氧基或羥基互相鍵結以形成5碳數以 上之環構造。惟除苯并二噁唑除外。而且,Ν 7Γ =6時該取 代基不含羥基。 特別是式(I )中之Ν 7Γ +( 1/2)NUne,在10〜40之範圍內 由於容易產生二次電子之構造故較佳。較佳的芳香環例如 有苯環 '萘環、蒽環、菲環、聯苯等,較佳的芳香環上之 取代基例如有羥基、甲氧基、乙氧基、異丙基等。 此外’ 7Γ電子總數Ν 7Γ爲1 0以上之芳香環(例如萘環、 I胃' $ _環、聯苯之芳香環)時,在該芳香環上之取代 8胃以不具非共有電子對(NUne = 0之基),例如氫、飽和烷 基等。 M If ffij胃本發明之鹼可溶性樹脂及酸分解性樹脂以具 W S ( 1 } ~ ( 5 )所示之重複單位爲構成成分較佳。 -134- 1226509 五、發明說明(彳33) -e I1: CH2C-)— ⑴ (Ra〇)|-^dr—(°Rc)n {〇Rb)r1226509 V. Description of the invention (129) (Synthesis of tetramethylammonium pentafluorobenzenesulfonate) Dissolved in 100 g of methanol in 25 g of pentafluorobenzenesulfonyl sulfonyl chloride under ice-cooling, and slowly add 100 g 25% tetramethylammonium hydroxide in water. After stirring at room temperature for 3 hours, a solution of tetramethylammonium pentafluorobenzenesulfonate was prepared. The solution was exchanged with a salt of a salt of iodonium and iodonium. (Synthesis of triphenylethenyl pentafluorobenzenesulfonate: Synthesis of specific examples (〗 _ 丨)) 50 g of diphenylsulfenyl sulfonate was dissolved in 800 ml of benzene, 200 g of aluminum chloride was added thereto, and refluxed for 24 hours. The reaction solution was slowly poured into 2 L of ice, 400 ml of concentrated hydrochloric acid was added thereto, and the mixture was heated at 70 ° C. for 10 minutes. The aqueous solution was washed with 500 ml of ethyl acetate, filtered, and 400 ml was added to dissolve 200 g.砩: Money changer. The precipitated powder is filtered, washed with water, washed with ethyl acetate, and dried to obtain 70 g of triphenyl iodide. 30.5 g of triphenyl iodide is dissolved in 10 In 〇m 1 methanol, 19.1 g of silver oxide was added to the solution, and the mixture was stirred at room temperature for 4 hours. The solution was filtered, and an excessive solution of tetramethylammonium pentafluorobenzenesulfonate was added thereto. The reaction solution was concentrated and dissolved in 500 ml of dichloromethane, and the solution was washed with a 5% tetramethylammonium hydroxide aqueous solution and water. The organic phase was dried over anhydrous sodium sulfate and concentrated to obtain Triphenyl pentafluorobenzene sulfonate (I-1) ° (Synthesis of triaryl pentafluorobenzene sulfonate: Synthesis of specific examples (I-9) and (II-1)) 50 g of triaryl Dissolved in base chloride (made by Fluka, 50% of triphenyl chloride) 131-1226509 V. Description of the invention (13〇) Aqueous solution) Dissolved In 500m 1 of water, an excessive amount of a solution of tetramethylamine pentafluorobenzenesulfonate was added to the solution to precipitate an oily substance. The upper liquid solution was removed with decane, and the obtained oily substance was washed with water and dried to obtain a triaryl group. Pentafluorobenzenesulfonate (Specific examples (I-9), (II-1) as main components). (Synthesis of di (4--3-pentylphenyl) iron iron pentafluorobenzenesulfonate: Synthesis of Specific Example (III-1)) 60 g of 3-pentylbenzene, 39.5 g of potassium iodate, 81 g of acetic anhydride, and 170 ml of dichloromethane were mixed, and 66.8 g of the solution was slowly dropped thereinto under ice-cooling. Sulfuric acid. After stirring under ice-cooling for 2 hours, it was stirred at room temperature for 10 hours. 500 ml of 1 water was added to the reaction solution under ice-cooling, and the mixture was extracted with dichloromethane. The organic phase was washed with sodium bicarbonate and water. It was concentrated to obtain bis (4-thi-methylphenyl) iodoferric sulfate. The sulfate was added to an excess of tetramethylammonium pentafluorobenzenesulfonate solution. 500 m of water was added to the solution to make it It was extracted with dichloromethane, and the organic phase was washed with 5% tetramethylammonium hydroxide aqueous solution, absorbed in water, and concentrated to obtain two (4-3- Pentylphenyl) iodopentafluorobenzenesulfonate. Other compounds can also be synthesized using the same method. Other acid generators that can be used as component (a) in the photoresist composition for electron or X-rays of the present invention, As the component (a), in addition to the above-mentioned preferred acid generators, a photoinitiator for photocationic polymerization, a photoinitiator for photoradical polymerization, a photochromic agent, and a photochromic agent may be appropriately selected and used. Or the photo-resistive compounds used in micro-resistance, etc. to generate acid compounds and these mixtures' are more specific. For example, the photoresist composition described above -132-1226509 5. In the description of the invention (131), those exemplified as photoacid generators . Further, the compound represented by the general formula (I) to the general formula (II) of the component (a) may use another photoacid generator. The amount of the acid generator used with the compound represented by the above-mentioned general formulae (I) to (III) according to the present invention is based on the odor ratio (compounds represented by the general formulae (I) to (III) / other acid generators) It is usually 100/0 ~ 20/80, preferably 100/0 ~ 40/60, and more preferably 100/0 ~ 50/50. The total content of the component (a) is generally 0.1 to 20% by weight, preferably 0.5 to 10% by weight, and more preferably all of the solid components of the positive electron beam or X-ray photoresist composition of the present invention. It is 1 to 7% by weight. The photoresist composition for an electron beam or X-ray of the present invention contains an alkali-soluble resin or an acid-decomposable resin as a component (b) or (b,). Alkali-soluble resins are aqueous resins that are insoluble in water and soluble in alkaline aqueous solutions (referred to as alkali-soluble resins). The alkali-dissolving rate of these alkali-soluble resins is preferably 20 A / sec or more at 0 · 26 1 N tetramethylammonium hydroxide (TMAH) measurement (23 ° C). More preferably, it is 200 A / sec or more (A is Angstrom). The acid-decomposable resin has a base which is decomposed by an acid, and becomes an alkali-soluble resin by the action of an acid. The alkali-soluble resin and the acid-decomposable resin used in the photoresist composition for electron or X-rays of the present invention can also satisfy the following conditions (1) and (2). (1) Derived from -133-1226509 derived from at least one aromatic ring having 6 to 20 carbon atoms and a monomer having an ethylenically unsaturated group bonded directly or through a bonding group on the aromatic ring. V. Description of the invention ( 132) The repeating unit, (2) The relationship between the 7 ^ electrons of the aromatic ring and the non-shared electron pair of the substituent on the aromatic ring is the formula (1). (Formula 1) Ν7Γ + Ni〇ne = 1 Here, N 7Γ represents the total number of π electrons, and N1 () ne represents a linear, branched, or ring having 1 to 12 carbons as a substituent. Alkoxy, alkenyloxy, aryloxy, aralkoxy, or total number of electrons of non-shared electron pairs of hydroxyl groups, 2 or more adjacent alkoxy groups or hydroxyl groups are bonded to each other to form 5 or more carbon atoms Ring structure. Except for benzodioxazole. Moreover, when N 7Γ = 6, the substituent does not contain a hydroxyl group. In particular, N 7Γ + (1/2) NUne in the formula (I) is preferably in the range of 10 to 40 because it is easy to generate secondary electrons. Preferred aromatic rings are, for example, benzene rings, naphthalene rings, anthracene rings, phenanthrene rings, biphenyls, etc., and preferred substituents on the aromatic rings are, for example, hydroxy, methoxy, ethoxy, isopropyl, and the like. In addition, when the total number of '7Γ electrons N7Γ is 10 or more aromatic rings (such as naphthalene ring, I stomach ring, biphenyl ring, biphenyl aromatic ring), the substitution of 8 stomachs on the aromatic ring does not have non-shared electron pairs ( NUne = 0), such as hydrogen, saturated alkyl, etc. M If ffij stomach The alkali-soluble resin and acid-decomposable resin of the present invention are preferably composed of repeating units represented by WS (1) to (5). -134- 1226509 V. Description of the invention (彳 33) -e I1: CH2C-) — ⑴ (Ra〇) |-^ dr— (° Rc) n {〇Rb) r
Ri〇1 —(-CH2C-)- (ORg)s (2)Ri〇1 — (-CH2C-)-(ORg) s (2)
(Rf〇)r (〇Ri)i (〇Rh)t(Rf〇) r (〇Ri) i (〇Rh) t
(0Rf)r (〇Ri)i ⑶(ORF) r (〇Ri) i ⑶
-135- 1226509 五、發明說明(134-135- 1226509 V. Description of the invention (134
^101 -^CH^~ L (〇Rj)v {Rd〇)P(明^ 101-^ CH ^ ~ L (〇Rj) v (Rd〇) P (Ming
⑷ (Rf〇)r (Rg°)s \ (〇R^ (ORi) (〇Rh)t R101 —^ch2c^ (〇Rk)w (5)⑷ (Rf〇) r (Rg °) s \ (〇R ^ (ORi) (〇Rh) t R101 — ^ ch2c ^ (〇Rk) w (5)
(叫丄:^ (叫 (Re〇)q-^3? >^(〇Rh)t (RfO)r 丫 \(〇RiL Ιί、 OCO,0^0,0¾(Called 丄: ^ (called (Re〇) q- ^ 3? ≫ ^ (〇Rh) t (RfO) r ^ \ RiL Ιί, OCO, 0 ^ 0,0¾
二價鍵結基,Ra、Rb、Rc、Rd、Re、Rf、Rg、Rh、Ri、Rj -136- 1226509 五、發明說明(135) 、Rk、R 1係各獨立地表示碳數1〜1 2之直鏈狀、支鏈狀、 或環狀烷基、烯基、芳基、芳烷基、或氫原子’而且,此 等可相互鍵結形成碳數24以下之5碳以上環,1、m、η、 P、q、r、s、t、u、v、w、χ係表不〇〜3之整數、可滿足 l+m + n = 2,3 、 p + q+r = 0,1,2,3 、 s + t+ u = 0,1,2,3 、 v + w + x二〇 , 1,2 , 3 o 惟通式(1 )中Ra、Rb、Rc不爲氫原子。 而且,通式(1 )除苯并二噁唑外。Divalent bond group, Ra, Rb, Rc, Rd, Re, Rf, Rg, Rh, Ri, Rj -136-1226509 5. Description of the invention (135), Rk, R 1 each independently represent a carbon number of 1 ~ 1 2 is a linear, branched, or cyclic alkyl, alkenyl, aryl, aralkyl, or hydrogen atom. Moreover, these may be bonded to each other to form a ring of 5 or more carbons having 24 or less carbon atoms, 1, m, η, P, q, r, s, t, u, v, w, and χ are integers of 0 to 3, which can satisfy l + m + n = 2,3, p + q + r = 0,1,2,3, s + t + u = 0,1,2,3, v + w + x20, 1, 2, 3 o Only Ra, Rb, Rc in the general formula (1) is not hydrogen atom. Moreover, the general formula (1) is other than benzodioxazole.
Ra、Rb、Rc例如有氫、甲基、乙基、丙基、異丙基、丁 基、異丁基、第3 -丁基、戊基、辛戊基、己基、環己基、 辛基、癸基、十二烷基、烯丙基、苯甲基、苯基、枯基等 。而且,例如爲互相鍵結形成甲基取代二噁茂環、乙基取 代一 U惡茂環、苯基取代二噁茂環、二甲基取代二噁茂環、 hi! 八Examples of Ra, Rb, and Rc include hydrogen, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, 3-butyl, pentyl, octyl, hexyl, cyclohexyl, octyl, Decyl, dodecyl, allyl, benzyl, phenyl, cumyl, etc. Moreover, for example, to form a methyl-substituted dioxocyclic ring, an ethyl group to replace a U-oxocyclic ring, a phenyl-substituted dioxocyclic ring, a dimethyl-substituted dioxocyclic ring, hi!
Kd、Re、R f、Rg 、乙基、丙基、異丙基、丁基、異丁基'帛3· 丁基、戊基 、辛戊基、己基、環己基、辛其、双甘 丄 半基、癸基、十二烷基、烯丙 基、苯甲基、苯基、枯基等 寺Rd〜Rf 、 Rg〜Ri或Rj〜R1 、例 如爲互相鍵結形成甲基取代一暇茂 恶戊、乙基取代二噁茂環 、苯基取代二噁茂環、二甲其πτ7 α 甲基取代二噁茂環、二噁烷環者 -C00- L例如有單鍵、-CH2-、 -〇CH2- 、 -CONH-等。 •C〇〇CH2-、-〇CH2CH2〇-、 -137- 1226509Kd, Re, R f, Rg, ethyl, propyl, isopropyl, butyl, isobutyl '帛 3-butyl, pentyl, octyl, hexyl, cyclohexyl, octyl, diglycerine Hexyl, decyl, dodecyl, allyl, benzyl, phenyl, cumyl and other radicals such as Rd ~ Rf, Rg ~ Ri, or Rj ~ R1, for example, are bonded to each other to form a methyl group instead of monomethyl Dioxane, ethyl substituted dioxocyclic ring, phenyl substituted dioxocyclic ring, dimethyl πτ7 α methyl substituted dioxocyclic ring, and dioxane ring -C00-L has a single bond, -CH2-, -〇CH2-, -CONH-, etc. • C〇〇CH2-, -〇CH2CH2〇-, -137-1226509
1226509 五、發明說明(137) oc—c H2c H2c CIC——c H31226509 V. Description of the invention (137) oc—c H2c H2c CIC——c H3
〇〇
ο —(ch29h)- —(ch2ch)- ',och3 ^Κ^〇〇2Η5 h3coο — (ch29h)-— (ch2ch)-', och3 ^ Κ ^ 〇〇2Η5 h3co
c2h5oc2h5o
—(ch2ch)—— (Ch2ch) —
Y^o I 〇 -139- 1226509 五、發明說明(138)Y ^ o I 〇 -139-1226509 V. Description of the invention (138)
c2h5〇"ta〇 -140- 1226509 五、發明說明(139 —(ch2ch)- h3coc2h5〇 " ta〇 -140-1226509 V. Description of the invention (139 — (ch2ch)-h3co
OCH 3 OCH3 —j-CH2CH]— —(CH2CH)— —(-CH2CHf- 1 ,〇CH3 H3C〇v^k^〇CH3OCH 3 OCH3 —j-CH2CH] — — (CH2CH) — — (-CH2CHf-1, 〇CH3 H3C〇v ^ k ^ 〇CH3
h3co,了 〇ch3 och3 —(ch2ch)—h3co, 〇ch3 och3 — (ch2ch) —
och3och3
och3 —(ch2ch)- h3co^ y 0 〇v^ —(ch2ch|- 〇och3 — (ch2ch)-h3co ^ y 0 〇v ^ — (ch2ch |-〇
〇〇
H3CO,了 0CH3 C2H50 T 〇 〇ch3 ch3 —(-ch2ch)-coo -fCH2C-)-H3CO, 0CH3 C2H50 T 〇 〇ch3 ch3 — (-ch2ch) -coo -fCH2C-)-
coocoo
H3CO,了、〇ch3 H3CCT 了 〇ch3 och3 OCH3 -141 - 1226509 五、發明說明(14〇H3CO, 〇ch3 H3CCT 〇ch3 och3 OCH3 -141-1226509 V. Description of the invention (14〇
-fCHsCHj- O -fCH2CH|--fCHsCHj- O -fCH2CH |-
O 00 oO 00 o
OH —(-ch2ch|- o oOH — (-ch2ch |-o o
OCH3 ^ch2ch^-OCH3 ^ ch2ch ^-
—(-ch2ch-)— ch2ch-)—— (-Ch2ch-) — ch2ch-) —
OHOH
OCH3 -142- 1226509OCH3 -142- 1226509
1226509 五、發明說明(1 42 ch2ch-)— —( CH2CH")— coo coo1226509 V. Description of the invention (1 42 ch2ch-) — — (CH2CH ") — coo coo
och3 ch2ch-)— —(-ch2ch-)— —(-ch2ch-)—'ί φο ¢0 OH OH OC2H5och3 ch2ch-) — — (-ch2ch-) — — (-ch2ch-) — 'ί φο ¢ 0 OH OH OC2H5
—^ch2ch-]—^ch2ch-]— —^ch2ch— ^ Ch2ch-] — ^ ch2ch-] — — ^ ch2ch
oc2h5 -144- 1226509 五、發明說明(143 -(ch2ch-)- COOόο coooc2h5 -144- 1226509 V. Description of the invention (143-(ch2ch-)-COOόο coo
OH CH3 -(-ch2ch·)— CH2CH^— -(- CH2C-)— coo cooOH CH3-(-ch2ch ·) — CH2CH ^ —-(-CH2C-) — coo coo
coo00 och3 och3coo00 och3 och3
1226509 五、發明說明(144 —CH2CH-)— —( CH2CH-)- —^ ch2ch-)-1226509 V. Description of the invention (144 —CH2CH-) — — (CH2CH-)-— ^ ch2ch-)-
och3och3
0 〇c2h5 00 〇c2h5 0
-(ch2ch-)- --(ch2ch·)- o o o o-(ch2ch-)--(ch2ch ·)-o o o o
OHOH
och3och3
-14 6- 1226509-14 6- 1226509
1226509 五、發明說明(146 ch2ch-)— —( ch2ch-)— —f ch2ch·)— coo OCH3 OC2H5 -CH2CH-)— —(; CH2CH-)— —(-CH2CH-j— coo coo coo oc2h5 och3 -148- 12265091226509 V. Description of the invention (146 ch2ch-) — — (ch2ch-) — —f ch2ch ·) — coo OCH3 OC2H5 -CH2CH-) — — (; CH2CH-) — — (-CH2CH-j— coo coo coo oc2h5 och3 -148- 1226509
1226509 五、發明說明(148 )1226509 V. Description of the invention (148)
-150- 1226509 五、發明說明(149) —(-ch2ch-)- 0-150- 1226509 V. Description of the invention (149) — (-ch2ch-)-0
OCH3OCH3
(-ch2ch^—(-ch2ch ^ —
•CH2CH^—• CH2CH ^ —
-151 - 1226509 五、發明說明(15〇)-151-1226509 V. Description of the invention (15〇)
1226509 五、發明說明(151 ch3 —(-ch2ch-)— —(* CH2CH-}- —f - CH2C-^— coo coo coo1226509 V. Description of the invention (151 ch3 — (-ch2ch-) — — (* CH2CH-}-—f-CH2C-^ — coo coo coo
OCH3OCH3
OCH3 CHcOCH3 CHc
ch2ch-)— —CH2C-)-ch2ch-) — —CH2C-)-
CH2〇H*^- o 0'CH2〇H * ^-o 0 '
coocoo
〇c2h5 酸分解性樹脂係具有以藉由酸作用分解成鹼可溶性之基 、即使鹼可溶性基以酸分解性基保護之基。 -153- 1226509 五、發明說明(152 ) 鹼可溶性基以苯酚性羥基、羧酸基較佳。 此等作爲鹼可溶性基之保護基的酸分解性基以縮醛基、 縮酮基、3級羧酸酯基、3級碳酸酯基較佳。3級羧酸酯基 例如有第3 - 丁酯、2 -甲基-2 -金剛烷酯等。3級碳酸酯基 例如有第3 - 丁氧基羧酸酯等。其中以縮醛、3級羧酸酯較 佳,更佳者爲縮醛。 使鹼可溶性基以酸分解性基保護的基可以在上述(1 )〜 (6 )之重複單位中作爲取代基(Ra〜R 1中任一種爲酸分解性 基),或可以存在在構成酸分解性樹脂之其他重複單位中 〇 酸分解性樹脂中具有酸分解性基之重複單位的比例通常 爲5〜40莫耳%、較佳者爲1〇〜3〇莫耳%。 於下述中例舉酸分解性樹脂之具體例,惟不受此等所限 制。而且,下述中R爲烷基、芳烷基、芳基。 —f-CH^CH-i--i-CH^CH-^—〇c2h5 The acid-decomposable resin is a group that is decomposed into an alkali-soluble group by the action of an acid, even if the alkali-soluble group is protected by an acid-decomposable group. -153- 1226509 5. Description of the invention (152) The alkali-soluble group is preferably a phenolic hydroxyl group or a carboxylic acid group. These acid-decomposable groups which are protective groups of the alkali-soluble group are preferably an acetal group, a ketal group, a tertiary carboxylic acid ester group, and a tertiary carbonate group. Tertiary carboxylic acid ester groups include, for example, 3-butyl ester and 2-methyl-2-adamantyl ester. The tertiary carbonate group includes, for example, a 3-butoxycarboxylic acid ester. Among them, acetal and tertiary carboxylic acid ester are more preferable, and acetal is more preferable. The group in which the alkali-soluble group is protected by an acid-decomposable group may be a substituent (any one of Ra to R 1 is an acid-decomposable group) in the repeating unit of the above (1) to (6), or may exist in the constituent acid Among other repeating units of the decomposable resin, the proportion of the repeating unit having an acid-decomposable group in the acid-decomposable resin is usually 5 to 40 mol%, preferably 10 to 30 mol%. Specific examples of the acid-decomposable resin are exemplified in the following, but are not limited thereto. In the following, R is an alkyl group, an aralkyl group, or an aryl group. —F-CH ^ CH-i--i-CH ^ CH-^ —
—(-CH2CH·)--f CH2CH^—— (-CH2CH ·)-f CH2CH ^ —
-154- 1226509 五、發明說明(153 —f-CH2CH-)--{· CH2CH*)—-154- 1226509 V. Description of the invention (153 —f-CH2CH-)-{· CH2CH *) —
H3CCT 了 OCH3 OCH3 0 丫0R —(·οη2〇η-)--(-ch2ch·)—H3CCT got OCH3 OCH3 0 丫 0R — (· οη2〇η-)-(-ch2ch ·) —
0CH3 OCH30CH3 OCH3
—^CH2CH^— ^CHsCH^ .OCH3 ^— ^ CH2CH ^ — ^ CHsCH ^ .OCH3 ^
H3COH3CO
'〇、.OR —(-ch2ch-)--(· ch2ch^—'〇 、 .OR — (-ch2ch-)-(· ch2ch ^ —
Hr^CCT 丫 〇CH3 och3Hr ^ CCT 〇 〇CH3 och3
—("CH2<pH^ ^CH2CH^ ',och3 J-— (&Quot; CH2 < pH ^ ^ CH2CH ^ ', och3 J-
och3 OChU O^/OR —(-CH2CH-)--f-CH2CH*)—och3 OChU O ^ / OR — (-CH2CH-)-f-CH2CH *) —
〇丫 OR -155- 1226509〇 丫 OR -155- 1226509
12265091226509
1226509 五、發明說明(156) —f-CH2CH-)--f-CH2CH-)—1226509 V. Description of the invention (156) —f-CH2CH-)-f-CH2CH-) —
COOCOO
0…OR —(-ch2ch)— —f ch2ch)—coo0… OR — (-ch2ch) — —f ch2ch) —coo
OROR
-158- 1226509-158- 1226509
12265091226509
1226509 五、發明說明(彳59)1226509 V. Description of Invention (彳 59)
〇ch3 —f-CH2CH-)--(-CH2CH^—〇ch3 —f-CH2CH-)-(-CH2CH ^ —
-161 - 1226509 五、發明說明(16〇 ) —(CH2CH-)--f-CH2CH-)一、0-161-1226509 V. Description of the invention (16)-(CH2CH-)-f-CH2CH-) I, 0
—f-CH2CH-)--f-CH2CH-)— 〇 〇6〇 —f-CH2CH)-—F-CH2CH-)-f-CH2CH-) — 〇 〇〇〇—f-CH2CH)-
〇、/OR〇, / OR
—[ch2ch^—— [Ch2ch ^ —
Cy〇R —{· CH2CH·卜--f-CH2CH·)— CH 2Cy〇R — {· CH2CH · Bu--f-CH2CH ·) — CH 2
—f-CH2CH-j--{-CH2CH-)——F-CH2CH-j-{-CH2CH-) —
OHOH
〇 O〇 O
CX /OR -162- 1226509 五、發明說明(161) —(-ch2ch|—CX / OR -162- 1226509 V. Description of the invention (161) — (-ch2ch | —
-163- 1226509-163- 1226509
12265091226509
本發明鹼可溶性樹脂可藉由游離基聚合、陽離子聚合、 陰離子聚合等習知方法予以合成。組合對應的單體進行游 離基聚合爲最簡便的方法,惟藉由單體時以利用陽離子聚The alkali-soluble resin of the present invention can be synthesized by conventional methods such as radical polymerization, cationic polymerization, and anionic polymerization. Free radical polymerization is the easiest way to combine the corresponding monomers.
