1284354 (1) 九、發明說明 【發明所屬之技術領域】 本發明係有關基板之顯像處理方法、及顯像處理裝置 者0 【先前技術】 在半導體裝置之製造製程的微影步驟中，進行例如在 P 晶圓表面上塗佈光阻液形成光阻膜之光阻塗佈處理、或使 晶圓於所定之圖型上施行曝光的曝光處理，於晶圓上供給 顯像液使光阻膜選擇性溶解，在晶圓上形成光阻圖型之顯 像處理等。 上述之顯像處理中，在晶圓上供給顯像液使晶圓進行 靜止顯像，其後在晶圓上供給純水停止顯像，之後將晶圓 高速旋轉使晶圓乾燥。不過，在晶圓乾燥時，將晶圓高速 旋轉，造成晶圓表面的水份四處飛散，由於此飛散水份之 Φ 作用，導致晶圓表面之圖型倒塌。因此，有在使晶圓高速 旋轉之際，於晶圓上供給界面活性劑，使水份容易自晶圓 脫離，可抑制圖型倒塌之提案（參照專利文獻1)。 不過，近年來，例如已可形成線寬爲80nm以下之極 微細的光阻圖型。相對於如此微細的圖型，如上所述在顯 像後之乾燥時供給界面活性劑於晶圓上，不能充分抑制圖 型倒塌。進而，於顯像後之乾燥時供給界面活性劑於晶圓 上的情況，依本發明的工作同仁之硏究，確認受界面活性 劑之影響晶圓上的圖型大膨潤。光阻圖型膨潤時，線寬不 -5- (2) 1284354 穩定且不均一，不能在晶圓上形成所期望的光阻圖型。 專利文獻1 :特開平6-163391號公報。 【發明內容】 [發明所欲解決之課題] 本發明鑑於各項問題，以提供即使相對於極其微細的 光阻圖型，亦能充分抑制圖型倒塌，並且可防止圖型之膨 φ 潤的顯像處理方法及顯像處理裝置，爲其目的。 [課題之解決手段] 爲達成上述目的，本發明係基板之顯像處理方法；其 特徵爲具有： 在基板上供給顯像液，使基板進行顯像之步驟、與 其後，在基板上供給顯像停止液，使顯像停止之步驟 、及 φ 其後，在基板上供給含有具有極性的氟化碳系化合物 之液體，使基板旋轉進行乾燥之步驟。 依本發明，即使相對於微細的圖型，亦能抑制顯像後 之乾燥時的圖型倒塌與圖型之膨潤。 該液體可爲含有甲基全氟異丁基醚與甲基全氟丁基醚 之混合物、乙基全氟異丁基醚與乙基全氟丁基醚之混合物 、分子結構相異之兩種以上的二氯五氟丙烷之混合物、四 氟乙基三氟乙基醚、十氟戊烷、或七氟環戊烷之任一種。 該液體，以電容率爲2.1以上，對水之溶解度爲 -6- (3) 1284354 2 1 ppm(重量）以上爲佳。更佳爲該液體之電容率爲7以上 、對水之溶解度爲90ppm以上。 從另外的觀點而言，本發明係基板之顯像處理裝置； 其特徵爲具有： 支撐基板旋轉之旋轉支撐構件、與 相對於該旋轉支撐構件所支撐之基板，供給含有具有 極佳之氟化碳系化合物的液體供給噴嘴。 依本發明，藉由液體供給噴嘴，使具有極性之氟化碳 系化合物的液體供給至基板，可使基板旋轉而乾燥。藉此 ，能抑制顯像後之乾燥時的圖型倒塌與圖型之膨潤。 該液體，可爲含有甲基全氟異丁基醚與甲基全氟丁基 醚之混合物、乙基全氟異丁基醚與乙基全氟異丁基醚之混 合物、分子結構相異之兩種以上的二氯五氟丙烷之混合物 、四氟乙基三氟乙基醚、十氟戊烷、或七氟環戊烷之任一 種。 該液體，以電容率在2.1以上，對水之溶解度在 21 ppm(重量）以上爲佳。更佳爲該液體之電容率在7以上 、對水之溶解度在90ppm以上。 [發明之功效] 依本發明，可抑制顯像後的乾燥時之圖型倒塌與圖型 的膨潤之故，能在基板上形成所期望之圖型。 【實施方式】 •7- (4) 1284354 [發明之實施形態] 就本發明之較佳實施形態說明如下° 圖1爲，表示本實施形態中顯像處理裝置1之構成的 槪略縱剖面之說明圖；圖2爲，顯像處理裝置1之構成的 槪略平面圖。 如圖1所示，顯像處理裝置1在中央部具備作爲保持 晶圓W旋轉之旋轉支撐構件的旋轉夾盤1 〇。旋轉夾盤1 〇 P 具有水平的平面，在該平面上設置例如吸附晶圓W之吸 引口（圖上未標示）。藉由自吸引口之吸引，可使晶圓W吸 附於旋轉夾盤1 〇上。 旋轉夾盤10上設置例如使旋轉夾盤1〇旋轉及升降之 夾盤驅動機構11。夾盤驅動機構11具備例如使旋轉夾盤 10在垂直方向之軸周以所定速度旋轉的馬達等旋轉驅動 部（圖上未標示）、或使旋轉夾盤10升降之馬達或圓筒等 升降驅動部（圖上未標示）。藉由此夾盤驅動機構11，可使 Φ 旋轉夾盤10上晶圓W以所定之時機升降、以所定之速度 旋轉。 在旋轉夾盤10之周圍，設置接受來自晶圓W之飛散 或落下的液體之回收杯1 2。杯1 2，分別具備例如將旋轉 夾盤10之周圍包圍的內杯13、與將該內杯13之更外周 包圍的外杯14、及將內杯13與外杯14之下面包覆的下 杯1 5。藉由內杯1 3與外杯14，可接受主要在晶圓W之 外方的飛散之液體，藉由下杯1 5，可回收來自內杯1 3與 外杯14之內壁或晶圓W落下的液體。 -8- (5) 1284354 內杯1 3，例如形成爲略圓筒狀，其上端部向內側上 方傾斜。內杯1 3，可藉由例如圓筒等升降驅動部1 6上下 移動。外杯14，如圖2所示，從平面看形成爲四角形之 略筒狀。外杯14，如圖1所示，可藉由例如圓筒等升降 驅動部17上下移動。旋轉夾盤10貫穿下杯15之中央部 。在旋轉夾盤1 〇之周圍的下杯1 5之平坦面，設置例如使 自晶圓W之表面流回背面的液體遮斷之環狀構件1 8。此 _ 環狀構件1 8，具備例如接近於晶圓W之背面的頂上部， 在其頂上部可將流到晶圓背面之液體遮斷。下杯1 5，連 接有例如連通至工場之排液部的接出管1 9 ;杯1 2中之回 收的液體，可自排出管19排出於顯像處理裝置1之外部 〇 如圖2所示，在杯12之X方向的負方向（圖2之下方 )側，形成沿Y方向（圖2之左右方向）延伸之導軌30。導 軌30，例如形成於自杯12的Y方向之負方向（圖2之左 φ 方）側的外方，至杯1 2的Y方向之正方向（圖2之右方）側 的外方爲止。導軌30上，安裝例如二支臂桿31、32。第 1臂桿31支撐顯像液供給噴嘴3 3。第1臂桿31，藉由噴 嘴驅動部34，可在導軌30上之Y方向移動。藉由此第1 臂桿31，顯像液供給噴嘴33，可自設置於杯12的Y方 向之負方向側的外方之待機部35至杯1 2內爲止進行移動 ，可在晶圓W之表面上移動。又，第1臂桿31，例如藉 由噴嘴驅動部34，亦可在上下方向自由移動，能使顯像 液供給噴嘴33升降。 -9 · (6) 1284354 顯像液供給噴嘴3 3，在沿X方向具有例如與晶圓W 之直徑尺寸相等或較其長的細長形狀。如圖1所示’在顯 像液供給噴嘴3 3之上部，連接有連通於顯像液供給源40 之顯像液供給管4 1。在顯像液供給噴嘴3 3之下部，形成 沿長度方向形成一列的複數之吐出口 3 3 a。顯像液供給噴 嘴33，可使自上部之顯像液供給管4 1導入之顯像液，通 過顯像液供給噴嘴3 3，由下部之各吐出口 3 3 a —樣的吐 出。 第2臂桿32，如圖2所示，支撐洗滌液供給噴嘴50 。第2臂桿32，例如藉由噴嘴驅動部51可在導軌30上 之Y方向移動。藉由此第2臂桿32，洗滌液供給噴嘴50 ，可自設置於杯1 2的Y方向之正方向側的外方之待機部 52至杯12內之晶圓W上移動。又，第2臂桿32，藉由 噴嘴驅動部5 1，亦可在上下方向移動。 洗滌液供給噴嘴50，如圖1所示，連接有連通於洗 φ 滌液供給源53之洗滌液供給管54。在本實施形態中，例 如於洗滌液供給源53儲存作爲顯像停止液（洗滌液）之純 水。 如圖2所示，在杯12的X方向之正方向（圖2之上方 )側，形成沿Y方向延伸之導軌60。導軌60，例如形成於 自杯12的Y方向之正方向側的外方，至杯12的Y方向 之負方向側的外方爲止。導軌60上安裝例如第3臂桿6 1 。第3臂桿藉由驅動部62，可在導軌60上自由移動。第 3臂桿61支撐液體供給噴嘴63。在杯12的Y方向之正 -10- (7) 1284354 方向側的外方，設置液體供給噴嘴6 3之收容容器6 4 ;液 體供給噴嘴63，藉由第3臂桿61之移動，可自收容容器 64至杯12內之晶圓W上爲止移動。又，第3臂桿61， 例如藉由驅動部6 2，亦可在上下方向自由移動，可使液 體供給噴嘴63升降而調整高度。 液體供給噴嘴63，如圖1所示，連接有連通於液體 供給源65之液體供給管66。液體供給源65中儲存含有 p 具有極性之氟化碳系化合物的液體，例如以甲基全氟異丁 基醚與甲基全氟異丁基醚之混合物爲主成份的液體（例如 後述之液體A)、以乙基全氟丁基醚與乙基全氟異丁基醚 之混合物爲主成份的液體（例如後述之液體B)、以分子結 構相異之兩種以上的二氯五氟丙烷之混合物爲主成份的液 體（例如後述之液體F)、以四氟乙基三氟乙基醚爲主成份 之液體（例如後述之液體G)、以十氟戊烷爲主成份之液體（ 例如後述之液體H)、或以七氟環戊烷與2-甲基-2-丁醇之 φ 混合物爲主成份的液體（例如後述之液體I)之任一種。 其次，就使用如上述所構成之顯像處理裝置1進行顯 像處理，詳細加以說明。圖3爲顯像處理之流程的說明圖 。此顯像處理係，使表面上形成化學增強型之光阻膜、於 所定圖型經曝光之晶圓W，進行顯像處理。 首先，晶圓 W，如圖1所示，吸附保持於旋轉夾盤 10上。接著，如圖2所示，在待機部35待機之顯像液供 給噴嘴33於Y方向之正方向側移動，從平面看，移動至 晶圓W之Y方向的負方向側之端部的面前位置P 1 (圖2 -11 - (8) 1284354 中之虛線位置）。其後，自顯像液供給噴嘴3 3吐出顯像液 ，顯像液供給噴嘴3 3吐出顯像之同時，移動至晶圓W之 Y方向的正方向側之端部的外方位置P2(圖2中之虛線部） 。藉此，在晶圓W上之光阻膜的表面上佈滿顯像液，開 始進行光阻膜之靜止顯像[圖3(a)]。藉由此靜止顯像，例 如進行光阻膜之曝光部份的選擇性溶解，在晶圓W上形 成光阻圖型。 B 經過所定時間後，例如在待機部52待機之洗滌液供 給噴嘴50移動至晶圓W之中心部上方。自洗滌液供給噴 嘴50吐出洗滌液，例如吐出純水，與其同時晶圓W以所 定之低速度旋轉[圖3之（b)]。藉此，晶圓表面之顯像液取 代爲純水，晶圓W之顯像停止。 其後，停止自洗滌液供給噴嘴50供給洗滌液，替代 洗滌液供給噴嘴50，液體供給噴嘴63移動至晶圓W之中 心部上方。例如使晶圓 W之轉速維持於上述所定的低速 φ 度之狀態，自液體供給噴嘴63吐出含有具有極性之氟化 碳系化合物的所定之液體，供給於晶圓表面，晶圓表面的 純水被氟化碳系化合物之液體所取代[圖3(c)]。 