200538888 九、發明說明： 【發明所屬之技術領域】 本發明係相關於從積體電路元件、濾色片、液晶顯示元 件等的基板或光阻塗布裝置，溶解或剝離去除不需的硬化 及未硬化光阻、抗反射膜等所需的微影用洗淨劑及沖洗液。 ^ 【先前技術】 ' 以往，爲了要製造積體電路元件、濾色片、液晶顯示元 件等，而使用微影技術。使用微影技術的積體電路元件等 之製造，例如依需求在基板上形成抗反射膜後，塗布正型 ® 或負型光阻，經由烘烤去除溶劑後依需求在光阻上形成抗 反射膜，藉由紫外線、遠紫外線、電子射線、X線等各種 放射線進行曝光，顯像後形成光阻圖案。 上述光阻等的塗布係採用旋轉塗布、輥塗、逆塗布、流 延塗布、塗膠塗布、浸漬塗布等各種公知的方法，例如製 造積體電路元件時，光阻塗布法係主要採用旋轉塗布法。 旋轉塗布法係將光阻溶液滴於基板上，此滴落的光阻溶液 因基板的旋轉而流向基板外緣方向，過剩的光阻溶液係從 ® 基板外緣飛散而去除，形成具有期望的膜厚度的光阻。 惟，此時部分的光阻溶液流至基板的背面、或殘留在基 板外緣的光阻溶液較其他部分厚亦即形成粒狀物等缺點， 爲要去除粒狀物必須從基板側面周圍或裡面去除多餘的光 阻溶液。此現象不僅發生於積體電路元件的製造，亦發生 於濾色片、液晶顯示元件等的製造。又，除旋轉塗布法之 外的塗布方法亦和旋轉塗布法相同，有光阻附著於不需要 的部分之現象。 200538888 又，積體電路元件的基板和光阻之間具有反射膜時，形 成圖案後必須去除抗反射膜。因光阻溶液附著於塗布裝 置，故下回使用前必須先洗淨塗布裝置。 上述問題的解決方法，例如特公平4-4993 8號公報的實 例中，使用由丙二醇甲醚和丙二醇甲醚乙酸酯的比例爲1 : 1的混合物組成之剝離劑，使光阻層脫離之方法。 特開平6-3 24499號公報的實例中，使用由β型丙二醇一 甲醚乙酸酯組成的洗淨去除光阻用溶劑，及以β型丙二醇 一甲醚乙酸酯爲主成分且含α型丙二醇一甲醚乙酸酯的洗 淨去除用溶劑，去除多餘的光阻形成用塗布物。 特開200 1 - 1 1 7242號公報的實例中，使用1，3-丙二醇甲醚 或1,3-丙二醇甲醚乙酸酯作爲洗淨劑以去除多餘的光阻。 又，特開200 1 - 1 1 7 24 1號公報的實例中，使用1，3-丙二醇甲 醚或1，3-丙二醇甲醚乙酸酯和水的混合液作爲沖洗液以去 除多餘的光阻。 惟，上述的溶劑或溶劑組成物對於光阻的溶解性、剝離 性不足，且須較長的溶解時間等缺點不利於實用性。 [專利文獻1]特公平4-49938號公報 [專利文獻2]特開平6-324499號公報 [專利文獻3]特開200 1 -1 1 7242號公報 [專利文獻4]特開200 1 - 1 1 724 1號公報 【發明內容】 發明所欲解決的問顆 本發明的目的係提供不具上述缺點，對由有機溶劑溶液 形成的光阻或抗反射膜及由水溶液形成的抗反射膜具有良 200538888 好的溶解性、剝離性之微影用洗淨劑及沖洗液。 本發明的其他目的，係提供除具有上述特性之外又具改 善火災的危險性、操作性優異之微影用沖洗液。 解決問顆的方法 本案發明者們經硏究的結果，發現藉由組合特定的有機 溶劑或特定多數的有機溶劑，或上述溶劑與水的混合液， 可完成上述目的而達成本發明。 亦即’本發明係提供包含至少1種選自（a 1)烷基的碳數爲 2以上之一丙二醇一烷基醚、（a2)—丙二醇二烷基醚、（a3) 二或三丙二醇烷基醚、（a4) —、二或三丙二醇芳基醚、 (&5)1，3-丁二醇或丙三醇的烷基醚、（1)1)烷基的碳數爲2以 上之α型一丙二醇烷基醚乙酸酯、（b2)二或三丙二醇烷基 醚乙酸酯、（b3)—、二或三丙二醇芳基醚乙酸酯、（b4)l，3-丁二醇或丙三醇的烷基醚乙酸酯、及（b5)C3.4鏈烷多醇乙酸 酯等有機溶劑作爲主成分之微影用洗淨劑。 此微影用洗淨劑的理想樣態，係包含至少1種醚類選自 (al)烷基的碳數爲2以上之一丙二醇一烷基醚、U2)—丙二 醇二烷基醚、（a3)二或三丙二醇烷基醚、U4)—、二或三丙 二醇芳基醚、及（a5)l，3 -丁二醇或丙三醇的烷基醚’和至少 1種乙酸酯類選自（bl，）一丙二醇烷基醚乙酸酯、（b2)二或三 丙二醇烷基醚乙酸酯、（b3)—、二或三丙二醇芳基醚乙酸 酯、（b4)l，3-丁二醇或丙三醇的烷基醚乙酸酯、及（b5)C3·4 鏈烷多醇乙酸酯作爲主成分。 又，上述微影用洗淨劑的其他理想樣態’係包含至少1種 醚類選自（al，）一丙二醇一烷基醚、（a2) 一丙二醇二烷基 200538888 醚、（a3)二或三丙二醇烷基醚、（a4) —、二或三丙二醇芳基 醚、及（a5)l，3-丁二醇或丙三醇的烷基醚，和至少1種乙酸 醋類選自（bl)院基的碳數爲2以上之α型一'丙二醇院基釀 乙酸酯、（b 2)二或三丙二醇烷基醚乙酸酯、（b 3)—、二或三 丙二醇芳基醚乙酸酯、（b4)l，3-丁二醇或丙三醇的烷基醚乙 • 酸酯、及（b5)C^4鏈烷多醇乙酸酯作爲主成分。 * 本發明尙提供一種微影用沖洗液，其特徵係使上述微影 用洗淨劑中含有水而形成均質溶液。 又，本詳細說明書中若無特別說明，「丙二醇」係包含 ® α型丙二醇（1，2-丙二醇）及β型丙二醇（1，3-丙二醇）。 發明的效果 本發明的微影用洗淨劑及沖洗液，不僅對由有機溶劑溶 液形成的光阻或抗反射膜等，對由水溶液形成的抗反射膜 亦具有良好的溶解性、剝離性。又，本發明的微影用沖洗 液已改善火災的危險性、且操作性優異。 【實施方式】 實施發明之最佳形態 φ 本發明的微影用洗淨劑係含有至少1種有機溶劑選自（a 1) 烷基的碳數爲2以上之一丙二醇一烷基醚、（a2)—丙二醇二 烷基醚、U3)二或三丙二醇烷基醚、（a4)—、二或三丙二醇 芳基醚、U5) 1,3-丁二醇或丙三醇的烷基醚、（bl)烷基的碳 數爲2以上之ex型一丙二醇烷基醚乙酸酯、（b2)二或三丙 二醇烷基醚乙酸酯、（b 3)—、二或三丙二醇芳基醚乙酸酯、 (b4)l，3_ 丁二醇或丙三醇的烷基醚乙酸酯、及（b5)C3.4鏈烷 多醇乙酸酯等作爲主成分。 可分別單獨使用這些有機溶劑或以任何的比例混合2種 ⑧ 200538888 以上而使用。特別是分別含至少1種選自上述U1)〜（a5)的 醚類和上述（bl)〜（b5)的乙酸酯類之混合系較理想。又，上 述各有機溶劑中的「烷基」例如甲基、乙基、丙基、丁基 等碳數1〜4的直鏈狀或分枝鏈狀烷基較理想。又，「芳基」 例如苯基、萘基等碳數6〜1 0的芳基較理想。 上述烷基的碳數爲2以上的一丙二醇一烷基醚（ai)，例如 丙二醇-1-乙醚、丙二醇-1-丙醚、丙二醇-1-丁醚等一丙二醇 一烷基醚（特別是烷基的碳數爲3或4的一丙二醇一烷基醚） 等。其中又以α型一丙二醇一烷基醚較理想。 上述一丙二醇二烷基醚（a2)，例如丙二醇二甲醚、丙二醇 甲基乙醚、丙二醇甲基丙醚、丙二醇甲基丁醚、丙二醇二 乙醚、丙二醇乙基丙醚、丙二醇乙基丁醚、丙二醇二丙醚、 丙二醇丙基丁醚、丙二醇二丁醚等。 上述二或三丙二醇烷基醚U3)中，二丙二醇烷基醚例如二 丙二醇-1-甲醚、二丙二醇乙醚、二丙二醇-1β丙醚、二丙 二醇-1-丁醚等二丙二醇一烷基醚；二丙二醇二甲醚、二丙200538888 IX. Description of the invention: [Technical field to which the invention belongs] The present invention relates to a substrate or a photoresist coating device for integrated circuit elements, color filters, liquid crystal display elements, etc., to dissolve or peel off unnecessary hardening and Detergents and rinsing liquids for lithography required for curing photoresist and anti-reflection film. ^ [Prior art] 'In the past, lithography was used to manufacture integrated circuit elements, color filters, liquid crystal display elements, and so on. Manufacture of integrated circuit components using lithography technology, for example, after forming an anti-reflection film on a substrate as required, apply positive or negative photoresist, and remove the solvent through baking to form antireflection on the photoresist as required The film is exposed to various radiations such as ultraviolet rays, extreme ultraviolet rays, electron rays, and X-rays, and a photoresist pattern is formed after development. The above-mentioned photoresist is applied by various known methods such as spin coating, roll coating, reverse coating, cast coating, gluing coating, and dip coating. For example, when manufacturing integrated circuit components, the photoresist coating method mainly uses spin coating. law. The spin coating method drops a photoresist solution onto a substrate. The dropped photoresist solution flows toward the outer edge of the substrate due to the rotation of the substrate. The excess photoresist solution is scattered from the outer edge of the ® substrate and removed to form the desired Film thickness photoresist. However, at this time, a part of the photoresist solution flows to the back of the substrate, or the photoresist solution remaining on the outer edge of the substrate is thicker than the other parts, that is, to form particles. In order to remove the particles, it must be removed from around the side of the substrate or Remove excess photoresist solution inside. This phenomenon occurs not only in the manufacture of integrated circuit elements, but also in the manufacture of color filters, liquid crystal display elements, and the like. In addition, the coating method other than the spin coating method is the same as the spin coating method, and a photoresist may adhere to an unnecessary portion. 