-165- 1226509 五、發明說明(164) 合、陰離子聚合合成更佳。而且,視聚合起始種類而定會 引起除去單體聚合外之反應時,可使導入有適當保護基之 單體聚合,且於聚合後藉由脫保護以製得企求的聚合物。 此外,具有烷氧基之聚合物亦可藉由使具有對應羥基之聚 合物的羥基進行醚反應以製得企求的聚合物。有關聚合法 如實驗化學講座28高分子合成、新實驗化學講座1 9高分 子化學[I ]等記載。 另外,本發明鹼可溶性樹脂及酸分解性樹脂之分子量爲 3, 000〜1,000,000 。 較佳的重量平均分子量爲 3,000〜500,000。較佳者爲 300,000以下、更佳者爲 1 50,000以下、尤佳者爲1 00, 000以下、最佳者爲50,000 以下。 可藉由上述合成方法合成的鹼可溶性樹脂的分子量分佈 (Mw/Mn)係以1.0〜1.5較佳,藉此尤其可使光阻高感度化 。而且,該分子量分佈之樹脂於上述合成方法中,可利用 活性陰離子聚合予以合成。 而且,可倂用其他的鹼可溶性樹脂。 本發明所使用的其它鹼可溶性樹脂例如有酚醛淸漆樹脂 、氫化酚醛淸漆樹脂、丙酮-焦培酚樹脂、鄰-聚羥基苯乙 烯、間-聚羥基苯乙烯、對•聚羥基苯乙烯、氫化聚羥基苯 乙烯、鹵素或烷基取代聚羥基苯乙烯、羥基苯乙烯-N-取 代馬來醯亞胺共聚物、鄰/對-及間/對-羥基苯乙烯共聚物 、對聚羥基苯乙烯之羥基而言部分鄰·烷基化物(例如5〜3 〇 -16 6- 1226509 五、發明說明(165) 莫耳%之鄰-甲基化物、鄰_(1_甲氧基)乙基化物、鄰-(1_ 乙氧基))乙基化物、鄰-2-四氫吡喃化物、鄰第3 -丁氧 基羧基)甲基化物等)或鄰-醯基化物(例如5〜3 0莫耳%之鄰 -醯基化物、鄰-(第3 - 丁氧基)醯基化物等)、苯乙烯-馬來 酸酐共聚物、苯乙烯-羥基苯乙烯共聚物、α -甲基苯乙烯 -羥基苯乙烯共聚物、含羧基之甲基丙烯酸系樹脂及其衍 生物,惟不受此等所限制。 更佳的其他鹼可溶性樹脂係爲酚醛淸漆樹脂、鄰-聚羥 基苯乙烯、間-聚羥基苯乙烯、對-羥基苯乙烯及此等之共 聚物、烷基取代的聚羥基苯乙烯、部分聚羥基苯乙烯鄰-烷基化、或α -甲基苯乙烯-羥基苯乙烯共聚物。該酚醛淸 漆樹脂以下述所定單體爲主成分、在酸性觸媒存在下與醛 類加成縮合所得者。 所定的單體可單獨使用或2種以上混合使用苯酚、間_ 甲酚、鄰-甲酚、對-甲酚等甲酚類、2,5 -二甲苯酣、3,5-二甲苯酚、3,4 -二甲苯酚、2,3 -二甲苯酚等二甲苯酚類、 間·乙基苯酚、對-乙基苯酚、鄰-乙基苯酣、對-第3 -丁基 苯酚、對-辛基苯酚、2,3, 5 -三甲基苯酣類等院基苯分類 、對-甲氧基苯酚、間-甲氧基苯酚、3, 5_一甲氧基苯酸、 2 -甲氧基-4-甲基苯酚、間-乙氧基苯酚、對-乙氧基本酣 、間-丙氧基苯酚、對-丙氧基苯酚、間-丁氧基苯酚、對-丁氧基苯酚等烷氧基苯酚類、2 -甲基_心異丙基本酸等雙 烷基苯酚類、間-氯苯酚、對-氯苯酚、鄰-氯苯酚、二羥 -167- 1226509 五、發明說明(166) 基聯苯、雙酚A、苯基苯酚、間苯二酚、萘酚等之羥基芳 香化合物,惟不受此等所限制。 醛類例如有甲醛、對甲醛、乙醛、丙醛、苯甲醛、苯基 乙醛、α -苯基丙醛、A -苯基丙醛、鄰-羥基苯甲醛、間-羥基苯甲醛、對-羥基苯甲醛、鄰-氯苯甲醛、間-氯苯甲 醛、對-氯苯甲醛、鄰-硝基苯甲醛、間-硝基苯甲醛、對_ 硝基苯甲醛、鄰-甲基苯甲醛、間-甲基苯甲醛、對-甲基 苯甲醛、對-乙基苯甲醛、對-正丁基苯甲醛、糠醛、氯乙 醯醛及此等之縮醛物,例如氯乙醯基醛二乙基縮醛等,其 中以使用甲醛較佳。 此等之醛類可單獨使用或2種以上組合使用。酸性觸媒 可使用鹽酸、硫酸、甲酸、醋酸、乙二酸等。 如此所得的酚醛淸漆樹脂之重量平均分子量係以 1 ,000〜30, 000較佳。若小於1,000時曝光部於顯像後膜減 少量大,而若大於 30,000時顯像速度小。更佳者爲 2,000〜20,000 。 而且,除酚醛淸漆樹脂外上述之聚羥基苯乙烯、及其衍 生物、共聚物之重量平均分子量爲2,000以上、較佳者爲 2,000〜30,000、更佳者爲 2000〜20,000。 此處,重量平均分子量係以凝膠滲透色層分析法之聚苯 乙嫌換算値予以定義。 本發明中此等鹼可溶性樹脂或酸分解性樹脂亦可以2種 以上混合使用。鹼可溶性樹脂之使用量以光阻組成物全部 -168- 1226509 五、發明說明(167) 重量爲基準通常爲30〜90重量%、較佳者爲50〜80重量% 〇 本發明特徵成分之鹼可溶性樹脂或酸分解性樹脂的使用 量以光阻組成物全部重量(除溶劑外)爲基準,通常爲 30〜90重量%、較佳者爲50〜80重量%。 本發明電子線或X線用光阻組成物亦可含有藉由酸作用 分解、且可藉由酸作用增大對鹼像液之溶解性的低分子化 合物(稱爲「低分子酸分解性溶解阻止化合物」或「( c )成 分」)。 本發明電子線或X線用光阻組成物中所配合較佳的(c ) 成分係爲在其構造中至少具有2個以酸分解的基、且該酸 分解性基間之距離在最遠的位置上至少經由8個除酸分解 性基外之鍵結原子的化合物。 更佳的(c )成分係爲在其構造中至少具有2個以酸分解 的基、且該酸分解性基間之距離在最遠的位置上至少經由 1 〇個(較佳者爲11個、更佳者爲1 2個)除酸分解性基外之 鍵結原子的化合物,或在其構造中至少具有3個以酸分解 的基、且該酸分解性基之間的距離在最遠的位置上至少經 由9個(較佳者爲1 〇個、更佳者爲1 1個)除酸分解性基外 之鍵結原子的化合物。此外,上述鍵結原子之上限以50 個較佳、更佳者爲30個。 本發明電子線或X線用光阻組成物中(C )成分之化合物 的使用量,對全部組成物之固成分而言以3〜45重量%較 -169- 1226509 五、發明說明(168) 佳、更佳者爲5〜30重量%、最佳者爲10〜30重量%。 本發明電子線或X線用光阻組成物以使用陽離子聚合性 化合物((d )成分)較佳。 於本發明中陽離子聚合係指生長鏈爲碳鐵離子或氧鏺離 子之正離子加成聚合之意。本發明中係指使該陽離子聚合 所得的單體具有陽離子聚合性機能之化合物。例如爲乙烯 化合物時,乙烯單體之陽離子聚合性爲以游離子聚合所使 用的Q- e値。換言之,e値約爲小於-0 . 3時具有的陽離子 聚合性,係爲已知。 另外,陽離子聚合性化合物之構造特徵爲(1 ) 7Γ -供應體 之碳-碳不飽和鍵、(2 )某種(大部分時候飽和)雜環化合物 中可見到的η -共硬體之雜環原子(氧、硫、氮、磷)的非共 有電子對、(3 )鏈烷中可見到的在特殊條件下σ -供應體之 具有含碳之單鍵。 (1)爲乙烯、亞乙烯基化合物、伸乙烯基化合物等。(2) 爲內酯化合物、環醚化合物、及噁唑啉類、氮雜環丙烷類 、環狀矽氧烷等。例如異丁烯、異戊二烯、丁二烯、環戊 二烯、環己二烯、原菠二烯、苯乙烯、茚、萘嵌戊烯、苯 并呋喃、對-甲氧基苯乙烯、α -甲基苯乙烯、乙烯醚、Ν-乙烯基咔唑、Ν -乙烯基吡咯烷酮。 其中,以使用乙烯化合物較佳。 本發明電子線或X線用光阻組成物中(d )之化合物的添 加量,對組合物全部重量(固成分)而言以0 . 5〜50重量% -170- 1226509 五、發明說明(169) 較佳、更佳者爲3〜30重量%。 此外,本發明電子線或X線用光阻組成物以含有至少一 種選自於乙烯化合物、環鏈烷化合物、環狀醚化合物、內 酯化合物、醛化合物之化合物((d’)成分)較佳。 乙烯化合物可使用下述之乙烯醚化合物、苯乙烯、α-甲基苯乙烯、間-甲氧基苯乙烯、對-甲氧基苯乙烯、鄰-氯化苯乙烯、間-氯化苯乙烯、對-氯化苯乙烯、鄰-硝基 苯乙烯、間-硝基苯乙烯、對-溴化苯乙烯、3 , 4 -二氯化苯 乙烯、2,5-二氯化苯乙烯、對-二甲基胺基苯乙烯等之苯 乙烯類、2 -異丙烯基呋喃、2 -乙烯基苯并呋喃、2 -乙烯基 二苯并呋喃類、2 -異丙烯基噻吩、2 ·乙烯基吩噻嗯等之乙 烯基噻吩類、Ν -乙烯基 唑類、乙烯萘、乙烯蒽、乙烯伸 萘基等。 環鏈烷化合物可使用苯基環丙烷、螺旋[2,4 ]庚烷、螺 旋[2,5 ]辛烷、螺旋[3,4 ]辛烷、4 ·甲基螺旋[2,5 ]辛烷、 螺旋[2,7 ]癸烷等。 環狀醚化合物可使用4 -苯基-1 , 3 ·二噁烷等之二噁烷類 、3,3 -雙氯化甲基氧化環丁烷類、三噁烷、1,3 -二氧化環 丙烷等之化合物。另外可使用烯丙基環氧丙醚、苯基環氧 丙醚等環氧丙醚類、丙烯酸環氧丙酯、甲基丙烯酸環氧丙 酯等環氧丙酯類、耶皮克頓(譯音)商品名之市售的雙酚A 型環氧樹脂、四溴雙酚A型環氧樹脂、雙酚F型環氧樹脂 、苯酚酚醛淸漆樹脂型環氧樹脂、甲酚酚醛淸漆樹脂型環 -171 - 1226509 五、發明說明(17〇 ) 氧樹脂等之化合物。 內酯化合物可使用丙內酯、丁內酯、戊內酯、己內酯、 -甲基- /3-丙內酯、α,α -二甲基丙內酯、α -甲基 -/3 -丙內酯等之化合物。 醛化合物可使用戊醛、己醇、庚醇、辛醇、壬醇、癸醇 、環己基胺基甲醯醛、苯基乙醯醛等脂肪族飽和醛化合物 、甲基丙烯醛、巴豆醛、2 -甲基-2-丁烯醛、2-丁炔醇、 藏花醛等脂肪族不飽和醛化合物、苯甲醛、甲苯醛、肉桂 醛等芳香族醛化合物、三溴化乙醯醛、2,2,3 -三氯化丁醛 、氯化苯甲醛等鹵素取代的醛化合物、甘油醛、醛醇、水 楊醛、間-羥基苯甲醛、2,4 -二羥基苯甲醛、4 -羥基-3 -甲 氧基苯甲醛、胡椒醛等之羥基及烷氧基取代的醛化合物、 胺基苯甲醛、硝基苯甲權等之胺基及硝基取代的醛化合物 、琥珀醛、戊二醛、酞酸醛、對酞酸醛等之二醛化合物、 苯基乙二醛、苯甲醯基乙醯醛等之縮醛化合物及此等之衍 生物。 上述(d )陽離子聚合性化合物、與(d’)乙烯化合物、環 鏈烷化合物、環狀醚化合物、內酯化合物、醛化合物之關 係,爲下述1 )〜3 )之任一關係。 係爲(d)陽離子聚合性化合物、不爲(d’)乙烯化合物、 環鏈烷化合物、環狀醚化合物、內酯化合物、醛化合物者 係爲(d ’)乙烯化合物、環鏈烷化合物、環狀醚化合物、 內酯化合物、醛化合物、不爲(d )陽離子聚合性化合物者 -172- 1226509 五、發明說明(171 ) 係爲(d )陽離子聚合性化合物、且爲(d,)乙烯化合物、 環鏈烷化合物、環狀醚化合物、內酯化合物、醛化合物者 而且,本發明適合的化合物爲上述3種類,此等皆具有 本發明之同等效果。 惟如下述中,乙烯化合物之效果顯著。 該(d ’)化合物就本發明之效果顯著而言,以乙烯化合物 較佳、更佳者爲乙烯醚化合物,尤以通式[A ]所示化合物 較佳。 於通式(A)中,Ra、Rb及Rc爲芳基時,一般具有4〜20 個碳原子、且可以烷基、芳基、烷氧基、芳氧基、醯基、 醯氧基、烷基硫醇基、胺基醯基、羰基烷氧基、硝基、磺 醯基、氰基或鹵素原子取代。此處,碳數4〜20個之芳基 例如有苯基、甲苯基、二甲苯基、聯苯基、萘基、蒽基、 菲基等。 Ra、Rb及Rc爲烷基時係表示碳數1〜20之飽和或不飽 和直鏈、支鏈或脂環烷基,可以鹵素原子、氰基、酯基、 氧基、烷氧基、芳氧基或芳基取代。此處,碳數1〜20之 飽和或不飽和直鏈、支鏈或脂環烷基例如有甲基、乙基、 丙基、異丙基、丁基、異丁基、第3-丁基、戊基、異戊基 、新戊基、己基、異己基、辛基、異辛基、壬基、癸基、 十一院基、十—·院基、十二院基、十四院基、乙嫌基、丙 烯基、丁烯基、2-丁烯基、3-丁烯基、異丁烯基、戊烯基 、2 -戊儲基、己燒基、庚烯基、辛儲基、環丙基、環丁基 -173- 1226509 五、發明說明(172 ) 、環戊基、環己基、環庚基、環辛基、環戊烯基、環己烯 基等。 而且,Ra、Rb及Rc中任二個鍵結形成飽和或烯性不飽 和環,具體而言環鏈烷或環鏈烯通常爲3〜8、較佳者爲5 或6環。 本發明中通式(I)中,較佳者Ra、Rb及Rc中一個爲甲 基、或乙基、其餘爲具氫原子之乙醇醚,更佳者Ra、Rb 及Rc全部爲氫原子之下述通式[A-1]。 一般式[A— 1] CH2 =CH— 0 — R (其中,R :烷基、取代烷基) 此處,烷基係爲碳數1〜30個直鏈狀、支鏈或環狀烷基 〇 取代烷基爲碳數1〜30個直鏈狀、支鏈或環狀烷基。 於上述中碳數1〜30個直鏈狀、支鏈或環狀烷基例如有 乙基、直鏈狀、支鏈狀或環狀丙基、丁基、戊基、己基、 庚基、辛基、壬基、癸基、~ί •院基、十二院基、十三院 基、十四院基、十五院基、十六院基、十七院基、十八院 基、十九烷基、二十烷基等。 於上述中烷基之另外取代基例如有羥基、烷基、烷氧基 、胺基、硝基、鹵素原子、氰基、醯基、醯氧基、磺醯基 、磺醯氧基、磺醯胺基、芳基、芳烷基、醯亞胺基、羥基 甲基、 -174- 1226509 五、發明說明(173 ) -〇、1、 -c ( = 〇)-r2、 一〇〜c ( = 0) 一只3、 一 C (>〇)一〇一;r4、 -s〜r5、 -C (=S) 一 R6、 -〇〜C (=S) 一 r7、 -c (=s) —〇-r8、 ( 等之取代基。此處,1^〜1^係各獨立地表示直鏈狀、支 鏈狀或環狀;U基、丨兀氧_、胺基、硝基、鹵素原子、氰基 、醯基、磺醯基、磺醯氧基、磺醯胺基、醯亞胺基、-(CH2CH2-〇)n-R9(其中’ η係表示1〜20之整數,R9係表不 氫原子或烷基)、可具取代基之芳基或芳烷基(此處,取代 基例如有直鏈狀、支鏈狀或環狀烷基、烷氧基、胺基、硝 基、鹵素原子、氰基、醯基、芳基、芳烷基)。 通式(A )所示之化合物例如以下述者爲較佳的形態,惟 不受此等所限制。-165- 1226509 V. Description of the invention (164) Synthesis by anion and anion polymerization is better. Moreover, depending on the kind of polymerization initiation, when a reaction other than the polymerization of the monomer is caused, a monomer having an appropriate protective group introduced can be polymerized, and after the polymerization, a desired polymer can be obtained by deprotection. In addition, a polymer having an alkoxy group can also be obtained by subjecting a hydroxyl group of a polymer having a corresponding hydroxyl group to an ether reaction to obtain a desired polymer. About the polymerization method, such as the lecture on experimental chemistry 28, polymer synthesis, the lecture on new experimental chemistry 19, and high molecular chemistry [I]. The molecular weight of the alkali-soluble resin and the acid-decomposable resin of the present invention is 3,000 to 1,000,000. A preferred weight average molecular weight is 3,000 to 500,000. It is preferably 300,000 or less, more preferably 1 50,000 or less, even more preferably 100,000 or less, and most preferably 50,000 or less. The molecular weight distribution (Mw / Mn) of the alkali-soluble resin that can be synthesized by the above-mentioned synthesis method is preferably 1.0 to 1.5, whereby the photoresist can be highly sensitive. The molecular weight distribution resin can be synthesized by living anionic polymerization in the above synthesis method. Moreover, other alkali-soluble resins can be used. Other alkali-soluble resins used in the present invention include, for example, phenolic resin, hydrogenated phenolic resin, acetone-pyrophenol resin, o-polyhydroxystyrene, m-polyhydroxystyrene, p-polyhydroxystyrene, Hydrogenated polyhydroxystyrene, halogen- or alkyl-substituted polyhydroxystyrene, hydroxystyrene-N-substituted maleimide copolymer, o / p- and m / p-hydroxystyrene copolymer, p-polyhydroxybenzene The hydroxyl group of ethylene is partially ortho-alkylate (for example, 5 ~ 3 0-16 6-1226509. V. Description of the invention (165) Mole% of o-methylate, o- (1_methoxy) ethyl Compound, ortho- (1_ethoxy)) ethylate, ortho-2-tetrahydropyranide, ortho-3-butoxycarboxyl) methylate, etc.) or ortho-fluorenylate (e.g. 5 to 3 0 mol% o-fluorenyl compound, o- (3-butoxy) fluorenyl compound, etc.), styrene-maleic anhydride copolymer, styrene-hydroxystyrene copolymer, α-methylbenzene Ethylene-hydroxystyrene copolymers, carboxyl-containing methacrylic resins, and derivatives thereof are not limited thereto. More preferred alkali-soluble resins are phenolic resins, o-polyhydroxystyrene, m-polyhydroxystyrene, p-hydroxystyrene and copolymers thereof, alkyl-substituted polyhydroxystyrene, partially Polyhydroxystyrene ortho-alkylated, or alpha-methylstyrene-hydroxystyrene copolymer. This phenolic lacquer resin is obtained by adding and condensing aldehydes in the presence of an acidic catalyst with the monomers specified below as a main component. The specified monomers can be used alone or in combination of two or more types of cresols such as phenol, m-cresol, o-cresol, and p-cresol, 2,5-xylylene hydrazone, 3,5-xylenol, Dimethylphenols such as 3,4-xylenol, 2,3-xylenol, m-ethylphenol, p-ethylphenol, o-ethylphenylhydrazone, p-third-butylphenol, p-phenol -Octylphenol, 2,3,5-trimethylphenyl hydrazone, etc. classification of benzene, p-methoxyphenol, m-methoxyphenol, 3,5-monomethoxybenzoic acid, 2- Methoxy-4-methylphenol, m-ethoxyphenol, p-ethoxybenzidine, m-propoxyphenol, p-propoxyphenol, m-butoxyphenol, p-butoxy Alkoxyphenols such as phenol, dialkylphenols such as 2-methyl-isoisopropyl basic acid, m-chlorophenol, p-chlorophenol, o-chlorophenol, dihydroxy-167-1226509 5. Description of the invention (166) Hydroxy aromatic compounds such as biphenyl, bisphenol A, phenylphenol, resorcinol, naphthol, etc., but are not limited by these. Examples of the aldehydes include formaldehyde, p-formaldehyde, acetaldehyde, propionaldehyde, benzaldehyde, phenylacetaldehyde, α-phenylpropionaldehyde, A-phenylpropionaldehyde, o-hydroxybenzaldehyde, m-hydroxybenzaldehyde, p-aldehyde -Hydroxybenzaldehyde, o-chlorobenzaldehyde, m-chlorobenzaldehyde, p-chlorobenzaldehyde, o-nitrobenzaldehyde, m-nitrobenzaldehyde, p_nitrobenzaldehyde, o-methylbenzaldehyde , M-methylbenzaldehyde, p-methylbenzaldehyde, p-ethylbenzaldehyde, p-n-butylbenzaldehyde, furfural, chloroacetaldehyde, and acetals such as chloroacetamidaldehyde Diethyl acetal and the like are preferably formaldehyde. These aldehydes can be used alone or in combination of two or more. Acidic catalysts include hydrochloric acid, sulfuric acid, formic acid, acetic acid, and oxalic acid. The weight-average molecular weight of the phenolic lacquer resin thus obtained is preferably 1,000 to 30,000. If it is less than 1,000, the exposure portion will be large after the development, and if it is more than 30,000, the development speed will be small. The better is 2,000 ~ 20,000. The weight average molecular weight of the polyhydroxystyrene, its derivatives and copolymers other than the phenolic lacquer resin is 2,000 or more, preferably 2,000 to 30,000, and more preferably 2,000 to 20,000. Here, the weight average molecular weight is defined in terms of polystyrene conversion ratio of gel permeation chromatography. In the present invention, these alkali-soluble resins or acid-decomposable resins may be used in combination of two or more kinds. The amount of alkali-soluble resin used is based on the entire photoresist composition -168-1226509 V. Description of the invention (167) The weight is generally 30 to 90% by weight, preferably 50 to 80% by weight 〇 Base of the characteristic component of the present invention The amount of the soluble resin or acid-decomposable resin used is based on the total weight of the photoresist composition (except for the solvent), and is usually 30 to 90% by weight, preferably 50 to 80% by weight. The photoresist composition for an electron beam or X-ray of the present invention may also contain a low-molecular compound (referred to as "low-molecular acid-dissolving dissolution") "Block compounds" or "(c) ingredients"). The preferred (c) component to be incorporated in the photoresist composition for an electron wire or X-ray of the present invention is to have at least two groups decomposed by an acid in its structure, and the distance between the acid-decomposable groups is the farthest. Compounds that have at least 8 atoms bonded to them at positions other than acid-decomposable groups. More preferably, the component (c) has at least two groups decomposed by an acid in its structure, and the distance between the acid-decomposable groups passes through at least 10 at the furthest position (preferably 11). 12 or more) Compounds that bond to atoms other than acid-decomposable groups, or have at least 3 acid-decomposable groups in their structure, and the distance between the acid-decomposable groups is the farthest A compound having at least 9 (preferably 10, more preferably 11) bonded atoms other than the acid-decomposable group at the position of. In addition, the upper limit of the above bonding atoms is preferably 50, more preferably 30. The amount of the compound of the component (C) in the photoresist composition for electronic or X-rays of the present invention is 3 to 45% by weight compared to -169-1226509 for the solid content of the entire composition. 5. Description of the invention (168) The best and better are 5 to 30% by weight, and the best is 10 to 30% by weight. In the photoresist composition for an electron beam or X-ray of the present invention, a cationically polymerizable compound ((d) component) is preferably used. In the present invention, cationic polymerization refers to the addition polymerization of positive ions in which the growth chain is a carbon iron ion or an oxygen ion. The present invention refers to a compound having a cationic polymerizable function in a monomer obtained by the cationic polymerization. For example, in the case of an ethylene compound, the cationic polymerizability of the ethylene monomer is Q-e 値 used for free ion polymerization. In other words, the cationic polymerizability which e 値 is about less than -0.3 is known. In addition, the cationically polymerizable compounds are characterized by (1) 7Γ-carbon-carbon unsaturated bonds of the donor, and (2) η-cohard hybrids seen in some (mostly saturated) heterocyclic compounds. Non-shared electron pairs of ring atoms (oxygen, sulfur, nitrogen, phosphorus), (3) alkane can be seen under special conditions σ-the donor has a carbon-containing single bond. (1) is ethylene, vinylidene compound, vinylidene compound, and the like. (2) It is a lactone compound, a cyclic ether compound, and an oxazoline type, an azacyclopropane type, a cyclic siloxane, etc. For example, isobutene, isoprene, butadiene, cyclopentadiene, cyclohexadiene, ortho-sadiene, styrene, indene, naphthalene, benzofuran, p-methoxystyrene, α -Methylstyrene, vinyl ether, N-vinylcarbazole, N-vinylpyrrolidone. Among them, an ethylene compound is preferably used. The amount of the compound (d) in the photoresist composition for electronic or X-rays of the present invention is 0.5 to 50% by weight -170-1226509 for the total weight (solid content) of the composition. 