晶圓表面被該氟化碳系化合物之液體取代後，停止該 液體之供給。其後，升高晶圓W之轉速，晶圓W以較上 述所定之低速度快的高速度旋轉[圖3(d)]。藉此，晶圓表 面上之液體飛散，晶圓W即乾燥。其後，停止晶圓W之 旋轉，將晶圓W自顯像處理裝置1取出，完成一連串之 顯像處理。 -12- (9) 1284354 於此，在如上所述之顯像處理的供給洗滌液後，供給 具有極性之氟化碳系化合物的液體於晶圓W，就使晶圓w 旋轉乾燥時之效果進行檢測。 圖4爲，在洗滌液之供給後不供給液體，使晶圓乾燥 時（僅洗滌液），在供給洗滌液後供給界面活性劑或A〜I之 各液體，使晶圓乾燥時之晶圓面內的圖型有無倒塌之實驗 數據。 B 液體A爲甲基全氟丁基醚與甲基全氟異丁基醚之混 合物，液體B爲乙基全氟異丁基醚與乙基全氟異丁基醚之 混合物，液體C爲完全氟化物之全氟己烷，液體D爲全 氟庚烷，液體 E爲全氟壬烷，液體 F爲 3,3·二氯-1，1，1，2,2-五氟丙烷（CF3-CF2-CHC12)、與 1，3-二氯-1，1，2,2,3-五氟丙烷（(：(：1?2-€?2-(：1^1?)之混合物，液體0 爲 1，1，2,2-四氟乙基-2,2,2-三氟乙基醚（CF3-CH2-0-CF2-CF2H) ，液體 Η 爲 1，1,1，2,2,3,4,5,5,5-十氟戊烷（〔？3-(：}^-<：1^-φ CF2-CF3)，液體I爲1,1，2,2,3,3,4-七氟環庚烷與2-甲基- 2-丁醇[CH3CH2(CH3)2COH]之混合物。 該液體A係，甲基全氟丁基醚爲30〜50質量％、甲基 全氟異丁基醚爲50〜70質量％之混合物。液體B係’乙基 全氟異丁基醚爲 30〜50質量％、乙基全氟異丁基醚爲 50〜70質量％之混合物。液體F係3,3-二氯-1，1,1，2,2-五氟 丙烷爲45質量％、1，3-二氯-1，1，2,2,3-五氟丙烷55質量％ 之混合物。液體Μ系，1，1，2,2,3,3,4-七氟環戊烷爲94質量 %以上、2-甲基-2-丁醇爲未達5質量％之混合物。 -13- (10) 1284354 液體A〜I之中，含有具有極性之氟化碳系化合物者， 爲液體A、B、F、G、H、I。無極性者爲液體C、D、E。 又，在圖4所示之實驗中所使用的晶圓，增加於下方 向進行之曝光量（D〇se) ’使於右方向進行之曝光的焦點增 大而施行圖型曝光。增加曝光量時圖型之線寬變窄、增大 曝光之焦點時，如圖5所示，圖型之根源部份的寬度K 加厚，就是說，在圖4所示之晶圓面內，形成靠近左下角 φ 容易倒塌的圖型。此實驗之條件係，使用化學增強型之丙 烯系光阻作爲光阻材料，使用ArF光爲曝光光源。 依圖4所示之實驗結果，供給液體A、B、F、G、Η 、I時，與供給僅爲洗滌液、界面活性劑、或無極性之液 體C、D、E時比較，確認圖型難以倒塌。又，確認供給 具有極性之液體A、B、F、G、Η、I時，相對於供給無極 性之液體C、D、Ε時，飛躍的減少圖型倒塌。 圖6爲，在供洗滌液後不供給液體時（僅爲洗滌液）， φ 在洗滌液供給後供給界面活性劑、各液體Α〜I時，圖型不 產生倒塌之界限線寬（最細線寬）的實驗數據。依圖6所示 之實驗數據，確認供給具有極性之液體A、B、F、G、Η 、：[時，與供給僅爲洗滌液、界面活性劑或無機性之液體 C、D、Ε時比較，界限線寬較細。供給具有極性之液體A 、B、F、G、Η、I時之界限線寬爲80nm以下。由此亦可 確認，具有極性之液體A、B、F、G、Η、I時，與供給界 面活性劑時、或供給無極性之液體C、D、Ε時比較，難 以產生圖型倒塌。 -14- (11) 1284354 由上述之結果可確認，在洗滌液之供給後，藉由供給 含有具極性之氟化碳系化合物的液體於晶圓W上，能抑 制在晶圓W之甩脫乾燥時的圖型倒塌。 圖7爲，在供給洗滌液後，供給界面活性劑、具有極 性之各液體A、B、F、G、Η、I時，晶圓W之乾燥前後 的圖型線寬變動量之實驗數據。依圖7所示之實驗結果， 與供給界面活性劑時比較，確認供給具有極性之液體A、 φ B、F、G、Η、I時，線寬變動量小。由此結果可確認，供 給具有極性之液體A、Β、F、G、Η、I時，與供給界面活 性劑時比較，能抑制圖型之膨脹。 因此’如上述之實施形態，在顯像處理之洗滌液供給 後，藉由供給含有具有極佳之氟化碳系化合物的液'體，使 晶圓旋轉進行乾燥’能抑制乾燥時之圖型倒塌與圖型之膨 潤。 其次，檢測該液體a、b、c、d、e、g、i之電容率 # 的結果，如圖8所示；檢測此等液體之對水的溶解度 [ppm(重量）]之結果，如圖9所示。還有，圖8中之數字 爲電容率的具體値’圖9中之數字爲對水的溶解度之具體 値。1284354 (1) The present invention relates to a method for developing a substrate and a development processing device. [Prior Art] In the lithography step of a manufacturing process of a semiconductor device, For example, a photoresist coating process for applying a photoresist solution on a surface of a P wafer to form a photoresist film, or an exposure process for exposing a wafer to a predetermined pattern, and supplying a developing solution on the wafer to cause a photoresist The film is selectively dissolved, and a development process of a photoresist pattern is formed on the wafer. In the development process described above, the developer is supplied with a developer on the wafer to perform still development, and then pure water is supplied to the wafer to stop development, and then the wafer is rotated at a high speed to dry the wafer. However, when the wafer is dried, the wafer is rotated at a high speed, causing the water on the surface of the wafer to scatter everywhere. Due to the Φ effect of the scattered water, the pattern on the surface of the wafer collapses. Therefore, when the wafer is rotated at a high speed, the surfactant is supplied to the wafer, and the moisture is easily detached from the wafer, and the pattern collapse can be suppressed (see Patent Document 1). However, in recent years, for example, a very fine photoresist pattern having a line width of 80 nm or less has been formed. With respect to such a fine pattern, as described above, the surfactant is supplied onto the wafer during drying after development, and the pattern collapse cannot be sufficiently suppressed. Further, in the case where the surfactant was supplied to the wafer during drying after development, it was confirmed by the work of the present invention that the pattern was greatly swollen by the surfactant. When the photoresist pattern is swollen, the line width is not -5- (2) 1284354 is stable and non-uniform, and the desired photoresist pattern cannot be formed on the wafer. Patent Document 1: JP-A-6-163391. SUMMARY OF THE INVENTION [Problems to be Solved by the Invention] The present invention has been made in view of various problems, and it is possible to sufficiently suppress the collapse of a pattern even with respect to an extremely fine photoresist pattern, and to prevent the expansion of the pattern. The