200538888 In addition, if there is a reflective film between the substrate of the integrated circuit element and the photoresist, the anti-reflection film must be removed after patterning. Since the photoresist solution is attached to the coating device, the coating device must be washed before the next use. The solution to the above problem, for example, in the example of Japanese Patent Publication No. 4-4993 8, uses a release agent composed of a mixture of propylene glycol methyl ether and propylene glycol methyl ether acetate at a ratio of 1: 1 to release the photoresist layer. method. In the example of Japanese Patent Application Laid-Open No. 6-3 24499, a solvent for photoresist removal using β-propylene glycol monomethyl ether acetate is used for cleaning, and β-propylene glycol monomethyl ether acetate is the main component and contains α Type propylene glycol monomethyl ether acetate is used as a solvent for cleaning and removal to remove excess photoresist-forming coatings. In the example of JP-A No. 200 1-1 1 7242, 1,3-propanediol methyl ether or 1,3-propanediol methyl ether acetate is used as a cleaning agent to remove excess photoresist. Also, in the example of JP-A-200 1-1 1 7 24 1, a mixture of 1,3-propanediol methyl ether or 1,3-propanediol methyl ether acetate and water is used as a rinse solution to remove excess light. Resistance. However, the above-mentioned solvents or solvent compositions are inadequate in solubility and peelability with respect to photoresist, and have disadvantages such as a long dissolution time, which are disadvantageous in practicality. [Patent Document 1] JP 4-49938 [Patent Document 2] JP 6-324499 [Patent Document 3] JP 200 1 -1 1 7242 [Patent Document 4] JP 200 1-1 1 724 Publication No. 1 [Summary of the Invention] The object of the present invention is to provide a photoresist or antireflection film formed of an organic solvent solution and an antireflection film formed of an aqueous solution without the above disadvantages. 200538888 Good solubility and peeling lithographic cleaning agent and rinse solution. Another object of the present invention is to provide a lithographic washing solution which has the above-mentioned characteristics and has the advantages of improving fire hazard and excellent operability. Method for solving the problem As a result of intensive research, the inventors of the present case found that by combining a specific organic solvent or a specific majority of organic solvents, or a mixture of the above-mentioned solvent and water, the above-mentioned object can be achieved and the invention can be achieved. That is, the present invention provides at least one kind of propylene glycol monoalkyl ether having a carbon number of 2 or more selected from (a 1) alkyl groups, (a2) -propylene glycol dialkyl ether, (a3) di- or tripropylene glycol Alkyl ethers, (a4)-, di- or tripropylene glycol aryl ethers, (& 5) alkyl ethers of 1,3-butanediol or glycerol, (1) 1) alkyl groups have 2 carbon atoms Alpha type monopropylene glycol alkyl ether acetate, (b2) di- or tripropylene glycol alkyl ether acetate, (b3)-, di- or tripropylene glycol aryl ether acetate, (b4) 1, 3- An organic solvent such as butanediol or glycerol alkyl ether, and (b5) C3.4 alkane alcohol acetate, and other organic solvents as a main component of a lithographic cleaner. The ideal aspect of this lithographic detergent comprises at least one ether selected from the group consisting of (al) alkyl carbon number one or more propylene glycol monoalkyl ether, U2) -propylene glycol dialkyl ether, ( a3) di or tripropylene glycol alkyl ether, U4) —, di or tripropylene glycol aryl ether, and (a5) 1,3-butanediol or glycerol alkyl ether 'and at least one acetate From (bl,) monopropylene glycol alkyl ether acetate, (b2) di or tripropylene glycol alkyl ether acetate, (b3)-, di or tripropylene glycol aryl ether acetate, (b4) 1, 3 -Alkyl ether acetates of butanediol or glycerol, and (b5) C3 · 4 alkanol acetates as main components. In addition, the above-mentioned other ideal aspect of the lithographic detergent includes at least one ether selected from (al,) propylene glycol monoalkyl ether, (a2) propylene glycol dialkyl 200538888 ether, and (a3) diamine. Or tripropylene glycol alkyl ether, (a4)-, di or tripropylene glycol aryl ether, and (a5) 1,3-butanediol or glycerol alkyl ether, and at least one acetate is selected from ( bl) Alpha -'- propylene glycol courtyard-based acetate with a carbon number of 2 or more, (b 2) di- or tri-propylene glycol alkyl ether acetate, (b 3)-, di- or tri-propylene glycol aryl Ether acetate, (b4) alkyl ether acetate of 1,3-butanediol or glycerol, and (b5) C ^ 4 alkane polyol acetate are main components. * The present invention provides a lithographic rinse solution, which is characterized in that the above-mentioned lithographic detergent contains water to form a homogeneous solution. In addition, unless otherwise specified in this detailed description, "propylene glycol" includes ® α-propylene glycol (1,2-propanediol) and β-propylene glycol (1,3-propanediol). Effects of the Invention The cleaning agent and rinsing liquid for lithography of the present invention have good solubility and peelability not only for photoresist or antireflection film formed from an organic solvent solution, but also for antireflection film formed from an aqueous solution. Further, the lithographic rinsing liquid of the present invention has improved the danger of fire and is excellent in operability. [Embodiment] The best mode for carrying out the invention φ The cleaning agent for lithography of the present invention contains at least one organic solvent selected from (a 1) propylene glycol monoalkyl ether having a carbon number of 2 or more alkyl groups, ( a2) —propylene glycol dialkyl ether, U3) di or tripropylene glycol alkyl ether, (a4) —, di or tripropylene glycol aryl ether, U5) 1,3-butanediol or glycerol alkyl ether, (Bl) ex-type monopropylene glycol alkyl ether acetate having an alkyl group of 2 or more carbon atoms, (b2) di- or tripropylene glycol alkyl ether acetate, (b 3)-, di- or tripropylene glycol aryl ether Acetate, (b4) alkyl ether acetate of 1,3-butanediol or glycerol, and (b5) C3.4 alkane polyol acetate and the like are main components. These organic solvents can be used individually or as a mixture of two or more 38 200538888 at any ratio. In particular, a mixed system containing at least one ether selected from the above U1) to (a5) and the acetates (bl) to (b5), respectively, is preferable. The "alkyl" in each of the organic solvents is preferably a linear or branched alkyl group having 1 to 4 carbon atoms, such as methyl, ethyl, propyl, or butyl. The "aryl" is preferably an aryl group having 6 to 10 carbon atoms such as a phenyl group and a naphthyl group. Monopropylene glycol monoalkyl ether (ai) having a carbon number of 2 or more, such as monopropylene glycol monoalkyl ether such as propylene glycol-1-ether, propylene glycol-1-propyl ether, and propylene glycol-1-butyl ether (especially Monopropylene glycol monoalkyl ether having 3 or 4 carbon atoms; and the like. Among them, α-propylene glycol monoalkyl ether is more preferable. The monopropylene glycol dialkyl ether (a2) is, for example, propylene glycol dimethyl ether, propylene glycol methyl ether, propylene glycol methyl propyl ether, propylene glycol methyl butyl ether, propylene glycol diethyl ether, propylene glycol ethyl propyl ether, propylene glycol ethyl butyl ether, Propylene glycol dipropyl ether, propylene glycol propyl butyl ether, propylene glycol dibutyl ether, and the like. Among the above di- or tripropylene glycol alkyl ethers U3), dipropylene glycol alkyl ethers such as dipropylene glycol-1-methyl ether, dipropylene glycol ethyl ether, dipropylene glycol-1 β propyl ether, dipropylene glycol monobutyl ether and the like Ether; dipropylene glycol dimethyl ether, dipropylene
二醇甲基乙醚、二丙二醇甲基丙醚、二丙二醇甲基丁醚、 二丙二醇二乙醚、二丙二醇乙基丙醚、二丙二醇乙基丁醚、 二丙二醇二丙醚、二丙二醇丙基丁醚、二丙二醇二丁醚等 三丙二醇烷基醚，例如三丙二醇-丨_甲醚、三丙二醇-^ 乙醚、三丙二醇-1-丙醚、三丙二醇- ；l -丁醚等三丙二醇一烷 基醚；三丙二醇二甲醚、三丙二醇甲基乙醚、三丙二醇甲 基丙醚、三丙二醇甲基丁醚、三丙二醇二乙醚、三丙二醇 乙基丙醚、三丙二醇乙基丁醚、三丙二醇二丙醚、三丙二 200538888 醇丙基丁醚、三丙二醇二丁醚等三丙二醇二烷基醚。 上述一、二或三丙二醇芳基醚（a4)中，一丙二醇芳基 如丙二醇一苯基醚等一丙二醇一芳基醚；丙二醇二苯 等一丙二醇二芳基醚。二丙二醇芳基醚例如二丙二醇 基醚等二丙二醇一芳基醚；二丙二醇二苯基醚等二丙 '二芳基醚。三丙二醇芳基醚例如三丙二醇一苯基醚等 二醇一芳基醚；三丙二醇二苯基醚等三丙二醇二芳基 上述1，3-丁二醇或丙三醇的烷基醚（a5)中，1，3-丁二 g 基醚例如可使用任一種一烷基醚和二烷基醚。一烷基 如1，3-丁二醇一甲醚、1，3-丁二醇一乙醚、1，3-丁二醇 醚、1，3-丁二醇一丁醚等。二烷基醚例如與上述1，3-丁 一烷基醚對應的1,3-丁二醇二烷基醚（2個烷基可爲相 相異）。 丙三醇烷基醚包含丙三醇一烷基醚、丙三醇二烷基 丙三醇三烷基醚。丙三醇烷基醚的代表例，例如丙三 甲醚、丙三醇二甲醚、丙三醇三甲醚、丙三醇一乙醚 三醇二乙醚、丙三醇三乙醚、丙三醇一丙醚、丙三醇 ®醚、丙三醇三丙醚、丙三醇一丁醚、丙三醇二丁醚、 醇三丁醚等。 上述烷基的碳數爲2以上之α型一丙二醇烷基醚乙 (bl)，例如ex型丙二醇乙醚乙酸酯、α型丙二醇丙醚乙酉 α型丙二醇丁醚乙酸酯等α型一丙二醇C2.4烷基醚乙 (特別是α型一丙二醇C3.4烷基醚乙酸酯）等。 上述二或三丙二醇烷基醚乙酸酯（b 2)中，二丙二醇 醚乙酸酯例如二丙二醇甲醚乙酸酯、二丙二醇乙醚 醚例 基醚 一苯 二醇 三丙 醇烷 醚例 一丙 二醇 同或 醚、 醇一 、丙 二丙 V-Γ f * 丙二 酸酯 隻酯、 酸酯 垸基 乙酸 ⑧ -10- 200538888 酯、二丙二醇丙醚乙酸酯、二丙二醇丁醚乙酸酯等。 三丙二醇烷基醚乙酸酯，例如三丙二醇甲醚乙酸酯、三 丙二醇乙醚乙酸酯、三丙二醇丙醚乙酸酯、三丙二醇丁醚 乙酸酯等。 上述一、二或三丙二醇芳基醚乙酸酯（b3)，例如丙二醇 ‘苯醚乙酸酯、二丙二醇苯醚乙酸酯、三丙二醇苯醚乙酸酯 等。 上述1,3-丁二醇或丙三醇的烷基醚乙酸酯（b4)中，1，3-丁 g 二醇烷基醚乙酸酯例如1，3-丁二醇甲醚乙酸酯、1，3-丁二醇 乙醚乙酸酯、1,3-丁二醇丙醚乙酸酯、1，3-丁二醇丁醚乙酸 酯等。丙三醇烷基醚乙酸酯例如丙三醇一甲醚乙酸酯、丙 三醇一乙醚乙酸酯、丙三醇一丙醚乙酸酯、丙三醇二甲醚 乙酸酯、丙三醇二乙醚乙酸酯、丙三醇二丙醚乙酸酯等。 上述〇3·4鏈烷多醇乙酸酯（b 5)中，碳數爲3或4的鏈烷多 醇的乙酸酯，例如包括1，2·丙二醇乙酸酯、1，3 -丙二醇乙酸 酯、1，3-丁二醇乙酸酯、丙三醇乙酸酯等。1，2-丙二醇乙酸 酯例如1,2 -丙二醇一乙酸酯、1,2-丙二醇二乙酸酯。1,3 -丙 ® 二醇乙酸酯例如1,3-丙二醇一乙酸酯、1,3 -丙二醇二乙酸 酯。1,3-丁二醇乙酸酯例如l，3-丁二醇一乙酸酯、1,3-丁二 醇二乙酸酯。丙三醇乙酸酯例如丙三醇一乙酸酯、丙三醇 二乙酸酯、丙三醇三乙酸酯。 其中，特別理想的有機溶劑例如丙二醇-1 -丙醚等一丙二 醇一 Cm烷基醚；丙二醇二丙醚等一丙二醇二Cm烷基醚； 二丙二醇-1-甲醚、二丙二醇二甲醚、三丙二醇-丨-丁醚等二 或三丙二醇一或二Ci·4烷基醚；丙二醇一苯醚等一、二或 -11- 200538888 三丙二醇一或二苯醚；1，3 丁二醇-1-乙醚、1，3 丁二醇二乙 醚等1，3 丁二醇一或二Ch烷基醚；丙三醇-1-甲醚、丙三 醇-1，2-二甲醚、丙三醇三甲醚等丙三醇的一、二或三Cm 烷基醚；ex型丙二醇-1-丙醚乙酸酯等α型一丙二醇C2.4烷 基醚乙酸酯（特別是α型一丙二醇C3.4烷基醚乙酸酯）；二丙 二醇-1-甲醚乙酸酯、三丙二醇-1-丁醚乙酸酯等二或三丙二 醇Cm烷基醚乙酸酯；丙二醇-1-苯醚乙酸酯等一、二或三 丙二醇苯醚乙酸酯；1，3-丁二醇-1·乙醚乙酸酯等ι，3-丁二 g 醇或丙三醇的Cm烷基醚乙酸酯類；1，3-丁二醇二乙酸酯、 丙三醇三乙酸酯等C 3.4鏈烷多醇的一、二或三乙酸酯等。 單獨使用且具優良效果的溶劑，例如二丙二醇-1-甲醚、 二丙二醇二甲醚等二丙二醇一或二Cl_4烷基醚；1，3 丁二醇 二乙醚等1，3 丁二醇二Cm烷基醚；丙三醇-1-甲醚、丙三 醇-1，2·二甲醚、丙三醇三甲醚等丙三醇的一、二或三Cm 院基醚；α型丙一醇-1-丙醚乙酸醋等α型一丙二醇C2.4焼 基醚乙酸酯（特別是（X型一丙二醇c3.4烷基醚乙酸酯）；1,3-丁二醇-1-乙醚乙酸酯等1，3-丁二醇烷基醚乙酸酯；1，3-® 丁二醇二乙酸酯、丙三醇三乙酸酯等C3.4鏈烷多醇的二或 三乙酸酯等。 倂用2種以上的有機溶劑時，較理想的組合例如（1)至少 一種醚類選自（al)烷基的碳數爲2以上之一丙二醇一烷基 醚、（a2)—丙二醇二烷基醚、（a3)二或三丙二醇烷基醚、（a4) 一、二或三丙二醇芳基醚、（a5)l，3· 丁二醇或丙三醇的烷基 醚等，和至少一種乙酸酯類選自（bl’）一丙二醇烷基醚乙酸 酯、（b 2)二或三丙二醇烷基醚乙酸酯、（b 3) —、二或三丙二 -12- 200538888 醇芳基醚乙酸酯、（b4)l，3_ 丁二醇或丙三醇的烷基醚乙酸 酯、及（b 5 )Ci4鏈烷多醇乙酸酯等之組合，（2)至少一種醚類 選自（al’）一丙二醇一烷基醚、（a2)—丙二醇二烷基醚、U3) 二或三丙二醇烷基醚、（a4) —、二或三丙二醇芳基醚、 (a5)l，3-丁二醇或丙三醇的烷基醚等，和至少一種乙酸酯類 選自（bl)烷基的碳數爲2以上之α型一丙二醇烷基醚乙酸 酯、（b2)二或三丙二醇烷基醚乙酸酯、（b 3) —、二或三丙二 醇芳基醚乙酸酯、（b4) 1,3-丁二醇或丙三醇的烷基醚乙酸 酯、及（b5)C3.4鏈烷多醇乙酸酯等之組合。 (al)、（a2)、U3)、（a4)、（a5)、（bl)、（b2)、（b3)、（b4)、 (b5)和上述相同。上述Ul’）一丙二醇一烷基醚除了（al)包含 的溶劑之外，例如一丙二醇一甲醚。（b 1 ’）一 Η二醇院基醚 乙酸酯除了（bl)包含的溶劑之外’例如（X型一丙二醇甲醚 乙酸酯；β型一丙二醇甲醚乙酸酯等β型一丙二醇烷基醚 乙酸酯。 更具體而言，2種以上的有機溶劑之組合，例如丙二醇 丙醚和丙二醇丙醚乙酸酯（或一丙二醇一 C3.4院基醚和一丙Glycol methyl ether, dipropylene glycol methyl propyl ether, dipropylene glycol methyl butyl ether, dipropylene glycol diethyl ether, dipropylene glycol ethyl propyl ether, dipropylene glycol ethyl butyl ether, dipropylene glycol dipropyl ether, dipropylene glycol propyl butoxide Ethers, tripropylene glycol alkyl ethers such as dipropylene glycol dibutyl ether, such as tripropylene glycol- 丨 _ methyl ether, tripropylene glycol- ^ diethyl ether, tripropylene glycol-1-propyl ether, tripropylene glycol-; tripropylene glycol monoalkane such as l-butyl ether Ethers; tripropylene glycol dimethyl ether, tripropylene glycol methyl ether, tripropylene glycol methyl propyl ether, tripropylene glycol methyl butyl ether, tripropylene glycol diethyl ether, tripropylene glycol ethyl propyl ether, tripropylene glycol ethyl butyl ether, tripropylene glycol Tripropylene glycol dialkyl ethers such as dipropyl ether, tripropylene glycol 200538888, propylene glycol butyl ether, and tripropylene glycol dibutyl ether. Among the above-mentioned mono-, di- or tripropylene glycol aryl ethers (a4), a monopropylene glycol aryl group such as propylene glycol monoaryl ether such as propylene glycol monoaryl ether; monopropylene glycol diaryl ether such as