.201239972 六、發明說明： 【發明所屬之技術領域】 本發明係關於藉由洗淨液洗淨基板的基板洗淨裝置及 基板洗淨方法，以及，顯示裝置之製造裝置及顯示裝置之 製造方法。 【先前技術】 基板洗淨裝置，係於液晶顯示裝置或半導體裝置等的 製造步驟，對玻璃基板或半導體晶圓等基板的表面供給洗 淨液’洗淨該基板表面。於此基板洗淨裝置之中，例如， 存在著搬送洗淨對象之基板同時對該基板表面供給洗淨液 的基板洗淨裝置。 於使用洗淨液的基板洗淨，例如藉由掀離（lift-off ) 法進行基板洗淨的場合，進行根據臭氧水（〇3水）之有機 物除去及氧化膜形成’其後，進行根據稀氟酸溶液（DHF 溶液）進行氧化膜除去（例如參照專利文獻1 )。藉此， 由基板表面上除去污染粒子。 〔專利文獻1〕日本特開2002-131777號公報 然而，在前述之基板洗淨，必須要根據臭氧水進行有 機物除去及氧化膜形成的步驟，與根據稀氟酸溶液進行氧 化膜除去的步驟等2道洗淨步驟。此外，在根據稀蕹酸之 氧化膜除去後，會有一旦被除去的污染粒子再度附著於基 板表面的情形。 201239972 【發明內容】 本發明係有鑑於前述情形而完成之發明，其目的在於 提供可以減少洗淨步驟數，可防止污染粒子對基板之再附 著的基板洗淨裝置及基板洗淨方法，以及，顯示裝置之製 造裝置及顯示裝置之製造方法。 相關於本發明的實施型態的第1特徵，係於基板洗淨 裝置，具備：搬送基板的搬送部、對藉由搬送部搬送的基 板的被洗淨面，供給在可以除去氧化膜的液體中以溶存狀 態及微小氣泡的狀態具有氧化性氣體之洗淨液的供給噴嘴 :供給噴嘴，以使到達被洗淨面上的微小氣泡抑制尺寸改 變同時以移動至基板的外緣的流速供給洗淨液。 相關於本發明的實施型態之第2特徵，係於基板洗淨 裝置，具備：搬送基板的搬送部，及對藉由搬送部搬送的 基板的被洗淨面，分別供給在可以除去氧化膜的液體中以 溶存狀態及微小氣泡狀態具有氧化性氣體之洗淨液的複數 供給噴嘴；複數供給噴嘴，沿著基板的被洗淨面排列設置 在交叉於基板的搬送方向的方向上，在平行於基板的被洗 淨面的平面內對基板的搬送方向分別傾斜於相同的方向， 對基板的被洗淨面分別傾斜於相同的方向。 相關於本發明的實施型態的第3特徵，係於基板洗淨 方法，使用具備：搬送基板的搬送部、對藉由搬送部搬送 的基板的被洗淨面，供給在可以除去氧化膜的液體中以溶 存狀態及微小氣泡的狀態具有氧化性氣體之洗淨液的供給 噴嘴的基板洗淨裝置來洗淨基板之基板洗淨方法；藉由供 -6- .201239972 給噴嘴，對藉由搬送部搬送的基板之被洗淨面，以使到達 • 被洗淨面上的微小氣泡抑制尺寸改變同時以移動至基板的 • 外緣的流速供給洗淨液。 相關於本發明的實施型態之第4特徵，係於基板洗淨 方法，使用具備：搬送基板的搬送部，及對藉由搬送部搬 送的基板的被洗淨面，分別供給在可以除去氧化膜的液體 中以溶存狀態及微小氣泡狀態具有氧化性氣體之洗淨液的 複數供給噴嘴之基板洗淨裝置，來洗淨基板之基板洗淨方 法：複數供給噴嘴，沿著基板的被洗淨面排列設置在交叉 於基板的搬送方向的方向上，在平行於基板的被洗淨面的 •平面內對基板的搬送方向分別傾斜於相同的方向，對基板 的被洗淨面分別傾斜於相同的方向，藉由複數供給噴嘴， 對藉由搬送部搬送的基板之被洗淨面供給洗淨液。 相關於本發明的實施型態之第5特徵，係於顯示裝置 之製造裝置，具備洗淨使用於顯示裝置的基板之基板洗淨 裝置的顯示裝置之製造裝置，該基板洗淨裝置，係相關於 前述第1或第2特徵之基板洗淨裝置。 相關於本發明的實施型態之第6特徵，係於顯示裝置 之製造方法，具有洗淨使用於顯示裝置的基板之基板洗淨 • 步驟的顯示裝置之製造方法，於基板洗淨步驟，使用相關 • 於前述第3或第4特徵之基板洗淨方法洗淨基板。 根據前述第1至第6之任一特徵，可以減少洗淨步驟 數，進而，可以防止污染粒子對基板之再附著。 201239972 【實施方式】 (第1實施形態） 參照圖1至圖4說明本發明之第1實施型態。 相關於本發明的第1實施型態之基板洗淨裝置1 (參 照圖1)，係作爲製造顯示裝置之液晶顯示器的製造裝置 的一部分而設置的，此顯示裝置之製造裝置，具備：於基 板W上製作液晶驅動用的TFT電路及電極圖案之製造裝 置（未圖示），在被形成TFT電路及電極圖案等的基板W 上形成配向膜之配向膜形成裝置（未圖示），於被形成配 向膜的基板W上形成包圍各胞單位的顯示區域之框狀的 密封之密封形成裝置（未圖示），於被形成密封的基板W 之各胞單位的顯示區域上使液晶材料滴下的液晶供給裝置 (未圖示），使被滴下液晶材料的基板W與其他基板貼 合的基板貼合裝置（未圖示），在貼合基板後使密封硬化 之密封硬化裝置（未圖示），進而，於各製造裝置內及裝 置間的基板移動步驟之必要的地點具備進行洗淨之基板洗 淨裝置1。 如圖1所示，相關於第1實施型態之基板洗淨裝置1 ，具備搬送基板w的搬送部2、對藉由該搬送部2搬送的 基板W之被洗淨面S供給洗淨液之供給噴嘴3、使氣體溶 解於洗淨液的加壓溶解部4、送液用泵5、供給洗淨液的 液體供給部6、供給氣體的氣體供給部7、控制各部之控 制部8。 搬送部2，具有相互平行排成一列的複數輥2a及旋轉 -8 - 201239972 這些輥2a的驅動源之旋轉馬達2b»各輕2a被設爲可以分 別旋轉，等間隔地排列著。旋轉馬達2b被導電連接於控 制部8，其驅動藉由控制部8而被控制。此搬送部2 ’藉 由旋轉馬達2b而旋轉各輥2a，使被載置於這些輥2a上的 矩形狀的基板W移動於圖1中的箭頭A的方向。 供給噴嘴3，設於搬送部2的上方，朝向藉由搬送部 2移動的基板W之被洗淨面S噴射洗淨液，供給至該被洗 淨面S上。此供給噴嘴3，例如，使用噴射洗淨液之一流 體噴嘴（一流體用之噴射噴嘴）。 加壓溶解部4，藉由成爲液體供給流路的配管11被連 接於供給噴嘴3，使氣體在高壓下溶解於洗淨液中，將該 氣體溶解的洗淨液中介著配管U供給至供給噴嘴3。此加 壓溶解部4，做爲使氣體溶解於洗淨液之溶解部而發揮功 能。 於配管1 1，使調整流量之閥1 1 a位於供給噴嘴3的附 近而設置。此閥1 1 a被導電連接於控制部8，其驅動藉由 控制部8而被控制。此外，於配管1 1，設有計測流量之流 量計1 1 b。此流量計1 1 b被導電連接於控制部8，其計測 結果被輸入控制部8。 此處，閥11a被打開時，包含溶存氣體的洗淨液由供 給噴嘴3被噴射出。此時，洗淨液被壓力解放至大氣壓’ 被壓力解放的洗淨.液對於溶存氣體成爲過飽和狀態’所以 於該洗淨液中大量產生微小氣泡。亦即，供給噴嘴3 ’朝 向移動的基板W之被洗淨面S噴射洗淨液，成爲於該被 5 -9 - 201239972 洗淨面S上供給包含微小氣泡的洗淨液。 又，微小氣泡，是包含微泡（micro-bubble, MB)或 微奈米泡（micro-nano-bubble，MNB)、奈米泡（11311〇-bubble，NB)等槪念之細微氣泡。例如，微泡是具有ΙΟμιιι 〜數十μηι直徑的氣泡，微奈米泡爲具有數百nm〜ΙΟμιη 直徑之氣泡，奈米泡具有數百nm以下的直徑的氣泡。 泵5，於流體供給流路被設於比加壓溶解部4更位於 上游側，成爲對供給噴嘴3供給洗淨液的驅動源。此泵5 被導電連接於控制部8，其驅動藉由控制部8而被控制。 液體供給部6，藉由成爲液體供給流路的配管1 2中介 著泵5被連接於加壓溶解部4，對該加壓溶解部4供給液 體。此處，作爲液體，使用可除去氧化膜的液體，例如稀 氟酸（DHF)溶液。除此以外，使用界面活性劑等亦爲可 能。 氣體供給部7，藉由成爲氣體供給流路的配管13被連 接於液體供給流路之配管12的途中，對通過該配管12的 洗淨液供給而使含有氣體。此處，作爲氣體，使用氧化性 氣體，例如臭氧（〇3 )。 於配管13，設有調整流量之閥13a。此閥13a被導電 連接於控制部8，其驅動藉由控制部8而被控制。此外， 於配管1 3，設有計測流量之流量計1 3 b。此流量計1 3 b被 導電連接於控制部8，其計測結果被輸入控制部8。 控制部8，具備集中控制各部分的微電腦、及記憶關 於基板洗淨之基板洗淨資訊或各種程式等之記憶部。此控 -10- 201239972 制部8，根據基板洗淨資訊或各種程式，藉由搬送部2搬 送基板W，同時藉由供給噴嘴3朝向移動中的基板W的 被洗淨面S噴射洗淨液，進行對該被洗淨面S上供給包含 多數微小氣泡的洗淨液，詳言之，是在可除去氧化膜的液 體之稀氟酸溶液中以溶存狀態及微小氣泡狀態具有氧化性 氣體之臭氧的洗淨液的基板洗淨。又，微小氣泡的產生量 ，藉由控制部8調整閥1 3 a的開口度，可以藉由調整對洗 淨液供給的氣體量而改變。 前述洗淨液被供給至基板W的被洗淨面S上時，如 圖2所示，藉由洗淨液中的臭氧〇3除去被洗淨面s上的 有機物F1+，同時，藉由此臭氧03改質被洗淨面S，於該 被洗淨面S形成氧化膜F2。藉此，爲有機物F1覆蓋的污 染粒子Μ爲氧化膜F2所覆蓋，存在於有機物F1上的污 染粒子Μ，藉由臭氧〇3氧化，成爲氧化金屬Ma。進而， 如圖3所示，藉由洗淨液中的氟化氫HF除去被洗淨面S 上的氧化膜F2。藉此，爲氧化膜F2覆蓋的污染粒子Μ以 及氧化金屬Ma由被洗淨面S上被除去。又，臭氧〇3與有 機物F1反應，藉由被分解而產生C02、C0、H20 (參照 圖2 )。 此外，如圖4所示，負電位的微小氣泡複數個附著於 正電位的污染粒子（例如，鋁粒子）Μ，包圍該污染粒子 Μ。此時，基板W爲正電位的場合，負電位的微小氣泡複 數個附著於基板W之被洗淨面S上。藉此，包圍污染粒 子Μ的多數微小氣泡成爲與基板W的被洗淨面S上的多 -11 - 201239972 數微小氣泡成電位排斥，防止一旦被除去的污染粒子Μ再 附著於基板W的被洗淨面S。又，即使基板W爲負電位 的場合，包圍污染粒子Μ的多數微小氣泡也成爲與基板 W的被洗淨面S成電位排斥，所以防止污染粒子Μ再附 著於基板W的被洗淨面S。 這樣的3個現象（圖2、圖3及圖4所示的現象）依 序在基板W之被洗淨面S上之各處發生。藉此，可以同 時進行根據臭氧之有機物除去及氧化膜形成，以及，根據 稀氟酸溶液之除去氧化膜，所以可以削減洗淨步驟數。進 而，複數個微小氣泡附著於污染粒子Μ而包圍該污染粒子 Μ，所以可以防止一度被除去的污染粒子Μ再附著於基板 W之被洗淨面S。 此處，爲了提高藉由包含微小氣泡的洗淨液洗淨基板 w的被洗淨面S之洗淨性能，由供給噴嘴3所噴射的洗淨 液所包含的微小氣泡，到達基板W的被洗淨面S後，抑 制其尺寸變化，例如維持直徑而到達基板W的外緣變得 重要。被洗淨面S上的微小氣泡會與其他微小氣泡結合而 變大’或者是伴隨著時間經過而消滅，所以不會在維持其 直徑的狀態下到達被洗淨面S的外緣。在此場合，前述防 止附著的效果變得不充分，使得洗淨能力降低。此外，爲 了使根據前述3個現象的洗淨能力更爲提高，有必要依序 置換基板W的被洗淨面S上的洗淨液。 例如，在使用將圓形狀的基板W載置於台座上，以 此台座的中央爲旋轉中心使台座旋轉，同時對台座上的基 -12- 201239972 板W供給洗淨液的形式之洗淨裝置的場合，被供給至基 板W上的洗淨液藉由基板W的旋轉導致的離心力朝向基 板W的外緣擴開。這樣的場合，洗淨液只要單純地被供 給至基板W的被洗淨面S的中央附近即可，但如本發明 的第1實施型態那樣將基板W往一方向搬送的場合，有 必要著眼於基板W之被洗淨面S的洗淨液的擴開。 在此，在本發明之第1實施型態，藉由供給噴嘴3噴 射的洗淨液的流速，設定爲抑制到達基板W的被洗淨面S 上的微小氣泡之尺寸改變，亦即維持容許範圍內的尺寸之 容許尺寸同時移動至基板W的外緣之流速。例如，該流 速，設定爲維持·微小氣泡的直徑同時移動至基板W的外 緣的流速。作爲供實現此流速的設定値，預先藉由實驗而 求得，被記憶於控制部8具備的記憶部，而控制部8打開 閥Π a直到根據該設定値決定的開口度。因應於此，供給 噴嘴3以前述之流速噴射洗淨液。又，在僅藉由使閥1 1 a 開口而調整流速還不夠充分的場合，因應於藉由流量計 1 1 b計測的流量藉由控制部8調整閥1 1 a的開口度以及根 據泵5之送液力等，可以使流速配合前述設定値。 以前述之流速使洗淨液由供給噴嘴3噴射時，該洗淨 液中的多數微小氣泡分別到達基板W的被洗淨面S上， 其後，維持直徑而到達基板W的外緣。結果，多數的微 小氣泡可以確實地包圍由被洗淨面S上被除去的污染粒子 Μ，所以可以確實防止一度被除去的污染粒子Μ再附著於 基板W之被洗淨面S。而且，多數之微小氣泡維持直徑同 -13- 201239972 時到達基板W的外緣，導致可以得到確實進行初 上的洗淨液的置換之流速，所以促進在被洗淨面 處產生的前述之3個現象，可以提高洗淨能力。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a substrate cleaning apparatus and a substrate cleaning method for cleaning a substrate by a cleaning liquid, and a manufacturing apparatus of the display apparatus and a manufacturing method of the display apparatus . [Prior Art] The substrate cleaning apparatus is a step of manufacturing a liquid crystal display device or a semiconductor device, and supplies a cleaning liquid to the surface of a substrate such as a glass substrate or a semiconductor wafer to clean the surface of the substrate. In the substrate cleaning apparatus, for example, there is a substrate cleaning apparatus that transports a substrate to be cleaned and supplies a cleaning liquid to the surface of the substrate. When the substrate is washed with a cleaning liquid, for example, when the substrate is cleaned by a lift-off method, organic material removal and oxide film formation according to ozone water (〇3 water) are performed, and then The dilute hydrofluoric acid solution (DHF solution) is subjected to oxide film removal (for example, refer to Patent Document 1). Thereby, contaminating particles are removed from the surface of the substrate. [Patent Document 1] Japanese Laid-Open Patent Publication No. 2002-131777. However, in the above-described substrate cleaning, a step of removing organic substances and forming an oxide film according to ozone water, a step of removing an oxide film from a dilute hydrofluoric acid solution, and the like are required. 