development processing method and the development processing device are for the purpose. [Means for Solving the Problem] In order to achieve the above object, the present invention provides a method for developing a substrate, which is characterized in that: a step of supplying a developing solution on a substrate to develop a substrate, and then supplying the substrate thereon The step of stopping the development like the stop liquid, and the step of φ thereafter, supplying a liquid containing a fluorinated carbon compound having a polarity to the substrate, and rotating the substrate to dry the step. According to the present invention, pattern collapse and pattern swelling during drying after development can be suppressed even with respect to a fine pattern. The liquid may be a mixture containing methyl perfluoroisobutyl ether and methyl perfluorobutyl ether, a mixture of ethyl perfluoroisobutyl ether and ethyl perfluorobutyl ether, and two different molecular structures. Any of the above mixtures of dichloropentafluoropropane, tetrafluoroethyl trifluoroethyl ether, decafluoropentane, or heptafluorocyclopentane. The liquid has a permittivity of 2.1 or more and a solubility in water of -6-(3) 1284354 2 1 ppm by weight or more. More preferably, the liquid has a permittivity of 7 or more and a solubility in water of 90 ppm or more. From another viewpoint, the present invention is a development processing apparatus for a substrate; characterized by: a rotary support member that supports rotation of the substrate, and a substrate supported with respect to the rotary support member, the supply contains an excellent fluorination A liquid supply nozzle of a carbon-based compound. According to the invention, the liquid supply nozzle is used to supply a liquid having a polar fluorinated carbon compound to the substrate, whereby the substrate can be rotated and dried. Thereby, the pattern collapse and the swelling of the pattern at the time of drying after development can be suppressed. The liquid may be a mixture containing methyl perfluoroisobutyl ether and methyl perfluorobutyl ether, a mixture of ethyl perfluoroisobutyl ether and ethyl perfluoroisobutyl ether, and the molecular structure is different. Any one of two or more kinds of dichloropentafluoropropane, tetrafluoroethyl trifluoroethyl ether, decafluoropentane, or heptafluorocyclopentane. The liquid preferably has a permittivity of 2.1 or more and a solubility of water of 21 ppm by weight or more. More preferably, the liquid has a permittivity of 7 or more and a solubility in water of 90 ppm or more. [Effects of the Invention] According to the present invention, it is possible to suppress the pattern collapse during drying after development and the swelling of the pattern, and to form a desired pattern on the substrate. [Embodiment] 7-(4) 1284354 [Embodiment of the Invention] The preferred embodiment of the present invention will be described below. FIG. 1 is a schematic longitudinal cross-sectional view showing the configuration of the development processing device 1 of the present embodiment. 2 is a schematic plan view showing the configuration of the development processing device 1. As shown in Fig. 1, the development processing device 1 is provided with a rotary chuck 1 作为 as a rotation supporting member that holds the wafer W in rotation at the center. The rotating chuck 1 〇 P has a horizontal plane on which, for example, an suction port for adsorbing the wafer W (not shown) is disposed. The wafer W can be attracted to the spin chuck 1 by suction from the suction port. The chuck chuck 10 is provided with, for example, a chuck drive mechanism 11 for rotating and lifting the rotary chuck. The chuck drive mechanism 11 includes, for example, a rotation drive unit (not shown) such as a motor that rotates the rotary chuck 10 at a predetermined speed in the vertical direction, or a motor or a cylinder that elevates and lowers the rotary chuck 10 Department (not shown on the map). By the chuck driving mechanism 11, the wafer W on the Φ rotating chuck 10 can be raised and lowered at a predetermined timing and rotated at a predetermined speed. Around the rotating chuck 10, a recovery cup 12 that receives the liquid from the wafer W scattered or dropped is provided. Each of the cups 12 has, for