propylene glycol diphenyl. Examples of dipropylene glycol aryl ethers include dipropylene glycol monoaryl ethers such as dipropylene glycol ether; and dipropylene 'diaryl ethers such as dipropylene glycol diphenyl ether. Tripropylene glycol aryl ethers such as glycol monoaryl ethers such as tripropylene glycol monophenyl ether; tripropylene glycol diaryl groups such as tripropylene glycol diphenyl ether; alkyl ethers of the above 1,3-butanediol or glycerol (a5 In), 1,3-butanediyl ether can be used, for example, any of monoalkyl ether and dialkyl ether. Examples of the monoalkyl group are 1,3-butanediol monomethyl ether, 1,3-butanediol monoethyl ether, 1,3-butanediol ether, 1,3-butanediol monobutyl ether, and the like. The dialkyl ether is, for example, a 1,3-butanediol dialkyl ether corresponding to the aforementioned 1,3-butane alkyl (the two alkyl groups may be different from each other). The glycerol alkyl ether includes glycerol monoalkyl ether and glycerol dialkyl glycerol trialkyl ether. Representative examples of glycerol alkyl ethers, such as glycerol, glycerol dimethyl ether, glycerol trimethyl ether, glycerol monoethyl ether triol diethyl ether, glycerol triethyl ether, glycerol monopropyl ether , Glycerol® ether, glycerol tripropyl ether, glycerol monobutyl ether, glycerol dibutyl ether, alcohol tributyl ether, etc. Α-propylene glycol alkyl ether ethyl (bl) having a carbon number of 2 or more, for example, α-propylene glycol such as ex-type propylene glycol ether acetate, α-propylene glycol propyl ether ethane α-propylene glycol butyl ether acetate, and the like C2.4 alkyl ether ethyl (especially α-propylene glycol C3.4 alkyl ether acetate) and the like. Among the above-mentioned di- or tripropylene glycol alkyl ether acetates (b 2), dipropylene glycol ether acetates such as dipropylene glycol methyl ether acetate, dipropylene glycol ether ether, phenyl ether, benzene glycol tripropanol alkyl ether, and the like Propylene Glycol Ether, Alcohol I, Propylene Dipropylene V-Γ f * Malonate Monoester, Ethyl Acetate Acetate -10- 200538888 Ester, Dipropylene Glycol Propyl Acetate, Dipropylene Glycol Butyl Ether Acetate Wait. Tripropylene glycol alkyl ether acetates, such as tripropylene glycol methyl ether acetate, tripropylene glycol ethyl ether acetate, tripropylene glycol propyl ether acetate, tripropylene glycol butyl ether acetate, and the like. The above mono-, di- or tripropylene glycol aryl ether acetates (b3) are, for example, propylene glycol 'phenyl ether acetate, dipropylene glycol phenyl ether acetate, tripropylene glycol phenyl ether acetate and the like. Among the above-mentioned 1,3-butanediol or glycerol alkyl ether acetates (b4), 1,3-butane g of glycol alkyl ether acetates such as 1,3-butanediol methyl ether acetate Esters, 1,3-butanediol ether acetate, 1,3-butanediol propyl ether acetate, 1,3-butanediol butyl ether acetate, and the like. Glycerol alkyl ether acetates such as glycerol monomethyl ether acetate, glycerol monoethyl ether acetate, glycerol monopropyl ether acetate, glycerol dimethyl ether acetate, glycerol Triol diethyl ether acetate, glycerol dipropyl ether acetate, and the like. Among the above-mentioned alkanepolyol acetates (b 5), the alkanol polyols having 3 or 4 carbon atoms include, for example, 1,2 · propanediol acetate and 1,3-propanediol Acetate, 1,3-butanediol acetate, glycerol acetate, and the like. Examples of the 1,2-propylene glycol acetate are 1,2-propylene glycol monoacetate and 1,2-propylene glycol diacetate. 1,3-propanediol glycol acetates such as 1,3-propanediol monoacetate and 1,3-propanediol diacetate. Examples of 1,3-butanediol acetate are 1,3-butanediol monoacetate and 1,3-butanediol diacetate. Glycerol acetates such as glycerol monoacetate, glycerol diacetate, glycerol triacetate. Among them, particularly desirable organic solvents are, for example, propylene glycol mono-Cm alkyl ethers such as propylene glycol-1-propane ether; propylene glycol di Cm alkyl ethers such as propylene glycol dipropyl ether; dipropylene glycol-1-methyl ether, dipropylene glycol dimethyl ether, Tripropylene glycol- 丨 -Butyl ether and other di- or tripropylene glycol mono- or di Ci · 4 alkyl ethers; propylene glycol mono-phenyl ether and other mono-, di- or -11-200538888 Tripropylene glycol mono- or diphenyl ether; 1,3-butanediol- 1-ether, 1,3 butanediol diethyl ether, etc. 1,3 butanediol mono- or di-Ch alkyl ether; glycerol-1-methyl ether, glycerol-1,2-dimethyl ether, glycerin Mono-, di-, or tri-Cm alkyl ethers of glycerol such as trimethyl ether; alpha-propylene glycol C2.4 alkyl ether acetates such as ex-type propylene glycol-1-propyl ether acetate (especially α-propylene glycol) C3.4 alkyl ether acetate); dipropylene glycol-1-methyl ether acetate, tripropylene glycol-1-butyl ether acetate and other di- or tripropylene glycol Cm alkyl ether acetate; propylene glycol-1-benzene Ethyl acetate, mono-, di- or tripropylene glycol phenyl ether acetate; 1,3-butanediol-1 · ethyl ether acetate, etc. 1,3-butanediol or Cm alkyl ether acetate of glycerol Esters; 1,3-butanediol diacetate, glycerin Triacetate C 3.4 alkane polyol mono-, di- or triacetate. Solvents that are used alone and have excellent effects, such as dipropylene glycol monomethyl ether and dipropylene glycol dimethyl ether such as dipropylene glycol mono- or di-Cl_4 alkyl ether; 1,3 butanediol diethyl ether and the like Cm alkyl ether; glycerol-1-methyl ether, glycerol-1, 2 · dimethyl ether, glycerol trimethyl ether, mono-, di- or tri-Cm academic ether; alpha-type glycerol Alcohol-1-propyl ether acetate and other α-propylene glycol C2.4 fluorenyl ether acetate (especially (X-type propylene glycol c3.4 alkyl ether acetate); 1,3-butanediol-1 -1,3-butanediol alkyl ether acetates, such as diethyl ether acetate; 1,3-®butanediol diacetate, glycerol triacetate, etc. Or triacetate, etc. 