2 washing steps. Further, after the oxide film of dilute citrate is removed, there is a case where the contaminated particles once removed are attached to the surface of the substrate again. The present invention has been made in view of the above circumstances, and an object of the invention is to provide a substrate cleaning apparatus and a substrate cleaning method capable of reducing the number of cleaning steps and preventing re-adhesion of contaminating particles to a substrate, and A manufacturing device of a display device and a method of manufacturing the display device. According to the first aspect of the present invention, the substrate cleaning apparatus includes a transport unit that transports the substrate, and a surface to be cleaned by the transport unit, and is supplied to the liquid that can remove the oxide film. a supply nozzle having a cleaning liquid for an oxidizing gas in a state of a dissolved state and a state of fine bubbles: a supply nozzle that supplies a nozzle so as to suppress a change in size of minute bubbles reaching the surface to be washed while supplying a flow rate to the outer edge of the substrate Clean liquid. According to a second aspect of the present invention, in the substrate cleaning apparatus, the substrate is provided with a transport unit for transporting the substrate, and the surface to be cleaned of the substrate transported by the transport unit is separately supplied to the oxide film. a plurality of supply nozzles having a cleaning liquid of an oxidizing gas in a dissolved state and a fine bubble state; and a plurality of supply nozzles arranged in a direction intersecting the transport direction of the substrate along the washed surface of the substrate, in parallel The transport direction of the substrate in the plane of the surface to be cleaned of the substrate is inclined in the same direction, and the washed surfaces of the substrate are inclined in the same direction. According to a third aspect of the present invention, in the substrate cleaning method, the transporting unit including the transport substrate and the cleaned surface of the substrate transported by the transport unit are supplied to the substrate to be removed. a substrate cleaning method for cleaning a substrate by a substrate cleaning device having a supply nozzle for a cleaning solution of an oxidizing gas in a state of a dissolved state and a fine bubble; and a nozzle for supplying a nozzle to the -6-.201239972 The washed surface of the substrate conveyed by the transport unit is supplied with the cleaning liquid at a flow rate that moves to the outer edge of the substrate while suppressing the size change of the fine bubbles on the surface to be cleaned. According to a fourth aspect of the present invention, in the substrate cleaning method, the transport unit including the transport substrate and the cleaned surface of the substrate transported by the transport unit are separately supplied and oxidized. A substrate cleaning device that supplies a plurality of cleaning nozzles having a oxidizing gas in a liquid state in a liquid state and a microbubble state, and a substrate cleaning method for cleaning the substrate: a plurality of supply nozzles are washed along the substrate The surface is arranged in a direction intersecting the transport direction of the substrate, and the transport direction of the substrate is inclined in the same direction in a plane parallel to the surface to be cleaned of the substrate, and the washed surfaces of the substrate are inclined to be the same In the direction, the cleaning liquid is supplied to the surface to be cleaned of the substrate conveyed by the conveying unit by the plurality of supply nozzles. According to a fifth aspect of the present invention, in a manufacturing apparatus of a display device, there is provided a manufacturing apparatus for a display device for cleaning a substrate cleaning device for a substrate of a display device, the substrate cleaning device being related to A substrate cleaning apparatus according to the first or second aspect described above. According to a sixth aspect of the present invention, in a method of manufacturing a display device, there is provided a method of manufacturing a display device for cleaning a substrate cleaning step of a substrate used in a display device, which is used in a substrate cleaning step. Relatedly, the substrate is cleaned by the substrate cleaning method according to the third or fourth feature described above. According to any one of the first to sixth features described above, the number of cleaning steps can be reduced, and further, the reattachment of the contaminating particles to the substrate can be prevented. [Embodiment] (First Embodiment) A first embodiment of the present invention will be described with reference to Figs. 1 to 4 . A substrate cleaning apparatus 1 (see FIG. 1) according to the first embodiment of the present invention is provided as a part of a manufacturing apparatus of a liquid crystal display for manufacturing a display device, and the manufacturing apparatus of the display device includes: a substrate An aligning film forming device (not shown) for forming an alignment film on a substrate W on which a TFT circuit and an electrode pattern are formed, and a device for manufacturing a TFT circuit for driving a liquid crystal and an electrode pattern (not shown) are formed on the substrate. A seal forming device (not shown) that forms a frame-like seal surrounding the display region of each cell unit is formed on the substrate W on which the alignment film is formed, and the liquid crystal material is dropped on the display region of each cell unit of the substrate W on which the sealing is formed. A liquid crystal supply device (not shown), a substrate bonding device (not shown) that bonds a substrate W to which a liquid crystal material is dropped, and a substrate sealing device (not shown) that is bonded to the substrate, and is sealed and cured by sealing (not shown) Further, a substrate cleaning device 1 for cleaning is provided at a place necessary for the substrate moving step in each of the manufacturing apparatuses and between the apparatuses. As shown in FIG. 1, the substrate cleaning apparatus 1 according to the first embodiment includes a transport unit 2 that transports the substrate w, and supplies a cleaning liquid to the washed surface S of the substrate W transported by the transport unit 2. The supply nozzle 3, the pressurized dissolution unit 4 that dissolves the gas in the cleaning liquid, the liquid supply pump 5, the liquid supply unit 6 that supplies the cleaning liquid, the gas supply unit 7 that supplies the gas, and the control unit 8 that controls each unit. The conveying unit 2 has a plurality of rollers 2a and a rotation -8 - 201239972 which are arranged in parallel with each other. The rotation motors 2b» of the driving sources of the rollers 2a are arranged to be rotatable and arranged at equal intervals. The rotary motor 2b is electrically connected to the control unit 8, and its drive is controlled by the control unit 8. The conveying unit 2' rotates the respective rollers 2a by the rotary motor 2b, and moves the rectangular substrate W placed on the rollers 2a in the direction of the arrow A in Fig. 1 . The supply nozzle 3 is provided above the transport unit 2, and ejects the cleaning liquid toward the washed surface S of the substrate W moved by the transport unit 2, and supplies it to the surface S to be cleaned. The supply nozzle 3 is, for example, a fluid nozzle (a spray nozzle for a fluid) which