169) It is preferably 3 to 30% by weight. In addition, the photoresist composition for electron or X-rays according to the present invention contains at least one compound ((d ') component) selected from the group consisting of an ethylene compound, a cycloalkane compound, a cyclic ether compound, a lactone compound, and an aldehyde compound. good. As the vinyl compound, the following vinyl ether compounds, styrene, α-methylstyrene, m-methoxystyrene, p-methoxystyrene, o-chlorostyrene, and m-chlorostyrene can be used. , P-chlorostyrene, o-nitrostyrene, m-nitrostyrene, p-brominated styrene, 3, 4-dichlorostyrene, 2,5-dichlorostyrene, -Styrenes such as dimethylaminostyrene, 2-isopropenylfuran, 2-vinylbenzofuran, 2-vinyldibenzofuran, 2-isopropenylthiophene, 2-vinyl Vinylthiophenes, such as phenothiones, N-vinylazoles, ethylene naphthalene, ethylene anthracene, ethylene naphthyl and the like. As the cycloalkane compound, phenylcyclopropane, helix [2,4] heptane, helix [2,5] octane, helix [3,4] octane, and 4-methyl helix [2,5] octane can be used. , Helix [2,7] decane, etc. As the cyclic ether compound, dioxanes such as 4-phenyl-1,3-dioxane, 3,3-dichloromethyl oxide cyclobutanes, trioxane, and 1,3-dioxide can be used. Cyclopropane and other compounds. In addition, glycidyl ethers such as allyl glycidyl ether, phenylglycidyl ether, glycidyl acrylate, glycidyl methacrylate, etc. can be used. ) Commercially available bisphenol A epoxy resin, tetrabromobisphenol A epoxy resin, bisphenol F epoxy resin, phenol novolac resin type epoxy resin, cresol novolac resin type Ring-171-1226509 V. Description of the invention (17〇) Oxygen resin and other compounds. As the lactone compound, propiolactone, butyrolactone, valerolactone, caprolactone, -methyl- / 3-propiolactone, α, α-dimethylpropiolactone, α-methyl- / 3 -Compounds such as propiolactone. As the aldehyde compound, aliphatic saturated aldehyde compounds such as valeraldehyde, hexanol, heptanol, octanol, nonanol, decanol, cyclohexylaminoformaldehyde, and phenylacetaldehyde, methacrylaldehyde, crotonaldehyde, 2-Methyl-2-butenal, 2-butynyl alcohol, crocetin and other aliphatic unsaturated aldehyde compounds, benzaldehyde, tolualdehyde, cinnamaldehyde and other aromatic aldehyde compounds, acetaldehyde tribromide, 2 , 2,3-trichlorobutyraldehyde, halogenated aldehyde compounds such as butyraldehyde, benzaldehyde, glyceraldehyde, aldol, salicylaldehyde, m-hydroxybenzaldehyde, 2,4-dihydroxybenzaldehyde, 4-hydroxy -3 -Hydroxy and alkoxy-substituted aldehyde compounds such as methoxybenzaldehyde, piperaldehyde, amines and nitro-substituted aldehyde compounds such as aminobenzaldehyde, nitrobenzyl, succinaldehyde, glutaraldehyde Dialdehyde compounds such as aldehydes, phthalic acid aldehydes, terephthalic acid, etc., acetal compounds such as phenylglyoxal, benzamylacetaldehyde, and their derivatives. The relationship between the (d) cationically polymerizable compound and (d ') an ethylene compound, a cycloalkane compound, a cyclic ether compound, a lactone compound, and an aldehyde compound is any one of the following 1) to 3). Those which are (d) cationic polymerizable compounds, not (d ') ethylene compounds, cycloalkane compounds, cyclic ether compounds, lactone compounds, and aldehyde compounds are (d') ethylene compounds, cycloalkane compounds, Cyclic ether compounds, lactone compounds, aldehyde compounds, and those other than (d) cationic polymerizable compounds -172-1226509 5. Description of the invention (171) is (d) cationic polymerizable compounds and (d,) ethylene Compounds, cycloparaffin compounds, cyclic ether compounds, lactone compounds, and aldehyde compounds. In addition, the compounds suitable for the present invention are the three types mentioned above, all of which have the same effects as the present invention. However, as described below, the effect of the ethylene compound is remarkable. In view of the remarkable effect of the (d ') compound, an ethylene compound is preferred, and a vinyl ether compound is more preferred, and a compound represented by the general formula [A] is particularly preferred. In the general formula (A), when Ra, Rb and Rc are aryl groups, they generally have 4 to 20 carbon atoms, and may be alkyl, aryl, alkoxy, aryloxy, fluorenyl, fluorenyl, Alkylthiol, aminofluorenyl, carbonylalkoxy, nitro, sulfofluorenyl, cyano, or halogen atoms are substituted. Here, the aryl group having 4 to 20 carbon atoms includes, for example, phenyl, tolyl, xylyl, biphenyl, naphthyl, anthryl, and phenanthryl. When Ra, Rb and Rc are alkyl groups, they represent saturated or unsaturated straight-chain, branched-chain or alicyclic alkyl groups having 1 to 20 carbon atoms, and may be a halogen atom, a cyano group, an ester group, an oxy group, an alkoxy group, or an aromatic group. Oxy or aryl substitution. Here, the saturated or unsaturated linear, branched or alicyclic alkyl group having 1 to 20 carbon atoms is, for example, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, or 3-butyl , Pentyl, isopentyl, neopentyl, hexyl, isohexyl, octyl, isooctyl, nonyl, decyl, eleven-yuan, ten- · yuan, twelve-yuan, fourteen-yuan , Ethylene, propenyl, butenyl, 2-butenyl, 3-butenyl, isobutenyl, pentenyl, 2-pentyl, hexyl, heptenyl, octyl, cyclopropyl Cyclobutyl-173-1226509 V. Description of the Invention (172) Cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclopentenyl, cyclohexenyl and the like. Moreover, any two of Ra, Rb and Rc are bonded to form a saturated or ethylenically unsaturated ring. Specifically, the cycloalkane or cycloalkene is usually 3 to 8, preferably 5 or 6 rings. In the general formula (I) of the present invention, one of Ra, Rb, and Rc is preferably a methyl group or an ethyl group, and the remainder is an ethanol ether having a hydrogen atom. More preferably, all of Ra, Rb, and Rc are hydrogen atoms. The following general formula [A-1]. General formula [A— 1] CH 2 = CH— 0 — R (where R: alkyl group, substituted alkyl group) Here, the alkyl group is a linear, branched, or cyclic alkyl group having 1 to 30 carbon atoms. The substituted alkyl group is a linear, branched or cyclic alkyl group having 1 to 30 carbon atoms. Examples of the linear, branched, or cyclic alkyl group having 1 to 30 carbon atoms include ethyl, linear, branched, or cyclic propyl, butyl, pentyl, hexyl, heptyl, and octyl Base, nong base, decyl base, ~ ί • base, 12 base, 13 base, 14 base, 15 base, 16 base, 17 base, 18 base, 10 base Nine alkyl, eicosyl and the like. Examples of the other substituents of the alkyl group include a hydroxyl group, an alkyl group, an alkoxy group, an amine group, a nitro group, a halogen atom, a cyano group, a fluorenyl group, a fluorenyl group, a sulfonyl group, a sulfonyloxy group, and a sulfonyl group. Amino group, aryl group, aralkyl group, fluorenimine group, hydroxymethyl group, -174-1226509 V. Description of the invention (173) -0, 1, -c (= 〇) -r2, -0 ~ c (= 0) one 3, one C (> 〇) one one; r4, -s ~ r5, -C (= S) one R6, -〇 ~ C (= S) one r7, -c (= s) —〇-r8, (and other substituents. Here, 1 ^ ~ 1 ^ each independently represents a linear, branched or cyclic; U group, pentoxide, amine, nitro, halogen Atom, cyano, fluorenyl, sulfonyl, sulfonyloxy, sulfonamido, sulfinamido,-(CH2CH2-〇) n-R9 (where 'η is an integer from 1 to 20, and R9 is It means a hydrogen atom or an alkyl group), an aryl group or an aralkyl group which may have a substituent (here, the substituent is, for example, a linear, branched or cyclic alkyl group, an alkoxy group, an amine group, a nitro group , Halogen atom, cyano, fluorenyl, aryl, aralkyl) The compound represented by the general formula (A) is, for example, the following Preferred form, but not limited these.
-175- 1226509-175- 1226509
1226509 五、發明說明(175) A —15 A —16 A —17 A —18 A —19 A-20 A — 21 A—22 A — 23 〇^\^ 〇\/^ 〇^\^· 〇、产 o^^nh2 /产 N 一 〇=*4^201226509 V. Description of the invention (175) A —15 A —16 A —17 A —18 A —19 A-20 A — 21 A—22 A — 23 〇 ^ \ ^ 〇 \ / ^ 〇 ^ \ ^ · 〇, Product o ^^ nh2 / Product N 〇 = * 4 ^ 20
1226509 五、發明說明(176) A-24 产0〜〇v〇 A — 25 A — 26 A—27 产。〜。 A—28 A-29 0 11 八 产。〜々0 0 A — 30 上述通式[A-1]所示化合物之合成法例如可藉由Stephen. C 歐 lapin , Polymers Paint Colour Journals ’ 1 79 ( 423 7 ),3 2 1 ( 1 988 )所記載的方法,即醇類或苯酚類與 -178- 1226509 五、發明說明(177) 乙烯之反應、或醇類或苯酚類與鹵化烷基乙烯醚之反應予 以合成。而且,亦可藉由羧酸化合物與鹵化烷基乙烯醚反 應予以合成。 本發明電子線或X線用光阻組成物中(d’)之化合物(較 佳者爲上述通式(A )所示化合物)的添加量,對組成物全部 重量(固成分)而言以0· 5〜50重量%較佳、更佳者爲3〜30 重量% 〇 另外,本發明電子線或X線光阻組成物以含有上述有機 鹼性化合物較佳。 更佳的化合物例如有胍、1,1 -二甲基胍、1,1,3,3 -四甲 基胍、2 -胺基吡啶' 3 -胺基吡啶、4 -胺基吡啶、2 -二甲基 胺基吡啶、4 -二甲基胺基吡啶、2 -二乙基胺基吡啶、2 -( 胺基甲基)吡啶、2 -胺基-3-甲基吡啶、2 -胺基-4-甲基吡 啶、2 -胺基-5 -甲基吡啶、2 -胺基-6 -甲基吡啶、3 -胺基乙 基吡啶、4 -胺基乙基吡啶、3 -胺基吡咯烷、哌畊、N - ( 2 -胺基乙基)哌畊、N - ( 2 -胺基乙基)哌啶、4 -胺基-2,2 , 6,6 -四甲基哌啶、4 -吡喃基哌啶、2 -亞胺基哌啶、1-(2 -胺基 乙基)吡咯烷、吡唑、3 -胺基-5 -甲基吡唑、5 -胺基-3 -甲 基-1 -對-三壯哩、吡畊、2 -(胺基甲基)-5 -甲基啦哄、嚼 啶、2,4 -二胺基嘧啶、4,6 -二羥基嘧啶、2 -吡唑啉、3 -吡 唑啉、N-胺基嗎啉、N-( 2-胺基乙基)嗎啉、二偶氮二環壬 烯、二偶氮二環十一烯等,惟不受此等所限制。 此等之(e )有機鹼性化合物可單獨使用或2種以上組合 -179- 1226509 五、發明說明(178) 使用。有機鹼性化合物之使用量對本發明(a )藉由電子線 或X線照射產生酸之化合物而言通常爲〇 · 0 1〜1 0莫耳%、 較佳者爲0 . 1〜5莫耳%。若小於0 · 0 1莫耳%時無法得到其 添加效果。 反之,若大於1 0莫耳%時會有感度降低或非照射部份之 顯像性惡化的傾向。 本發明電子線或X線用光阻組成物以含有作爲界面活性 劑之上述氟系及/或矽系界面活性劑較佳。添加量亦相同 〇 本發明電子線或X線用光阻組成物視其所需另可含有染 料、顏料、可塑劑、光增感劑、及對顯像液而言促進溶解 性之具有2個以上苯酚性基的化合物等。 本發明可使用的具有2個以上苯酚性基之化合物以分子 量爲1 000以下之苯酚化合物較佳。而且,必須分子中至 少具有2個苯酚性羥基。若大於1 〇時會失去顯像範圍之 改良效果。而且,若苯酚性羥基與芳香環之比例小於〇 . 5 時’膜厚相關性大且顯像範圍狹窄。該比例大於1 . 4時, 該組成物之安定性不佳且不易得到高解像力及良好的膜厚 相關性,故不爲企求。 該苯酚化合物之較佳添加量對(g )鹼可溶性樹脂而言爲2 〜50重量%、更佳者爲5〜30重量%。若大於50重量%時, 顯像殘渣惡化、且於顯像時圖案會產生變形之新缺點,故 不爲企求。 -180· 1226509 五、發明說明(彳79) 該分子量1 0 0 0以下之苯酚化合物例如日本特開平4 -122938號、特開平2-28531號、美國專利第49 1621〇號、 歐洲專利第2 1 9294號等記載的方法,爲該業者可容易地 予以合成。 苯酉分化合物之具體例如"F述所不,惟本發明可使用的化 合物不受此等所限制。 例如間苯二酚、氯苯酚、2 , 3,4 -三羥基二苯甲酮、 2,3,4,4’ -四羥基二苯甲酮、2,3,4,3’,4’,5、五羥基二苯 甲酮、丙酮-焦培酚縮合樹脂、氟化糖精、2,4,2’,4’-聯苯 基呋喃、4,4’-硫代雙(1,3-二羥基)苯、2,2’,4,4’-四羥基 二苯醚、2,2’,4,4’ -四羥基二苯基亞碾I、2,2’,4,4’ -四羥 基二苯基碾、參(4 -羥基苯基)甲烷、1,1-雙(4 -羥基苯基) 、環己烷、4,4-(α -甲基次苯基)雙酚、α,α’,α” -參 (4-羥基苯基)-1,3,5-三異丙基苯、“,0’,^”-參(4-羥 基苯基)-1-乙基-4-異丙苯、1,2,2-參(羥基苯基)丙烷、 1,1,2-參(3,5-二甲基-4-羥基苯基)丙烷、2,2,5,5-肆(4-羥基苯基)己烷、1,2 -肆(4 -羥基苯基)乙烷、1,1,3 -參(4 -羥基苯基)丁烷、對[α,α,α’,α’-肆(4 -羥基苯基)]-二 甲苯等。 本發明之組成物係使上述各成分溶解於溶劑中’塗覆於 載體上。此處所使用的溶劑以二氯化乙烯、環己酮、環戊 酮、2 -庚酮、r-丁內酯、甲基乙酮、乙二醇單甲醚、乙 二醇單乙醚、2 -甲氧基乙基乙酸酯、乙二醇單乙醚乙酸酯 -181 - 1226509 五、發明說明(180 ) 、丙二醇單甲醚、丙二醇單甲醚乙酸酯、甲苯、醋酸乙酯 、乳酸甲酯、乳酸乙酯、甲氧基丙酸甲酯、乙氧基丙酸乙 酯、丙酮酸甲酯、丙酮酸乙酯、丙酮酸丙酯、N,N -二甲基 甲醯胺、二甲基亞碾、N-甲基吡咯烷酮、四氫呋喃、碳數 6〜9之直鏈狀酮、7 - 丁內酯等較佳,此等之溶劑可單獨 使用或混合使用。 於本發明中,塗覆溶劑以丙二醇單甲醚乙酸酯更佳’藉 此可使面內均一性優異。 爲追求更進步的半導體時,除本質之高解像力等性能外 、就感度、塗覆性、最小塗覆必要量、與基板之密接性、 耐熱性、組成物之保存安定性等各種觀點而言要求高性能 之組成物。 最近,爲增加晶片之取得絕對量,使用大口徑之晶圓 (Wafer)以作成裝置之傾向。 然而,塗覆於大口徑時,由於塗覆性、尤其是會有面內 之膜厚均一性降低的情形,故要求提高對大口徑之晶圓而 言之膜後面內均一性。可確認該均一性的方法係在晶圓內 之多數點上進行膜厚測定,求取各測定値之標準偏差,以 其3倍之値確認均一性。該値愈小時,面內均一性愈高。 標準偏差之3倍値以100以下較佳、更佳者爲50以下。 另外,於製造微影術用光罩時,最重視CD直線性、要 求提高胚料內膜厚面內均一性。 本發明電子線或X線用光阻組成物可溶解於溶劑後予以 -182- 1226509 五、發明說明(181) 過濾。故所使用的過濾器可選自光阻領域中所使用者’具 體的過濾器材質係使用含有聚乙烯、耐龍或聚楓者。 更具體例如米里伯阿(譯音)公司製微卡頓(譯音)、微卡 頓Plus、微卡頓米尼肯姆(譯音)-D、微卡頓米尼肯姆-D PR、米里伯阿歐部基買拉(譯音)、DEV/DEV-C、米里伯阿 歐部基買拉1 6 / 1 4、伯魯(譯音)公司製烏魯基伯阿(譯音 )N66、伯基拉恩(譯音)耐龍法魯孔(譯音)等。而且,有關 過濾器之孔徑可藉由下述方法予以確認。總之’在超純水 中分散PSL標準粒子(聚苯乙烯乳膠珠粒徑〇 · 1〇〇 V m), 以管狀幫浦在1次過濾器側上連續以定流量流通,且藉由 粒子計算器測定範圍濃度,可以捕捉90%以上者作爲孔徑 0 . 1 // m過濾器。 使本發明電子線或X線用光阻組成物於製造精密積體電 路構件時所使用的基板(例如矽/二氧化矽被覆)上(視其所 需在設置有上述反射防止膜之基板上)藉由旋轉器、滾筒 等適當塗覆方法予以塗覆後,通過所定的遮光罩予以曝光 ,進行烘烤、藉由顯像製得良好光阻圖案。 本發明組成物之顯像液可使用氫氧化鈉、氫氧化鉀、碳 酸鈉、矽酸鈉、甲基矽酸鈉、銨水等無機鹼類,乙胺、正 丙胺等一級胺,二乙胺、二正丙胺等二級胺,三乙胺、甲 基二乙胺等三級胺,二甲基乙醇胺、三乙醇胺等醇胺類, 四甲銨氫氧化物、四乙銨氫氧化物等四級銨鹽,吡咯、 啶等環狀胺類等之鹼性水溶液。 -183- 1226509 五、發明說明(182) 另外’在上述鹼性水溶液中亦可添加適量的醇類、界面 活性劑。 【實施例】 於下述中藉由實施例等更具體地說明本發明,惟本發明 不受此等所限制。而且,%在沒有特別指定下係表示重量% 〇 合成例1 使32.4g(〇. 2莫耳)對-乙醯氧基苯乙烯溶解於120ml醋 酸丁酯中,且在氮氣氣氛及攪拌下,於83 °C下以3次添加 〇.〇3 3g偶氮雙異丁腈(AIBN),最後另外攪拌6小時以進行 聚合反應。將反應液投入1 200ml己烷中,以使白色樹脂 析出。使所得的樹脂乾燥後,溶解於150ml甲醇中。於其 中添加7 . 7g(0 . 19莫耳)氫氧化鈉/ 50ml水溶液,藉由3小 時加熱回流予以加水分解。另外,溶解200m 1水予以稀釋 ,以鹽酸中和、析出白色樹脂。使該樹脂過濾分別、水洗 、乾燥。另溶解於200ml四氫呋喃中且在激烈的攪拌下滴 入5L超純水中以進行再沉澱。使該再沉澱操作重複3次 。使所得的樹脂在真空乾燥器中、120°C乾燥12小時,製 得聚(對-羥基苯乙烯)[樹脂R - 1 ]。所得的樹脂之重量平均 分子量爲1 3,000。 合成例2 使35.25g(0.2莫耳)以常法爲基準予以脫水、蒸餾精製 的對-第3-丁氧基苯乙烯單體及5.21g(0.05莫耳)苯乙烯 -184- 1226509 五、發明說明(183) 單體溶解於l〇〇nll四氫呋喃中。在氮氣氣氛及攪拌下,於 8 3°C下在3小時內以3次添加0 . 〇33g偶氮雙異丁腈(AIBN) ’且另外攪拌6小時以進行聚合反應。將反應液投入 1200ml己烷中,以使白色樹脂析出。使所得的樹脂乾燥後 ’溶解於150ml四氫呋喃中。於其中添加4N鹽酸且藉由6 小時加熱回流予以加水分解後,在5L超純水中再沉澱, 使該樹脂過濾分別、水洗、乾燥。另外,溶解200m 1四氫 呋喃中,在激烈的攪拌下滴入5L超純水中以進行再沉澱 。反覆該再沉澱操作3次。使所得的樹脂在真空乾燥器中 ' 120°C乾燥12小時,製得聚(對-羥基苯乙烯/苯乙烯)共 聚物[樹脂R-2]。所得的樹脂之重量平均分子量爲1 1,〇〇〇 〇 合成例3 使40g(0.33莫耳對-羥基苯乙烯)與10.7g(0.08莫耳) 丙烯酸第3-丁酯溶解於50g二噁烷中,加入8g偶氮雙異 丁腈(A I BN ),在氮氣氣流、6 0 °C下進行攪拌8小時。將反 應液投入1 200ml己烷中,析出白色樹脂。使所得樹脂乾 燥後、溶解於丙酮中且在激烈的攬拌下滴入5L超純水中 以進行再沉澱。使該再沉澱操作重複3次。使所得的樹脂 在真空乾燥器中、120°C乾燥丨2小時,製得聚(對-羥基苯 乙烯/丙烯酸第3 - 丁酯)共聚物[樹脂R - 3 ]。所得的樹脂之 重量平均分子量爲21,000。 合成例4 -185- 1226509 五、發明說明(184 ) 使24g聚(對-羥基苯乙烯)日本曹達(譯音)公司製(分子 量8,000 )溶解於lOOrnl二噁烷後,在氮氣中進行起泡3〇 分鐘。在該溶液中加入13. lg二-第3 -丁基-二碳酸酯,攪 拌且滴入36g三乙胺。於滴完後將反應液攪拌5小時。使 該反應液滴入1重量%銨水溶液,且析出聚合物。使所得 樹脂乾燥後、溶解於丙酮中且在激烈的攪拌下滴入5L超 純水中以進行再沉澱。使該再沉澱操作重複3次。使所得 的樹脂在真空乾燥器中、在1 20°C下乾燥1 2小時,製得聚 (對-羥基苯乙烯/對-第3 -丁氧基羰氧基苯乙烯)共聚物[樹 脂R-4]。所得的樹脂之重量平均分子量爲8,300。 合成例5 使70g聚(對-羥基苯乙烯)日本曹達(譯音)公司製(分子 量8,000 )溶解於320g丙二醇甲醚乙酸酯(PGMEA)後,另加 入0 · 3 5 g對-甲苯磺酸吡啶鹽,在6 0 °C下加熱溶解。使該 混合物在60°C下、減壓至20mmHg、在系中殘存有約40g 溶劑、與水一起餾去。冷卻至20°C、且添加溶解1 8 . 9g苯 甲醇。然後,添加17.5g二-第3-丁基乙烯醚,且在20°C 下持續攪拌5小時。另外添加5 · 5 g吡啶、再加入5 . 9 g醋 酸酐、在20°C下進行攪拌1小時30分鐘。在反應混合物 中加入280ml醋酸乙酯、另加入140ml水及12ml丙嗣以 進行萃取操作。重複3次水洗操作後,在60°C、20mmHg 下進行餾去、除去系中之水分。 另將所得的樹脂溶液以丙酮稀釋、在大量的己烷中沉澱 -186- 1226509 五、發明說明(185) 、製得白色樹脂。使該操作重複3次,使所得的樹脂在真 空乾燥器中、在4(TC下加熱、乾燥24小時,製得聚(對-羥基苯乙烯/對- (1-苯甲氧基乙氧基)苯乙烯/對-乙醯氧基 本乙嫌)共聚物[樹脂R-5]。重量平均分子量爲8, 400。 合成例6 除使用70g聚(對-羥基苯乙烯)[鹼可溶性樹脂R - 1 ]、使 用2 2 · 0 g苯乙醇取代苯甲醇外,與上述合成例5進行同一 操作,製得聚(對-羥基苯乙烯/對- (1-苯乙基乙氧基)苯乙 烯/對-乙醯氧基苯乙烯)共聚物[樹脂R-6]。重量平均分子 量爲 13,800。 合成例7 使70g聚(對-羥基苯乙烯/苯乙烯)[鹼可溶性樹脂R-2] 溶解於3 20gPGMEA中、另加入0.35g對-甲苯磺酸吡啶鹽 ,在60 °C下加熱溶解。使該混合物在60t下、減壓至 20mmHg、在系中殘存有約40g溶劑、與水一起餾去。冷卻 至20°C、且添加溶解8 . 7g乙基乙烯醚。然後,在2(TC下 持續攪拌5小時。另外添加0.3g三乙胺後、在反應混合 物中加入280ml醋酸乙酯、另加入140ml水及12ml丙酮 以進行萃取操作。重複3次水洗操作後,在60°C、20mmHg 下進行餾去、除去系中之水分,製得聚(對-羥基苯乙烯/ 對·(卜乙氧基乙氧基)苯乙烯/苯乙烯)共聚物[樹脂R-7]。 重量平均分子量爲丨2,600。 合成例8 -187- 1226509 五、發明說明(186 ) 除使用70g聚(對-羥基苯乙烯/丙烯酸第丁酯)[樹脂 R - 7 ]外,與上述合成例7進行相同操作,製得聚(對-羥基 本乙嫌/對- (1-乙氧基乙氧基)苯乙烯/丙燒酸第3-丁酯)共 聚物[樹脂R-8]。重量平均分子量爲22, 0 00。 合成例9 使原菠烯、2 -甲基-2 -金剛烷基丙烯酸酯、馬來酸酐以 莫耳比3 5 / 3 0 / 3 5加入反應容器中、溶解於甲基乙酮中, 調整成固成分爲60%之溶液。使其在氮氣氣流下加熱至6〇 °C。使反應溫度安定時,加入1 .5莫耳%和光純藥(股)製 起始劑V - 6 0 1以開始反應。反應1 0小時後,使反應混合 物以甲基乙酮予以2倍稀釋後,投入大量的第3 - 丁基甲酸 中,析出白色粉末。使結晶的粉體過濾、取出、乾燥,製 得目的物之樹脂[R-9]。 使所得的樹脂[R - 9 ]的分子量藉由GPC測定結果、以聚 苯乙烯換算爲9700 (重量平均)。而且,藉由NMR光譜之樹 脂[R - 9 ]的組成,本發明之原菠烯/ 2 -甲基-2 -金剛烷基丙 烯酸酯/馬來酸酐以莫耳比32 / 28 / 40。 合成例1〇 使42.4g(0.10莫耳)1-[甲基·α-(4’-羥基苯基)乙基]-4-[α,,α ’ -雙(4”-羥基苯基)乙基]苯溶解於300mlN,Ν-二甲基甲醯胺中,且加入 49.5g( 0.35莫耳)碳酸鉀及 84.8g(〇.33莫耳)溴化醋酸枯酯。然後,在120°C下攪拌7 小時。將反應混合物投入2 L離子交換水中、以醋酸中和 -188- 1226509 五、發明說明(187) 後、以醋酸乙酯萃取。使醋酸乙酯萃取液濃縮、精製、製 得7〇g酸分解性溶解阻止化合物[I - 1 ](羥基之氫原子全部 以-CH2COOC(CH3)2C6H5 基取代)。 合成例11 使44gl,3,3,5-肆-(4-羥基苯基)戊烷溶解於250mlN,N-二甲基甲醯胺中,且加入70 . 7g碳酸鉀及90 . 3g溴化醋酸 第3-丁酯,在12(TC下攪拌7小時。將反應混合物投入2L 離子交換水中、且水洗所得的黏稠物。以柱色層分析法精 製、製得87g酸分解性溶解阻止化合物[1-2](羥基之氫原 子全部以-CH2COOC4H9( t)取代)。 合成例1 2 使 20ga ,α,α ’,α ’,α ”,α ” -陸(4-羥基苯基)-1,3,5-三乙基苯溶解於400ml二乙醚中。400ml二甲醚。在該溶 液中、氮氣氣氛下42.4g3,4 -二氫- 2H -吡喃、加入觸煤量 之鹽酸、回流24小時。於反應終了後,加入少量的氫氧 化鈉予以過濾。濃縮過濾液、使其以柱色層分離法精製、 製得5 5 . 3 g酸分解性溶解阻止化合物[I - 3 ](羥基全部爲 THP 基)。 合成例13 藉由在以烤箱乾燥、以氬氣純化的施嫩克管中塡充(預 先在60 °C之真空下乾燥一晚的)脫氧膽酸第3-丁酯(2g、 4 · 457毫莫耳)、(自CaH2蒸餾的)N -甲基嗎啉(1 . lmL、10 毫莫耳)及氯化伸甲基(8mL),以合成第3-丁基脫氧膽酸酯 -189- 1226509 五、發明說明(188) 〇 冷卻至0°C、再將蒸餾完成的二氯化谷氨醯基(〇.552g、 4.324毫莫耳、97莫耳%)使用氣密注入器慢慢地添加。於 該添加完成時,開始有鹽沉澱。攪拌所得漿料,於30分 鐘內昇溫至室溫,再於40°C下加溫30分鐘。 然後,使該混合物注入含有氯化伸甲基(40mL)與水 (40mL )。使有機層以稀醋酸銨水溶液洗淨4次,再予以濃 縮、製得固體物。使該固體物自二噁烷凍結乾燥,製得粉 末。 使該粉末分散於水(100mL)中,攪拌1小時。予以過濾 、再回收粉末,在真空中乾燥。收量爲1.5g(收率64%)。 使該方法重複使用四氫呋喃(THF )時,收量爲1 . 7 g (收率 7 4%)。以該寡聚物爲酸分解性溶解阻止化合物[I _ 4 ]。 實施例1 a〜1 6 a (感放射線性樹脂組成物之調製與評估:K rF準分子雷射 曝光) 使8g下述表-1所示成分溶解於PGMEA(丙二醇單甲醚乙 酸酯)中,藉由0 . 1 // m鐵氟隆過濾器過濾以調製光阻溶液 。(以PGMEA溶液所得的樹脂以固成分濃度換算表示) 使該光阻組成物溶液利用旋轉塗覆器、塗覆於施有六甲 基二矽烷之矽晶圓上,且在130t下以真空吸附型熱板加 熱乾燥90秒鐘,形成膜厚0 · 4 // m之光阻膜。在該光阻膜 上使用KrF準分子雷射分檔曝光器(NA = 0.63)進行圖案曝 -190- 1226509 五、發明說明(189) 光’於曝光後各在110°C之真空吸附型熱板上進行加熱6〇 秒。另以2 · 38%四甲銨氫氧化物(TMAH)水溶液浸漬6〇秒, 且以純水沖洗3 0秒、並予以乾燥。 使所得的圖案藉由掃描型電子顯微鏡觀察’且評估下述 之光阻性能。 感度係以使0 . 2 5 " m之線與空間(間距1 : 1 )解像之曝光 能量決定。解像度係以該曝光量可以解像的臨界解像力表 示。同時,觀察殘留的0 · 20 // m孤立線(間距1 : 1 〇 )圖案 ,完全沒有圖案飛離者爲〇、殘留1/2以上者爲△、大部 分圖案飛離消失者爲x。 -191 - 1226509 五、發明說明(190)表-1正型光阻組成物之處方(實施力及比較例之處方) 樹脂(添加量) 酸分解性溶解 阻止化合物 :光酸發生劑 (添加量) 有機鹼性化合物 (添加量) 含氟化脂肪族基之 高分子化合物 實施例la R-3(l.6g) Μ J\W D-l(0.06g) E-l(0.005g) P-l(lOppm) 實施例2a R-4(1.6g) y\ w D-2(0.07g) E-2(0.005g) P-3(lOOppm) 實施例3a R-4(l.6g) ^frrr II": D-3(0.08g) Μ /1 \Ν P-4(lOOppm) 實施例4a R-5(l.6g) D-l/D/3 (0.04/0.04g) E-3(0.005g) P-6(150ppm) 實施例5a R-6(l.6g) 並 j\\\ D-l(0.08g) E-l(0.005g) P-7(5ppm) 實施例6a R-6(1.6g) M J \ w D_2(0.08g) E-2(0.003g) P-10(20ppm) 實施例7a R-6/R-1 (l.〇g/〇.5g) 無 D-3(0.08g) E-3(0.006g) P-ll(40ppm) 實施例8a R-6/R-1 (1.0g/0.5g) y i w D-2/D-3 (0.05/0.03g) E-l(0.002g) P-12(150ppm) 實施例9a R-7(l.6g) M j\\\ D-l(0.06g) M j\\\ P-13(350ppm) 實施例10a R-7(1.6g) M(0.43g) D-2(0.03g) E-l(0.005g) P-14(500ppm) 實施例11a R-8(90g) M / » \N D-3(0.10g) E-2(0.005g) P-8(lOOOppm) 實施例12a R-8(l.6g) 1-2(0.20g) D-l(0.05g) E-3(0_007g) P-16(500ppm) 實施例13a R-l(1.5g) 1-3(0.43g) D-2(0.08g) E-l(0.005g) P-17(300ppm) 實施例14a R-2(1.6g) 1-1(0.44g) D-3(0.07g) M /INN P-18(50ppm) 實施例15a R-3(1.6g) 1-2(0.20g) D-l(0.08g) E-l(0.005g) P-19(5ppm) 實施例16a R-4(l.6g) 1-3(0.20g) D-2(0.06g) E-2(0.005g) P-20(3ppm) 比較例la R-4(l.6g) M J » N\ D-3(0.09g) E-3(0.005g) M 比較例2a R-5(l.6g) 無 D-l(0.08g) E-l(O.OOlg) 比較例3a R-6(1.6g) y i w D-2(0.08g) E-2(0.004g) PR-l(5ppm) 比較例4a R-7(1.6g) 1-1(0.43g) D-l/D-3 (0.04/0,04g) E-3(0.005g) PR-2(150ppm) 比較例5a R-K1.5) 1-2(0.43g) D-2/D-3 (0.05/0.03g) E-l(0.005g) °R-3(500ppm) 比較例6a R-2(1.6g) 1-3(0.44g) D-3(0.08g) 無 j\ \\ 比較例7a R-2(1.6g) I-KO.20g) D-l(0.05g) E-2(0.005g) PR-4(lOOOppm) * :對樹脂之添加濃度ppm1226509 V. Description of the invention (176) A-24 produces 0 ~ 〇v〇 A — 25 A — 26 A-27. ~. A-28 A-29 0 11 ~ 々0 0 A — 30 The method for synthesizing the compound represented by the general formula [A-1] can be, for example, Stephen. C Europe Lapin, Polymers Paint Colour Journals' 1 79 (423 7), 3 2 1 (1 988) The method described is the synthesis of alcohols or phenols with -178-1226509 V. Description of the invention (177) Ethylene, or the reaction of alcohols or phenols with halogenated alkyl vinyl ethers. It can also be synthesized by reacting a carboxylic acid compound with a halogenated alkyl vinyl ether. The addition amount of the compound (d ′) in the photoresist composition for electron or X-rays of the present invention (preferably, the compound represented by the general formula (A)) is based on the total weight (solid content) of the composition. 