时 When two or more organic solvents are used, a preferable combination is, for example, (1) at least one ether is selected from (al) propylene glycol monoalkyl ether having a carbon number of 2 or more, (A2) -propylene glycol dialkyl ether, (a3) di- or tri-propylene glycol alkyl ether, (a4) mono-, di- or tri-propylene glycol aryl ether, (a5) 1,3-butanediol or glycerin Ether and the like, and at least one acetate is selected from (bl ')-propylene glycol alkyl ether Acid esters, (b 2) di- or tripropylene glycol alkyl ether acetates, (b 3)-, di- or tripropylene di-12-200538888 alcohol aryl ether acetates, (b4) 1, 3-butanediol Or a combination of alkyl ether acetate of glycerol and (b 5) Ci4 alkane polyol acetate, etc., (2) at least one ether is selected from (al ′)-propylene glycol-alkyl ether, ( a2) -propylene glycol dialkyl ether, U3) di- or tripropylene glycol alkyl ether, (a4)-, di- or tripropylene glycol aryl ether, (a5) 1,3-butanediol or glycerol alkyl ether And at least one acetate is selected from (bl) alkyl monopropylene glycol alkyl ether acetates having a carbon number of 2 or more, (b2) di- or tripropylene glycol alkyl ether acetates, (b 3 ) —, Di- or tripropylene glycol aryl ether acetate, (b4) alkyl ether acetate of 1,3-butanediol or glycerol, and (b5) C3.4 alkane polyol acetate And other combinations. (al), (a2), U3), (a4), (a5), (bl), (b2), (b3), (b4), (b5) are the same as above. In addition to the solvent contained in (al), the above-mentioned Ul ')-propylene glycol monoalkyl ether is, for example, propylene glycol monomethyl ether. (B 1 ′) diol glycol ether ether acetates other than the solvents included in (bl) ′, such as (X-type propylene glycol methyl ether acetate; β-type propylene glycol methyl ether acetate, etc. β-type one Propylene glycol alkyl ether acetate More specifically, a combination of two or more organic solvents, such as propylene glycol propyl ether and propylene glycol propyl ether acetate (or a propylene glycol-C3.4 alkyl ether and a propylene
二醇Cm烷基醚乙酸酯、例如α型一丙二醇一 C3·4院基酸 和α型一丙二醇Cm烷基醚乙酸醋）、二丙二醇丙醚和二丙 二醇丙醚乙酸酯（或二丙二醇一、二Cl·4院基醚和二丙二醇 烷基醚乙酸酯）、三丙二醇丁釀和三丙二醇丁醚乙酸醋 (或三丙二醇一、二Cm烷基醚和三丙二醇Cm烷基醚乙酸 酯）、丙二醇苯基醚和丙二醇苯基醚乙酸酯、丁二醇丙 酸和丨3_ 丁二醇丙醚乙酸酯（或1，3-丁二醇一、二C!.4烷基 醜和1，3-丁二醇Cm烷基醚乙酸酯）、丙三醇一甲醚和丙三 -13- 200538888 醇三乙酸酯（或丙三醇的一、二或三Cl_4烷基醚和丙三醇的 一或二乙酸酯）等較理想。特別是多醇部分係組合相似的2 種溶劑（例如和二醇醚類對應的二醇醚乙酸酯類、和二醇醚 乙酸酯類對應的一醇聚乙酸酯類、和二醇醚類對應的二醇 聚乙酸酯類等）較理想。 不單獨使用一丙二醇一甲醚、α型一丙二醇甲醚乙酸酯、 β型一丙二醇烷基醚乙酸酯，乃與上述醚類「（al)、（a2)、 (a3)、（a4)、（a5)」、乙酸酯類「（bl)、（b2)、（b3)、（b4)、 (b5)」倂用較理想。 如上述使用2種混合的有機溶劑時，依溶劑的種類和目 的適當選擇二者的混合比例。例如上述（1)或（2 )，使用醚類 (二醇醚類）和乙酸酯類的混合物時，二者的比例前者/後者 (重量比）=1/99〜99/1，較理想爲5/95〜95/5,又以10/90〜90/10 更佳。 本發明的微影用洗淨劑中，除了上述（al)、（a2)、（a3)、 (a4)、（a5)、（bl)、（b2)、（b3)、（b4)、（b5)之外，亦可含有 1 種或2種以上的先前光阻或防止反射膜等的溶劑或沖洗液 且爲水溶性之有機溶劑。相對於組成洗淨劑的全部有機溶 劑，這些有機溶劑的含量爲低於80重量％較佳，以60重量 %以下較理想，又以低於40重量％更適當。相對於組成洗 淨劑的全部有機溶劑，本發明的微影用洗淨劑中，選自上 述（al) 、 （a2) 、 （a3) 、 （a4) 、 （a5) 、 （bl) 、 （b2) 、 （b3) 、 （b4)及 (b5)的有機溶劑之總含量爲20重量以上％較佳，以超過40 重量％較理想，又以60重量％以上更適當（尤其80重量％以 上）。本發明的微影用洗淨劑亦可由選自（al)、（a2)、U3)、 -14- 200538888 (a4)、（a5)、（bl)、（b2)、（b3)、（b4)及（b5)的有機溶劑組成。 本發明中可倂用的水溶性有機溶劑除了上述一丙二醇一 甲醚、α型一丙二醇甲醚乙酸酯、β型一丙二醇烷基醚乙酸 酯之外，例如羧酸烷基酯類、脂肪族酮等。上述羧酸烷基 酯類包括含有乳酸烷基酯、醋酸烷基酯、丙酸烷基酯、烷 氧基丙酸烷基酯等的羥基、烷氧基（例如Cb4烷氧基等）等取 代基之碳數1〜4的脂肪族羧酸的烷基酯（例如Cm烷氧酯 等” 0 更具體而言，乳酸烷基酯例如乳酸甲酯、乳酸乙酯等乳 酸Cm烷基酯等，醋酸烷基酯例如醋酸丙酯、醋酸正丁酯、 醋酸正戊酯等醋酸Ci.6烷基酯等，丙酸烷基酯例如丙酸甲 酯、丙酸乙酯、丙酸丙酯、丙酸丁酯等丙酸Cl6烷基酯等， 烷氧基丙酸烷基酯例如甲氧基丙酸甲酯、乙氧基丙酸乙 酯、甲氧基丙酸乙酯、乙氧基丙酸甲酯等C!.4烷氧基丙酸 Cm烷基酯等。又，脂肪族酮例如2-丁酮、2-戊酮、2-己酮、 2-庚酮等碳數3〜10之脂肪族酮等。 本發明的微影用沖洗液係本發明的上述微影用洗淨劑中 ®含有水之均勻溶液。均勻溶液係指使用條件中，各溶劑及 水完全溶解的溶液之外，亦包括不形成分離層時一成分分 散於其他成分中之型態。 可由使用的有機溶劑適當地設定沖洗液中的水含量。通 常，相對於全有機溶劑100重量份，水量爲0.5〜30重量份（例 如5〜30重量份），以0.5〜20重量份較佳，又以〇.5〜1〇重量 份更理想。例如使用二丙二醇一甲醚等有機溶劑作爲洗淨 劑（有機溶劑）時，相對於100重量份的二丙二醇一甲醚等有 -15- 200538888 機溶劑，可添加1 0〜3 0重量份的水作成沖洗液 本發明的洗淨劑及沖洗液適用於任一種公 阻、負型光阻、抗反射膜等。適用本發明的洗 液的光阻之代表例，正型例如組合醌二疊氮類 溶性樹脂者、化學放大型光阻等，負型例如含 酸乙烯酯等感光性基的高分子化合物者、含有 氮基化合物者或由環化橡膠和雙疊氮基化合物 基化合物者、含重氮樹脂者、含加成聚合性不 g 之光聚合性組成物、化學放大型負光阻等。 適用本發明的沖洗液的理想光阻材料，例如 感光劑和鹼溶性樹脂形成之光阻材料。醌二疊 例如1,2-對苯醌二疊氮-4-磺酸、1，2-萘醌二疊 1，2 -萘醌二疊氮-5-磺酸、這些的磺酸酯或醯胺 溶性樹脂，例如由1種或2種以上的聚乙烯苯 醇、，丙烯酸或甲基丙烯酸的共聚物例如苯酚、 甲酚、對甲酚、二甲苯酚等苯酚類，和甲醛、 類製成的酚醛清漆樹脂等。 ® 又，化學放大型光阻亦爲本發明的洗淨劑及 的理想光阻。化學放大型光阻係藉由放射線 酸，藉由酸的催化作用之化學變化，使對於放 分的顯像液之溶解性發生變化而形成圖案，例 線照射產生酸的產酸化合物和酸的共存下分解 性羥基或羧基般鹼溶性基的含酸感應性基樹脂 溶性樹脂和交聯劑、產酸劑組成者。 另一方面，適用本發明的洗淨劑及沖洗液之 知的正型光 淨劑及沖洗 感光劑和鹼 有具聚肉桂 具芳香族疊 組成的疊氮 飽和化合物 醌二疊氮類 氮類感光劑 氮-4-磺酸、 等。又，鹼 酚、聚乙烯 鄰甲酚、間 仲甲醛等醛 沖洗液適用 照射使產生 射線照射部 如藉由放射 而生成苯酚 組成者，鹼 抗反射膜係 -16 - 200538888 由有機材料組成之抗反射膜即可。這類 添加染料的聚胺基酸或聚丁烯、添加染 酸酐聚合物、衣康酸酐聚合物、使染料 酸酯或聚甲基丙烯酸酯組成的聚合物者 團和含酐的聚合物之反應生成物、水溶 全氟羧酸之組合物、含水溶性高分子的 溶液、水溶性膜形成成分和氟類界面活 氟烷基羧酸、有機胺、聚乙烯吡咯烷酮 基磺酸、聚乙烯吡咯烷酮、水溶性烷基 合物等、由有機溶劑或水溶液形成的膜 又，本發明的沖洗液因含有水，和由 溶合性佳（接觸角小），對由水溶液形成 的沖洗效果。 本發明的洗淨劑及沖洗液的用法，可 「洗淨技術入門」和工業調查會編「及 術」等記載的方法。 本發明的洗淨劑及沖洗液之用法，除 方法之外，更詳細而言，首先以旋轉塗 法將光阻溶液塗布於依需要經過前處理 板。塗布光阻溶液前或塗布形成的光阻 止反射膜。例如在旋轉塗布法中，容易 或防止反射膜的粒狀物，藉著在旋轉邊 沖洗液，可促進粒狀物的流動，可在基 度的光阻或抗反射膜。 又，亦可藉著噴霧本發明的洗淨劑及 的抗反射膜，例如 料的共聚物、馬來 等接枝於由聚丙烯 、胺基芳香族發色 性聚合物和水溶性 四甲銨羥等有機鹼 性劑之組合物、全 之組合物、全氟烷 矽氧烷聚合物之組 〇 水溶液形成的膜之 的抗反射膜具良好 依據工業調査會編 時可使用的洗淨技 了光阻圖案的形成 布法等公知的塗布 的矽基板、玻璃基 上，依需求塗布防 在基板緣形成光阻 緣的粒狀物上噴霧 板上形成具均勻厚 沖洗液去除包圍在 -17- 200538888 基板側面週邊或背面的光阻或抗反射膜。又，爲正型光阻 時基板和光阻間具有抗反射膜時，經由曝光、顯像而形成 圖案後，亦可使用本發明的沖洗液以濕式法去除不具光阻 之防止反射膜。 塗布於基板的光阻溶液，例如在熱板上經預烘烤去除溶 劑，形成厚度爲1〜2 · 5 μ m的光阻。預烘烤的溫度依使用的 溶劑或光阻的種類而異，一般爲 20〜200°C ，較理想爲 5 0〜1 5 0 °C。之後，使用高壓水銀燈、金屬鹵素燈、超高壓 水銀燈、KrF準分子雷射、ArF準分子雷射、F2雷射、軟X 線照射裝置、電子射線描繪裝置，依需求加以遮蔽使光阻 進行曝光。 曝光後爲要改善顯像性、解像度、圖案形狀等，可依需 求進行後烘烤後，進行顯像形成光阻圖案。一般，光阻的 顯像係使用顯像液利用對曝光域和未曝光域溶劑或鹼溶液 的溶解性差進行顯像。鹼顯像液例如氫氧化鈉、氫氧化四 甲銨（T M A Η)等的水溶液或水性溶液。 上述使用塗布裝置塗布光阻或抗反射膜，在基板上塗布 光阻或抗反射膜之後，使用後的裝置有時作爲別種材料之 塗布裝置。例如光阻之後塗布抗反射膜、光阻之後塗布別 種的光阻、或抗反射膜之後塗布光阻等的塗布裝置。此時， 使用爲別種材料的塗布裝置時，使用前需先洗淨此塗布裝 置，此時可有效地使用本發明的洗淨劑及沖洗液。 實例 以下，以實例更具體地說明本發明，惟本發明不受限於 此。 ⑧ -18- 200538888 實例1〜1 4、比較例1 使100重量份的酚醛清漆樹脂（間甲酚/對甲酚二6/4和甲 醛的縮聚物）和24重量份的醌二疊氮感光劑（2,3,4,4’-四羥 二苯甲酮和1，2-萘醌二疊氮-5-磺醯氯的酯化物）溶解於α型 丙二醇一甲醚乙酸酯中，使形成固形分爲25重量％之光阻 溶液，以旋轉塗布法將此光阻溶液塗布於4英吋的矽基 板，使經過預烘烤後的膜厚度爲2μιη，在直接式加熱板上 以100 °C進行90秒的預烘烤，形成光阻膜。 