example, an inner cup 13 that surrounds the periphery of the rotating chuck 10, an outer cup 14 that surrounds the outer circumference of the inner cup 13, and a lower surface that covers the lower surface of the inner cup 13 and the outer cup 14. Cup 1 5. By the inner cup 13 and the outer cup 14, the scattered liquid mainly outside the wafer W can be accepted, and the inner wall or the wafer from the inner cup 13 and the outer cup 14 can be recovered by the lower cup 15 W drops the liquid. -8- (5) 1284354 The inner cup 13 is formed, for example, in a substantially cylindrical shape, and its upper end portion is inclined upward inward. The inner cup 13 can be moved up and down by, for example, a lifting and lowering driving unit 16 such as a cylinder. The outer cup 14, as shown in Fig. 2, is formed in a rectangular shape in a square shape as viewed in plan. As shown in Fig. 1, the outer cup 14 can be moved up and down by, for example, a lifting and lowering driving portion 17 such as a cylinder. The rotary chuck 10 extends through the central portion of the lower cup 15. An annular member 18 that blocks the liquid flowing from the surface of the wafer W back to the back surface is provided, for example, on the flat surface of the lower cup 15 around the rotating chuck 1 . The _ ring member 18 has, for example, a top portion close to the back surface of the wafer W, and the liquid flowing to the back surface of the wafer can be blocked at the top portion of the wafer. The lower cup 15 is connected, for example, to an outlet pipe 19 connected to the liquid discharge portion of the factory; the recovered liquid in the cup 12 can be discharged from the discharge pipe 19 to the outside of the development processing device 1, as shown in Fig. 2. It is shown that the guide rail 30 which extends in the Y direction (the horizontal direction of FIG. 2) is formed in the negative direction (lower side of FIG. 2) of the X direction of the cup 12. The guide rail 30 is formed, for example, from the outer side in the negative direction of the Y direction of the cup 12 (the left side φ side of FIG. 2) to the outer side of the positive direction of the Y direction of the cup 12 (the right side in FIG. 2). . On the guide rail 30, for example, two arm bars 31, 32 are mounted. The first arm 31 supports the developing liquid supply nozzle 33. The first arm 31 is movable in the Y direction on the guide rail 30 by the nozzle driving portion 34. By the first arm 31, the developing liquid supply nozzle 33 can be moved from the standby portion 35 to the inside of the cup 1 2 on the negative side in the Y direction of the cup 12, and can be moved on the wafer W. Move on the surface. Further, the first arm 31 can be moved in the vertical direction by the nozzle driving unit 34, for example, and the developing liquid supply nozzle 33 can be moved up and down. -9 (6) 1284354 The developing liquid supply nozzle 3 3 has an elongated shape which is equal to or longer than the diameter of the wafer W in the X direction. As shown in Fig. 1, a developing liquid supply pipe 41 connected to the developing liquid supply source 40 is connected to the upper portion of the developing liquid supply nozzle 33. At a lower portion of the developing liquid supply nozzle 33, a plurality of discharge ports 3 3 a which are formed in a row in the longitudinal direction are formed. The developing liquid is supplied to the nozzles 33, and the developing liquid introduced from the upper developing liquid supply pipe 41 is discharged through the developing liquid supply nozzles 3, and discharged from the respective lower discharge ports 3 3 a. The second arm 32 supports the washing liquid supply nozzle 50 as shown in Fig. 2 . The second arm 32 is movable in the Y direction on the guide rail 30 by, for example, the nozzle driving portion 51. By the second arm 32, the washing liquid supply nozzle 50 can be moved from the standby portion 52 provided on the positive side in the Y direction of the cup 12 to the wafer W in the cup 12. Further, the second arm 32 can be moved in the vertical direction by the nozzle driving unit 5 1. The washing liquid supply nozzle 50 is connected to a washing liquid supply pipe 54 that communicates with the washing liquid supply source 53 as shown in Fig. 1 . In the