is a jet cleaning liquid. The pressurized dissolved portion 4 is connected to the supply nozzle 3 by the pipe 11 serving as the liquid supply flow path, and the gas is dissolved in the cleaning liquid under high pressure, and the cleaning liquid in which the gas is dissolved is supplied to the supply via the pipe U. Nozzle 3. The pressure-dissolving portion 4 serves to dissolve the gas in the dissolved portion of the cleaning liquid. In the pipe 1, the valve 1 1 a for adjusting the flow rate is placed in the vicinity of the supply nozzle 3. This valve 11a is electrically connected to the control unit 8, and its driving is controlled by the control unit 8. Further, in the pipe 1 1, a flow meter 1 1 b for measuring a flow rate is provided. This flow meter 1 1 b is electrically connected to the control unit 8, and the measurement result is input to the control unit 8. Here, when the valve 11a is opened, the cleaning liquid containing the dissolved gas is ejected from the supply nozzle 3. At this time, the washing liquid is released from the pressure to the atmospheric pressure. The washing liquid is released from the pressure. The liquid is supersaturated with the dissolved gas. Therefore, a large amount of fine bubbles are generated in the washing liquid. In other words, the supply nozzle 3' ejects the cleaning liquid onto the washed surface S of the substrate W that has moved, and supplies the cleaning liquid containing the fine bubbles on the cleaning surface S of the 5-9 - 201239972. Further, the fine bubbles are fine bubbles including micro-bubble (MB), micro-nano-bubble (MNB), and nano-bubble (NB11). For example, the microbubbles are bubbles having a diameter of from ΙΟμιι to tens of μηι, and the micronano bubbles are bubbles having a diameter of several hundred nm to ΙΟμιη, and the nanobubbles have bubbles having a diameter of several hundred nm or less. The pump 5 is provided on the upstream side of the pressurized supply unit 4 in the fluid supply flow path, and serves as a drive source for supplying the cleaning liquid to the supply nozzle 3. This pump 5 is electrically connected to the control unit 8, and its driving is controlled by the control unit 8. The liquid supply unit 6 is connected to the pressurizing and dissolving unit 4 via a pipe 1 2 serving as a liquid supply path, and supplies the liquid to the pressurizing and dissolving unit 4. Here, as the liquid, a liquid capable of removing an oxide film, such as a dilute hydrofluoric acid (DHF) solution, is used. In addition to this, it is also possible to use a surfactant or the like. The gas supply unit 7 is connected to the pipe 12 of the liquid supply flow path by the pipe 13 serving as the gas supply flow path, and supplies the cleaning liquid supplied through the pipe 12 to contain the gas. Here, as the gas, an oxidizing gas such as ozone (〇3) is used. The pipe 13 is provided with a valve 13a for adjusting the flow rate. This valve 13a is electrically connected to the control unit 8, and its driving is controlled by the control unit 8. Further, in the pipe 13 , a flow meter 1 3 b for measuring a flow rate is provided. This flow meter 1 3 b is electrically connected to the control unit 8, and the measurement result is input to the control unit 8. The control unit 8 includes a microcomputer that centrally controls each part, and a memory unit that stores substrate cleaning information or various programs for cleaning the substrate. According to the substrate cleaning information or various programs, the substrate 8 is transported by the transport unit 2, and the cleaning liquid is ejected toward the washed surface S of the moving substrate W by the supply nozzle 3. A cleaning liquid containing a plurality of fine bubbles is supplied to the surface to be cleaned S, and in particular, an oxidizing gas is present in a dissolved state of the liquid and a state of fine bubbles in the dilute hydrofluoric acid solution of the liquid in which the oxide film can be removed. The substrate of the ozone cleaning solution is washed. Further, the amount of generation of the fine bubbles is adjusted by the control unit 8 by adjusting the opening degree of the valve 13 3 a by adjusting the amount of gas supplied to the cleaning liquid. When the cleaning liquid is supplied onto the cleaned surface S of the substrate W, as shown in FIG. 2, the organic substance F1+ on the surface to be cleaned s is removed by the ozone enthalpy 3 in the cleaning liquid. Ozone 03 is modified to be washed surface S, and oxide film F2 is formed on the washed surface S. Thereby, the contaminated particles 覆盖 covered with the organic substance F1 are covered with the oxide film F2, and the contaminated particles 存在 present on the organic substance F1 are oxidized by the ozone enthalpy 3 to become the oxidized metal Ma. Further, as shown in FIG. 3, the oxide film F2 on the surface S to be cleaned is removed by hydrogen fluoride HF in the cleaning liquid. Thereby, the contaminated particles 覆盖 and the oxidized metal Ma covered by the oxide film F2 are removed from the surface to be cleaned S. Further, ozone oxime 3 reacts with the organic substance F1 to generate C02, C0, and H20 by decomposition (see Fig. 2). Further, as shown in Fig. 4, a plurality of fine particles of a negative potential are attached to a positive potential of contaminating particles (for example, aluminum particles) to surround the contaminating particles. At this time, when the substrate W is at a positive potential, a plurality of fine bubbles having a negative potential adhere to the surface S of the substrate W to be cleaned. As a result, most of the fine bubbles surrounding the contaminated particles 成为 become potential repulsion with the number of micro-bubbles on the washed surface S of the substrate W, and prevent the contaminated particles 一旦 from being attached to the substrate W once removed. Wash the surface S. Further, even when the substrate W is at a negative potential, many of the fine bubbles surrounding the contaminated particles 成 become potential-repellent with the surface S of the substrate W, so that the contaminated particles Μ are prevented from adhering to the cleaned surface S of the substrate W. . Such three phenomena (the phenomena shown in Figs. 2, 3, and 4) occur sequentially on the washed surface S of the substrate W. Thereby, the organic matter removal by ozone and the formation of an oxide film can be simultaneously performed, and the oxide film can be removed by the dilute hydrofluoric acid solution, so that the number of washing steps can be reduced. Further, since a plurality of fine bubbles adhere to the contaminated particles and surround the contaminated particles, it is possible to prevent the contaminated particles 一 once removed from adhering to the washed surface S of the substrate W. Here, in order to improve the cleaning performance of the washed surface S of the substrate w by the cleaning liquid containing the fine bubbles, the fine bubbles contained in the cleaning liquid sprayed from the supply nozzle 3 reach the substrate W. After the surface S is cleaned, it is important to suppress the dimensional change, for example, to maintain the diameter and reach