將0.03ml表1表示的洗淨劑滴於光阻膜上，測定滴落後 至基底看見矽時所需的時間（秒），將光阻膜（埃）除以時間 (秒）的値（埃/秒）作爲溶解速度。結果如表1所示。Glycol Cm alkyl ether acetates, such as α-propylene glycol-C3.4 alkyl acid and α-propylene glycol Cm alkyl ether acetate), dipropylene glycol propyl ether, and dipropylene glycol propyl ether acetate (or two Propylene glycol mono-, di-Cl 4 ether and dipropylene glycol alkyl ether acetate), tripropylene glycol butanol and tripropylene glycol butyl ether acetate (or tripropylene glycol mono-, di-Cm alkyl ether and tripropylene glycol Cm alkyl ether) Acetate), propylene glycol phenyl ether and propylene glycol phenyl ether acetate, butanediol propionic acid, and 3_ butanediol propyl ether acetate (or 1,3-butanediol one or two C! .4 Alkyl and 1,3-butanediol Cm alkyl ether acetate), glycerol monomethyl ether and glycerol 13-200538888 alcohol triacetate (or glycerol mono-, di- or tri-Cl_4 Alkyl ethers and mono- or diacetates of glycerol are preferred. In particular, the polyol part is a combination of two solvents (for example, glycol ether acetates corresponding to glycol ethers, monoalcohol polyacetates corresponding to glycol ether acetates, and glycol ethers. Diol polyacetates, etc.) are preferred. Do not use monopropylene glycol monomethyl ether, alpha monopropylene glycol methyl ether acetate, or beta monopropylene glycol alkyl ether acetate. They are the same as the above-mentioned ethers "(al), (a2), (a3), (a4 ), (A5) ", acetates" (bl), (b2), (b3), (b4), (b5) "are ideally used. When two kinds of mixed organic solvents are used as described above, the mixing ratio of the two is appropriately selected depending on the type and purpose of the solvent. For example, in the above (1) or (2), when a mixture of ethers (glycol ethers) and acetates is used, the ratio of the former / the latter (weight ratio) = 1/99 to 99/1 is more preferable. 5/95 ~ 95/5, and more preferably 10/90 ~ 90/10. In the cleaning agent for lithography of the present invention, in addition to the above (al), (a2), (a3), (a4), (a5), (bl), (b2), (b3), (b4), ( In addition to b5), it may contain one or two or more types of solvents or rinsing liquids such as the previous photoresist or antireflection film, and it is a water-soluble organic solvent. The content of these organic solvents is preferably less than 80% by weight, more preferably 60% by weight or less, and more preferably less than 40% by weight, with respect to all organic solvents constituting the detergent. The cleaning agent for lithography of the present invention is selected from the above-mentioned (al), (a2), (a3), (a4), (a5), (bl), ( b2), (b3), (b4) and (b5) The total content of the organic solvents is preferably 20% by weight or more, more than 40% by weight is more desirable, and 60% by weight or more is more appropriate (especially 80% by weight or more). ). The cleaning agent for lithography of the present invention may also be selected from (al), (a2), U3), -14-200538888 (a4), (a5), (bl), (b2), (b3), (b4) ) And (b5). In addition to the monopropylene glycol monomethyl ether, alpha monopropylene glycol methyl ether acetate, and beta monopropylene glycol alkyl ether acetate, the water-soluble organic solvents that can be used in the present invention include, for example, alkyl carboxylates, Aliphatic ketones, etc. The above-mentioned carboxylic acid alkyl esters include substitutions including hydroxyl groups such as alkyl lactate, alkyl acetate, alkyl propionate, alkyl alkoxypropionate, and alkoxy groups (such as Cb4 alkoxy group). Alkyl esters of aliphatic carboxylic acids having 1 to 4 carbon atoms (e.g., Cm alkoxy esters, etc.) 0 More specifically, alkyl lactates such as Cm alkyl lactates, such as methyl lactate, ethyl lactate, etc., Alkyl acetates such as propyl acetate, n-butyl acetate, n-pentyl acetate, etc. Ci.6 alkyl acetates, etc., and alkyl propionates such as methyl propionate, ethyl propionate, propyl propionate, propyl Cl6 alkyl propionates such as butyl acid esters, etc. Alkoxy propionate alkyl esters such as methyl methoxypropionate, ethyl ethoxypropionate, ethyl methoxypropionate, ethoxypropionate C! .4 alkoxypropanoic acid Cm alkyl esters, etc. Also, aliphatic ketones such as 2-butanone, 2-pentanone, 2-hexanone, 2-heptanone, etc. Aliphatic ketones, etc. The lithographic washing solution of the present invention is a homogeneous solution containing water in the above-mentioned lithographic cleaning agent of the present invention. A homogeneous solution refers to a solution in which each solvent and water are completely dissolved under the conditions of use. It also includes the type in which one component is dispersed in other components when the separation layer is not formed. The water content in the washing solution can be appropriately set by the organic solvent used. Generally, the amount of water is 0.5 to 30 parts relative to 100 parts by weight of the entire organic solvent. Parts by weight (for example, 5 to 30 parts by weight), preferably 0.5 to 20 parts by weight, and more preferably 0.5 to 10 parts by weight. For example, an organic solvent such as dipropylene glycol monomethyl ether is used as a cleaning agent (organic solvent ), With respect to 100 parts by weight of dipropylene glycol monomethyl ether and other organic solvents of -15-200538888, 10 to 30 parts by weight of water can be added to make a washing solution. The detergent and washing solution of the present invention are applicable to any kind Public resistance, negative photoresist, anti-reflection film, etc. Representative examples of photoresist to which the lotion of the present invention is applied, positive type such as combination of quinonediazide soluble resin, chemical amplification type