present embodiment, for example, pure water as a development stop liquid (washing liquid) is stored in the washing liquid supply source 53. As shown in Fig. 2, on the side of the cup 12 in the positive direction (upper side of Fig. 2), a guide rail 60 extending in the Y direction is formed. The guide rail 60 is formed, for example, from the outside of the positive direction side of the cup 12 in the Y direction to the outside of the negative direction side of the cup 12 in the Y direction. For example, the third arm 6 1 is attached to the guide rail 60. The third arm is freely movable on the guide rail 60 by the driving portion 62. The third arm 61 supports the liquid supply nozzle 63. The storage container 6 4 of the liquid supply nozzle 6 3 is provided outside the positive -10 (7) 1284354 direction of the Y direction of the cup 12; the liquid supply nozzle 63 is movable by the movement of the third arm 61. The container 64 is moved up to the wafer W in the cup 12. Further, the third arm 61 can be freely moved in the vertical direction by the driving portion 62, for example, and the liquid supply nozzle 63 can be moved up and down to adjust the height. The liquid supply nozzle 63 is connected to a liquid supply pipe 66 that communicates with the liquid supply source 65 as shown in Fig. 1 . The liquid supply source 65 stores a liquid containing a fluorinated carbon compound having a polarity of p, for example, a liquid containing a mixture of methyl perfluoroisobutyl ether and methyl perfluoroisobutyl ether as a main component (for example, a liquid described later) A) a liquid containing a mixture of ethyl perfluorobutyl ether and ethyl perfluoroisobutyl ether as a main component (for example, liquid B described later) or two or more kinds of dichloropentafluoropropane having different molecular structures a mixture of a main component liquid (for example, liquid F described later), a liquid containing tetrafluoroethyl trifluoroethyl ether as a main component (for example, liquid G described later), and a liquid containing decafluoropentane as a main component (for example) The liquid H) to be described later, or a liquid containing a mixture of heptafluorocyclopentane and 2-methyl-2-butanol as a main component (for example, a liquid I to be described later). Next, the development processing using the development processing device 1 configured as described above will be described in detail. Fig. 3 is an explanatory diagram of the flow of development processing. In this development processing, a chemically-enhanced photoresist film is formed on the surface, and the exposed wafer W is subjected to development processing. First, the wafer W, as shown in Fig. 1, is adsorbed and held on the spin chuck 10. Then, as shown in FIG. 2, the developing liquid supply nozzle 33 that is in standby in the standby unit 35 moves in the positive direction side in the Y direction, and moves to the front side of the negative side of the Y direction of the wafer W as viewed in plan. Position P 1 (the dotted line position in Figure 2 -11 - (8) 1284354). Then, the developing liquid supply nozzle 33 discharges the developing liquid, and the developing liquid supply nozzle 33 discharges the image and moves to the outer position P2 of the end portion of the wafer W on the positive side in the Y direction ( The dotted line in Figure 2). Thereby, the surface of the photoresist film on the wafer W is filled with the developing liquid, and the still image of the photoresist film is started [Fig. 3 (a)]. By this still development, for example, selective dissolution of the exposed portion of the photoresist film is performed to form a photoresist pattern on the wafer W. B After a predetermined period of time, for example, the washing liquid supply nozzle 50 which is in standby in the standby unit 52 moves to the upper side of the center portion of the wafer W. The washing liquid supply nozzle 50 discharges the washing liquid, for example, discharges pure water, and at the same time, the wafer W is rotated at a predetermined low speed [Fig. 3 (b)]. Thereby, the developing liquid on the wafer surface is replaced by pure water, and the development of the wafer W is stopped. Thereafter, the supply of the washing liquid from the washing liquid supply nozzle 50 is stopped, and instead