the outer edge of the substrate W. The fine bubbles on the surface to be cleaned S become larger and larger than those of the other small bubbles, or are destroyed by the passage of time. Therefore, the outer edge of the surface to be cleaned S does not reach the state where the diameter is maintained. In this case, the above-described effect of preventing adhesion is insufficient, and the washing ability is lowered. Further, in order to further improve the cleaning ability according to the above three phenomena, it is necessary to sequentially replace the cleaning liquid on the surface to be cleaned S of the substrate W. For example, a cleaning device in which a substrate W having a circular shape is placed on a pedestal, a turret is rotated at the center of the pedestal, and a cleaning liquid is supplied to the base 12-201239972 plate W on the pedestal In this case, the cleaning liquid supplied onto the substrate W is expanded toward the outer edge of the substrate W by the centrifugal force caused by the rotation of the substrate W. In this case, the cleaning liquid may be simply supplied to the vicinity of the center of the surface to be cleaned S of the substrate W. However, when the substrate W is transported in one direction as in the first embodiment of the present invention, it is necessary. The expansion of the cleaning liquid on the surface S of the substrate W is focused on. Here, in the first embodiment of the present invention, the flow rate of the cleaning liquid sprayed by the supply nozzle 3 is set to suppress the change in the size of the fine bubbles on the surface to be cleaned S of the substrate W, that is, the maintenance tolerance is maintained. The allowable size of the size within the range is simultaneously moved to the flow velocity of the outer edge of the substrate W. For example, the flow rate is set to maintain the flow velocity of the microbubble while moving to the outer edge of the substrate W. As a setting for realizing this flow rate, it is experimentally obtained in advance, and is stored in the memory unit included in the control unit 8, and the control unit 8 opens the valve Π a until the opening degree determined based on the setting 。. In response to this, the supply nozzle 3 ejects the cleaning liquid at the aforementioned flow rate. Further, when the flow rate is not sufficiently adjusted by merely opening the valve 1 1 a , the opening degree of the valve 1 1 a is adjusted by the control unit 8 in accordance with the flow rate measured by the flow meter 1 1 b and according to the pump 5 The hydraulic force can be used to match the flow rate to the aforementioned setting. When the cleaning liquid is ejected from the supply nozzle 3 at the above-described flow rate, most of the fine bubbles in the cleaning liquid reach the washed surface S of the substrate W, and then the diameter is maintained to reach the outer edge of the substrate W. As a result, since many fine bubbles can surely surround the contaminated particles 由 removed by the surface to be cleaned S, it is possible to surely prevent the contaminated particles 一 once removed from adhering to the washed surface S of the substrate W. Further, since many of the fine bubbles maintain the outer diameter of the substrate W when the diameter is the same as that of -13-201239972, the flow rate of the replacement of the initial cleaning liquid can be obtained, so that the aforementioned 3 generated at the surface to be washed is promoted. A phenomenon that can improve the cleaning ability.
如以上說明的，根據本發明之第1實施型態 淨液’成爲在可除去氧化膜的液體之稀氟酸溶液 存狀態及微小氣泡狀態具有氧化性氣體之臭氧， 藉由供給噴嘴3而被供給至基板W的被洗淨面S 可以同時進行根據臭氧之有機物除去及氧化膜形 ，根據稀氟酸溶液之除去氧化膜，所以可以削減 數。此外，藉由供給噴嘴3，抑制到達基板W的 S上的微小氣泡的尺寸變化，例如以維持直徑同 基板W的外緣之流速噴射洗淨液，對基板W的 S上供給洗淨液，之後由被洗淨面S上除去的污 藉由多數的微小氣泡確實包圍，所以可以確實防 除去的污染粒子Μ再附著於基板W的被洗淨面S (第2實施形態） 參照圖5及圖6說明本發明之第2實施型態 本發明之第2實施型態基本上與第1實施型 在第2實施型態，說明與第1實施型態之不同處 1實施型態所說明過的部分相同的部分以相同符 ，省略其說明。 如圖5所示，在相關於本發明的第2實施型 洗淨裝置1，設有複數個供給噴嘴3。這些供給噴 :洗淨面S S上之各 的話，洗 中，以溶 此洗淨液 。藉此， 成，以及 洗淨步驟 被洗淨面 時移動至 被洗淨面 染粒子Μ 止一旦被 態相同。 ，與在第 號來表示 態之基板 嘴3，沿 -14 - 201239972 著基板W的被洗淨面S而在與基板W的搬送方向（圖5 中的箭頭A的方向）交叉的方向上，例如正交於搬送方向 的方向上被排成一列設置’進而，於平行於基板W的被 洗淨面S的平面內對基板w的搬送方向分別傾斜往相同 方向。進而，各供給噴嘴3，如圖6所示，對於基板W的 被洗淨面S分別傾斜方相同方向。此時，於各供給噴嘴3 ，供給洗淨液的供給口朝向搬送方向的下游側。 此處’基板W在今後有大型化的傾向，伴隨著其大 型化而如前所述設置複數個供給噴嘴3。但是，如在前述 第1實施型態所說明的，有必要著眼於基板W的被洗淨 面S之洗淨液的擴開·，僅是單純設置複數個供給噴嘴3， 鄰接的供給噴嘴3所噴射的洗淨液彼此會相互干涉，所以 到達基板W的被洗淨面S之微小氣泡很難抑制其尺寸變 化而到達基板W的外緣，要防止污染粒子μ對基板W的 被洗淨面S的再附著是困難的。 在此，如前所述各供給噴嘴3，沿著基板W的被洗淨 面S而在與基板W的搬送方向（圖5中的箭頭Α的方向 )交叉的方向上’例如正交於搬送方向的方向上被排成一 列設置，進而，於平行於基板W的被洗淨面S的平面內 對基板W的搬送方向分別往相同方向傾斜角度01，進而 對於基板W之被洗淨面S分別往相同方向傾斜僅角度0 2 。藉此，由鄰接的供給噴嘴3噴射的洗淨液彼此於基板W 的被洗淨面S上往相同方向流，抑制洗淨液彼此相互干涉 ，所以到達基板W的被洗淨面S的微小氣泡抑制其尺寸 -15- 201239972 改變同時容易到達基板W的外緣，可以抑制污染粒子Μ 對基板W的被洗淨面S之再附著。 又’於平行於被洗淨面S的平面內對基板w的搬送 方向之傾斜角度0 1 ’係以鄰接的供給噴嘴3所噴射的洗 淨液彼此於基板W的被洗淨面s上對於基板W的搬送方 向分別於相同方向上傾斜角度0 1的方式被設定的。此角 度0 1 ’係因應於由供給噴嘴3所噴射的洗淨液直接抵達 被洗淨面S之供給範圍的大小而設定的。又，供給噴嘴3 所噴射的洗淨液呈圓錐狀擴開，供給範圍成爲受到供給噴 嘴3與基板W之間隔距離所應想，因此也要考慮期間隔 距離。 如以上所說明的’根據本發明的第2實施型態的話， 可得到與第1實施型態同樣的效果。而且，各供給噴嘴3 如前所述沿著基板W的被洗淨面S而在與基板W的搬送 方向交叉的方向上排列設置，於平行於基板W的被洗淨 面S的平面內對基板W的搬送方向分別往相同方向傾斜 ，進而對於基板W之被洗淨面S分別往相同方向傾斜》 藉由這些供給噴嘴3對基板W的被洗淨面S供給洗淨液 時，鄰接的供給噴嘴3所噴射的洗淨液彼此於基板W之 被洗淨面S上往相通方向流，抑制洗淨液彼此相互干涉， 所以到達基板W的被洗淨面S的微小氣泡抑制其尺寸改 變同時容易到達基板w的外緣，可以抑制污染粒子Μ對 基板W的被洗淨面S之再附著。 -16- 201239972 (第3實施形態） 參照圖7(a)至（c)，圖8(a)至（c)，進而圖9 (a)及（b)說明本發明之第3實施型態。圖7至圖9爲 依照製造步驟順序之非晶矽薄膜電晶體（TFT )之製造方 法之一例之剖面圖，在本發明之第3實施型態，說明將相 關於第1實施型態之基板洗淨裝置1之基板洗淨方法適用 於非晶矽薄膜電晶體之製造方法的適用例。 首先’如圖7 ( a )所示，於玻璃基板1 1 1上形成閘極 電極112。閘極電極112，可以於前述玻璃基板111上， 使用濺鍍法或蒸鍍法堆積低電阻的導電性材料（電極材料 )’其後’於前述導電層上，形成光阻圖案膜，藉由以此 光阻圖案膜作爲遮罩進行光蝕刻而圖案化前述導電層而形 成的。前述閘極電極1 1 2例如形成爲島狀圖案。 又’具備前述TFT的薄膜電晶體基板（TFT基板）製 造主動矩陣式基板的場合，可以藉由圖案化前述導電層， 而同時圖案化形成閘極線與閘極電極1 1 2。 作爲前述導電性材料，可以舉出鋁、鈦、钽 '鉬、銦 錫氧化物、氧化錫、鎢、銅及鉻等低電阻之金屬及其合金 ’但並不以此爲限。此外’前述閘極線及閘極電極丨丨2， 可以單層形成’亦可組合複數由前述導電性材料所構成的 層之層積構造。 此外，前述圖案化，使用乾蝕刻或濕蝕刻之任一方皆 可〇 其次’如圖7(b)所示’以覆蓋前述閘極電極112的 -17- 201239972 方式，藉由例如電漿CVD法或者濺鍍法，由玻璃基板in 側起依序連續形成由氮化矽等所構成的閘極絕緣層1 1 3 ' 非晶矽層114、摻雜磷等η型不純物之n+矽所構成的歐姆 接觸層1 15。 其後，如ίΐ 7 ( c )所示，蝕刻前述非晶矽層1 1 4以及 歐姆接觸層1 1 5。 又，前述非晶矽層Π4及歐姆接觸層115的蝕刻，可 以使用例如使用氯氣、或氯化氫及六氟化硫系氣體等之乾 蝕刻法，或者把氟酸（HF )與硝酸（ΗΝ〇3 )之混酸以水 (Η20)或者醋酸（CH3COOH)來稀釋的水溶液作爲蝕刻 液使用的濕蝕刻法來進行。 此外，使用於前述蝕刻的光阻遮罩，在前述鈾刻後， 使用包含有機鹼的剝離液等來剝離除去。圖7(c)是將前 述非晶矽層114及歐姆接觸層115之2層圖案化爲島狀後 ’除去前述光阻遮罩的狀態。 其次，如圖8 ( a )所示，於前述閘極絕緣層1 1 3以及 非晶矽層114、以及歐姆接觸層115上，使用濺鍍法或蒸 鍍法堆積低電阻導電性材料（電極材料），形成成爲源極 電極116a及汲極電極116b (參照圖8(b))之導電層 116，於其上形成光阻遮罩。 其次，藉由蝕刻除去設於前述光阻遮罩的開口部之前 述導體層116，如圖8(b)所示’進行源極/汲極電極分 離圖案化。藉此，形成由前述導電層116所構成的源極電 極1 !6a及汲極電極1 16b。 -18- 201239972 其後，如圖8 ( c )所示，接著進行蝕刻，蝕刻前述歐 姆接觸層115。 此後，進而，如圖9 ( a )所示，連前述非晶矽層1 1 4 也部分被蝕刻，進行調整通道部的厚度之通道蝕刻處理。 前述通道蝕刻處理後，前述光阻遮罩，使用包含有機 鹼的剝離液等來剝離除去。 又，前述通道蝕刻處理後，前述非晶矽層Π 4表面成 爲疏水化，所以前述光阻遮罩剝離後，於前述非晶矽層 114的表面，成爲容易吸附導電層材料之金屬、矽、氮化 矽以及由光阻等所構成的細微的污染物（相當於第1實施 型態的污染粒子Μ )等的狀態，·所以前述光阻遮罩剝離後 ，附著多種細微污染物，而成爲產生不良以及特性降低的 原因。爲了除去這些污染物質，從前，使用在〇3(臭氧 )水處理後進行DHF (稀氟酸）處理之步驟，但是藉由使 03之ΜΝ Β包含於DHF，可以藉由氣泡的壓壞而改善非晶 矽表面的間隙的污染物除去效果。 因此，作爲前述光阻遮罩剝離後的洗淨處理，供給以 溶存狀態及爲小氣泡狀態具有在可除去氧化膜的液體之氟 酸溶液中具有氧化性氣體之臭氧的洗淨液，進行包含前述 非晶矽層1 1 4表面的基板（相當於相關於第1實施型態的 基板W)全體的洗淨，藉此可以除去存在於非晶矽層114 表面的污染物，也防止再附著。因此，基板表面被保持爲 清淨，可以貢獻於減低伴隨著污染物的再附著而發生之生 產率降低以及提高TFT特性。 201239972 其後，如圖9(b)所示，於玻璃基板11 電漿CVD法或者灑鍍法，形成氮化矽等之Μ 膜）1 17。 (第4實施形態） 參照圖10(a)至（c)，圖11(a)至 12說明本發明之第4實施型態。圖10至圖1: 步驟順序之多晶矽薄膜電晶體之製造方法之-，在本發明之第4實施型態，說明將相關於舞 之基板洗淨裝置1之基板洗淨方法適用於多I 體之製造方法的適用例》 如圖1〇 ( a)所示，藉由電漿CVD法， 21 1上，作爲下底絕緣膜形成 50nm的矽氮 2OOnm厚的矽氧化膜213。