photoresist, etc. Photosensitive polymer compounds such as vinyl acid esters, those containing nitrogen-based compounds, those made from cyclized rubber and double azide-based compounds, those containing diazo resins, and those containing addition polymerizability Composition, chemical release Negative photoresist, etc. Ideal photoresist materials for the rinse solution of the present invention, such as photoresist materials formed by photosensitizers and alkali-soluble resins. Quinones such as 1,2-p-benzoquinonediazide-4-sulfonic acid 1,1,2-naphthoquinone diazide 1,2-naphthoquinone diazide-5-sulfonic acid, these sulfonic acid esters or amidine-soluble resins, for example, one or two or more kinds of polyvinyl alcohols, Copolymers of acrylic acid or methacrylic acid such as phenols such as phenol, cresol, p-cresol, xylenol, and novolac resins made of formaldehyde, etc. ® Also, chemically amplified photoresist is also the present invention. Detergent and ideal photoresist. Chemically amplified photoresist uses radioactive acid to chemically change the acid's catalytic action to change the solubility of the released imaging solution to form a pattern. An acid-generating compound that generates an acid and an acid-sensitive group-containing resin-soluble resin, a cross-linking agent, and an acid generator that decompose a hydroxyl- or carboxy-like alkali-soluble group in the coexistence of an acid. On the other hand, the known positive light detergents and washing photosensitizers which are suitable for the detergents and washing liquids of the present invention and alkali have azide saturated compound quinonediazide nitrogen-based photosensitizer with polycinnamon and aromatic azide composition. Agent nitrogen-4-sulfonic acid, etc. In addition, aldehyde washing liquids such as alkali phenol, polyethylene o-cresol, and meta-formaldehyde are suitable for irradiation. If the radiation-generating part generates phenol by radiation, the alkali antireflection film is -16-200538888 made of organic materials. A reflective film is sufficient. Reaction of such dye-added polyamino acids or polybutenes, dye-anhydride polymers, itaconic anhydride polymers, polymers made of dye esters or polymethacrylates, and polymers containing anhydrides Product, water-soluble perfluorocarboxylic acid composition, water-soluble polymer-containing solution, water-soluble film-forming component and fluorine-based interfacial active fluoroalkyl carboxylic acid, organic amine, polyvinylpyrrolidone sulfonic acid, polyvinylpyrrolidone, water-soluble The film formed from an organic solvent or an aqueous solution, such as an alkaline alkyl compound, contains the water, and has good solubility (small contact angle) due to the fact that the washing solution of the present invention contains water, and has a washing effect on the aqueous solution. The usage of the detergent and rinsing liquid of the present invention can be described in "Introduction to Cleaning Technology" and "Industrial Survey" compiled by the Industrial Survey. In addition to the method, the usage of the cleaning agent and the rinsing liquid of the present invention is more detailed. First, a photoresist solution is applied to a pre-treatment plate as required by a spin coating method. The photoresistive reflective film is formed before or after the photoresist solution is applied. For example, in the spin coating method, it is easy to prevent or prevent the particles of the reflective film. By washing the liquid on the rotating side, the flow of the particles can be promoted. In addition, by spraying the detergent and the anti-reflection film of the present invention, for example, a copolymer such as a polymer, and malay can be grafted on polypropylene, an amine-based aromatic color-developing polymer, and water-soluble tetramethylammonium. Anti-reflection film of organic alkaline agent composition, total composition, perfluoroalkoxysilane polymer group, aqueous solution, and anti-reflection film based on industrial investigation meeting. The photoresist pattern is formed on a well-known coated silicon substrate, glass substrate, etc., as needed, to prevent the particles on the substrate from forming a photoresist edge to form a uniform thick rinse solution on the spray plate. 200538888 Photoresistor or anti-reflection film on the side or back of the substrate. In the case of a positive-type photoresist, when an anti-reflection film is provided between the substrate and the photoresist, after patterning through exposure and development, the anti-reflection film without photoresist can be removed by a wet method using the washing liquid of the present invention. The photoresist solution coated on the substrate is, for example, pre-baked on a hot plate to remove the solvent, thereby forming a photoresist having a thickness of 1 to 2 · 5 μm. The pre-baking temperature varies depending on the type of solvent or photoresist used. It is generally 20 ~ 200 ° C, and more preferably 50 ~ 150 ° C. After that, high-pressure mercury lamps, metal halide lamps, ultra-high-pressure mercury lamps, KrF excimer lasers, ArF excimer lasers, F2 lasers, soft X-ray irradiation devices, and electron ray drawing devices were used to shield the photoresist and expose it as required. . In order to improve the developability, resolution, pattern shape, etc. after exposure, post-baking can be performed as required to develop a photoresist pattern. Generally, the development of a photoresist uses a developing solution to develop the poor solubility of the solvent or alkali solution in the exposed and unexposed areas. The alkali developing solution is, for example, an aqueous solution or an aqueous solution of sodium hydroxide, tetramethylammonium hydroxide (T M A Η) and the like. After