0.5 to 50% by weight is preferable, and 3 to 30% by weight is more preferable. In addition, the electron beam or X-ray photoresist composition of the present invention preferably contains the above-mentioned organic basic compound. More preferred compounds are, for example, guanidine, 1,1-dimethylguanidine, 1,1,3,3-tetramethylguanidine, 2-aminopyridine '3-aminopyridine, 4-aminopyridine, 2- Dimethylaminopyridine, 4-dimethylaminopyridine, 2-diethylaminopyridine, 2- (aminomethyl) pyridine, 2-amino-3-methylpyridine, 2-amino 4-methylpyridine, 2-amino-5-methylpyridine, 2-amino-6-methylpyridine, 3-aminoethylpyridine, 4-aminoethylpyridine, 3-aminopyrrole Alkane, piperin, N- (2-aminoethyl) piperin, N- (2-aminoethyl) piperidine, 4-amino-2,2,6,6-tetramethylpiperidine, 4-pyranylpiperidine, 2-iminopiperidine, 1- (2-aminoethyl) pyrrolidine, pyrazole, 3-amino-5 -methylpyrazole, 5-amino-3 -Methyl-1 -p-triazolium, pyrenol, 2-(aminomethyl) -5 -methyllazine, chelation, 2,4-diaminopyrimidine, 4,6-dihydroxypyrimidine , 2-pyrazoline, 3-pyrazoline, N-aminomorpholine, N- (2-aminoethyl) morpholine, diazobicyclononene, diazobicycloundecene, etc. , But not limited by these. These (e) organic basic compounds can be used alone or in combination of two or more. -179-1226509 V. Description of the invention (178) Use. The amount of the organic basic compound used is generally 0. 01 to 10 mol%, preferably 0.1 to 5 mol for the compound of the present invention (a) which generates an acid by irradiation with electron rays or X rays. %. If it is less than 0 · 0 1 mol%, its addition effect cannot be obtained. On the other hand, if it is more than 10 mol%, the sensitivity tends to decrease or the image developability of the non-irradiated portion tends to deteriorate. The photoresist composition for an electron beam or X-ray of the present invention preferably contains the above-mentioned fluorine-based and / or silicon-based surfactant as a surfactant. The addition amount is also the same. The photoresist composition for electronic or X-rays of the present invention may further contain dyes, pigments, plasticizers, photosensitizers, and two for promoting solubility in a developing solution, as required. Compounds of the above phenolic groups and the like. The compound having two or more phenolic groups usable in the present invention is preferably a phenol compound having a molecular weight of 1,000 or less. In addition, it is necessary to have at least two phenolic hydroxyl groups in the molecule. If it is greater than 10, the improvement effect of the development range is lost. When the ratio of the phenolic hydroxyl group to the aromatic ring is less than 0.5, the correlation between the film thickness and the imaging range is narrow. When the ratio is more than 1.4, the stability of the composition is not good and it is difficult to obtain high resolution and good film thickness correlation, so it is not desirable. The preferable addition amount of the phenol compound is 2 to 50% by weight, and more preferably 5 to 30% by weight for the (g) alkali-soluble resin. If it is more than 50% by weight, the development residue is deteriorated, and a new defect that the pattern is deformed during development is not desirable. -180 · 1226509 V. Description of the invention (彳 79) Examples of phenol compounds having a molecular weight of less than 1 000 are, for example, Japanese Patent Laid-Open No. 4-122938, Japanese Patent Laid-Open No. 2-28531, US Patent No. 49 1621 0, European Patent No. 2 The methods described in No. 9294 and the like can be easily synthesized by those skilled in the art. Specific examples of the phenylhydrazone compound are not described in "F", but the compounds usable in the present invention are not limited thereto. Such as resorcinol, chlorophenol, 2, 3,4-trihydroxybenzophenone, 2,3,4,4'-tetrahydroxybenzophenone, 2,3,4,3 ', 4', 5. Pentahydroxybenzophenone, acetone-pyrophenol condensation resin, fluorinated saccharin, 2,4,2 ', 4'-biphenylfuran, 4,4'-thiobis (1,3-di (Hydroxyl) benzene, 2,2 ', 4,4'-tetrahydroxydiphenyl ether, 2,2', 4,4'-tetrahydroxydiphenylimine I, 2,2 ', 4,4' -tetra Hydroxydiphenyl mill, ginseng (4-hydroxyphenyl) methane, 1,1-bis (4-hydroxyphenyl), cyclohexane, 4,4- (α-methylphenylene) bisphenol, α ", Α ', α" -Shen (4-hydroxyphenyl) -1,3,5-triisopropylbenzene, ", 0', ^"-Shen (4-hydroxyphenyl) -1-ethyl- 4-cumene, 1,2,2-gins (hydroxyphenyl) propane, 1,1,2-gins (3,5-dimethyl-4-hydroxyphenyl) propane, 2,2,5, 5- (4-hydroxyphenyl) hexane, 1,2- (4-hydroxyphenyl) ethane, 1,1,3-(4-hydroxyphenyl) butane, p- [α, α , Α ', α'-(4-hydroxyphenyl)]-xylene, etc. The composition of the present invention is made by dissolving the above components in a solvent. Medium 'is coated on the carrier. The solvents used here are ethylene dichloride, cyclohexanone, cyclopentanone, 2-heptanone, r-butyrolactone, methyl ethyl ketone, ethylene glycol monomethyl ether, Ethylene glycol monoethyl ether, 2-methoxyethyl acetate, ethylene glycol monoethyl ether acetate -181-1226509 5. Description of the invention (180), propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, Toluene, ethyl acetate, methyl lactate, ethyl lactate, methyl methoxypropionate, ethyl ethoxypropionate, methyl pyruvate, ethyl pyruvate, propyl pyruvate, N, N -di Methylformamide, dimethylimine, N-methylpyrrolidone, tetrahydrofuran, linear ketones having 6 to 9 carbons, 7-butyrolactone, etc. are preferred. These solvents can be used alone or in combination. In the present invention, the coating solvent is preferably propylene glycol monomethyl ether acetate, thereby making the in-plane uniformity excellent. When pursuing a more advanced semiconductor, in addition to its inherent high resolution and other properties, the sensitivity, Various viewpoints, such as coatability, minimum required coating amount, adhesion to the substrate, heat resistance, and storage stability of the composition High-performance components are required. Recently, in order to increase the absolute amount of wafers, large-diameter wafers have been used to create devices. However, when coating on large-diameter wafers, coating properties, especially If the uniformity of the film thickness in the plane is reduced, it is required to improve the uniformity of the rear surface of the film for large-caliber wafers. The method for confirming the uniformity is to measure the film thickness at most points in the wafer. Calculate the standard deviation of each measurement, and confirm the homogeneity by 3 times the 値. The smaller the 値, the higher the in-plane uniformity. The 3 times the standard deviation is preferably 100 or less, and more preferably 50 or less. In the manufacture of photolithography photomasks, the linearity of CD is the most important factor, and the thickness in-plane uniformity of the inner film of the blank is required to be improved. The photoresist composition for electronic or X-rays of the present invention can be dissolved in a solvent and then -182-1226509 V. Description of the invention (181) Filtration. Therefore, the filter to be used may be selected from those used in the photoresist field. Specific filter materials are those containing polyethylene, dragon-resistant or poly-maple. More specifically, for example, Microcarton (Transliteration), Microcarton Plus, Microcarton Mininicum-D, Microcarton Mininicum-D PR, Miri Boa Obu Kimiara (Transliteration), DEV / DEV-C, Miribo Ao Bugimara 16/1 4, Ulukiboa (Transliteration) N66, Bo Kiran (transliterated), Nailong Farukon (transliterated), etc. The pore size of the filter can be confirmed by the following method. In short, PSL standard particles (polystyrene latex bead particle size 0.100V m) were dispersed in ultrapure water, and a tube pump was used to continuously circulate at a constant flow rate on the primary filter side, and calculated from the particles. The device measures the range concentration, and can capture more than 90% as a pore size of 0.1 / 1 m filter. The photoresist composition for electronic wires or X-rays of the present invention is applied to a substrate (such as a silicon / silicon dioxide coating) used in manufacturing precision integrated circuit components (as required, on a substrate provided with the above-mentioned antireflection film) ) After coating by a suitable coating method such as a rotator, a roller, etc., it is exposed through a predetermined hood, baked, and a good photoresist pattern is produced by development. The developing solution of the composition of the present invention can use inorganic bases such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium methyl silicate, ammonium water, primary amines such as ethylamine, n-propylamine, and diethylamine. , Secondary amines such as di-n-propylamine, tertiary amines such as triethylamine, methyldiethylamine, alcohol amines such as dimethylethanolamine, triethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, etc. Basic ammonium salts, cyclic amines such as pyrrole, pyridine and other alkaline aqueous solutions. -183- 1226509 V. Description of the invention (182) In addition, an appropriate amount of alcohol and surfactant may be added to the above-mentioned alkaline aqueous solution. [Examples] The present invention will be described in more detail by examples and the like in the following, but the present invention is not limited by these. Moreover,% means weight% unless otherwise specified. Synthesis Example 1 32.4 g (0.2 mol) of p-ethoxyloxystyrene was dissolved in 120 ml of butyl acetate, and under a nitrogen atmosphere with stirring, 0.03 3 g of azobisisobutyronitrile (AIBN) was added 3 times at 83 ° C, and finally stirred for another 6 hours to perform a polymerization reaction. The reaction solution was poured into 1,200 ml of hexane to precipitate a white resin. The obtained resin was dried and then dissolved in 150 ml of methanol. 7.7 g (0.19 mol) of sodium hydroxide / 50 ml of an aqueous solution was added thereto, and the mixture was hydrolyzed by heating and refluxing for 3 hours. In addition, 200 m 1 of water was dissolved and diluted, and neutralized with hydrochloric acid to precipitate a white resin. This resin was filtered, washed with water, and dried. It was dissolved in 200 ml of tetrahydrofuran and dropped into 5 L of ultrapure water with vigorous stirring to perform reprecipitation. This reprecipitation operation was repeated 3 times. The obtained resin was dried in a vacuum dryer at 120 ° C for 12 hours to obtain poly (p-hydroxystyrene) [resin R-1]. The obtained resin had a weight average molecular weight of 1 3,000. Synthesis Example 2 35.25 g (0.2 mol) of p-th-butoxystyrene monomer dehydrated and distilled and purified based on a conventional method and 5.21 g (0.05 mol) of styrene-184-1226509 Description of the invention (183) The monomer is dissolved in 100 nl of tetrahydrofuran. Under a nitrogen atmosphere and stirring, 0.033 g of azobisisobutyronitrile (AIBN) 'was added 3 times at 83 ° C over 3 hours and stirred for another 6 hours to perform the polymerization reaction. The reaction solution was poured into 1200 ml of hexane to precipitate a white resin. After the obtained resin was dried, it was dissolved in 150 ml of tetrahydrofuran. 4N hydrochloric acid was added thereto, and the mixture was hydrolyzed by heating and refluxing for 6 hours, and then reprecipitated in 5L of ultrapure water, and the resin was filtered, washed with water, and dried. In addition, 200 m 1 of tetrahydrofuran was dissolved, and 5 L of ultrapure water was dripped under vigorous stirring to perform reprecipitation. This reprecipitation operation was repeated 3 times. The obtained resin was dried in a vacuum dryer at 120 ° C for 12 hours to prepare a poly (p-hydroxystyrene / styrene) copolymer [Resin R-2]. The weight average molecular weight of the obtained resin was 1 1,000. Synthesis Example 3 40 g (0.33 mole p-hydroxystyrene) and 10.7 g (0.08 mole) of 3-butyl acrylate were dissolved in 50 g of dioxane To the mixture, 8 g of azobisisobutyronitrile (AI BN) was added, and the mixture was stirred for 8 hours at 60 ° C under a nitrogen gas stream. The reaction solution was poured into 1,200 ml of hexane to precipitate a white resin. After the obtained resin was dried, it was dissolved in acetone and dropped into 5 L of ultrapure water under vigorous stirring to perform reprecipitation. This reprecipitation operation was repeated 3 times. The obtained resin was dried in a vacuum dryer at 120 ° C for 2 hours to prepare a poly (p-hydroxystyrene / 3-butyl acrylate) copolymer [Resin R-3]. The weight average molecular weight of the obtained resin was 21,000. Synthesis Example 4 -185-1226509 5. Description of the Invention (184) 24 g of poly (p-hydroxystyrene) manufactured by Soda Co., Ltd. (molecular weight: 8,000) was dissolved in 100 nl of dioxane, and then foamed in nitrogen 3 〇minutes. To this solution was added 13. lg of di-third-butyl-dicarbonate, stirred and 36 g of triethylamine was added dropwise. After the dropping was completed, the reaction solution was stirred for 5 hours. This reaction solution was dropped into a 1% by weight aqueous ammonium solution, and a polymer was precipitated. After the obtained resin was dried, it was dissolved in acetone and dropped into 5 L of ultrapure water with vigorous stirring to perform reprecipitation. This reprecipitation operation was repeated 3 times. The obtained resin was dried in a vacuum drier at 120 ° C for 12 hours to obtain a poly (p-hydroxystyrene / p-3-thoxybutoxycarbonyloxystyrene) copolymer [Resin R -4]. The weight average molecular weight of the obtained resin was 8,300. Synthesis Example 5 After dissolving 70 g of poly (p-hydroxystyrene) manufactured by Soda Co., Ltd. (molecular weight 8,000) in 320 g of propylene glycol methyl ether acetate (PGMEA), 0. 