接著，於矽氧化膜 5 Onm厚的非晶矽膜2 1 4。接著，爲了減低非晶 的氫，在 450 °C的溫度下進行退火。接著， 2 1 4照射激光雷射，使非晶矽膜2 1 4變化爲多 〇 其次，在多晶矽膜2 1 5上塗布光阻，經纪 顯影步驟，形成特定的光阻圖案。接著，以Itl 遮罩，乾蝕刻多晶矽膜2 1 5，如圖10(b)戶/ 定的區域殘留多晶矽膜2 1 5 »其後，除去光阻 其次，供給於可除去氧化膜的液體之氟酸 存狀態及爲小氣泡狀態具有氧化性氣體之臭睾 1上側，藉由 巷化膜（保護 (c )以及圖 2爲依照製造 -例之剖面圖 $ 1實施型態 I矽薄膜電晶 於玻璃基板 ，化膜2 1 2， 2 1 3上形成 ^矽膜2 1 4中 對非晶矽膜 $晶矽膜2 1 5 I選擇曝光及 ：：光阻圖案爲 ί示，僅於特 圖案。 I溶液中以溶 I的洗淨液， -20- 201239972 進行包含多晶矽膜215的基板（相當於相關於第1實施型 態的基板W)表面的洗淨。基板表面的污染粒子（相當於 相關於第1實施型態的污染粒子Μ )以及照射激光雷射使 非晶矽膜2 1 4變化爲多晶矽膜的場合所產生的結晶粒界所 存在的異物（相當於相關於第1實施型態的污染粒子Μ) 等也同時被除去，也防止這些再附著。因此，確保基板表 面的清淨性以及平滑性，可以有效活用次一步驟之矽氧化 膜的功能。 其次，如圖10(c)所示，藉由電漿CVD法，於玻璃 基板211上側全面形成膜厚3 Onm的矽氧化膜216。接著 ，藉由濺鍍法於矽氧化膜216上形成·300ηιη厚的Al-Nd ( 鋁-銨：鈸含量2atm%)膜。此後，使用光阻劑，於Al-Nd 膜上形成特定的光阻圖案，以此光阻圖案爲遮罩，乾蝕刻 Al-Nd膜，形成金屬圖案217。其後，除去光阻圖案。接 著，以金屬圖案217爲遮罩，以加速電壓25kV，注入量7 X1014CnT2之條件對多晶矽膜215離子注入P (磷），形成 η型TFT之源極以及汲極所構成的η型不純物區域218。 其次，以激光雷射照射玻璃基板211之上面全面，電氣活 化被注入的Ρ (磷）。 其次，如圖1 1 ( a )所示，藉由濕式蝕刻除去金屬圖 案 217。 其次，如圖11(b)所示，藉由電漿CVD法，於矽氧 化膜2 1 6上側形成膜厚90nm的矽氧化膜2 1 9。接著，藉 由濺鍍法於矽氧化膜219上形成3 00ηηι厚的Al-Nd (鋁- -21 - 201239972 鈸：鈸含量2atm%)膜。此後，使用光阻劑，於Al-Nd膜 上形成特定的光阻圖案，以此光阻圖案爲遮罩，乾蝕刻 Al-Nd膜，形成閘極電極220。 此時，在TFT形成區域，由上方來看時，在閘極電極 220的邊緣部分與源極側不純物區域218之間設置成爲低 摻雜汲極（LDD: Lightly Doped Drain)區域221的區域 〇 其次，以閘極電極220爲遮罩，以加速電壓25kV， 注入量7x10 McnT2之條件對多晶矽膜215離子注入P (磷 )，於源極側及汲極側的不純物區域2 1 8的旁邊形成LDD 區域221。其後，以400°C的溫度進行退火，電氣活化被 注入LDD區域221的P (磷）。 其次，如圖11(c)所示，藉由電漿CVD法，於矽氧 化膜219及閘極電極220上形成膜厚3 50nm的矽氮化膜 222。其後，以400 °C之溫度進行退火，電氣活化被注入 LDD區域221的P (磷）同時藉由矽氮化膜222中的氫， 來氫化通道區域與閘極氧化膜之界面等所具有的缺陷，改 善TFT特性。 其次，使用光阻劑，於矽氮化膜222上形成具有接觸 孔形成用開口部的光阻膜。接著，以此光阻膜爲遮罩乾蝕 刻矽氮化膜222、矽氧化膜2 1 9及矽氧化膜2 1 6，如圖1 2 所示，形成通過TFT不純物區域2 1 8的接觸孔。 接著，藉由濺鍍法，於基板211之上側全面，依序堆 積lOOnmTi、20nmAl、50nmTi，以這些金屬掩埋接觸孔同 -22- 201239972 時，於矽氮化膜222上形成金屬膜。其後，藉由光蝕刻形成 遮罩圖案，乾蝕刻金屬膜，如圖12所示，形成導電連接 於TFT的源極以及汲極之電極223。 (其他實施形態） 又，相關於本發明之前述實施型態僅爲例示，發明的 範圍不限於這些內容。前述實施型態可以進行種種變更， 例如，由前述實施型態所示的所有構成要素削除一些構成 要素亦可，進而，適當組合相關於不同實施型態的構成要 素亦可。 於前述之實施型態，作爲微小氣泡的產生方法使用了 加壓溶解，但是並不以此爲限，例如，藉由微小氣泡產生 部等預先產生包含微小氣泡的洗淨液，將該洗淨液由供給 噴嘴3噴射亦可，或者是在供給噴嘴3的內部等使氣體被 捲入洗淨液的渦流中而產生微小氣泡，將包含該微小氣泡 的洗淨液由供給噴嘴3進行噴射亦可。 此外’於前述實施型態，到達基板W的被洗淨面S 上的微小氣泡以抑制尺寸變化，而移動至基板W的外緣 的方式來控制噴射洗淨液的流速，但是取代此法而控制噴 射洗淨液的壓力亦可。 此外，於前述實施型態，作爲供給噴嘴3使用一流體 噴嘴，但不以此爲限’使用高壓噴嘴或超音波噴嘴或二流 體噴嘴亦可。特別是使用高壓噴嘴或二流體噴嘴，可以更 爲提高由噴嘴噴射的洗淨液的流速或噴射壓力，洗淨液的 -23- 201239972 置換性變得更好，所以可提高洗淨效率。 此外，於前述之實施型態，基板W的被洗淨面S帶 有正電爲或者負電位之任一方皆可，例如，使用帶電裝置 使基板W的被洗淨面S帶電爲負電位的方式亦可。在此 場合，與基板W之被洗淨面S爲正電位的場合相比，負 電位的微小氣泡僅附著於污染粒子Μ，可以防止污染粒子 Μ對基板W的被洗淨面S的再附著。特別是附著於基板 W的被洗淨面S上的微小氣泡變成不需要，所以因此相應 地可以使洗淨液的流速調整變得容易。 此外，於前述實施型態，係以水平狀態搬送基板W， 但不以此爲限，亦可將基板W傾斜搬送。在此場合，與 水平狀態之基板W相比，在基板W的被洗淨面S上之洗 淨液的流速會上升，可以促進被洗淨面S上的洗淨液的置 換。又，洗淨液，朝向傾斜狀態的基板W的上端部供給 〇 此外，於前述實施型態，作爲氧化性氣體以臭氧（03 )爲例，但可以使用包含〇2(氧氣）及〇3(臭氧）之至 少1種氣體的氧化性氣體。此外，可除去氧化膜的液體， 可以使用包含DHF (稀氟酸）、NH4F (氟化銨）以及 H202 (過氧化氫）之至少1種液體的可除去氧化膜之液體 〇 此外，因應於用途，例如做爲基板W，可以使用供形 成薄膜電晶體之用的絕緣性基板或者單晶矽基板。在此場 合，進而基板W，可以使用藉由可除去氧化膜的液體之處 • 24- 201239972 理，而至少有一部分呈現疏水性者’或者是藉由氧化性氣 體的處理而至少有一部分呈現親水性者。而且，基板w , 亦可以是其至少一部份爲以砂爲主成分的材料者，此時， 可以使用基板W之至少一部份爲非晶質或者結晶性矽之 基板W。在此場合，該矽可以是非晶矽或者結晶性之p接 雜（注入）矽。 雖然說明了本發明之幾個實施型態，但這些實施型態 ’僅係作爲例子而提示的，並未意圖限定發明的範圍。這 些新穎的實施型態，可以在其他種種型態被實施，在不逸 脫於本發明要旨的範圍，可以進行種種的省略、置換、變 更。這些實施型態或其變形，包含於本發明的範圍或要旨 ，同時也包含與記載於申請專利範圍的發明均等的範圍。 【圖式簡單說明】 圖1係顯示相關於本發明的第1實施型態之基板洗淨 裝置的槪略構成之圖。 圖2係供說明圖1所示的基板洗淨裝置進行的基板洗 淨的洗淨過程之第1說明圖。 圖3係供說明前述洗淨過程之第2說明圖。 圖4係供說明前述洗淨過程之第3說明圖。 圖5係顯示相關於本發明的第2實施型態之基板洗淨 裝置具備的複數供給噴嘴之平面圖。 圖6係顯示圖5所示之供給噴嘴之側面圖。 圖7係供說明相關於本發明之第3實施型態之非晶矽 -25- 201239972 薄膜電晶體之製造步驟之第1說明圖。 圖8係供說明接在前述圖7後的製造步驟之第2說明 圖。 圖9係供說明接在前述圖8後的製造步驟之第3說明 圖。 圖1 〇係供說明相關於本發明之第4實施型態之多晶 矽薄膜電晶體之製造步驟之第1說明圖。 圖11係供說明接在前述圖10後的製造步驟之第2說 明圖。 圖12係供說明接在前述圖11後的製造步驟之第3說 明圖。 【主要元件符號說明】 1 :基板洗淨裝置 2 :搬送部 2 a ·聿昆 2b :旋轉馬達 3 :供給噴嘴 4 :加壓溶解部 5 :泵 6 :液體供給部 7 :氣體供給部 8 :控制部 1 1、1 2 ' 1 3 :配管 -26- 201239972 1 1 a、1 3 a :閥 1 1 b、1 3 b :流量計 S :被洗淨面 w :基板As described above, according to the first embodiment of the present invention, the clean liquid solution is in the state of a dilute hydrofluoric acid solution in which the oxide film can be removed, and the ozone having an oxidizing gas in the state of fine bubbles is supplied to the nozzle 3 by the supply nozzle 3 The washed surface S supplied to the substrate W can simultaneously remove the organic substance and form an oxide film according to ozone, and the oxide film can be removed by the dilute hydrofluoric acid solution, so that the number can be reduced. Further, by supplying the nozzle 3, the dimensional change of the fine bubbles on the S reaching the substrate W is suppressed. For example, the cleaning liquid is sprayed at a flow rate maintaining the diameter of the outer edge of the substrate W, and the cleaning liquid is supplied onto the S of the substrate W. After that, the dirt removed from the surface to be cleaned S is surely surrounded by a large number of fine bubbles, so that the contaminated particles that can be surely removed can be adhered to the washed surface S of the substrate W (second embodiment). Fig. 6 is a view showing a second embodiment of the present invention, and a second embodiment of the present invention is basically described in the second embodiment, and the first embodiment is different from the first embodiment. The same parts of the same parts are given the same characters, and the description thereof is omitted. As shown in Fig. 5, in the second embodiment of the cleaning device 1 according to the present invention, a plurality of supply nozzles 3 are provided. These supply sprays are washed in the washing surface S S to dissolve the washing liquid. Thereby, the cleaning step and the washing step are moved to the surface of the washed surface when the surface is washed, and the state is the same once. With the substrate surface 3 in the first representation state, the washed surface S of the substrate W is carried along the line -14 - 201239972, and the direction intersects with the transport direction of the substrate W (the direction of the arrow A in FIG. 5). For example, they are arranged in a row in the direction orthogonal to the transport direction. Further, the transport direction of the substrate w is inclined in the same direction in a plane parallel to the surface S of the substrate W to be cleaned. Further, as shown in Fig. 6, each of the supply nozzles 3 is inclined in the same direction with respect to the washed surface S of the substrate W. At this time, in each of the supply nozzles 3, the supply port for supplying the cleaning liquid faces the downstream side in the transport direction. Here, the substrate W tends to increase in size in the future, and a plurality of supply nozzles 3 are provided as described above in accordance with the enlargement. However, as described in the first embodiment, it is necessary to focus on the expansion of the cleaning liquid on the surface S of the substrate W. Only a plurality of supply nozzles 3 are provided, and the adjacent supply nozzles 3 are provided. Since the ejected cleaning liquids interfere with each other, it is difficult for the microbubbles reaching the cleaned surface S of the substrate W to suppress the dimensional change and reach the outer edge of the substrate W, and the contaminated particles μ are prevented from being washed on the substrate W. Reattachment of the face S is difficult. Here, as described above, each of the supply nozzles 3 is orthogonal to the conveyance in the direction in which the cleaning surface S of the