of the washing liquid supply nozzle 50, the liquid supply nozzle 63 is moved above the center of the wafer W. For example, the rotation speed of the wafer W is maintained at the predetermined low speed φ degree, and a predetermined liquid containing a fluorinated carbon compound having a polarity is discharged from the liquid supply nozzle 63, and is supplied to the surface of the wafer, and pure water on the surface of the wafer. It is replaced by a liquid of a fluorinated carbon compound [Fig. 3(c)]. After the surface of the wafer is replaced by the liquid of the fluorinated carbon compound, the supply of the liquid is stopped. Thereafter, the rotational speed of the wafer W is raised, and the wafer W is rotated at a high speed which is faster than the above-described low speed [Fig. 3(d)]. Thereby, the liquid on the surface of the wafer scatters and the wafer W is dried. Thereafter, the rotation of the wafer W is stopped, and the wafer W is taken out from the development processing device 1 to complete a series of development processing. -12- (9) 1284354 Here, after the supply of the washing liquid in the developing process as described above, the liquid of the polar fluorinated carbon compound is supplied to the wafer W, and the wafer w is rotated and dried. Test. 4 is a wafer in which no liquid is supplied after the supply of the washing liquid, the wafer is dried (cleaning liquid only), and the liquid is supplied to the surfactant or the liquid of A to I after the washing liquid is supplied to dry the wafer. The in-plane pattern has experimental data for collapse. B Liquid A is a mixture of methyl perfluorobutyl ether and methyl perfluoroisobutyl ether, liquid B is a mixture of ethyl perfluoroisobutyl ether and ethyl perfluoroisobutyl ether, liquid C is completely Fluoride perfluorohexane, liquid D is perfluoroheptane, liquid E is perfluorodecane, and liquid F is 3,3·dichloro-1,1,1,2,2-pentafluoropropane (CF3- CF2-CHC12), with 1,3-dichloro-1,1,2,2,3-pentafluoropropane ((:(:1?2-€?2-(:1^1?) mixture, liquid 0 is 1,1,2,2-tetrafluoroethyl-2,2,2-trifluoroethyl ether (CF3-CH2-0-CF2-CF2H), liquid Η is 1,1,1,2,2 , 3,4,5,5,5-decafluoropentane ([?3-(:}^-<:1^-φ CF2-CF3), liquid I is 1,1,2,2,3, a mixture of 3,4-heptafluorocycloheptane and 2-methyl-2-butanol [CH3CH2(CH3)2COH]. The liquid A system, methyl perfluorobutyl ether is 30 to 50% by mass, methyl Perfluoroisobutyl ether is a mixture of 50 to 70% by mass. The liquid B is a mixture of 30 to 50% by mass of ethyl perfluoroisobutyl ether and 50 to 70% by mass of ethyl perfluoroisobutyl ether. Liquid F is 3,3-dichloro-1,1,1,2,2-pentafluoropropane, 45 mass%, 1,3-dichloro-1,1 a mixture of 2,2,3-pentafluoropropane and 55% by mass. Liquid lanthanide, 1,1,2,2,3,3,4-heptafluorocyclopentane is 94% by mass or more, 2-methyl- 2-butanol is a mixture of less than 5% by mass. -13- (10) 1284354 Among the liquids A to I, those having a polar fluorinated carbon compound are liquids A, B, F, G, H, I. The non-polarizers are liquids C, D, and E. Further, the wafer used in the experiment shown in Fig. 4 is increased in exposure amount in the lower direction (D〇se) to cause exposure in the right direction. The focus is increased and the pattern exposure is performed. When the exposure is increased, the line width of the pattern is narrowed, and when the exposure focus is increased, as shown in FIG. 5, the width K of the root portion of the pattern is thickened, that is, In the wafer surface shown in Fig. 4, a pattern which is easily collapsed near the lower left corner φ is formed. The conditions of this experiment are that a chemically enhanced acryl-based photoresist is used as the photoresist material, and ArF light is used as the exposure light source. As shown in the experimental results shown in Fig. 4, when the liquids A, B, F, G, 、, and I are supplied, the comparison is performed when the supply is only the washing liquid, the surfactant, or the non-polar liquids C, D, and E. When it is confirmed that the liquids A, B, F, G, Η, and I having polarities are supplied, the pattern of the leap reduction is collapsed when the liquids C, D, and 无 are supplied without polarity. When no liquid is supplied after the washing liquid is supplied (only the washing liquid), φ is supplied to the surfactant after the supply