3.5 g of p-toluenesulfonic acid was added. Pyridine salt, dissolved by heating at 60 ° C. This mixture was depressurized to 20 mmHg at 60 ° C, and about 40 g of a solvent remained in the system, followed by distilling off with water. It was cooled to 20 ° C, and 18.9 g of benzyl alcohol was added and dissolved. Then, 17.5 g of di-third-butyl vinyl ether was added, and stirring was continued for 5 hours at 20 ° C. An additional 5.5 g of pyridine was added, and 5.9 g of acetic anhydride was added, followed by stirring at 20 ° C for 1 hour and 30 minutes. To the reaction mixture, 280 ml of ethyl acetate, 140 ml of water and 12 ml of propidium were added to perform an extraction operation. After repeating the water washing operation three times, the water was distilled off at 60 ° C and 20 mmHg to remove water from the system. In addition, the obtained resin solution was diluted with acetone and precipitated in a large amount of hexane. -186-1226509 V. Description of the invention (185) A white resin was prepared. This operation was repeated 3 times, and the obtained resin was heated and dried at 4 ° C. for 24 hours in a vacuum dryer to obtain poly (p-hydroxystyrene / p- (1-benzyloxyethoxy) ) Styrene / p-acetoxybenzyl) copolymer [Resin R-5]. Weight average molecular weight is 8, 400. Synthesis Example 6 Except using 70 g of poly (p-hydroxystyrene) [alkali soluble resin R- 1], except that 2 2 · 0 g of phenylethanol was used in place of benzyl alcohol, the same operation was performed as in Synthesis Example 5 above to obtain poly (p-hydroxystyrene / p- (1-phenethylethoxy) styrene / P-Ethyloxystyrene) copolymer [Resin R-6]. Weight-average molecular weight is 13,800. Synthesis Example 7 70 g of poly (p-hydroxystyrene / styrene) [alkali-soluble resin R-2] Dissolved in 3 20g of PGMEA, added another 0.35g of p-toluenesulfonic acid pyridine salt, and dissolved by heating at 60 ° C. The mixture was depressurized to 20mmHg at 60t, and about 40g of solvent remained in the system together with water. Distilled off. After cooling to 20 ° C, 8.7 g of ethyl vinyl ether was added and dissolved. Then, stirring was continued at 2 ° C for 5 hours. After adding 0.3 g of triethylamine, 280 ml of ethyl acetate was added to the reaction mixture, and 140 ml of water and 12 ml of acetone were added to perform the extraction operation. After repeating the water washing operation three times, it was distilled off at 60 ° C and 20 mmHg to remove the water in the system to prepare a poly (pair -Hydroxystyrene / p- (ethoxyethoxy) styrene / styrene) copolymer [Resin R-7]. Weight average molecular weight is 2,600. Synthesis Example 8 -187-1226509 V. Invention Explanation (186) Except that 70 g of poly (p-hydroxystyrene / dibutyl acrylate) [resin R-7] was used, the same operation as in the above Synthesis Example 7 was performed to prepare a poly (p-hydroxybenzidine / p-- (1-ethoxyethoxy) styrene / 3-butyl propionate) copolymer [Resin R-8]. The weight-average molecular weight is 22,000. Synthesis Example 9 Protospinene, 2- Methyl-2 -adamantyl acrylate and maleic anhydride are added to the reaction vessel at a molar ratio of 3 5/3 0/3 5 and dissolved in methyl ethyl ketone, and adjusted to a solution having a solid content of 60%. It was heated to 60 ° C under a nitrogen stream. The reaction temperature was stabilized, and 1.5 mol% of Wako Pure Chemical Industries, Ltd.'s starting agent V-6601 was added to start. Reaction. After 10 hours of reaction, the reaction mixture was diluted twice with methyl ethyl ketone, and then poured into a large amount of 3-butyl formic acid to precipitate a white powder. The crystal powder was filtered, taken out, and dried to obtain Resin [R-9] of the target object The molecular weight of the obtained resin [R-9] was measured by GPC, and the polystyrene conversion was 9700 (weight average). In addition, by the composition of the resin [R-9] in the NMR spectrum, the orthospinene / 2-methyl-2 -adamantyl acrylate / maleic anhydride of the present invention has a molar ratio of 32/28/40. Synthesis Example 10 42.4 g (0.10 mole) of 1- [methyl · α- (4'-hydroxyphenyl) ethyl] -4- [α ,, α'-bis (4 ”-hydroxyphenyl) Ethyl] benzene was dissolved in 300 ml of N, N-dimethylformamide, and 49.5 g (0.35 mole) of potassium carbonate and 84.8 g (0.33 mole) of cumyl bromide bromide were added. Then, at 120 ° Stir for 7 hours at C. Put the reaction mixture into 2 L of ion-exchanged water and neutralize -188-1226509 with acetic acid. 5. After the description of the invention (187), extract with ethyl acetate. The ethyl acetate extract is concentrated, refined, and prepared. 70 g of an acid-decomposable dissolution preventing compound [I-1] was obtained (the hydrogen atoms of the hydroxyl group were all replaced with -CH2COOC (CH3) 2C6H5 group). Synthesis Example 11 44 gl, 3, 3, 5-methyl- (4-hydroxyl Phenyl) pentane was dissolved in 250 ml of N, N-dimethylformamide, and 70.7 g of potassium carbonate and 90.3 g of 3-butyl bromoacetate were added and stirred at 12 ° C for 7 hours. The reaction The mixture was poured into 2 L of ion-exchanged water, and the viscous substance was washed with water. 87 g of an acid-decomposable dissolution preventing compound [1-2] was prepared by column chromatography, and all hydrogen atoms of the hydroxyl group were replaced by -CH2COOC4H9 (t). Together Example 1 2 20ga, α, α ', α', α ", α" -L (4-hydroxyphenyl) -1,3,5-triethylbenzene was dissolved in 400 ml of diethyl ether. 400 ml of dimethyl ether In this solution, 42.4g of 3,4-dihydro-2H-pyran under nitrogen atmosphere, add hydrochloric acid in contact with coal, and reflux for 24 hours. After the reaction is completed, add a small amount of sodium hydroxide to filter. Concentrate the filtrate Then, it was purified by column chromatography to obtain 55.3 g of an acid-decomposable dissolution preventing compound [I-3] (all hydroxyl groups are THP groups). Synthesis Example 13 Drying in an oven and using argon Purified Schlenk tubes were filled with (pre-dried overnight under vacuum at 60 ° C) 3-butyl deoxycholate (2g, 4.457 mmol), (distilled from CaH2) N- Methylmorpholine (1.1 mL, 10 mmol) and methyl chloride (8 mL) to synthesize 3-butyldeoxycholate-189-1226509 5. Description of the invention (188) 〇Cool to 0 At ° C, the glutamine dichloride (0.552 g, 4.324 mmol, 97 mole%) of distillate was added slowly using an airtight injector. When the addition was completed, salt precipitation started The resulting slurry was stirred, warmed to room temperature within 30 minutes, and heated at 40 ° C. for 30 minutes. Then, the mixture was poured into a solution containing methyl chloride (40 mL) and water (40 mL). Organic The layer was washed 4 times with a dilute ammonium acetate aqueous solution, and then concentrated to obtain a solid. This solid was freeze-dried from dioxane to obtain a powder. This powder was dispersed in water (100 mL) and stirred for 1 hour. It was filtered, and the powder was recovered and dried in vacuum. The yield was 1.5 g (64% yield). When this method was repeatedly used with tetrahydrofuran (THF), the yield was 1.7 g (yield 74%). Using this oligomer as an acid-decomposable dissolution preventing compound [I_4]. Example 1 a to 16 a (Preparation and evaluation of radiation-sensitive resin composition: K rF excimer laser exposure) 8 g of the components shown in Table-1 below were dissolved in PGMEA (propylene glycol monomethyl ether acetate) Medium, filtered through a 0.1 / 1m m Teflon filter to modulate the photoresist solution. (The resin obtained from the PGMEA solution is expressed in terms of solid content concentration.) The photoresist composition solution was coated on a silicon wafer to which hexamethyldisilanes was applied by a spin coater, and vacuum-adsorbed at 130t. The hot plate is heated and dried for 90 seconds to form a photoresist film with a film thickness of 0 · 4 // m. KrF excimer laser stepped exposure device (NA = 0.63) was used for pattern exposure on this photoresist film -190-1226509 V. Description of the invention (189) Light's vacuum adsorption type heat at 110 ° C after exposure The plate was heated for 60 seconds. In addition, it was immersed in a 2.38% tetramethylammonium hydroxide (TMAH) aqueous solution for 60 seconds, rinsed with pure water for 30 seconds, and dried. The obtained pattern was observed with a scanning electron microscope 'and the photoresist performance described below was evaluated. Sensitivity is determined by the exposure energy that enables resolution of 0.2 5 m lines and space (pitch 1: 1). Resolution is expressed in terms of the critical resolution at which this exposure can be resolved. At the same time, the remaining 0 · 20 // m isolated line (pitch 1: 1) pattern is observed. Those who have no pattern flying away at all are 0, those with more than 1/2 remaining are △, and most of the pattern flying away are x. -191-1226509 V. Description of the invention (190) Table-1 Formulas of positive photoresist composition (Executive power and comparative examples) Resin (addition amount) Acid decomposable dissolution preventing compound: Photoacid generator (addition amount ) Organic basic compound (addition amount) Example of high molecular compound containing fluorinated aliphatic group la R-3 (1.6 g) M J \ W Dl (0.06 g) El (0.005 g) Pl (10 ppm) Example 2a R-4 (1.6g) y \ w D-2 (0.07g) E-2 (0.005g) P-3 (100ppm) Example 3a R-4 (1.6g) ^ frrr II ": D-3 (0.08g) M / 1 / 1NP-4 (100ppm) Example 4a R-5 (1.6g) Dl / D / 3 (0.04 / 0.04g) E-3 (0.005g) P-6 (150ppm) Example 5a R-6 (1.6g) and j \\\ Dl (0.08g) El (0.005g) P-7 (5ppm) Example 6a R-6 (1.6g) MJ \ w D_2 (0.08g) E-2 (0.003g) P-10 (20ppm) Example 7a R-6 / R-1 (1.0g / 0.5g) without D-3 (0.08g) E-3 (0.006g) P- ll (40ppm) Example 8a R-6 / R-1 (1.0g / 0.5g) yiw D-2 / D-3 (0.05 / 0.03g) El (0.002g) P-12 (150ppm) Example 9a R -7 (l.6g) M j \\\ Dl (0.06g) M j \\\ P-13 (350ppm) Example 10a R-7 (1.6g) M (0.43g) D-2 (0.03g) El (0.005g) P-14 (500ppm) Example 11a R-8 (90g) M / »\ N D-3 (0.10g) E-2 (0.005g) P-8 (1000ppm) Example 12a R-8 (1.6g) 1-2 (0.20g) Dl (0.05g) E-3 (0_007g) P -16 (500ppm) Example 13a Rl (1.5g) 1-3 (0.43g) D-2 (0.08g) El (0.005g) P-17 (300ppm) Example 14a R-2 (1.6g) 1- 1 (0.44g) D-3 (0.07g) M / INN P-18 (50ppm) Example 15a R-3 (1.6g) 1-2 (0.20g) Dl (0.08g) El (0.005g) P- 19 (5ppm) Example 16a R-4 (1.6g) 1-3 (0.20g) D-2 (0.06g) E-2 (0.005g) P-20 (3ppm) Comparative example la R-4 (l .6g) MJ »N \ D-3 (0.09g) E-3 (0.005g) M Comparative Example 2a R-5 (1.6g) Without Dl (0.08g) El (O.OOlg) Comparative Example 3a R- 6 (1.6g) yiw D-2 (0.08g) E-2 (0.004g) PR-1 (5ppm) Comparative example 4a R-7 (1.6g) 1-1 (0.43g) Dl / D-3 (0.04 / 0,04g) E-3 (0.005g) PR-2 (150ppm) Comparative Example 5a R-K1.5) 1-2 (0.43g) D-2 / D-3 (0.05 / 0.03g) El (0.005 g) ° R-3 (500ppm) Comparative Example 6a R-2 (1.6g) 1-3 (0.44g) D-3 (0.08g) None j \ \\ Comparative Example 7a R-2 (1.6g) I- KO.20g) Dl (0.05g) E-2 (0.005g) PR-4 (1000ppm) *: Add concentration to resin ppm
-192- 1226509 五、發明說明(191) 光酸發生劑-192- 1226509 V. Description of the invention (191) Photoacid generator
-193- 1226509-193- 1226509
1226509 五、發明說明(193),達;側鏈上具有氟化脂肪族基之高分子化合物 號碼 -_ 氟系聚合物 氟化脂肪族側鏈 P-1 -左旦墨化學工業(股)製MEGAFAC F-178K 含有以短鏈聚合法製造的C8F17基 P-2 墨化學工業(股)製MEGAFAC F-470 含有以短鏈聚合法製造的C8F17基 P-3 左旦^墨化學工業(股)製MEGAFAC F-473 含有以短鏈聚合法製造的C8F17基 P-4 _^旦$迪墨化學工業(股)製MEGAFAC F-475 含有以短鏈聚合法製造的C8F17基 P-5 古旦查迪墨化學工業(股)製MEGAFAC F-476 含有以短鏈聚合法製造的C8F17基 P-6 墨化學工業(股)製MEGAFAC F-472 含有以短鏈聚合法製造的C8F17基 P-7 記載的重量平均分子量5萬 含有以短鏈聚合法製造的C8F17基 P-8 查記載的重量平均分子量1萬 含有以短鏈聚合法製造的C8F17基 P-9 記載 含有以短鏈聚合法製造的C8F17基 P-10 βϋΐ記載 含有以短鏈聚合法製造的C8F17基 P-11 記載 重量平均分子量2萬 P-12 記載 重量平均分子量1.5萬 -P-13— 连製111己載 重量平均分子量2萬 P-14 ----- ^11記載 重量平均分子量0.6萬 P-16 ---~^ 記載 重量平均分子量2萬 P*17 ------ 記載 重量平均分子量3萬 P-18 --—^ 記載 重量平均分子量2.5萬 JM9 記載 重量平均分子量1.5萬 記載 重量平均分子量2萬 Ith^ PR-2 (比較) _ 大曰本油墨化學工業(股)製MEGAFAC F-177 .___ 含有以電解氟化法製造的C8F17 f子式與Ρ-16〜Ρ-20相同,重量平均分子量2.7 萬 η=3,4,5,6之混合物,η=4成分之含 率對此等成分之總合而言爲35莫耳% ΙίΤ (比較) 、且η=3成分之含率爲28莫耳% ___ =子式與P-16〜P_20相同,重量平均分子量2·1 萬 η=3,4,5,6之混合物,η=4成分之含 率對此等成分之總合而言爲98.5莫 (比較) 耳% ___ ^子式與Ρ-16〜Ρ-20相同,重量平均分子量2.3 萬 η=3,4,5,6之混合物,η=3成分之含 率對此等成分之總合而言爲98.5莫 耳% -195- 1226509 五、發明說明(194)表-3光阻性能之評估 解像力(# m) 孤立線飛離 實施例la 0.21 〇 實施例2a 0.22 〇 實施例3a 0.21 〇 實施例4a 0.21 〇 實施例5a 0.22 〇 實施例6a 0.21 〇 實施例7a 0.20 〇 實施例8a 0.21 〇 實施例9a 0.21 〇 實施例10a 0.21 〇 實施例11a 0.22 〇 實施例12a 0.21 〇 實施例13a 0.20 〇 實施例14a 0.22 〇 實施例15a 0.21 〇 實施例16a 0.22 〇 比較例la 0.23 X 比較例2a 0.23 X 比較例3a 0.24 X 比較例4a 0.24 X 比較例5a 0.23 X 比較例6a 0.23 X 比較例7a 0.24 Δ -196- 1226509 五、發明說明(195 ) 實施例17a〜28a (感放射線性樹脂組成物之調製與評估:電子線曝光) 使8.2g下述表-4所示成分溶解於PGMEA,藉由〇· 1 // m 鐵氟隆過濾器過濾以調製光阻溶液。使各試料溶液利用旋 轉塗覆器、塗覆於矽晶圓上,且在12(TC、以真空吸附型 熱板乾燥90秒鐘,製得膜厚〇 . 5 // m之光阻膜。在該光阻 膜上使用電子線掃描裝置(加壓電速50kV )進行照射。 於照射後各在11 0°C之真空吸附型熱板上進行加熱60秒 ,以2 . 38%四甲銨氫氧化物(TMAH)水溶液浸漬60秒,且以 水沖洗30秒、並予以乾燥。使所得的接觸孔圖案及線與 空間圖案之截面形狀以掃描型電子顯微鏡觀察。 -197- 1226509 五、發明說明(196) 表-4 正型光阻組成物之處方(實 海力及比較例之處方) 樹脂 (添加量) 酸分解性溶 解阻止化合物 光酸發生劑 (添加量) 有機鹼性化合 物(添加量) 含氟化脂肪族基 之高分子化合物 實施例17a R-4(1.5g) Μ J \ w D-5(0.07g) E-l(0.005g) P-2(lOOppm) 實施例18a R-4(l.5g) 姐 j \ w D-6(0.08g) Μ y\\\ P-3(lOOpprn) 實施例19a R-5(l.6g) M D-4(0.04g) E-3(0.005g) P-4(150ppm) 實施例20a R-6(1.6g) /1 1 1 1*. "ittT: D-4(0.08g) E-2(0.005g) P-5(5ppm) 實施例21a R-6(1.6g) M / \\\ D-5(0.08g) E-l(0.003g) P-6(20ppm) 實施例22a R-6/R-1 (1.0/0.5g) te y\\\ D-6(0.05g) E-2(0.002g) P-12(150ppm) 實施例23a R-7(l.6g) M D-5(0.06g) te P-13(350ppm) 實施例24a R-7(1.3g) 1-1(0.43g) D-4(0.03g) E-l(0.005g) P-14(500ppm) 實施例25a R-8(90g) / D-4(0.10g) E-2(0.005g) P-7(lOOOppm) 實施例26a R-8(1.6g) 1-2(0.20g) D-6(0.05g) E-3(0.007g) P-16(500ppm) 實施例27a R-2(l.6g) 1-1(0.44g) D-4(0.07g) M j\\\ P-18(50ppm) 實施例28a R-3(1.6g) 1-2(0.20g) D-5(0.08g) E-l(0.〇05g) P-19(5ppm) 比較例8a R-4(l.6g) fiE D-4(0.09g) E-3(0.005g) M J \ w 比較例9a R-5(l.6g) te j\\\ D-5(0.05g) E-l(O.OOlg) M 川N 比較例10a R-6(l.6g) M j \\\ D-4(0.08g) E-2(0.004g) PR-l(5ppm) 比較例11a R-7(1.6g) 1-1(0.43g) D-4(0.04g) E-3(0.005g) PR-2(150ppm) 比較例12a R-l(1.5g) 1-2(0.43g) D-5(0.08g) E-l(0.005g) PR-3(500ppm) 比較例13a R-2(1.6g) 1-3(0.40g) D-6(0.08g) M j\\\ M j\\\ 比較例Ma R-2(1.6g) 1-1(0.2g) D-4(0.05g) E-2(0.005g) PR-4(lOOOppm) * :對樹脂之添加濃度ppm -198- 1226509 五、發明說明(197) 光酸發生劑1226509 V. Description of the invention (193), reached; Number of polymer compound with fluorinated aliphatic group on the side chain-Fluorine polymer fluorinated aliphatic side chain P-1-manufactured by Zuo Dan Mo Chemical Co., Ltd. MEGAFAC F-178K contains C8F17 based P-2 manufactured by short-chain polymerization method. Made by Ink Chemical Industry Co., Ltd. MEGAFAC F-470 contains C8F17 based P-3 manufactured by short-chain polymerization method. Zuo Dan ^ Ink Chemical Industry Co., Ltd. MEGAFAC F-473 containing C8F17 group P-4 manufactured by short-chain polymerization method _ ^ Dan MEGAFAC F-475 containing C8F17 group P-5 manufactured by short-chain polymerization method Gudancha MEGAFAC F-476 manufactured by Dimo Chemical Industry Co., Ltd. contains C8F17 based P-6 manufactured by short chain polymerization method MEGAFAC F-472 manufactured by Dimo Chemical Industry Co., Ltd. contains C8F17 based P-7 manufactured by short chain polymerization method The weight-average molecular weight of 50,000 contains the C8F17 group produced by the short-chain polymerization method P-8. The weight-average molecular weight of 10,000 contains the C8F17 group produced by the short-chain polymerization method. The P-9 is described as containing C8F17 produced by the short-chain polymerization method. P-10 βϋΐ is described as containing C8F17 group produced by short-chain polymerization. P-11 is a weight-average molecule. 20,000 P-12 recorded weight average molecular weight 15,000-P-13 — continuous system 111 already loaded weight average molecular weight 20,000 P-14 ----- ^ 11 recorded weight average molecular weight 0.6 million P-16 --- ~ ^ Recorded weight average molecular weight 20,000 P * 17 ------ Recorded weight average molecular weight 30,000 P-18 --- ^ Recorded weight average molecular weight 25,000 JM9 Recorded weight average molecular weight 15,000 Recorded weight average molecular weight 20,000 Ith ^ PR -2 (Comparison) _ MEGAFAC F-177 made by Daikoku Ink Chemical Industry Co., Ltd. ___ The formula containing C8F17 manufactured by electrolytic fluorination method is the same as P-16 ~ P-20, and the weight average molecular weight is 27,000 η = 3,4,5,6 mixture, η = 4 component content is 35 mol% for these components in total ΙίΤ (comparative), and η = 3 component content is 28 mol% ___ = The formula is the same as P-16 ~ P_20, with a weight average molecular weight of 210,000 η = a mixture of 3, 4, 5, 6 and the content ratio of η = 4 is 98.5 Mo for these components in total (Comparison) Ear% ___ ^ The formula is the same as P-16 ~ P-20, with a weight average molecular weight of 23,000, η = 3,4,5,6, and η = 3. For example, it is 98.5 mol% -195-1226509 V. Description of the invention (194) Table-3 Evaluation of photoresistance performance Resolution (# m) The isolated line flies away from Example la 0.21 〇 Example 2a 0.22 〇 Example 3a 0.21 〇 Example 4a 0.21 〇 Example 5a 0.22 〇 Example 6a 0.21 〇 Example 7a 0.20 〇 Example 8a 0.21 〇 Example 9a 0.21 〇 Example 10a 0.21 〇 Example 11a 0.22 〇 Example 12a 0.21 〇 Example 13a 0.20 〇 Example 14a 0.22 〇 Example 15a 0.21 〇 Example 16a 0.22 〇 Comparative Example la 0.23 X Comparative Example 2a 0.23 X Comparative Example 3a 0.24 X Comparative Example 4a 0.24 X Comparative Example 5a 0.23 X Comparative Example 6a 0.23 X Comparative Example 7a 0.24 Δ -196- 1226509 V. Description of the invention (195) Examples 17a to 28a (Modulation and evaluation of radiation-sensitive resin composition: electron beam exposure) 8.2 g of the components shown in Table-4 below were dissolved in PGMEA, and · 1 // m Teflon filter to modulate the photoresist solution. Each sample solution was coated on a silicon wafer using a spin coater, and dried at 12 ° C. for 90 seconds with a vacuum adsorption hot plate to obtain a photoresist film having a thickness of 0.5 // m. The photoresist film was irradiated with an electron beam scanning device (pressurized electric speed: 50kV). After the irradiation, each was heated on a vacuum adsorption hot plate at 110 ° C for 60 seconds, with 2.38% tetramethylammonium The hydroxide (TMAH) aqueous solution was immersed for 60 seconds, rinsed with water for 30 seconds, and dried. The cross-sectional shape of the obtained contact hole pattern and line and space pattern was observed with a scanning electron microscope. -197- 1226509 V. Invention Explanation (196) Table-4 Formulas of positive photoresist composition (Solenoid and Comparative Examples) Resin (addition amount) Acid-decomposable dissolution preventing compound Photoacid generator (addition amount) Organic basic compound (addition) Amount) Polymer compound containing fluorinated aliphatic group Example 17a R-4 (1.5g) M J \ w D-5 (0.07g) El (0.005g) P-2 (100ppm) Example 18a R-4 (l.5g) e.g. D-6 (0.08g) μy \\\ P-3 (100pprn) Example 19a R-5 (1.6g) M D-4 (0.04g) E-3 ( 0.005g) P-4 (150ppm) Example 20a R-6 (1.6g) / 1 1 1 1 *. &Quot; ittT: D-4 (0.08g) E-2 (0.005g) P-5 (5ppm) Example 21a R-6 (1.6g ) M / \\\ D-5 (0.08g) El (0.003g) P-6 (20ppm) Example 22a R-6 / R-1 (1.0 / 0.5g) te y \\\ D-6 (0.05 g) E-2 (0.002g) P-12 (150ppm) Example 23a R-7 (1.6g) M D-5 (0.06g) te P-13 (350ppm) Example 24a R-7 (1.3g ) 1-1 (0.43g) D-4 (0.03g) El (0.005g) P-14 (500ppm) Example 25a R-8 (90g) / D-4 (0.10g) E-2 (0.005g) P-7 (1000 ppm) Example 26a R-8 (1.6g) 1-2 (0.20g) D-6 (0.05g) E-3 (0.007g) P-16 (500ppm) Example 27a R-2 ( 1.6g) 1-1 (0.44g) D-4 (0.07g) M j \\\ P-18 (50ppm) Example 28a R-3 (1.6g) 1-2 (0.20g) D-5 ( 0.08g) El (0.05g) P-19 (5ppm) Comparative Example 8a R-4 (1.6g) fiE D-4 (0.09g) E-3 (0.005g) MJ \ w Comparative Example 9a R- 5 (l.6g) te j \\\ D-5 (0.05g) El (O.OOlg) M Sichuan N Comparative example 10a R-6 (l.6g) M j \\\ D-4 (0.08g) E-2 (0.004g) PR-1 (5ppm) Comparative Example 11a R-7 (1.6g) 1-1 (0.43g) D-4 (0.04g) E-3 (0.005g) PR-2 (150ppm) Comparative Example 12a Rl (1.5g) 1-2 (0.43g) D-5 (0.08g) El (0.005g) PR-3 (500ppm) Comparative Example 13a R-2 (1.6g) 1-3 (0.40g) D-6 (0.08g) M j \\\ M j \\ Comparative Example Ma R-2 (1.6g) 1-1 (0.2g) D-4 (0.05g) E-2 (0.005g) PR-4 (lOOppm) *: Adding concentration to resin ppm -198- 1226509 V. Description of the invention (197) Photoacid generator