substrate W intersects with the conveyance direction of the substrate W (the direction of the arrow 图 in FIG. 5). The direction of the direction is arranged in a line, and the direction of transport of the substrate W in the plane parallel to the surface S of the substrate W is inclined by the angle 01 in the same direction, and further, the surface to be cleaned S of the substrate W Tilt only the angle 0 2 in the same direction. As a result, the cleaning liquids ejected from the adjacent supply nozzles 3 flow in the same direction on the surface to be cleaned S of the substrate W, and the cleaning liquids are prevented from interfering with each other, so that the cleaning surface S of the substrate W is minute. The bubble suppresses the size -15 - 201239972 The change easily reaches the outer edge of the substrate W, and the adhesion of the contaminated particles Μ to the washed surface S of the substrate W can be suppressed. Further, the inclination angle 0 1 ' of the conveyance direction of the substrate w in the plane parallel to the surface to be cleaned S is such that the cleaning liquid sprayed by the adjacent supply nozzles 3 is on the cleaned surface s of the substrate W. The conveyance directions of the substrates W are set so as to be inclined by an angle of 0 1 in the same direction. This angle 0 1 ' is set in accordance with the magnitude of the supply range in which the cleaning liquid sprayed from the supply nozzle 3 directly reaches the surface to be cleaned S. Further, the cleaning liquid sprayed by the supply nozzle 3 is conically expanded, and the supply range is determined by the distance between the supply nozzle 3 and the substrate W. Therefore, the interval distance is also considered. As described above, according to the second embodiment of the present invention, the same effects as those of the first embodiment can be obtained. Further, each of the supply nozzles 3 is arranged in the direction intersecting the transport direction of the substrate W along the washed surface S of the substrate W as described above, and is parallel to the plane of the cleaned surface S of the substrate W. The transport direction of the substrate W is inclined in the same direction, and the washed surface S of the substrate W is inclined in the same direction. When the supply nozzle 3 supplies the cleaning liquid to the cleaned surface S of the substrate W, the adjacent one is adjacent. The cleaning liquid sprayed by the supply nozzles 3 flows in the communication direction on the surface to be cleaned S of the substrate W, and the cleaning liquids are prevented from interfering with each other. Therefore, the minute bubbles reaching the surface S of the substrate W are suppressed from changing in size. At the same time, it is easy to reach the outer edge of the substrate w, and re-adhesion of the contaminated particles Μ to the washed surface S of the substrate W can be suppressed. -16-201239972 (Third Embodiment) Referring to Figs. 7(a) to (c), Figs. 8(a) to (c), and Figs. 9(a) and (b), a third embodiment of the present invention will be described. . 7 to 9 are cross-sectional views showing an example of a method of manufacturing an amorphous germanium thin film transistor (TFT) in accordance with a manufacturing step, and in a third embodiment of the present invention, a substrate relating to the first embodiment will be described. The substrate cleaning method of the cleaning device 1 is applied to an application example of a method for producing an amorphous germanium film transistor. First, as shown in Fig. 7 (a), a gate electrode 112 is formed on the glass substrate 1 1 1 . The gate electrode 112 may be formed by depositing a low-resistance conductive material (electrode material) on the glass substrate 111 by a sputtering method or a vapor deposition method to form a photoresist pattern film on the conductive layer. The photoresist pattern film is photoetched as a mask to pattern the conductive layer. The gate electrode 1 1 2 is formed, for example, in an island pattern. Further, when an active matrix substrate is manufactured by a thin film transistor substrate (TFT substrate) having the TFT, the gate line and the gate electrode 1 1 2 can be simultaneously patterned by patterning the conductive layer. Examples of the conductive material include low-resistance metals such as aluminum, titanium, lanthanum-molybdenum, indium tin oxide, tin oxide, tungsten, copper, and chromium, and alloys thereof, but are not limited thereto. Further, the gate line and the gate electrode 丨丨2 may be formed in a single layer, or a laminated structure of a plurality of layers made of the above-mentioned conductive material may be combined. In addition, the foregoing patterning may be performed by either dry etching or wet etching, as shown in FIG. 7(b) to cover the gate electrode 112 in the manner of -17-201239972 by, for example, plasma CVD. Or a sputtering method in which a gate insulating layer 1 1 3 ' amorphous germanium layer 114 made of tantalum nitride or the like and n + germanium doped with an n-type impurity such as phosphorus are continuously formed in this order from the glass substrate in side. Ohmic contact layer 1 15. Thereafter, as described in ΐ 7 (c), the aforementioned amorphous germanium layer 1 14 and the ohmic contact layer 1 15 are etched. Further, for the etching of the amorphous germanium layer 4 and the ohmic contact layer 115, for example, dry etching using chlorine gas, hydrogen chloride or sulfur hexafluoride gas, or fluorine acid (HF) and nitric acid (ΗΝ〇3) can be used. The aqueous solution in which the mixed acid is diluted with water (Η20) or acetic acid (CH3COOH) is used as a wet etching method using an etching solution. Further, the photoresist mask used for the etching described above is removed and removed by using a stripping liquid or the like containing an organic base after the uranium engraving. Fig. 7 (c) shows a state in which the two layers of the amorphous germanium layer 114 and the ohmic contact layer 115 are patterned into an island shape, and the photoresist mask is removed. Next, as shown in FIG. 8( a ), a low-resistance conductive material (electrode) is deposited on the gate insulating layer 1 13 and the amorphous germanium layer 114 and the ohmic contact layer 115 by sputtering or vapor deposition. The material) is formed with a conductive layer 116 which serves as a source electrode 116a and a drain electrode 116b (see FIG. 8(b)), and a photoresist mask is formed thereon. Next, the conductor layer 116 provided in the opening of the photoresist mask is removed by etching, and the source/drain electrode separation pattern is formed as shown in Fig. 8(b). Thereby, the source electrode 1 ! 