of the washing liquid, and when the liquid Α~I, the pattern does not cause the line width of the collapse (the thinner line width). data. According to the experimental data shown in Fig. 6, it is confirmed that the liquids A, B, F, G, Η, and [with polarity] are supplied with the liquid C, D, and 供给 when the supply is only the washing liquid, the surfactant, or the inorganic liquid. In comparison, the limit line width is thinner. When the liquids A, B, F, G, Η, and I having polarity are supplied, the limit line width is 80 nm or less. From this, it was confirmed that when the liquids A, B, F, G, Η, and I having polarity were supplied, it was difficult to cause pattern collapse as compared with the case of supplying the non-polar liquids C, D, and Ε. -14- (11) 1284354 From the above results, it was confirmed that the supply of the liquid containing the polar fluorinated carbon compound to the wafer W after the supply of the washing liquid can suppress the removal of the wafer W. The pattern when it is dry collapses. Fig. 7 is experimental data showing the amount of variation in the pattern line width before and after drying of the wafer W when the surfactant is supplied and the liquids A, B, F, G, Η, and I are extremely supplied after the supply of the cleaning liquid. According to the experimental results shown in Fig. 7, when the supply of the liquid A, φ B, F, G, Η, and I having polarity is confirmed, the amount of variation in the line width is small as compared with the case of supplying the surfactant. From this result, it was confirmed that when the polar liquids A, Β, F, G, Η, and I were supplied, the expansion of the pattern was suppressed as compared with the case of supplying the interface active agent. Therefore, in the above-described embodiment, after the supply of the cleaning liquid for the development process, the liquid crystal body containing the excellent fluorinated carbon compound is supplied and the wafer is rotated and dried to suppress the pattern during drying. Collapse and swelling of the pattern. Next, the result of detecting the permittivity # of the liquids a, b, c, d, e, g, i is as shown in FIG. 8; the result of detecting the solubility of the liquids to water [ppm (by weight)], such as Figure 9 shows. Also, the number in Fig. 8 is the specific 电容 of the permittivity. The number in Fig. 9 is the specific 对 of the solubility to water.
首先，觀察此等液體之電容率，如圖8所示，液體C 、D、E之電容率爲2以下，相對於此，液體a、B、G、I 具有大約7以上之電容率。因此，由此結果可知，具有高 電容率之液體a、b、g、i，比電容率爲2以下之低電容 率的液體C、D、E ’更難以產生圖型倒塌，又具有防止圖 -15- (12) 1284354 型膨潤之效果。所以，依本發明的工作同仁之推測’具有 極性之液體，電容率爲2 · 1以上，更佳爲電容率在7以上 時，具有防止圖型倒塌之效果。 其次，觀測此等液體之對水的溶解度’如圖9所示’ 液體C、D、E之對水的溶解度爲l〇[PPm(重量）]以下，相 對於此，液體八、6、〇、1具有大約90[??111(重量）]以上 之對水的溶解度。因此，由此結果可知，具有高對水之溶 φ 解度的液體A、B、G、I，比溶解度爲1 0以下之低溶解度 的液體C、D、E，更難以產生圖型倒塌，又具有防止圖型 膨潤之效果。所以，依發明的工作同仁之推測，具有極體 之液體，對水之溶解度爲20[ppm(重量）]以上，更佳爲對 水之溶解度爲90[ppm(重量）]以上之液體，具有防止圖型 倒塌之效果。 由上述圖8、圖9之結果及觀察推測，含有具有極性 之氟化碳系化合物的液體，進而電容率爲2.1以上，更佳 φ 爲電容率在7以上，且對水之溶解度爲20[PPm(重量）]以 上，更佳爲對水之溶解度在90[ppm(重量）]以上的液體， 具有防止圖型倒塌的效果，又具有防止圖型之膨潤的效果 。此與圖4、圖6之結果對照亦爲符合者。 就本發明的實施形態之一例說明如上。本發明並非僅 限定於此例，可採用各種之形態。例如本發明亦可使用晶 圓以外之例如FPD (平板顯示器）、光罩用之光罩調製盤等 其他之基板的顯像處理方祛。 -16- (13) 1284354 [產業上利用性] 本發明係適合使用於，在顯像後之基板乾燥中，抑制 圖型倒塌或圖型之膨潤者。 【圖式簡單說明】 圖1爲本實施形態中顯像處理裝置之構成的槪略縱剖 面之說明圖。 B 圖2爲顯像處理裝置之構成的槪略平面圖。 圖3爲顯像處理之流程的說明圖。 圖4爲在顯像後之乾燥時，供給界面活性劑、所定之 液體A〜I時的表示有無圖型倒塌之實驗數據。 圖5爲圖型之根源部份的寬度之說明圖。 圖6爲界面活性劑、所定之液體A〜I，不產生圖型倒 塌之界限線寬的實驗數據。 圖7爲在顯像後之乾燥時，供給界面活性劑，液體A φ 、B、F、G、Η或I於晶圓上之情況的圖型之線寬變動量 的實驗數據。 圖8爲檢測液體A、B、C、D、E、G、I之電容率的 結果之表示圖表。 圖9爲檢測液體A、Β、C、D、Ε、G、I之對水的溶 解度之結果的表示圖表。 【主要元件符號說明】 1 :顯像處理裝置 -17- (14) 1284354 1 1 :夾盤驅動機構 1 2 :回收杯 1 3 :內杯 1 4 :外杯 1 5 :下杯 1 6 :升降驅動部 1 7 :升降驅動部 φ 1 8 :環狀構件 1 9 :排出管 30 :導軌 3 1 :第1臂桿 3 2 :第2臂桿 3 3 a :吐出口 34 :噴嘴驅動部 3 5 :待機部 φ 40 :顯像液供給源 4 1 :顯像液供給管 5 1 :噴嘴驅動部 52 :待機部 53 :洗滌液供給源 54 :洗滌液供給管 60 :導軌 61 :第3臂桿 6 2 ·驅動部 -18- (15) (15)1284354 64 :收容容器 65 :液體供給源 66 :液體供給管 P 1 :晶圓W之Y方向負方向側的端部之面前位置 P2 :晶圓W之Y方向正方向側的端部之外方位置First, the permittivity of these liquids is observed. As shown in Fig. 8, the capacitances of the liquids C, D, and E are 2 or less. In contrast, the liquids a, B, G, and I have a permittivity of about 7 or more. Therefore, it can be seen from the results that the liquids a, b, g, and i having a high permittivity are more difficult to cause pattern collapse than the liquids C, D, and E' having a low permittivity of 2 or less, and have a prevention map. -15- (12) 1284354 type swelling effect. Therefore, according to the work of the present invention, the liquid having a polarity, the permittivity is 2 · 1 or more, and more preferably, when the permittivity is 7 or more, the effect of preventing the pattern from collapsing is obtained. Next, observe the solubility of these liquids in water' as shown in Fig. 9 'The solubility of liquids C, D, and E in water is l〇 [PPm (by weight)] or less, and liquid VIII, 6, 〇 1 has a solubility in water of about 90 [?? 