(D-4) (D-5) 以線與空間係使0 . 2 // m設計大小1 量爲感度,以該照射量可以解像的最> 時,觀察殘留的0 . 1 5 // πι孤立線(間Η 圖案飛離者爲〇、殘留1 / 2以上者爲, 消失者爲X。 (D-6) :1解像之最小照射 、尺寸爲解像度。同 1 : 1 0),完全沒有 i、大部分圖案飛離 -199- 1226509 五、發明說明(198) 表-5光阻性能之評估 解像力(# m) 孤立線飛離 實施例17a 0.10 〇 實施例18a 0.09 〇 實施例19a 0.10 〇 實施例2〇a 0.11 〇 實施例21 a 0.09 〇 實施例22a 0.11 〇 實施例23a 0.11 〇 實施例24a 0.10 〇 實施例25a 0.11 〇 實施例26a 0.09 〇 實施例27a 0.11 〇 實施例28a 0.10 〇 比較例8a 0.12 X 比較例9a 0.12 X 比較例10a 0.12 X 比較例11a 0.13 X 比較例12a 0.12 X 比較例13a 0.12 X 比較例14a 0.12 Δ - 200 - 1226509 五、發明說明(1") 實施例29a〜34a (感放射線性樹脂組成物之調製與評估·· A rF準分子雷射 曝光) 使2g表6所示之樹脂、光酸發生劑、200mg酸分解性溶 解阻止化合物、5 m g有機鹼性化合物、及所定量配合含氟 化脂肪族基之高分子化合物、各以固成分重量%之比例溶 解於PGMEA後,以0 · 1 A m微過濾器過濾,調製正型光阻 組成物。 -201 - 1226509 五、發明說明(2〇〇) 表-6 正型光阻組成物之處方(1 f施力及比較例之處方) 樹脂 酸分解性溶解 光酸發生劑 有機鹼性化合物 含氟化脂肪族基 (添加量) 阻止化合物 (添加量) (添加量) 之高分子化合物 實施例29a R-9 並 j\w D-7 >fnT-ιΠΓ y» ν\ Ρ-3 45mg (lOOppm) 實施例30a R-9 Μ j\\\ D-8 E-l P-6 45mg (20ppm) 實施例31a R-9 te D-9 Ε-2 P-12 60mg (150ppm) 實施例32a R-9 te j\ w D-7 Ε-1 P-14 45mg (500ppm) 實施例33a R-9 1-4 D-8 Ε-3 P-16 2〇〇mg 45mg (500ppm) 實施例34a R-9 D-9 Ε-1 P-19 40mg (50ppm) 比較例15a R-9 te D-7 Ε-3 j ^ 45mg 比較例16a R-9 te j\w D-8 Ε-2 PR-1 60mg (50ppm) 比較例17a R-9 te J \ w D-9 Ε-3 PR-2 45mg (150ppm) 比較例18a R-9 1-4 D-7 Ε-1 PR-3 200mg 40mg (lOOOppm) 比較例19a R-9 1-4 D-8 Ε-2 PR-4 200mg 45mg (500ppm) * :對樹脂之添加濃度ppm - 202 - 1226509 五、發明說明(2〇1 )(D-4) (D-5) Using the line and space system to make 0. 2 // m design size 1 as the sensitivity, when the exposure dose can be resolved to the maximum, observe the remaining 0. 1 5 / / π solitary line (in the case where the pattern is flying away is 0, the remaining is more than 1/2, the disappearing is X. (D-6): the minimum irradiation of 1 resolution, the size is the resolution. Same as 1: 1 0) No pattern at all, most of the patterns fly away -199-1226509 V. Description of the invention (198) Table-5 Evaluation of photoresistance performance Resolution (#m) Isolated lines fly away Example 17a 0.10 〇 Example 18a 0.09 〇 Example 19a 0.10 〇Example 2 〇a 0.11 〇Example 21 a 0.09 〇Example 22a 0.11 〇Example 23a 0.11 〇Example 24a 0.10 〇Example 25a 0.11 〇Example 26a 0.09 〇Example 27a 0.11 〇Example 28a 0.10 〇 Comparative Example 8a 0.12 X Comparative Example 9a 0.12 X Comparative Example 10a 0.12 X Comparative Example 11a 0.13 X Comparative Example 12a 0.12 X Comparative Example 13a 0.12 X Comparative Example 14a 0.12 Δ-200-1226509 V. Description of the Invention (1 ") Example 29a ~ 34a (Modulation and evaluation of radiation-sensitive resin composition ... A rF excimer (Radiation exposure) 2 g of the resin shown in Table 6, a photoacid generator, 200 mg of an acid decomposable dissolution preventing compound, 5 mg of an organic basic compound, and a quantitatively compounded polymer compound containing a fluorinated aliphatic group, each of After dissolving the component in weight percent in PGMEA, it was filtered through a 0 · 1 A m micro filter to prepare a positive photoresist composition. -201-1226509 V. Description of the invention (200) Table-6 Formulas of positive photoresist composition (1 f force and comparative example) Resin acid decomposable dissolving photoacid generator organic basic compound containing fluorine Macromolecular compound of an aliphatic compound (addition amount) blocking compound (addition amount) (addition amount) Example 29a R-9 and j \ w D-7 > fnT-ιΠΓ y »ν \ Ρ-3 45mg (lOOppm ) Example 30a R-9 Μ j \\ D-8 El P-6 45mg (20ppm) Example 31a R-9 te D-9 E-2 P-12 60mg (150ppm) Example 32a R-9 te j \ D-7 E-1 P-14 45mg (500ppm) Example 33a R-9 1-4 D-8 E-3 P-16 200mg 45mg (500ppm) Example 34a R-9 D- 9 Ε-1 P-19 40mg (50ppm) Comparative Example 15a R-9 te D-7 Ε-3 j ^ 45mg Comparative Example 16a R-9 te j \ w D-8 Ε-2 PR-1 60mg (50ppm) Comparative Example 17a R-9 te J \ w D-9 Ε-3 PR-2 45mg (150ppm) Comparative Example 18a R-9 1-4 D-7 Ε-1 PR-3 200mg 40mg (1000ppm) Comparative Example 19a R -9 1-4 D-8 Ε-2 PR-4 200mg 45mg (500ppm) *: Addition concentration to resin ppm-202-1226509 V. Description of the invention 2〇1)
CF3SO3- (D-9) 在矽晶圓上塗覆西普雷(譯音)公司製反射防止膜AR-19 ,在215°C下燒成90秒鐘、以850A膜厚塗覆。如此所得 的基板上塗覆上述調製的光阻液,在1 35°C下燒成90秒鐘 以製得0.30// πι之膜厚。 、 . 如此所得的晶圓在A rF準分子雷射分檔曝光器(I S I公司 製ArF曝光機9300 )裝置解像力光罩,變化曝光量且予以 曝光。然後,在溫室中、1 50°C下加熱90秒鐘後,以四甲 銨氫氧化物顯像液(2 · 3 8重量% )顯像6 0秒鐘,以超純水洗 淨、乾燥、製得圖案。 - 203 - 1226509 五、發明說明(202 ) 以線與空間係使0 . 1 6 // m設計大小1 : 1解像之最小照 射量爲感度,以該照射量可以解像的最小尺寸爲解像度。 同時,觀察殘留的0 . 1 2 // m孤立線(間距1 ·· 1 0 ),完全沒 有圖案飛離者爲〇、殘留1/2以上者爲△、大部分圖案飛 離消失者爲X。 表-7光阻ΰ 匕能之評估 __ 解像力(# m) 孤立線飛離 實施例29a 0.13 〇 實施例30a 0.13 〇 實施例31a 0.125 〇 實施例32a 0.125 〇 實施例33a 0.13 〇 實施例34a 0.13 〇 比較例15a 0.14 X 比較例16a 0.14 X 比較例17a 0.14 X 比較例18a 0.145 X 比較例19a 0.135 Δ ^ 可知藉由本發明係提供一種可提高化學放大型光阻之解 像力、特別是可抑制孤立圖案飛離之光阻組成物。 其次,爲電子線或X線用光阻組成物。 1 .構成原料之合成例 (1 )藉由電子線或X線產生酸之化合物 - 204 - 1226509 五、發明說明(203 ) (1-1)五氟苯磺酸四甲錢鹽之合成 在冰冷下100ml甲醇中溶解25g五氟苯磺基氯化物,於 其中徐徐地加入100g之25%四甲銨氫氧化物。在室溫下攪 拌3小時,製得五氟苯磺酸四甲銨鹽溶液。使該溶液使用 與銃鹽、碘鐵鹽之鹽交換。 (1 - 2 )三苯基五氟苯磺酸毓鹽之合成 使50g二苯基亞 溶解於800ml苯,於其中加入200g 氯化鋁、回流24小時。使反應液慢慢地注入2L冰中,於 其中加入400ml濃鹽酸、在70°C下加熱10分鐘。使該水 溶液以500ml醋酸乙酯洗淨、過濾後加入400ml溶解有 200g碘化銨者。使析出的粉體過濾、水洗後以醋酸乙酯洗 淨、乾燥,製得70g三苯基毓碘化物。 使3 0. 5g三苯基毓碘化物溶解於1000ml甲醇中,在該 溶液中加入1 9 . 1 g氧化銀,在室溫下攪拌4小時。使溶液 過濾、且於其中加入過量的五氟苯磺酸四甲銨鹽之溶液, 使反應液濃縮、且使其溶解於500ml二氯甲烷,且使該溶 液以5%四甲銨氫氧化物水溶液、及水洗淨。使有機相以無 水硫酸鈉乾燥後、予以濃縮’製得三苯基五氟苯磺酸毓鹽 (I - 1 ) ° (1-3)二(4 -第3 -醯基苯基)五氟苯磺酸碘鐵鹽之合成 使60g第3 -戊基苯、39.5g碘酸鉀、81g醋酸酐、170ml 二氯甲烷混合,且在冰冷下於其中慢慢地滴入66 .8g濃硫 酸。在冰冷下攪拌2小時後’在室溫下攪拌1 〇小時。在 - 205 - 1226509 五、發明說明(204 ) 反應液中、冰冷下加入500ml水,使其以二氯甲烷萃取、 使有機相以碳酸氫鈉、水洗淨後予以濃縮,製得二(4 -第 3 -戊基苯基)硫酸碘鏺鹽。使該硫酸鹽加入過量的五氟苯 磺酸四甲銨溶液中。在該溶液中加入500m水,使其以二 氯甲烷萃取、使有機相以5%四甲銨氫氧化物水溶液、吸水 洗淨後予以濃縮,製得二(4 -第3 -戊基苯基)五氟苯磺酸碘 鏺鹽(I I I - 1 )。 下述所示之酸發生劑PAG - 1及PAG-2亦以與上述相同的 方法予以合成。 (其他的酸發生劑)CF3SO3- (D-9) Coat an anti-reflection film AR-19 manufactured by Siple Corporation on a silicon wafer, fire it at 215 ° C for 90 seconds, and apply it at a thickness of 850A. The thus-prepared photoresist was coated on the substrate thus obtained, and fired at 1 35 ° C for 90 seconds to obtain a film thickness of 0.30 // m. The wafer obtained in this way was equipped with a resolution mask in an ArF excimer laser stepped exposure device (ArF exposure machine 9300 manufactured by IS Company), and the exposure amount was changed and exposed. Then, it was heated in a greenhouse at 150 ° C for 90 seconds, and then developed with tetramethylammonium hydroxide imaging solution (2.88% by weight) for 60 seconds, washed with ultrapure water, and dried. And make a pattern. -203-1226509 V. Description of the invention (202) Use line and space system to make 0.1 6 // m design size 1: 1 minimum exposure as the sensitivity and the minimum size that can be resolved by the exposure as the resolution . At the same time, observe the residual 0.1 2 // m isolated lines (spacing 1 ·· 1 0). Those who have no pattern flying away at all are 0, those with more than 1/2 remaining are △, and those with most patterns flying away are X. . Table-7 Evaluation of photoresistance __ Resolution (# m) The isolated line flies away from Example 29a 0.13 〇Example 30a 0.13 〇Example 31a 0.125 〇Example 32a 0.125 〇Example 33a 0.13 〇Example 34a 0.13 〇Comparative Example 15a 0.14 X Comparative Example 16a 0.14 X Comparative Example 17a 0.14 X Comparative Example 18a 0.145 X Comparative Example 19a 0.135 Δ ^ It is understood that the present invention provides a solution capable of improving the resolution of a chemically amplified photoresist, and particularly capable of suppressing isolated patterns. Fly away photoresist composition. Secondly, it is a photoresist composition for electron or X-rays. 1. Synthetic examples of constituent raw materials (1) Compounds that generate acids by electron or X-rays-204-1226509 V. Description of the invention (203) (1-1) Synthesis of pentafluorobenzenesulfonic acid tetramethyl salt In 100 ml of methanol, 25 g of pentafluorobenzenesulfochloride was dissolved, and 100 g of 25% tetramethylammonium hydroxide was slowly added thereto. After stirring at room temperature for 3 hours, a tetramethylammonium pentafluorobenzenesulfonate solution was prepared. This solution was exchanged with a salt of a phosphonium salt and an iodonium salt. (1-2) Synthesis of triphenylpentafluorobenzenesulfonic acid salt 50 g of diphenylene was dissolved in 800 ml of benzene, 200 g of aluminum chloride was added thereto, and the mixture was refluxed for 24 hours. The reaction solution was slowly poured into 2 L of ice, 400 ml of concentrated hydrochloric acid was added thereto, and the mixture was heated at 70 ° C for 10 minutes. The aqueous solution was washed with 500 ml of ethyl acetate, and after filtration, 400 ml of 200 g of ammonium iodide was dissolved. The precipitated powder was filtered, washed with water, washed with ethyl acetate, and dried to obtain 70 g of triphenyl erythroiodide. 30.5 g of triphenyl erythroiodide was dissolved in 1000 ml of methanol, and 19.1 g of silver oxide was added to the solution, followed by stirring at room temperature for 4 hours. The solution was filtered, and an excessive solution of tetramethylammonium pentafluorobenzenesulfonate was added thereto, and the reaction solution was concentrated and dissolved in 500 ml of dichloromethane, and the solution was adjusted to 5% tetramethylammonium hydroxide Wash with water and water. The organic phase was dried over anhydrous sodium sulfate, and then concentrated to obtain triphenylpentafluorobenzenesulfonic acid salt (I-1) ° (1-3) bis (4- 3rd-fluorenylphenyl) pentafluoro Synthesis of ferric iodobenzene besylate 60 g of 3-pentylbenzene, 39.5 g of potassium iodate, 81 g of acetic anhydride, and 170 ml of dichloromethane were mixed, and 66.8 g of concentrated sulfuric acid was slowly added thereto under ice-cooling. After stirring under ice-cooling for 2 hours', it was stirred at room temperature for 10 hours. -205-1226509 V. Description of the invention (204) 500 ml of water was added to the reaction solution under ice cooling, and the mixture was extracted with dichloromethane. The organic phase was washed with sodium bicarbonate and water and concentrated to obtain two (4 -3 -pentylphenyl) iodophosphonium sulfate. This sulfate was added to an excess of tetramethylammonium pentafluorobenzenesulfonate solution. 500 m of water was added to the solution, and the solution was extracted with dichloromethane, and the organic phase was washed with 5% tetramethylammonium hydroxide aqueous solution, washed with water, and concentrated to obtain di (4-thi-pentylphenyl). ) Iodophosphonium pentafluorobenzenesulfonate (III-1). The acid generators PAG-1 and PAG-2 shown below were also synthesized in the same manner as described above. (Other acid generators)
Br I CH2CHCH2BrBr I CH2CHCH2Br
Br BrCH2CHCH2Br BrCH2CHCH2
Br I CH2CHCH2Br PAG-1: PAG-2: (2 )驗可溶性樹脂之合成 (1^1)使16.4g(〇.l莫耳)3,4-二甲氧基苯乙烯、 158· 7g( 0.9莫耳)仁第3-丁氧基苯乙烯溶解於乾燥THF中 ,且在氮氣氣流下加熱至701,加入上述單體總莫耳數之 2旲耳%的和光純藥製偶氮系游離基起始劑V - 60 1。於反應 - 206 - 1226509 五、發明說明(205 ) 8小時後,以THF稀釋反應液、並沉澱於己烷中、精製、 取出聚合物。藉由常法以酸分解、製得(p _ 1 )。以G P C測 定求取重量平均分子量(Mw)及分子量分散度(Mw/Mn)。 (1 - 2 )使用與上述約相同的方法、及使用保護的單體(例 :4-苯甲氧基苯乙烯)、藉由BF3 · Et〇2予以陽離子聚合 ,合成(P-1,)、(Ρ-Γ,)、(P-2)〜(P — 51)。 (1-3)使1.64g(0.01莫耳)3,4-二甲氧基苯乙烯及 15.9g(0.09莫耳)4 -第3 -丁氧基苯乙烯溶解於- 78°C之脫 氣乾燥THF中,在封管中、-78°C下使用1毫莫耳第2-丁 基鋰、衝破玻璃密封、開始反應。在大量的己院中集中沉 澱的粉體予以精製。藉由常法以酸處理製得(p - 1 ’)。 (3 )溶解阻止化合物之合成 (溶解阻止劑化合物之合成例-1 :化合物1 8之合成) 使42.4g(0.10莫耳)1-[α-甲基-α_(4,-羥基苯基)乙 基]-4 - [ α,,α ’ -雙(4” -羥基苯基)乙基]苯溶解於 300mlN,N-二甲基乙醯胺中,且加入49.5g(0.35莫耳)碳 酸鉀及84 · 8g(0 · 33莫耳)溴化醋酸枯酯。然後,在120°C 下攪拌7小時。將反應混合物投入2L離子交換水中、以 醋酸中和後、以醋酸乙酯萃取。使醋酸乙酯萃取液濃縮、 精製、製得7〇g化合物18(全部R爲- CH2COOC(CH3)2C6H5基) 〇 (溶解阻止劑化合物之合成例-2 :化合物例42之合成) 使 2 0 g α,α,α,,α ’,α,,,α,,-陸(4 -羥基苯基)-1,3,5 - - 207 - 1226509 五、發明說明(206 ) 二乙基苯溶解於4 0 0 m 1二甲醚。在該溶液中、氮氣氣氛下 42 . 4g3 , 4-二氫-2H-吡喃、加入觸煤量之鹽酸、回流24小 時。於反應終了後,加入少量的氫氧化鈉予以過濾。濃縮 過濾液、使其以柱色層分離法精製、製得5 5 . 3 g化合物 42(全部R爲THP基)。 (溶解阻止劑化合物之合成例-3 :化合物例42 - 2之合成) 使 20g α , α,α ’,α ’,α ”,α ” -陸(4 -羥基苯基)_ 1,3,5-三乙基苯溶解於200〇11^^二甲基乙醯胺中,且加 入28.2g碳酸鉀及3 6.0g溴化醋酸丁酯,在120°C下攪拌 7小時。將反應生成物投入2L離子交換水中、水洗所得的 黏稠物。使其以柱色層分析法精製、製得37g上述化合物 例 42-2(全部 R 爲- CH2COOC4H9( t ))。 (4 )通式(A )所示化合物之合成例 (合成例-1)上述A-22(苯甲醯氧基乙基乙烯醚)之合成 將244g(2莫耳)苯甲酸溶解於300〇ml甲苯中,且加入 320g2 -氯化乙基乙烯醚、另加入88g氫氧化鈉、25g四丁 銨溴化物、100g三乙胺、在120 °C加熱攪拌5小時。 水洗反應液、減壓I留去以除去過量的2 -氯化乙基乙;(:希 醚與甲苯。自所得的油份、藉由減壓餾去、製得300g目 的物之苯甲醯氧基乙基乙烯醚。 (合成例-2〜8)上述A-23〜A-29之合成 與上述A-22相同地合成上述A-23〜A-29。 2 .實施例[實施例、比較例] - 208 - 1226509 五、發明說明(2〇7 ) 光阻之塗設 使8.2g下述表8〜11所示成分溶解於丙二醇單甲醚乙 酸酯’藉由〇 · 1 # m鐵氟隆過灑器過爐以調製光阻溶液。 使各試料溶液利用旋轉塗覆器、塗覆於矽晶圓上,且在 120°C、以真空吸附型熱板乾燥90秒鐘,製得膜厚0.5// m 之光阻膜。 光阻圖案之作成 在該光阻膜上使用電子線掃描裝置(加壓電速50kV)進行 照射。 於照射後各在1 1 (TC之真空吸附型熱板上進行加熱60秒 ’以2.38%四甲銨氫氧化物(TMAH)水溶液浸漬60秒,且以 水沖洗30秒、並予以乾燥。 使所得的接觸孔圖案及線與空間圖案之截面形狀藉由掃 描型電子顯微鏡觀察。 (3 )感度及解像力之評估 以接觸孔圖案之臨界解像力(孔之最小直徑)作爲解像力 、以可使該臨界解像力解像之最小照射能量作爲感度。 而且,有關0 . 20 // m線(線:空間=1 : 1 )解像的照射量 爲感度、且可在該照射量解像之最小尺寸作爲解像度。 - 209 - 1226509 五、發明說明(2〇8) 表-8光阻膜-線與空間 酸發生劑 驗可溶 性樹脂 (d)或(d,) 溶解阻止劑 有機鹼性 化合物 界面活性劑 氺 實施例1 (ΠΙ-1) 0.072g (P-1) 〇.78g 無 / > w (42-2) 0.36g B-1 0.002g W-l lOOOppm 實施例2 同上 (P-1) 0.60g (A-22) 0.18g 同上 同上 同上 實施例3 同上 (P-1,) 0.60g 同上 同上 同上 同上 實施例4 同上 (P-1,,)0.60g 同上 同上 同上 同上 實施例5 同上 (P-1,,,)0.60g 同上 同上 同上 同上 實施例6 同上 (P-2) 0.60g 同上 同上 同上 同上 實施例7 同上 (P-3) 0.60g 同上 同上 同上 同上 實施例8 同上 (P-3,) 0.60g 同上 同上 同上 同上 實施例9 同上 (P-4) 0.60g 同上 同上 同上 同上 實施例10 同上 (P-5) 0.60g 同上 同上 同上 同上 實施例11 同上 (P-5,,)0.60g 同上 同上 同上 同上 實施例12 同上 (P-6) 0.60g 同上 同上 同上 同上 實施例13 同上 (P-6,) 0.60g 同上 同上 同上 同上 實施例14 同上 (P-6,,)0.60g 同上 同上 同上 同上 實施例15 同上 (P-7) 0.60g 同上 同上 同上 同上 實施例16 同上 (P-8) 0.60g 同上 同上 同上 同上 實施例17 同上 (P-9) 0,60g 同上 同上 同上 同上 實施例18 同上 (P-10) 0.60g 同上 同上 同上 同上 實施例19 同上 (P-11) 0.60g 同上 同上 同上 同上 實施例20 同上 (P-12) 0.60g 同上 同上 同上 同上 實施例21 同上 (P-13) 0.60g 同上 同上 同上 同上 實施例22 同上 (P-10,) 0.60g 同上 同上 同上 同上 實施例23 同上 (P-10”) 0.60g 同上 同上 同上 同上 實施例24 同上 (P-12,) 0.60g 同上 同上 同上 同上 實施例25 同上 (P-14) 0.60g 同上 同上 同上 同上 實施例26 同上 (P-15) 0.60g 同上 同上 同上 同上 實施例27 同上 (P-16) 0.60g 同上 同上 同上 同上 實施例28 同上 (P-17) 0.60g 同上 同上 同上 同上 實施例29 同上 (P-18) 0.60g 同上 同上 同上 同上 實施例30 同上 (P-19) 0.6〇g 同上 同上 同上 同上 -210- 1226509 五、發明說明(209 )表-9光阻膜-線與空間 酸發生劑 鹼可溶性樹脂 (d)或(d,) 溶解阻止劑 有機鹼性 化合物 界面活性劑* 實施例31 (m-1) 0.072g (P-20) 0.60g (A-22) 0.18g (42-2) 0.36g B-1 0.002g W-l lOOOppm 實施例32 同上 (P-21) 0.60g 同上 同上 同上 同上 實施例33 同上 (P-22) 0.60g 同上 同上 同上 同上 實施例34 同上 (P-23) 0.60g 同上 同上 同上 同上 實施例35 同上 (P-24 0.60g 同上 同上 同上 同上 實施例36 同上 (P-25) 0.60g 同上 同上 同上 同上 實施例37 同上 (P-26) 0.60g 同上 同上 同上 同上 實施例38 同上 (P-27) 0.60g 同上 同上 同上 同上 實施例39 同上 (P-28) 0.60g 同上 同上 同上 同上 實施例40 同上 (P-29) 0.60g 同上 同上 同上 同上 實施例41 同上 (P-30) 0.60g 同上 同上 同上 同上 實施例42 同上 (P-31) 0.60g 同上 同上 同上 同上 實施例43 同上 (P-32) 0.60g 同上 同上 同上 同上 實施例44 同上 (P-33) 0.60g 同上 同上 同上 同上 實施例45 同上 (P-34) 0.60g 同上 同上 同上 同上 實施例46 同上 (P-35) 0.60g 同上 同上 同上 同上 實施例47 同上 (P-36) 0.60g 同上 同上 同上 同上 實施例48 同上 (P-37) 0.60g 同上 同上 同上 同上 實施例49 同上 (P-38) 0.60g 同上 同上 同上 同上 實施例50 (PAG-1) 0.072g (P-1) 0.60g 同上 同上 同上 同上 比較例1 (1-1) 0.072g P-101 0.78g - (18) 0.36g — — 比較例2 (PAG-1) 0.072g P-102 1.14g - - — - 比較例3 (II-3) 0.072g P-103 0.78g 一 (42) 0.36g — — 比較例4 (PAG-2) 0.072g P-104 0.78g - (42-2) 0.36g — - *對固成分 -211- 1226509 五、發明說明(210)表-1 0光阻膜-線與空間 酸發生劑 鹼可溶性樹脂 (d)或(d,) 溶解阻止劑 有機鹼性化合物 界面活性劑* 實施例51 (m-1) 0.072g (P-1) 〇.78g 無 (42-2) 0.36g B-1 0.002g W-l lOOOppm 實施例52 同上 (P-1) 0.60g (A-22) 0.18g 同上 同上 同上 實施例53 同上 (p-n o.6〇g 同上 同上 同上 同上 實施例54 同上 (P-1,,)0.60g 同上 同上 同上 同上 實施例55 同上 (P-1,,,)0.60g 同上 同上 同上 同上 實施例56 同上 (P-2) 0.60g 同上 同上 同上 同上 實施例57 同上 (P-3) 0.60g 同上 同上 同上 同上 實施例58 同上 (P-3,) 0.60g 同上 同上 同上 同上 實施例59 同上 (P-4) 0.60g 同上 同上 同上 同上 實施例60 同上 (P-5) 0.60g 同上 同上 同上 同上 實施例61 同上 (P-5,,)0.60g 同上 同上 同上 同上 實施例62 同上 (P-6) 0.60g 同上 同上 同上 同上 實施例63 同上 (P-6,) 0.60g 同上 同上 同上 同上 實施例64 同上 (P-6,,)0.60g 同上 同上 同上 同上 實施例65 同上 (P-7) 0.60g 同上 同上 同上 同上 實施例66 同上 (P-8) 0.60g 同上 同上 同上 同上 實施例67 同上 (P-9) 0.60g 同上 同上 同上 同上 實施例68 同上 (P-10) 0.60g 同上 同上 同上 同上 實施例69 同上 (P-11) 0.60g 同上 同上 同上 同上 實施例70 同上 (P-12) 0.60g 同上 同上 同上 同上 實施例71 同上 (P-13) 0.60g 同上 同上 同上 同上 實施例72 同上 (P-10,) 0.60g 同上 同上 同上 同上 實施例73 同上 (P-10,,)0.60g 同上 同上 同上 同上 實施例74 同上 (P-12) 0.60g 同上 同上 同上 同上 實施例75 同上 (P-14) 0.60g 同上 同上 同上 同上 實施例76 同上 (P-15) 0.60g 同上 同上 同上 同上 實施例77 同上 (P-16) 0.60g 同上 同上 同上 同上 實施例78 同上 (P-17) 0.60g 同上 同上 同上 同上 實施例79 同上 (P-18) 0.60g 同上 同上 同上 同上 實施例80 同上 (P-19) 0.60g 同上 同上 同上 同上 *對固成分 -212- 1226509 五、發明說明(211) 表 1光阻膜-線與空間 酸發生劑 鹼可溶性樹脂 (d)或(d,) 溶解阻止劑 有機鹼性 化合物 界面活性劑* 實施例81 (m-1) 0.072g (P-20) 0.60g (A-22) 0.18g (42-2) 0.36g B-1 0.002g W-l lOOOppm 實施例82 同上 (P-21) 0.60g 同上 同上 同上 同上 實施例83 同上 (P-22) 0.60g 同上 同上 同上 同上 實施例84 同上 (P-23) 0.60g 同上 同上 同上 同上 實施例85 同上 (P-24) 0.60g 同上 同上 同上 同上 實施例86 同上 (P-25) 0.60g 同上 同上 同上 同上 實施例87 同上 (P-26) 0.60g 同上 同上 同上 同上 實施例88 同上 (P-27) 0.60g 同上 同上 同上 同上 實施例89 同上 (P-28) 0.60g 同上 同上 同上 同上 實施例90 同上 (P-29) 0.60g 同上 同上 同上 同上 實施例91 同上 (P-30) 0.60g 同上 同上 同上 同上 實施例92 同上 (P-31 0.60g 同上 同上 同上 同上 實施例93 同上 (P-32) 0.60g 同上 同上 同上 同上 實施例94 同上 (P-33) 0.60g 同上 同上 同上 同上 實施例95 同上 (P-34) 0.60g 同上 同上 同上 同上 實施例96 同上 (P-35) 0.60g 同上 同上 同上 同上 實施例97 同上 (P-36) 0.60g 同上 同上 同上 同上 實施例98 同上 (P-37) 0.60g 同上 同上 同上 同上 實施例99 同上 (P-38) 0.60g 同上 同上 同上 同上 實施例100 (PAG-1) 0.072g (P-1) 0.60g 同上 同上 同上 同上 比較例5 (1-1) 0.072g P-101 0.78g (18) 0.36g — - 比較例6 (PAG-1) 0.072g P-102 1.14g — — — - 比較例7 (II-3) 0.072g P-103 0.78g - (42) 0.36g - - 比較例8 (PAG-2) 0.072g P-104 0.78g - (42-2) 0.36g - - *對固成分 -213- 1226509 五、發明說明(212 )表8〜1 1中所使用的簡稱爲下述之內容。 <構成本發明之鹼可溶性樹脂> (P-1) ^CH2CH^ -fCH2CH^Br I CH2CHCH2Br PAG-1: PAG-2: (2) Synthesis of soluble resin (1 ^ 1): 16.4 g (0.1 mol) of 3,4-dimethoxystyrene, 158.7 g (0.9 Moore) Ren 3rd-butoxystyrene is dissolved in dry THF and heated to 701 under a stream of nitrogen, and 2 mole% of the total moles of the above monomers are added. Starter V-60 1. After reaction-206-1226509 V. Description of the invention (205) 8 hours, the reaction solution was diluted with THF, precipitated in hexane, purified, and the polymer was taken out. (P _ 1) is produced by acid decomposition by a common method. The weight average molecular weight (Mw) and molecular weight dispersion (Mw / Mn) were determined by G P C measurement. (1-2) Using the same method as above, and using a protected monomer (example: 4-benzyloxystyrene), cationic polymerization was performed by BF3 · Et〇2 to synthesize (P-1,) , (P-Γ,), (P-2) ~ (P-51). (1-3) Dissolve 1.64 g (0.01 mole) of 3,4-dimethoxystyrene and 15.9 g (0.09 mole) of 4 -3 -butoxystyrene at -78 ° C In dry THF, 1 millimolar 2-butyllithium was used at -78 ° C in a sealed tube, the glass seal was broken, and the reaction was started. The powders concentrated in a large number of hospitals were refined. (P-1 ') was prepared by acid treatment by a conventional method. (3) Synthesis of dissolution preventing compound (Synthesis Example of Dissolution Preventing Compound-1: Synthesis of Compound 18) 42.4 g (0.10 mole) of 1- [α-methyl-α_ (4, -hydroxyphenyl) Ethyl] -4-[α, α'-bis (4 ”-hydroxyphenyl) ethyl] benzene was dissolved in 300 ml of N, N-dimethylacetamide, and 49.5 g (0.35 mole) of carbonic acid was added Potassium and 84.8 g (0. 33 mol) of cumyl bromide bromide were stirred at 120 ° C. for 7 hours. The reaction mixture was poured into 2 L of ion-exchanged water, neutralized with acetic acid, and extracted with ethyl acetate. The ethyl acetate extract was concentrated and purified to obtain 70 g of compound 18 (all R is -CH2COOC (CH3) 2C6H5 group). ○ (Synthesis Example 2 of Dissolution Inhibitor Compound: Synthesis of Compound Example 42) 20 g α, α, α ,, α ', α ,,, α ,,-Lu (4-hydroxyphenyl) -1,3,5--207-1226509 V. Description of the invention (206) Diethylbenzene dissolution Dimethyl ether at 400 m. In this solution, 42.4 g of 3,4-dihydro-2H-pyran under nitrogen atmosphere, add hydrochloric acid in contact with coal, and reflux for 24 hours. After the reaction is completed, add a small amount Hydroxide It was filtered. The filtrate was concentrated and purified by column chromatography to obtain 55.3 g of compound 42 (all R are THP groups). (Synthesis Example 3 of Compound for Dissolution Inhibitor: Compound Example 42-2 Synthesis) 20 g of α, α, α ', α', α ", α" -L (4-hydroxyphenyl) -1,3,5-triethylbenzene was dissolved in 200,001 ^^ dimethyl To acetamide, 28.2 g of potassium carbonate and 3 6.0 g of butyl bromoacetate were added, and the mixture was stirred at 120 ° C. for 7 hours. The reaction product was put into 2 L of ion-exchanged water, and the viscous product was washed with water. 37g of the above-mentioned compound Example 42-2 (all R is -CH2COOC4H9 (t)) was purified by chromatography analysis method. (4) Synthesis example of compound represented by general formula (A) (Synthesis Example-1) A-22 above Synthesis of (benzyloxyethyl vinyl ether) 244 g (2 moles) of benzoic acid was dissolved in 300 ml of toluene, and 320 g of 2-chloroethyl vinyl ether was added, and 88 g of sodium hydroxide and 25 g of tetrahydrofuran were added. Butyl ammonium bromide, 100 g of triethylamine, and heating and stirring at 120 ° C for 5 hours. The reaction solution was washed with water and reduced under pressure I to remove excess 2-ethyl ethyl chloride; (: Hexyl ether and toluene. Since The obtained oil content was distilled off under reduced pressure to obtain 300 g of the desired benzophenoxyethyl vinyl ether. (Synthesis Examples-2 to 8) The synthesis of the above A-23 to A-29 and the above A- 22 The above-mentioned A-23 to A-29 were synthesized in the same manner. 2. Examples [Examples, Comparative Examples]-208-1226509 V. Description of the invention (207) Coating of photoresist 8.2 g of the components shown in Tables 8 to 11 below were dissolved in propylene glycol monomethyl ether acetate 'Oil through a 0.1 m Teflon sprinkler to prepare a photoresist solution. Each sample solution was coated on a silicon wafer using a spin coater, and dried at 120 ° C. for 90 seconds with a vacuum adsorption hot plate to obtain a photoresist film having a thickness of 0.5 // m. Preparation of Photoresist Pattern This photoresist film was irradiated with an electron line scanner (50 kV applied voltage). After the irradiation, each was heated on a 1 1 (TC vacuum adsorption hot plate for 60 seconds', immersed in a 2.38% tetramethylammonium hydroxide (TMAH) aqueous solution for 60 seconds, rinsed with water for 30 seconds, and dried. The obtained contact hole pattern and the cross-sectional shape of the line and space pattern were observed with a scanning electron microscope. (3) Evaluation of sensitivity and resolution The critical resolution (minimum diameter of the hole) of the contact hole pattern was used as the resolution to make the critical The minimum irradiation energy for resolution is used as the sensitivity. Furthermore, the exposure amount for 0. 20 // m-line (line: space = 1: 1) is the sensitivity, and the smallest size that can be resolved at this exposure amount is the resolution. -209-1226509 V. Description of the invention (208) Table-8 Photoresist film-line and space acid generator test soluble resin (d) or (d,) dissolution inhibitor organic alkaline compound surfactant 氺 implementation Example 1 (ΠΙ-1) 0.072g (P-1) 〇.78g None /> w (42-2) 0.36g B-1 0.002g Wl 1000ppm Example 2 Ibid (P-1) 0.60g (A- 22) 0.18g Ibid. Ibid. Example 3 Ibid. (P-1,) 0.60g Ibid. Ibid. Ibid. Example 4 as above (P-1 ,,) 0.60g Ibid. Ibid. Ibid. Example 5 Ibid. (P-1, I.) 0.60g Ibid. Ibid. Ibid. Example 6 Ibid. (P-2) 0.60g Ibid. Ibid. Same as above Example 7 Same as above (P-3) 0.60g Same as above Same as above Same as above Example 8 Same as above (P-3,) 0.60g Same as above Same as above Ibid Example 9 Same as above (P-4) 0.60g Same as above Ibid Same as above Example 10 Same as above (P-5) 0.60g Same as above Same as above Example 11 Same as above (P-5 ,,) 0.60g Same as above Same as above Example 12 Same as above (P-6) 0.60g Same as above Same as above Example 13 Same as above (P -6 ,) 0.60g Ibid. Ibid. Ibid. Example 14 Ibid. (P-6 ,.) 0.60g Ibid. Ibid. Ibid. Example 15 Ibid. (P-7) 0.60g Ibid. Ibid. Ibid. Example 16 Ibid. (P-8 ) 0.60g as above, same as above, Example 17 Same as above (P-9) 0,60g as above, same as above, as above Example 18 as above (P-10) 0.60g, as above, as above, Example 19, above (P-11) 0.60g as above Ibid ibid ibid Example 20 Same as above (P-12) 0.60g Same as above Same as above Example 21 Same as above (P-13) 0.60g Same as above Same as above Example 22 Ibid (P-10,) 0.60g Same as above Same as above Example 23 Same as above (P-10 ”) 0.60g Ibid. Ibid. Ibid. Example 24 Ibid. (P-12,) 0.60g Ibid. Ibid. Ibid. Example 25 Ibid. (P-14) 0.60g Ibid. Ibid. Ibid. Example 26 Ibid. (P- 15) 0.60g, as above, same as above, Example 27, same as above (P-16), 0.60g, as above, same as above, Example 28, as above (P-17), 0.60g, as above, as above, and Example 29, as above (P-18), 0.60g, as above Ibid. Ibid. Example 30 Ibid. (P-19) 0.60 g Ibid. Ibid. Ibid.-210-1226509 V. Description of the invention (209) Table-9 Photoresist film-line and space acid generator alkali-soluble resin (d) or (d,) Dissolution inhibitor organic basic compound surfactant * Example 31 (m-1) 0.072g (P-20) 0.60g (A-22) 0.18g (42-2) 0.36g B-1 0.002 g Wl 1000 ppm Example 32 Ibid (P-21) 0.60 g Ibid Ibid Same as above Example 33 Same as above (P-22) 0.60g Same as above Same as above Same as above Example 34 Same as above (P-23) 0.60g Same as above Ibid Same as above Example 35 Ibid (P-24 0.60g Same as above Ibid Same as above Example 36 Ibid ( P-25) 0.60g Ibid. Ibid. Ibid. Example 37 Ibid. (P-26) 0.60g Ibid. Ibid. Ibid. Example 38 Ibid. (P-27) 0.60g Ibid. Ibid. Ibid. Example 39 Ibid. (P-28) 0.60 g Same as above Same as above Example 40 Same as above (P-29) 0.60 g Same as above Same as above Example 41 Same above (P-30) 0.60 g Same as above Same as above Example 42 Same as above (P-31) 0.60 g Same as above and above Example 43 Ibid. (P-32) 0.60g Ibid. Ibid. Ibid. Example 44 Ibid. (P-33) 0.60g Ibid. Ibid. Ibid. Example 45 Ibid. (P-34) 0.60g Ibid. Ibid. Ibid. Example 46 Ibid. (P-35) 0.60g Ibid. Ibid. Ibid. Example 47 Ibid. (P-36) 0.60g Ibid. Ibid. Ibid. Example 48 Ibid. (P-37) 0.60g Ibid. Ibid. Ibid. Example 49 Same (P-38) 0.60g Ibid. Ibid. Ibid. Example 50 (PAG-1) 0.072g (P-1) 0.60g Ibid. Ibid. Ibid. Comparative Example 1 (1-1) 0.072g P-101 0.78g-( 18) 0.36g — — Comparative Example 2 (PAG-1) 0.072g P-102 1.14g — — — — Comparative Example 3 (II-3) 0.072g P-103 0.78g One (42) 0.36g — — Comparative Example 4 (PAG-2) 0.072g P-104 0.78g-(42-2) 0.36g —-* Constant composition -211-1226509 V. Description of the invention (210) Table-1 0 Photoresist film-line and space acid Generator alkali-soluble resin (d) or (d,) dissolution inhibitor organic basic compound surfactant * Example 51 (m-1) 0.072g (P-1) 〇.78g None (42-2) 0.36g B-1 0.002g Wl 1000ppm Example 52 Ibid. (P-1) 0.60g (A-22) 0.18g Ibid. Ibid. Example 53 Ibid. (Pn 0.6.g Ibid. Ibid. Ibid. Example 54 Ibid. (P- 1 ,,) 0.60g, as above, same as above, Example 55 55, as above (P-1 ,,,) 0.60g, as above, same as above, Example 56, as above (P-2) 0.60g, as above, as above, and Example 57 as above (P- 3) 0.60g Ibid Ibid Ibid Example 58 Same as above (P-3,) 0.60g Same as above Same as above Example 59 Same as above (P-4) 0.60g Same as above Same as above Example 60 60 Same as above (P-5) 0.60g Same as above Same as above Example 61 Same as above (P -5 ,,) 0.60g, as above, same as above, Example 62 62, as above (P-6), 0.60g, as above, same as above, Example 63, as above (P-6,) 0.60g, as above, as above, and above Example 64 as above (P-6) 0.60g Same as above Same as above Example 65 Same as above (P-7) 0.60g Same as above Same as above Example 66 Same as above (P-8) 0.60g Same as above Same as above Example 67 Same as above (P-9) 0.60g Same as above Same as above Example 68 Same as above (P-10) 0.60 g Same as above Same as above Example 69 69 Same as above (P-11) 0.60 g Same as above Same as above Example 70 Same as above (P-12) 0.60 g Same as above and same as above Example 71 Same as above (P-13) 0.60g Same as above Same as above Example 72 Same as above (P-10,) 0.60g Same as above Same as above Example 73 Ibid (P-10,) 0.60g Same as above and same as above 74 Same as above (P-12) 0.60g Same as above Same as above Example 75 75 Same as above (P-14) 0.60g Same as above Same as above Example 76 76 Same as above (P-15) 0.60g Same as above Same as above Example 77 Same as above (P- 16) 0.60g, as above, same as above, Example 78, same as above (P-17), 0.60g, as above, same as above, Example 79, as above (P-18), 0.60g, as above, as above, Example 80, as above (P-19), 0.60g, as above Same as above Same as above * Anti-solid content -212-1226509 V. Description of the invention (211) Table 1 Photoresist film-line and space acid generator alkali-soluble resin (d) or (d,) Dissolution inhibitor interfacial activity of organic alkaline compound Agent * Example 81 (m-1) 0.072g (P-20) 0.60g (A-22) 0.18g (42-2) 0.36g B-1 0.002g Wl 1000ppm Example 82 Ibid (P-21) 0.60 g Same as above Same as above Example 83 Same as above (P-22) 0.60 g Same as above Same as above Example 84 Same as above (P-23) 0.60 g Same as above Same as above Example 85 Same as above (P-24) 0.60 g Same as above and above Example 86 Ibid. (P-25) 0.60 g Ibid. Ibid. Ibid. Example 87 Same as above (P-26) 0.60g Same as above Same as above Ibid Example 88 Same as above (P-27) 0.60g Same as above Ibid Same as above Example 89 Ibid (P-28) 0.60g Same as above Ibid Same as above Example 90 Ibid ( P-29) 0.60g Same as above Same as above Example 91 Same as above (P-30) 0.60g Same as above Same as above Example 92 Ibid (P-31 0.60g Same as above Same as above Example 93 Ibid (P-32) 0.60g Same as above Same as above Example 94 Same as above (P-33) 0.60g Same as above Same as above Example 95 Same as above (P-34) 0.60g Same as above Same as above Example 96 Same as above (P-35) 0.60g Same as above and same as above Example 97 Same as above (P-36) 0.60g Same as above Same as above Example 98 Same as above (P-37) 0.60g Same as above Same as above Example 99 99 Same as above (P-38) 0.60g Same as above Same as above Example 100 (PAG- 1) 0.072g (P-1) 0.60g Ibid. Ibid. Ibid. Comparative Example 5 (1-1) 0.072g P-101 0.78g (18) 0.36g —-Comparative Example 6 (PAG-1) 0.072g P-102 1.14g — — —-Comparative Example 7 (II-3) 0.072g P-103 0.78g-(42) 0.36g--Comparative Example 8 (PAG-2) 0.072g P-104 0.78g-(42-2) 0.36g--* Anti-solid content -213-1226509 V. Description of the invention (212) The abbreviations used in Tables 8 to 11 are as follows. < Alkali-soluble resin constituting the present invention > (P-1) ^ CH2CH ^ -fCH2CH ^
12,00012,000
OCH3 OCH3 OH (P-V) —{-ch2ch)y —(-ch2ch^-OCH3 OCH3 OH (P-V) — {-ch2ch) y — (-ch2ch ^-
11,900 och3 och3 oh (Ρ-Γ) —(-CH2CH-)— -f ch2ch^j-11,900 och3 och3 oh (Ρ-Γ) — (-CH2CH-) — -f ch2ch ^ j-
12,500 och3 och3 oh (P-r) —f-CH2CH^ —(ch2ch-^12,500 och3 och3 oh (P-r) —f-CH2CH ^ — (ch2ch- ^
5,000 och3 och3 oh5,000 och3 och3 oh
(P-2) ^ch2ch)^ —f ch2ch)^-' H3ccA(P-2) ^ ch2ch) ^ --f ch2ch) ^-'H3ccA
OH 11.500OH 11.500
Mw/Mn 1.88 1.89 1.92 1.12 1.79 -214- 1226509 五、發明說明(213Mw / Mn 1.88 1.89 1.92 1.12 1.79 -214-1226509 V. Description of the invention (213
Mw/MnMw / Mn
10,200 1.6910,200 1.69
h3c〇,了 och3 OCH3 OHh3c〇, och3 OCH3 OH
11,000 1.69 h3cct 了 och3 OCH3 OH (P-r) _(.CH2CH)^ -fCH2CH)^11,000 1.69 h3cct och3 OCH3 OH (P-r) _ (. CH2CH) ^ -fCH2CH) ^
10.100 2.1510.100 2.15
h3cct 了 och3 OCH3 OH (P-4) ^ch2ch)^--(ch2ch^h3cct och3 OCH3 OH (P-4) ^ ch2ch) ^-(ch2ch ^
och3 OCH3och3 OCH3
OH (P-5) _^ch2ch^-f ch2ch^-,och3 .OH (P-5) _ ^ ch2ch ^ -f ch2ch ^-, och3.