6a and the drain electrode 1 16b composed of the above-mentioned conductive layer 116 are formed. -18-201239972 Thereafter, as shown in Fig. 8(c), etching is performed to etch the aforementioned ohmic contact layer 115. Thereafter, as shown in Fig. 9(a), the amorphous ruthenium layer 141 is partially etched, and a channel etching process for adjusting the thickness of the channel portion is performed. After the channel etching treatment, the photoresist mask is removed by lift-off using a stripping solution containing an organic alkali or the like. Further, after the channel etching treatment, the surface of the amorphous germanium layer 4 is hydrophobized. Therefore, after the photoresist mask is removed, the surface of the amorphous germanium layer 114 is made of a metal or a metal which is easy to adsorb the conductive layer material. In the state of cerium nitride and fine contaminants (corresponding to the contaminated particles 第 of the first embodiment), etc., the photoresist mask is peeled off, and various fine contaminants are adhered thereto. Causes of poor performance and reduced characteristics. In order to remove these pollutants, the process of DHF (dilute hydrofluoric acid) treatment after 〇3 (ozone) water treatment has been used, but by including 033 in DHF, it can be improved by bubble collapse. The effect of contaminant removal on the gap of the amorphous germanium surface. Therefore, as a cleaning process after the peeling of the photoresist mask, a cleaning liquid having an oxidizing gas in a fluoric acid solution of a liquid capable of removing an oxide film in a dissolved state and in a small bubble state is supplied, and is contained. The entire substrate on the surface of the amorphous germanium layer 141 (corresponding to the substrate W according to the first embodiment) is cleaned, whereby the contaminants present on the surface of the amorphous germanium layer 114 can be removed, and reattachment can be prevented. . Therefore, the surface of the substrate is kept clean, which contributes to a reduction in productivity which is accompanied by re-adhesion of contaminants and an improvement in TFT characteristics. 201239972 Thereafter, as shown in Fig. 9(b), a ruthenium film such as tantalum nitride (1, 17) is formed on the glass substrate 11 by a plasma CVD method or a sputtering method. (Fourth Embodiment) Referring to Figs. 10(a) to (c), Figs. 11(a) to 12 show a fourth embodiment of the present invention. 10 to FIG. 1 : a method of manufacturing a polycrystalline germanium film transistor in a step sequence - in the fourth embodiment of the present invention, a substrate cleaning method relating to the substrate cleaning apparatus 1 for dancing is applied to a multi-body Application Example of Manufacturing Method As shown in Fig. 1(a), a tantalum oxide film 213 having a thickness of 20 nm of niobium nitrogen of 50 nm is formed as a lower insulating film by a plasma CVD method. Next, an amorphous germanium film 2 1 4 thick on the 5 nm thick film. Next, in order to reduce amorphous hydrogen, annealing was performed at a temperature of 450 °C. Next, 2 1 4 is irradiated with a laser laser to change the amorphous tantalum film 2 14 into a plurality of layers. Next, a photoresist is applied on the polycrystalline tantalum film 2 15 , and a development step is formed to form a specific photoresist pattern. Next, the polycrystalline germanium film 2 1 5 is dry-etched with Itl, as shown in FIG. 10(b), the residual polycrystalline germanium film 2 1 5 is removed, and then the photoresist is removed, and then supplied to the liquid which can remove the oxide film. The state of the fluoric acid and the upper side of the septic test 1 having an oxidizing gas in a small bubble state, and the mode I 矽 film electrocrystal by the roadway film (protection (c) and FIG. 2 according to the manufacturing-example cross-sectional view $1 On the glass substrate, the film 2 2 2, 2 1 3 is formed on the film 2 1 4 in the amorphous germanium film $ 矽 film 2 1 5 I selective exposure and:: photoresist pattern is shown, only In the I solution, the surface of the substrate containing the polycrystalline germanium film 215 (corresponding to the substrate W according to the first embodiment) is washed by the cleaning solution of the solution I, -20-201239972. The foreign matter existing in the crystal grain boundary generated when the amorphous ruthenium film 2 14 is changed to the polycrystalline ruthenium film by the laser beam irradiated with the laser beam (corresponding to the first embodiment) The type of contaminated particles Μ) and so on are also removed at the same time, and these re-adhesion are also prevented. The surface of the glass substrate 211 can be effectively formed by the plasma CVD method, as shown in FIG. 3 Onm tantalum oxide film 216. Next, a 300-μm thick Al-Nd (aluminum-ammonium: germanium content 2 atm%) film is formed on the tantalum oxide film 216 by sputtering. Thereafter, a photoresist is used for Al. Forming a specific photoresist pattern on the -Nd film, using the photoresist pattern as a mask, dry etching the Al-Nd film, and forming a metal pattern 217. Thereafter, the photoresist pattern is removed. Then, the metal pattern 217 is used as a mask. P (phosphorus) is ion-implanted into the polysilicon film 215 under the conditions of an acceleration voltage of 25 kV and an implantation amount of 7 X1014 CnT2 to form an n-type impurity region 218 composed of a source of the n-type TFT and a drain. Next, the glass substrate is irradiated with a laser laser. The upper surface of 211 is fully integrated to electrically inject the germanium (phosphorus). Next, as shown in Fig. 11 (a), the metal pattern 217 is removed by wet etching. Next, as shown in Fig. 11(b), Plasma CVD method, forming a 90 nm thick helium oxide on the upper side of the tantalum oxide film 2 16 Film 2 1 9 Next, a film of Al-Nd (aluminum - 21 - 201239972 钹: 钹 content 2 atm%) having a thickness of 300 Å η is formed on the tantalum oxide film 219 by sputtering. Thereafter, a photoresist is used. A specific photoresist pattern is formed on the Al-Nd film, and the photoresist pattern is used as a mask to dry-etch the Al-Nd film to form the gate electrode 220. At this time, in the TFT formation region, when viewed from above, the gate is formed. Between the edge portion of the electrode electrode 220 and the source side impurity region 218, a region which is a low-density drain (LDD) region 221 is disposed, and the gate electrode 220 is used as a mask to accelerate the voltage by 25 kV. The implantation amount of 7x10 McnT2 ion-implants P (phosphorus) into the polysilicon film 215, and the LDD region 221 is formed beside the impurity side region 2 1 8 on the source side and the drain side. Thereafter, annealing is performed at a temperature of 400 ° C to electrically activate P (phosphorus) which is injected into the LDD region 221. Next, as shown in Fig. 11 (c), a tantalum nitride film 222 having a thickness of 3 50 nm is formed on the tantalum oxide film 219 and the gate electrode 220 by a plasma CVD method. Thereafter, annealing is performed at a temperature of 400 ° C to electrically activate P (phosphorus) injected into the LDD region 221 while hydrogenating the silicon nitride film 222 to form an interface between the hydrogenation channel region and the gate oxide film. Defects to improve TFT characteristics. Next, a photoresist film having an opening for forming a contact hole is formed on the tantalum nitride film 222 by using a photoresist. Then, the photoresist film is dry-etched by the photoresist film 222, the tantalum oxide film 2 19 and the tantalum oxide film 2 1 6 , as shown in