111 (by weight) or more. Therefore, as a result of the above, it is understood that the liquids A, B, G, and I having a high degree of solubility in water are more difficult to cause pattern collapse than the liquids C, D, and E having a solubility of less than 10%. It also has the effect of preventing the swelling of the pattern. Therefore, according to the speculation of the working colleagues of the invention, a liquid having a polar body having a solubility in water of 20 [ppm (by weight) or more, more preferably a solubility in water of 90 [ppm] or more, has Prevent the effect of pattern collapse. From the results and observations of Figs. 8 and 9, it is estimated that the liquid containing a polar fluorinated carbon compound has a permittivity of 2.1 or more, more preferably φ has a permittivity of 7 or more, and solubility in water is 20 [ A liquid having a PPm (by weight) or more, more preferably a water solubility of 90 [ppm] or more, has an effect of preventing the pattern from collapsing, and has an effect of preventing swelling of the pattern. This is also consistent with the results of Figures 4 and 6. The above is explained as an example of an embodiment of the present invention. The present invention is not limited to this example, and various forms can be employed. For example, in the present invention, a development processing method of other substrates such as an FPD (Flat Panel Display) or a photomask reticle for a photomask may be used. -16- (13) 1284354 [Industrial Applicability] The present invention is suitably used for suppressing pattern collapse or pattern swelling during drying of a substrate after development. BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is an explanatory view showing a schematic longitudinal section of a configuration of a developing device in the embodiment. B Fig. 2 is a schematic plan view showing the configuration of the development processing apparatus. Fig. 3 is an explanatory diagram of the flow of development processing. Fig. 4 is an experimental data showing the presence or absence of pattern collapse when a surfactant and a predetermined liquid A to I are supplied during drying after development. Figure 5 is an explanatory diagram of the width of the root portion of the pattern. Fig. 6 is experimental data showing the boundary line width of the surfactant, the predetermined liquids A to I, and no pattern collapse. Fig. 7 is experimental data of the variation in the line width of the pattern in which the surfactant A, φ, B, F, G, Η or I is applied to the wafer during drying after development. Fig. 8 is a graph showing the results of detecting the permittivity of the liquids A, B, C, D, E, G, and I. Fig. 9 is a graph showing the results of detecting the solubility of liquids A, Β, C, D, Ε, G, and I with respect to water. [Description of main component symbols] 1 : Development processing device-17- (14) 1284354 1 1 : Chuck drive mechanism 1 2 : Recycling cup 1 3 : Inner cup 1 4 : Outer cup 1 5 : Lower cup 1 6 : Lifting Drive unit 17: Lifting drive unit φ 1 8 : Annular member 1 9 : Discharge pipe 30 : Guide rail 3 1 : First arm 3 2 : Second arm 3 3 a : Discharge port 34 : Nozzle drive unit 3 5 : standby unit φ 40 : developing solution supply source 4 1 : developing solution supply pipe 5 1 : nozzle driving unit 52 : standby unit 53 : washing liquid supply source 54 : washing liquid supply pipe 60 : guide rail 61 : third arm 6 2 · Drive unit -18- (15) (15) 1284354 64 : Storage container 65 : Liquid supply source 66 : Liquid supply pipe P 1 : Front position P2 of the end of the wafer W on the negative side in the Y direction: Crystal Outside the end of the positive side of the Y direction of the circle W
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