H3COH3CO
OH (P-5*) —^c^CH^ -fCH2CH·)^ ,och3 〆OH (P-5 *) — ^ c ^ CH ^ -fCH2CH ·) ^, och3 〆
hhCOhhCO
、OH 7,500 2.33 6,800 2.29 5,200 1.63 -215- 1226509 五、發明說明(214OH 7,500 2.33 6,800 2.29 5,200 1.63 -215-1226509 5. Description of the invention (214
Mw/M 门 (P-6) ^ch2ch^--f ch2ch^Mw / M gate (P-6) ^ ch2ch ^-f ch2ch ^
h3cct 丫 '〇ch3 och3h3cct ya '〇ch3 och3
5,900 2.155,900 2.15
OHOH
h3cct 丫 och3 och3h3cct ya och3 och3
11.600 2.1411.600 2.14
OH (P-6^) _^ch2ch)^ -(ch2ch)^OH (P-6 ^) _ ^ ch2ch) ^-(ch2ch) ^
h3cct 了 och3 och3h3cct got och3 och3
9,300 2.549,300 2.54
OH (P~7) _(ch2ch)^ -f ch2ch-/9〇 ,〇ch3 ^OH (P ~ 7) _ (ch2ch) ^ -f ch2ch- / 9〇, 〇ch3 ^
12,500 2.2312,500 2.23
OCH3 OCH3 OH (P-8) _|ch2CH^ —f-CH2CH^-OCH3 OCH3 OH (P-8) _ | ch2CH ^ —f-CH2CH ^-
OH 11,800 2.00 -216- 1226509OH 11,800 2.00 -216- 1226509
12265091226509
1226509 五、發明說明(217)1226509 V. Description of the invention (217)
13,100 2.28 10,300 2.49 11,400 1.68 11,600 2.43 13,000 1.7713,100 2.28 10,300 2.49 11,400 1.68 11,600 2.43 13,000 1.77
Mw Mw/MnMw Mw / Mn
-219- 1226509-219- 1226509
1226509 五、發明說明(219)1226509 V. Description of Invention (219)
Mw Mw/MnMw Mw / Mn
12,700 1.76 9,000 1.90 9,800 1.90 10,700 2.22 -221 - 122650912,700 1.76 9,000 1.90 9,800 1.90 10,700 2.22 -221-1226509
12265091226509
Mw Mw/Mn 11,600 1.91 5.500 2.13 6,100 2.11 4.500 2.13 - 2 2 3 - 1226509Mw Mw / Mn 11,600 1.91 5.500 2.13 6,100 2.11 4.500 2.13-2 2 3-1226509
1226509 五、發明說明(2之3 P-1031226509 V. Description of the invention (2 of 3 P-103
Mw Mw/MnMw Mw / Mn
OH 7,500 2.10 P-104OH 7,500 2.10 P-104
10,000 1.5510,000 1.55
OH OH OH 有機鹼性化合物如下所述。 8-1:2,4,5-三苯基咪唑啉 Β-2: 1,5·二偶氮二環[4,3,0]壬-5-烯 Β-3 : 4-二甲基胺基吡啶 Β-4: 1,8 -二偶氮二環[5,4,0]十一 -7-烯 Β-5 : Ν-環己基-Ν’-嗎啉代乙基硫化尿素 界面活性劑如下所述。 w - 1 :頓龍衣羅魯(譯音)S - 366(頓龍衣(譯音)化學(股)製) W - 2 :梅卡法克(譯音)F 1 7 6 (大曰本油墨(股)製)(氟系) W-3 :梅卡法克(譯音)R08(大日本油墨(股)製)(氟系及聚 石夕氧烷系) W-4 :聚矽氧烷聚合物-KP-341(信越化學工業(股)製) w - 5 :賽氟隆(譯音)S - 3 8 2 (旭玻璃(股)製) - 225 - 1226509 五、發明說明(224) 表12 3 吃阻膜-接觸孔 感度("C/cm2) 解像力(// π〇 圖案輪廓 實施例1 3.5 0.08 矩形 2 2.5 0.09 矩形 3 2.0 0.07 矩形 4 2.5 0.06 矩形 5 2.0 0.05 矩形 6 2.5 0.09 矩形 7 2.0 0.08 矩形 8 2.5 0.07 矩形 9 2.5 0.06 矩形 10 3.5 0.05 矩形 11 3.5 0.05 矩形 12 4.0 0.05 矩形 13 3.5 0.06 矩形 14 3.5 0.06 矩形 15 4.0 0.05 矩形 16 4.5 0.05 矩形 17 2.0 0.05 矩形 18 3.5 0.06 矩形 19 3.5 0.05 矩形 20 2.0 0.06 矩形 21 1.5 0.06 矩形 22 3.5 0.05 矩形 23 2.5 0.05 矩形 24 1.5 0.05 矩形 25 1.5 0.06 矩形 26 2.0 0.05 矩形 27 3.5 0.06 矩形 28 3.5 0.06 矩形 29 3.0 0.05 矩形 30 3.0 0.05 矩形 - 226 - 1226509 五、發明說明(225) 表13光β 且膜-接觸孔 感度(# C/cm2) 解像力(# m) 圖案輪廓 實施例31 3.5 0.04 矩形 32 3.0 0.05 矩形 33 3.5 0.05 矩形 34 3.5 0.06 矩形 35 3.0 0.05 矩形 36 1.0 0.06 矩形 37 1.0 0.05 矩形 38 1.5 0.06 矩形 39 1.5 0.05 矩形 40 1.5 0.06 矩形 41 1.5 0.05 矩形 42 1.0 0.05 矩形 43 1.0 0.05 矩形 44 1.0 0.06 矩形 45 1.0 0.05 矩形 46 1 .0 0.05 矩形 47 1.0 0.05 矩形 48 1 .0 0.05 矩形 49 1.0 0.05 矩形 50 3.5 0.10 矩形 比較例1 5.0 0.15 2 8.0 0.20 3 8.0 0.18 4 4.0 0.25 - 227 - 1226509 五、發明說明(226) 表14光 阻膜-線與空間 感度(# C/cm2) 解像力(ju m) 圖案輪廓 實施例51 2.5 0.07 矩形 52 1.5 0.08 矩形 53 1.0 0.06 矩形 54 1.5 0.05 矩形 55 1 .0 0.04 矩形 56 1.5 0.08 矩形 57 1.0 0.07 矩形 58 1.5 0.06 矩形 59 1.5 0.05 矩形 60 2.5 0.04 矩形 61 2.5 0.04 矩形 62 3.0 0.04 矩形 63 2.5 0.05 矩形 64 2.5 0.05 矩形 65 3.0 0.04 矩形 66 3.5 0.04 矩形 67 1.0 0.04 矩形 68 1.5 0.04 矩形 69 1.5 0.04 矩形 70 1.0 0.05 矩形 71 0.5 0.04 矩形 72 2.5 0.04 矩形 73 1 .5 0.04 矩形 74 0.5 0.04 矩形 75 0.5 0.05 矩形 76 1.0 0.04 矩形 77 2.5 0.05 矩形 78 2.5 0.05 矩形 79 2.0 0.04 矩形 80 2.0 0.04 矩形 - 228 - 1226509 五、發明說明(227) 表1 5光阻膜-線與空間 感度(# C/cm2) 解像力(//m) 圖案輪廓 實施例81 2.5 0.04 矩形 82 2.0 0.04 矩形 83 2.5 0.04 矩形 84 2.5 0.05 矩形 85 2.0 0.04 矩形 86 0.5 0.05 矩形 87 0.5 0.04 矩形 88 0.5 0.05 矩形 89 0.5 0.04 矩形 90 0.5 0.05 矩形 91 0.5 0.04 矩形 92 0.5 0.04 矩形 93 0.5 0.04 矩形 94 0.5 0.05 矩形 95 0.5 0.04 矩形 96 0.5 0.04 矩形 97 0.5 0.04 矩形 98 0.5 0.04 矩形 99 0.5 0.04 矩形 100 2.5 0.08 矩形 比較例5 4.5 0.14 倒錐形、T-Top 6 7.5 0.19 “ 7 7.5 0.17 “ 8 3.5 0.23 倒錐形、膜邊 由表1 2〜1 5之結果可知,本發明正型光阻組成物具有 高感度、高解像力、矩形圖案輪廓良好。OH OH OH Organic basic compounds are described below. 8-1: 2,4,5-triphenylimidazoline B-2: 1,5 · diazobicyclo [4,3,0] non-5-ene B-3: 4-dimethylamine Pyridine B-4: 1,8-diazobicyclo [5,4,0] undec-7-ene B-5: N-cyclohexyl-N'-morpholinoethyl sulfide urea surfactant As described below. w-1: Dun Long Yi Luolu (transliteration) S-366 (Dun Long Yi (transliteration) chemical (stock) system) W-2: Mekafak (transliteration) F 1 7 6 (Da Yueben Ink (stock) )) (Fluorine-based) W-3: Mekafak (translated) R08 (made by Dainippon Ink Co., Ltd.) (fluorine-based and polyoxanthane-based) W-4: polysiloxane polymer- KP-341 (made by Shin-Etsu Chemical Industry Co., Ltd.) w-5: Seflon (transliterated) S-3 8 2 (made by Asahi Glass (Stock))-225-1226509 V. Description of the invention (224) Table 12 3 Eat Resist Film-Contact Hole Sensitivity (" C / cm2) Resolution (// π〇 Pattern Outline Example 1 3.5 0.08 Rectangle 2 2.5 0.09 Rectangle 3 2.0 0.07 Rectangle 4 2.5 0.06 Rectangle 5 2.0 0.05 Rectangle 6 2.5 0.09 Rectangle 7 2.0 0.08 Rectangle 8 2.5 0.07 Rectangle 9 2.5 0.06 Rectangle 10 3.5 0.05 Rectangle 11 3.5 0.05 Rectangle 12 4.0 0.05 Rectangle 13 3.5 0.06 Rectangle 14 3.5 0.06 Rectangle 15 4.0 0.05 Rectangle 16 4.5 0.05 Rectangle 17 2.0 0.05 Rectangle 18 3.5 0.06 Rectangle 19 3.5 0.05 Rectangle 20 2.0 0.06 Rectangle 21 1.5 0.06 Rectangle 22 3.5 0.05 Rectangle 23 2.5 0.05 Rectangle 24 1.5 0.05 Shape 25 1.5 0.06 Rectangle 26 2.0 0.05 Rectangle 27 3.5 0.06 Rectangle 28 3.5 0.06 Rectangle 29 3.0 0.05 Rectangle 30 3.0 0.05 Rectangle-226-1226509 V. Description of the invention (225) Table 13 Light β and film-contact hole sensitivity (# C / cm2) Resolution (# m) Pattern outline example 31 3.5 0.04 Rectangle 32 3.0 0.05 Rectangle 33 3.5 0.05 Rectangle 34 3.5 0.06 Rectangle 35 3.0 0.05 Rectangle 36 1.0 0.06 Rectangle 37 1.0 0.05 Rectangle 38 1.5 0.06 Rectangle 39 1.5 0.05 Rectangle 40 1.5 0.06 Rectangle 41 1.5 0.05 Rectangle 42 1.0 0.05 Rectangle 43 1.0 0.05 Rectangle 44 1.0 0.06 Rectangle 45 1.0 0.05 Rectangle 46 1 .0 0.05 Rectangle 47 1.0 0.05 Rectangle 48 1 .0 0.05 Rectangle 49 1.0 0.05 Rectangle 50 3.5 0.10 Rectangle Comparative Example 1 5.0 0.15 2 8.0 0.20 3 8.0 0.18 4 4.0 0.25-227-1226509 V. Description of the invention (226) Table 14 Photoresist film-line and space sensitivity (# C / cm2) Resolution (ju m) Pattern outline example 51 2.5 0.07 Rectangle 52 1.5 0.08 rectangle 53 1.0 0.06 rectangle 54 1.5 0.05 rectangle 55 1 .0 0.04 rectangle 56 1.5 0.08 rectangle 57 1.0 0.07 rectangle 58 1.5 0. 06 rectangle 59 1.5 0.05 rectangle 60 2.5 0.04 rectangle 61 2.5 0.04 rectangle 62 3.0 0.04 rectangle 63 2.5 0.05 rectangle 64 2.5 0.05 rectangle 65 3.0 0.04 rectangle 66 3.5 0.04 rectangle 67 1.0 0.04 rectangle 68 1.5 0.04 rectangle 69 1.5 0.04 rectangle 70 1.0 0.05 rectangle 71 0.5 0.04 rectangle 72 2.5 0.04 rectangle 73 1 .5 0.04 rectangle 74 0.5 0.04 rectangle 75 0.5 0.05 rectangle 76 1.0 0.04 rectangle 77 2.5 0.05 rectangle 78 2.5 0.05 rectangle 79 2.0 0.04 rectangle 80 2.0 0.04 rectangle-228-1226509 5. Description of the invention (227) Table 1 5 Photoresist Film-Line and Space Sensitivity (# C / cm2) Resolution (// m) Pattern Outline Example 81 2.5 0.04 Rectangle 82 2.0 0.04 Rectangle 83 2.5 0.04 Rectangle 84 2.5 0.05 Rectangle 85 2.0 0.04 Rectangle 86 0.5 0.05 rectangle 87 0.5 0.04 rectangle 88 0.5 0.05 rectangle 89 0.5 0.04 rectangle 90 0.5 0.05 rectangle 91 0.5 0.04 rectangle 92 0.5 0.04 rectangle 93 0.5 0.04 rectangle 94 0.5 0.05 rectangle 95 0.5 0.04 rectangle 96 0.5 0.04 rectangle 97 0.5 0.04 rectangle 98 0.5 0.04 Rectangle 99 0.5 0.04 Rectangle 100 2.5 0.08 Rectangle Comparative Example 5 4.5 0 .14 Inverted tapered, T-Top 6 7.5 0.19 "7 7.5 0.17" 8 3.5 0.23 Inverted tapered, film edge From the results of Table 1 2 ~ 15, it can be seen that the positive photoresist composition of the present invention has high sensitivity, high The resolution and the contour of the rectangular pattern are good.
- 229 - 1226509 五、發明說明(228 ) 另外,藉由使用作爲酸發生劑之通式(I )〜(I I I )所示化 合物、或通式(A - 1 )所示化合物,可更爲提高優異性能。 實施例 1、8、9、18、19、20、23、29、30、39、40、 41、51、58、59、68、69、70、73、79、80、89、90 及 9 1中,有機鹼性化合物由B - 1變更爲B - 2、B - 3、B - 4、B -5予以實施時,可得相同的性能。 而且,實施例 1、8、9、18、19、20、23、29、.3 0、39 、40 、 41 、 51 、 58 、 59 、 68 、 69 、 70 、 73 、 79 、 80 、 89 、 90及91中,界面活性劑由W-1變更爲W-2、W-3、W-4、 W- 5予以實施時,可得相同的性能。 實施例 1、8、9、18、19、20、23、29、30、39、40、 41、51、58、59、68、69、70、73、79、80、89、90 及 9 1中,溶劑改爲丙二醇單甲醚乙酸酯/丙二醇單甲醚 = 80 / 20 (重量比)予以實施時,可得相同的性能。 (4)另外,使表16所示成分溶解於8· 2g丙二醇單甲醚 乙酸酯中’使其以〇 · 1 // m之鐵氟龍過濾器過濾,調製光 阻溶液。 使各試料溶液利用旋轉塗覆器塗覆於矽晶圓上,且在 1 20°C下以真空吸附型熱板乾燥90秒鐘,製得膜厚0 . 5 // m 之光阻膜。 進行與上述相同的照射與顯像,觀察所得接觸孔圖案之 截面形狀。評估方法與上述相同。 - 230 - 1226509 五、發明說明(229) 表16 酸發生劑 黏合劑 有機鹼性化合物 界面活性劑* 實施例101 1-1 0.072g P-41 1.73g B-1 0.002g W-l O.OOlg 實施例102 同上 P-42 同上 同上 同上 實施例103 同上 P-43 同上 同上 同上 實施例104 同上 P-44 同上 同上 同上 實施例105 同上 P-45 同上 同上 同上 實施例106 同上 P-46 同上 同上 同上 實施例107 同上 P-47 同上 同上 同上 實施例108 同上 P-48 同上 同上 同上 實施例109 同上 P-49 同上 同上 同上 實施例110 同上 P-50 同上 同上 同上 實施例111 同上 P-51 同上 同上 同上 實施例112 同上 P-521 同上 同上 同上 實施例113 同上 P-53 同上 同上 同上 實施例114 同上 P-54 同上 同上 同上 實施例115 同上 P-55 同上 同上 同上 實施例116 同上 P-56 同上 同上 同上 實施例117 同上 P-41 同上 B-2 0.002g 同上 實施例118 同上 同上 同上 B-3 0.002g 同上 實施例119 同上 同上 同上 B-4 0.002g 同上 實施例12〇 同上 同上 同上 B-5 0.002g 同上 比較例101 同上 P-111 同上 同上 同上-229-1226509 V. Description of the invention (228) In addition, by using a compound represented by the general formulae (I) to (III) as an acid generator or a compound represented by the general formula (A-1), it can be further improved. Excellent performance. Examples 1, 8, 9, 18, 19, 20, 23, 29, 30, 39, 40, 41, 51, 58, 59, 68, 69, 70, 73, 79, 80, 89, 90, and 9 1 However, when the organic basic compound is changed from B-1 to B-2, B-3, B-4, and B-5, the same performance can be obtained. Furthermore, Examples 1, 8, 9, 18, 19, 20, 23, 29, .3 0, 39, 40, 41, 51, 58, 59, 68, 69, 70, 73, 79, 80, 89, In 90 and 91, when the surfactant is changed from W-1 to W-2, W-3, W-4, and W-5, the same performance can be obtained. Examples 1, 8, 9, 18, 19, 20, 23, 29, 30, 39, 40, 41, 51, 58, 59, 68, 69, 70, 73, 79, 80, 89, 90, and 9 1 However, when the solvent was changed to propylene glycol monomethyl ether acetate / propylene glycol monomethyl ether = 80/20 (weight ratio) and the same performance was obtained. (4) In addition, the components shown in Table 16 were dissolved in 8.2 g of propylene glycol monomethyl ether acetate ', and filtered through a Teflon filter of 0.1 m // to prepare a photoresist solution. Each sample solution was coated on a silicon wafer using a spin coater, and dried on a vacuum adsorption hot plate at 120 ° C for 90 seconds to obtain a photoresist film having a film thickness of 0.5 / m. The same irradiation and development were performed as described above, and the cross-sectional shape of the obtained contact hole pattern was observed. The evaluation method is the same as above. -230-1226509 V. Description of the invention (229) Table 16 Acid generator, binder, organic alkaline compound surfactant * Example 101 1-1 0.072g P-41 1.73g B-1 0.002g Wl O.OOlg Example 102 Same as above P-42 Same as above Example 103 Same as above P-43 Same as above Example 104 Same as above P-44 Same as above Example 105 Same as above P-45 Same as above Example 106 Same as above P-46 Same as above Same as above 107 Same as above P-47 Same as above Example 108 Same as above P-48 Same as above Example 109 Same as above P-49 Same as above Example 110 Same as above P-50 Same as above Example 111 Same above P-51 Same as above Same as above 112 Ibid. P-521 Ibid. Ibid. 113 Id. P-53 Id. Ibid. 114 Id. P-54 Id. Id. 115 Id. P-55 Id. Id. 116 Id. P-56 Id. Id. 117 Same as above P-41 Same as above B-2 0.002g Same as above Example 118 Same as above Ibid B-3 0.002g Same as above Example 119 Same Ditto ditto ditto embodiment 0.002g Example 4 B-12〇 ditto ditto B-5 0.002g Comparative Example P-111 101 ditto ditto
-231 - 1226509-231-1226509
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1226509 五、發明說明(236) 表17 感度(# C/cm2) 解像力(U m) 圖案輪廓 實施例101 4.5 0.11 矩形 102 5.0 0.12 矩形 103 4.0 0.11 矩形 104 4.5 0.12 矩形 105 4.0 0.11 矩形 106 5.0 0.12 矩形 107 4.5 0.11 矩形 108 5.0 0.11 矩形 109 5.0 0.11 矩形 110 5.0 0. 11 矩形 111 4.5 0.11 矩形 112 4.5 0.11 矩形 113 5.0 0.12 矩形 114 4.0 0.11 矩形 115 5.0 0.11 矩形 116 5.0 0.12 矩形 117 5.0 0.11 矩形 118 5.0 0.11 矩形 119 5.0 0.12 矩形 120 5.0 0.11 矩形 比較例101 10.0 0.15 庇 - 2 3 8 -1226509 V. Description of the invention (236) Table 17 Sensitivity (# C / cm2) Resolution (U m) Pattern outline example 101 4.5 0.11 Rectangle 102 5.0 0.12 Rectangle 103 4.0 0.11 Rectangle 104 4.5 0.12 Rectangle 105 4.0 0.11 Rectangle 106 5.0 0.12 Rectangle 107 4.5 0.11 rectangle 108 5.0 0.11 rectangle 109 5.0 0.11 rectangle 110 5.0 0. 11 rectangle 111 4.5 0.11 rectangle 112 4.5 0.11 rectangle 113 5.0 0.12 rectangle 114 4.0 0.11 rectangle 115 5.0 0.11 rectangle 116 5.0 0.12 rectangle 117 5.0 0.11 rectangle 118 5.0 0.11 rectangle 119 5.0 0.12 Rectangle 120 5.0 0.11 Rectangle Comparative Example 101 10.0 0.15 Py-2 3 8-
1226509 五、發明說明(237 ) 由表1 7可知,本發明組成物之評估項目皆優異。 (5 )藉由等倍X線曝光之圖案化 各使用上述實施例2 〇與比較例丨與2之光阻組成物, 以與上述(1 )相同的方法製得膜厚〇 . 4〇 // m之光阻膜。然 後’除使用等倍X光照射裝置(間隙値;2 0 n m )外,與上述 (2 )相同地進行圖案化,以與上述(3 )相同的方法評估光阻 性能(感度、解像力、及圖案型狀)。評估結果如表1 8所 /R ° 表18 _光阻組成物 感度(mJ /cm2) 解像力(# m) 圖案形狀 *施例20 70 0.10 矩形 上匕較例1 180 0.18 錐形形狀、凹槽 上匕較例2 230 0.17 錐形形狀 由表1 8可知,本發明之光阻組成物於X線曝光中具有 極爲優異的性能。 【發明效果】 本發明係提供一種於製造半導體裝置中可提高化學放大 型光阻之解像力、特別是可抑制孤立線飛離情形的光阻組 成物、或高感度、高解像力、輪廓形狀佳的正型電子線或 X線光阻組成物。 - 2 3 9 -1226509 V. Description of the invention (237) It can be seen from Table 17 that the evaluation items of the composition of the present invention are all excellent. (5) The patterning by equal-time X-ray exposure each uses the photoresist composition of Example 20 and Comparative Examples 丨 and 2 described above to obtain a film thickness of 0.40 / in the same manner as in (1) above. / m of photoresist film. Then 'except for using an equal magnification X-ray irradiation device (gap 2; 20 nm), patterning was performed in the same manner as in (2) above, and the photoresist performance (sensitivity, resolution, and Pattern shape). The evaluation results are shown in Table 1 / R ° Table 18 _Photoresist composition sensitivity (mJ / cm2) Resolution (# m) Pattern shape * Example 20 70 0.10 Comparative example of a rectangular upper blade 1 180 0.18 Conical shape, groove Comparative Example 2 of the upper dagger 230 230 0.17 It can be seen from Table 18 that the photoresist composition of the present invention has extremely excellent performance in X-ray exposure. [Effects of the Invention] The present invention provides a photoresist composition capable of improving the resolution of a chemically amplified photoresist, particularly a photoresist composition capable of inhibiting the flying away of an isolated line, or a high-sensitivity, high-resolution, and excellent-profile-shaped semiconductor semiconductor device. Positive electron wire or X-ray photoresist composition. -2 3 9-
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CN108241257A (en) * | 2016-12-27 | 2018-07-03 | 奇美实业股份有限公司 | Chemically amplified positive photosensitive resin composition, method for producing substrate with mold, and method for producing molded article by plating |
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JP6003833B2 (en) * | 2013-07-10 | 2016-10-05 | 信越化学工業株式会社 | Positive resist material, polymerizable monomer, polymer compound and pattern forming method using the same |
KR102114116B1 (en) * | 2018-06-15 | 2020-05-22 | 인하대학교 산학협력단 | Resist materials comprising highly fluorinated polymers having a solubility in highly fluorinated solvents |
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KR100302651B1 (en) * | 1992-10-21 | 2001-11-22 | 무네유키 가코우 | Positive photosensitive composition |
DE4405108A1 (en) * | 1993-02-18 | 1994-08-25 | Fuji Photo Film Co Ltd | Positive-working photosensitive composition |
JP3297199B2 (en) * | 1993-09-14 | 2002-07-02 | 株式会社東芝 | Resist composition |
JP3743986B2 (en) * | 1996-04-09 | 2006-02-08 | Jsr株式会社 | Radiation sensitive resin composition |
JPH1090882A (en) * | 1996-09-17 | 1998-04-10 | Fuji Photo Film Co Ltd | Chemical amplification type positive resist composition |
JP3720970B2 (en) * | 1998-01-13 | 2005-11-30 | 株式会社東芝 | Photosensitive composition, pattern forming method using the same, and method for manufacturing semiconductor device |
JP2000019732A (en) * | 1998-06-29 | 2000-01-21 | Toshiba Corp | Polymer for photosensitive composition and pattern forming method using it |
JP3504156B2 (en) * | 1998-09-24 | 2004-03-08 | 株式会社東芝 | Semiconductor device manufacturing method, photosensitive composition and pattern forming method |
JP2000122283A (en) * | 1998-10-09 | 2000-04-28 | Mitsubishi Electric Corp | Resist material, photosensitive resin composition using the material, and method for using the composition for production of semiconductor device |
JP4007570B2 (en) * | 1998-10-16 | 2007-11-14 | 富士フイルム株式会社 | Positive resist composition |
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CN108241257B (en) * | 2016-12-27 | 2022-11-08 | 奇美实业股份有限公司 | Chemically amplified positive photosensitive resin composition, method for producing substrate with mold, and method for producing molded article by plating |
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