FIG. 12, forming a contact hole through the TFT impurity region 2 18 . Then, by sputtering, a total of 100 nm of Ti, 20 nm of Al, and 50 nm of Ti are sequentially deposited on the upper side of the substrate 211, and a metal film is formed on the tantalum nitride film 222 by burying the contact holes with these metals at the same time as -22 to 201239972. Thereafter, a mask pattern is formed by photolithography, and the metal film is dry-etched, as shown in Fig. 12, to form an electrode 223 electrically connected to the source of the TFT and the drain. (Other Embodiments) The foregoing embodiments of the present invention are merely illustrative, and the scope of the invention is not limited to these. The above-described embodiments may be variously modified. For example, some constituent elements may be deleted from all the constituent elements shown in the above-described embodiments, and further, constituent elements related to different embodiments may be combined as appropriate. In the above-described embodiment, the method of generating fine bubbles is performed by using a pressure-dissolving method. However, the cleaning is not limited thereto. For example, the cleaning liquid containing fine bubbles is generated in advance by the fine bubble generating portion or the like. The liquid may be ejected from the supply nozzle 3, or the gas may be trapped in the vortex of the cleaning liquid inside the supply nozzle 3 to generate fine bubbles, and the cleaning liquid containing the microbubbles may be ejected from the supply nozzle 3. can. Further, in the foregoing embodiment, the microbubbles on the cleaned surface S of the substrate W are controlled to move to the outer edge of the substrate W to suppress the dimensional change, but the flow rate of the jet cleaning liquid is controlled, but instead of this method The pressure of the jet washing liquid can also be controlled. Further, in the above embodiment, a fluid nozzle is used as the supply nozzle 3, but not limited thereto, a high pressure nozzle, an ultrasonic nozzle or a two-fluid nozzle may be used. In particular, by using a high-pressure nozzle or a two-fluid nozzle, the flow rate or the injection pressure of the cleaning liquid sprayed from the nozzle can be further increased, and the -23-201239972 replacement property of the cleaning liquid becomes better, so that the cleaning efficiency can be improved. Further, in the above-described embodiment, the cleaned surface S of the substrate W may have either a positive power or a negative potential. For example, the charged surface S of the substrate W is charged to a negative potential by using a charging device. The way is also. In this case, compared with the case where the cleaned surface S of the substrate W has a positive potential, the microbubbles having a negative potential adhere only to the contaminated particles, and the reattachment of the contaminated particles Μ to the washed surface S of the substrate W can be prevented. . In particular, the fine bubbles adhering to the surface S of the substrate W are unnecessary, so that the flow rate of the cleaning liquid can be easily adjusted accordingly. Further, in the above embodiment, the substrate W is transported in a horizontal state, but the substrate W may be obliquely transported without limitation. In this case, the flow rate of the cleaning liquid on the surface to be cleaned S of the substrate W is increased as compared with the substrate W in the horizontal state, and the replacement of the cleaning liquid on the surface to be cleaned S can be promoted. Further, the cleaning liquid is supplied to the upper end portion of the substrate W in an inclined state. In the above embodiment, ozone (03) is exemplified as the oxidizing gas, but 〇2 (oxygen) and 〇3 may be used. An oxidizing gas of at least one gas of ozone. Further, as the liquid capable of removing the oxide film, a liquid ruthenium containing a removable oxide film containing at least one liquid of DHF (dilute hydrofluoric acid), NH4F (ammonium fluoride), and H202 (hydrogen peroxide) may be used, depending on the use. For example, as the substrate W, an insulating substrate or a single crystal germanium substrate for forming a thin film transistor can be used. In this case, in addition, the substrate W can be used in a liquid where the oxide film can be removed, and at least a part of the substrate is rendered hydrophobic or at least partially hydrophilic by the treatment of the oxidizing gas. Sex. Further, the substrate w may be one in which at least a part of the material is mainly composed of sand. In this case, at least a portion of the substrate W may be a substrate W which is amorphous or crystalline. In this case, the ruthenium may be amorphous or crystalline p-doped (injected) ruthenium. While a few embodiments of the invention have been described, these embodiments have been shown by way of example only and are not intended to limit the scope of the invention. These novel embodiments can be implemented in other various forms, and various omissions, substitutions and changes can be made without departing from the scope of the invention. These embodiments and their modifications are intended to be included within the scope and spirit of the invention, and also include the scope of the invention as described in the appended claims. BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a schematic view showing a schematic configuration of a substrate cleaning apparatus according to a first embodiment of the present invention. Fig. 2 is a first explanatory view for explaining a washing process of the substrate cleaning by the substrate cleaning apparatus shown in Fig. 1; Fig. 3 is a second explanatory diagram for explaining the above washing process. Fig. 4 is a third explanatory diagram for explaining the above washing process. Fig. 5 is a plan view showing a plurality of supply nozzles provided in a substrate cleaning apparatus according to a second embodiment of the present invention. Fig. 6 is a side view showing the supply nozzle shown in Fig. 5. Fig. 7 is a first explanatory view for explaining a manufacturing procedure of an amorphous germanium-25-201239972 thin film transistor according to a third embodiment of the present invention. Fig. 8 is a second explanatory view for explaining the manufacturing steps after the above Fig. 7; Fig. 9 is a third explanatory view for explaining the manufacturing steps after the above Fig. 8; Fig. 1 is a first explanatory view for explaining a manufacturing procedure of a polycrystalline germanium film transistor according to a fourth embodiment of the present invention. Fig. 11 is a second explanatory view for explaining the manufacturing steps after the above Fig. 10; Fig. 12 is a third explanatory view for explaining the manufacturing steps after the above-mentioned Fig. 11; [Description of Main Components] 1 : Substrate cleaning device 2 : conveying unit 2 a • 聿 2 2 : Rotating motor 3 : supply nozzle 4 : pressurizing and dissolving unit 5 : pump 6 : liquid supply unit 7 : gas supply unit 8 : Control unit 1 1 , 1 2 ' 1 3 : Piping -26- 201239972 1 1 a, 1 3 a : Valve 1 1 b, 1 3 b : Flow meter S: Washed surface w: Substrate