coating the photoresist or antireflection film using a coating device as described above, after coating the photoresist or antireflection film on a substrate, the used device may be used as a coating device for other materials. For example, an antireflection film is applied after the photoresist, another photoresist is applied after the photoresist, or a photoresist is applied after the antireflection film. At this time, when a coating device made of another material is used, the coating device needs to be washed before use. In this case, the detergent and the rinsing liquid of the present invention can be effectively used. Examples Hereinafter, the present invention will be described more specifically with examples, but the present invention is not limited thereto. ⑧ -18- 200538888 Example 1 ~ 1 4. Comparative Example 1 Photosensitized 100 parts by weight of novolac resin (condensate of m-cresol / p-cresol di 6/4 and formaldehyde) and 24 parts by weight of quinone diazide The agent (the esterified product of 2,3,4,4'-tetrahydroxybenzophenone and 1,2-naphthoquinonediazide-5-sulfonyl chloride) is dissolved in α-propylene glycol monomethyl ether acetate, The photoresist solution with a solid content of 25% by weight was formed, and the photoresist solution was applied to a 4-inch silicon substrate by spin coating so that the film thickness after pre-baking was 2 μm. Pre-bake at 100 ° C for 90 seconds to form a photoresist film. 0.03ml of the cleaning agent shown in Table 1 was dropped on the photoresist film, and the time (seconds) required for the silicon to be seen after the substrate was dropped, and the photoresist film (A) was divided by the time (second) of 値 (A) Per second) as the dissolution rate. The results are shown in Table 1.
(表1) 洗淨劑組成(重量比） 溶解速度(埃/秒）'^ 實例1 DPM : DPMA = 50 : 50 12,400 實例2 PNP ： PNPA = 50 ： 50 14,500 實例3 TPNB : TPNBA=40 : 60 13,200 實例4 PNDP : PNPA=40 : 60 14,000 實例5 1，3-BE : 1，3-BEA 二 50 : 50 13,500 實例6 1,3-BDE 12,500 實例7 GME : GTA=20 : 80 14,200 實例8 DPM=100 13,000 實例9 DPDM-100 12,500 實例10 PNPA=100 13,500 實例11 1,3-BEA=100 -- 13,000 實例12 GTA=100 12,800 實例13 GDME=100 12,800 實例Μ GTME=100 12,700 比較例1 1,3-PDME ： 1,3-PDMEA=50 ： 50 11,600 -19- 200538888 實例15〜24、比較例2 除了以表2表示的沖洗液取代洗淨劑之外，進行和上述 實例1〜1 4、比較例1相同的操作，求得光阻的溶解速度（埃 /秒）。結果如表2所示。 (表2) _—---- —— 沖洗液組成(龍比） 溶解速度(埃渺） 實例15 DPM : DPMA :水=50 : 30 : 20 11,200 實例16 PNP : PNPA :水=50 : 30 : 20 12,300 實例17 TPNB : TPNBA :水=60 : 20 : 20 11,500 實例18 PNDP : PNPA :水=50 : 30 : 20 12,700 實例19 1，3-BE : 1，3-BEA ··水=80 ·· 10 : 10 11,300 實例20 GME : GTA :水=80 : 10 : 10 12,200 實例21 DPM :水=80 : 20 11,200 實例22 DPDM :水=80 : 20 10,800 實例23 GDME :水=80 : 20 10,200 實例24 GTME :水=80 : 20 10,100 比較例2 1，3-PDME : 1，3-PDMEA :水=50 : 30 : 20 8,500(Table 1) Detergent composition (weight ratio) Dissolution rate (Angstroms / second) '^ Example 1 DPM: DPMA = 50: 50 12,400 Example 2 PNP: PNPA = 50: 50 14,500 Example 3 TPNB: TPNBA = 40: 60 13,200 Example 4 PNDP: PNPA = 40: 60 14,000 Example 5 1,3-BE: 1,3-BEA Two 50:50 13,500 Example 6 1,3-BDE 12,500 Example 7 GME: GTA = 20: 80 14,200 Example 8 DPM = 100 13,000 Example 9 DPDM-100 12,500 Example 10 PNPA = 100 13,500 Example 11 1,3-BEA = 100-13,000 Example 12 GTA = 100 12,800 Example 13 GDME = 100 12,800 Example M GTME = 100 12,700 Comparative Example 1 1, 3-PDME: 1, 3-PDMEA = 50: 50 11,600 -19- 200538888 Examples 15 to 24 and Comparative Example 2 Except that the washing liquid shown in Table 2 was used instead of the detergent, the same procedures as in Examples 1 to 1 were performed. In the same manner as in Comparative Example 1, the dissolution rate (Angstroms / second) of the photoresist was determined. The results are shown in Table 2. (Table 2) _—---- —— Composition of the rinse solution (Long ratio) Dissolution rate (Angel) Example 15 DPM: DPMA: Water = 50: 30: 20 11,200 Example 16 PNP: PNPA: Water = 50: 30 : 20 12,300 Example 17 TPNB: TPNBA: Water = 60: 20: 20 11,500 Example 18 PNDP: PNPA: Water = 50: 30: 20 12,700 Example 19 1, 3-BE: 1, 3-BEA ·· Water = 80 · 10: 10 11,300 instances 20 GME: GTA: water = 80: 10: 10 12,200 instances 21 DPM: water = 80: 20 11,200 instances 22 DPDM: water = 80: 20 10,800 instances 23 GDME: water = 80: 20 10,200 instances 24 GTME: Water = 80: 20 10,100 Comparative Example 2 1,3-PDME: 1,3-PDMEA: Water = 50: 30: 20 8,500
上述各表中的縮寫符號如下所示。 DPM :二丙二醇-1-甲醚 DPDM :二丙二醇二甲醚 DPMA:二丙二醇-1-曱醚乙酸酯 PNP :丙二醇-1-丙醚 PNDP :丙二醇二丙醚 PNPA :丙二醇-1-丙醚乙酸酯 TPNB :三丙二醇-1-丁醚 ⑧ -20- 200538888 ΤΡΝΒΑ :三丙二醇-1-丁醚乙酸酯 1，3-ΒΕ: 1,3 -丁二醇-1-乙醚 1.3- BDE: 1，3 -丁二醇二乙醚 1.3- BEA: 1,3-丁二醇-1-乙醚乙酸酯 GME :丙三醇-1-甲醚The abbreviations in the above tables are shown below. DPM: dipropylene glycol-1-methyl ether DPDM: dipropylene glycol dimethyl ether DPMA: dipropylene glycol-1-methyl ether acetate PNP: propylene glycol-1-propyl ether PNDP: propylene glycol dipropyl ether PNPA: propylene glycol-1-propyl ether Acetate TPNB: Tripropylene glycol-1-butyl ether⑧ -20- 200538888 TPPNBA: Tripropylene glycol-1-butyl ether acetate 1,3-ΒΕ: 1,3-Butanediol-1-ether 1.3- BDE: 1,3-butanediol diethyl ether 1.3- BEA: 1,3-butanediol-1-ether acetate GME: glycerol-1-methyl ether
GDME:丙三醇-1，2·二甲醚 GTME :丙三醇甲醚 GTA :丙三醇三乙酸酯 1，3-PDME : 1，3-丙二醇-1-甲醚 1，3-PDMEA: 1，3-丙二醇-1-甲醚乙酸酯 產業上利用可能性 本發明的洗淨劑及沖洗液係光阻、抗反射膜的溶解性 高，實用性佳。又，本發明的沖洗液可安全地應用於製造 現場、工廠且其操作簡便。GDME: glycerol-1,2-dimethyl ether GTME: glycerol methyl ether GTA: glycerol triacetate 1,3-PDME: 1,3-propanediol-1-methyl ether 1,3-PDMEA : 1,3-propanediol-1-methyl ether acetate Industrial application possibility The detergent and the washing liquid of the present invention have high solubility in photoresist and antireflection film, and good practicality. Moreover, the flushing liquid of the present invention can be safely applied to manufacturing sites and factories, and its operation is simple.
(g -21 -(g -21-