201041030 六、發明說明： 【發明所屬之技術領域】 發明領域 本發明係有關於以處理液將用於液晶顯示面板之玻璃 基板或半導體晶圓等基板處理之基板處理裝置及處理方法。 【先前技術;j 發明背景 0 舉例言之，在液晶顯示裝置或半導體裝置之製程中， 藉將抗蝕劑塗佈於為該等對象物之玻璃基板或半導體晶圓 等基板，以顯像液進行顯像處理後，進行蝕刻處理，而於 基板表面精达、地形成電路圖形。當於基板形成電路圖形 後，進行以剝離液去除附著殘留於該基板表面之抗蝕膜或 抗蝕劑殘渣等有機物的剝離處理。 作為用於此種基板處理之處理液之上述顯像液或剝離 液咼價。因此，考慮藉回收業經處理上述基板之處理液來 Ο 反覆 使用’而謀求基板之處理成本之減低。 於專利文獻1顯示以剝離液去除附著殘留於基板表面 之抗蝕劑。然而，未揭示使剝離液循環來反覆使用。 先行技術文獻 專利文獻 專利文獻1日本專利公開公報2006-278509號 而於將剝離液或顯像液等處理液在使用後回收，反覆 使用時’處理液無法避免在循環路徑接觸大氣。特別是當 以處理部將處理液從喷嘴朝基板噴射供給時，因與大氣之 3 201041030 接觸程度増大，故此時，大氣中所含之氣體元素進入，與 該氣體元素反應，而有早期惡化之情形。 +例5之，為顯像液時，有與大氣中之二氧化碳(co2) 中和反應而惡化之情形，為剝離液時，有與氧㈣氧化反應 而惡化之情形。[Technical Field] The present invention relates to a substrate processing apparatus and a processing method for processing a substrate such as a glass substrate or a semiconductor wafer used for a liquid crystal display panel with a processing liquid. [Prior Art; J BACKGROUND OF THE INVENTION For example, in a process of a liquid crystal display device or a semiconductor device, a resist is applied to a substrate such as a glass substrate or a semiconductor wafer which is such an object, and a developing liquid After the development process, an etching process is performed to form a circuit pattern on the surface of the substrate. After the circuit pattern is formed on the substrate, the peeling treatment is performed to remove the organic material such as the resist film or the resist residue remaining on the surface of the substrate. The above-mentioned developing liquid or peeling liquid is used as a treatment liquid for such substrate processing. Therefore, it is considered that the processing cost of the substrate is reduced by the recycling of the processing liquid of the substrate by the recycling industry. Patent Document 1 discloses that a resist remaining on the surface of a substrate is removed by a peeling liquid. However, it has not been disclosed that the stripping solution is circulated for repeated use. In the case of using a treatment liquid such as a peeling liquid or a developing liquid, it is recovered after use, and when it is used repeatedly, the treatment liquid cannot avoid contact with the atmosphere in the circulation path. In particular, when the processing liquid is ejected from the nozzle toward the substrate by the processing unit, the degree of contact with the atmosphere 3 201041030 is large, and therefore, the gas element contained in the atmosphere enters and reacts with the gas element, and is deteriorated at an early stage. situation. In the case of the developing solution, the case of the developing solution is deteriorated by the neutralization reaction with carbon dioxide (co2) in the atmosphere, and when it is a stripping solution, it may be deteriorated by the oxidation reaction with oxygen (tetra).
而且，顯像液含有碳酸氫鉀(KHC〇3)或碳酸氫鈉(NaH c〇3)。然後，當以循環泵將顯像液加壓，使其在循環路徑 衣夺有於上述碳酸氫鉀或碳酸氫納施加因循 環路徑^流路阻力等產生之熱能，以該熱能分解，而產生 ―軋化碳之情形。因此，此情形也成為使處理液早期惡化 的原因。 Γ韻^明内容^ 發明概要 發明欲解決之課題 本發明在於提供藉使處理液循環來反覆使用之際，去 *處理液所含之氣體，而防止處理液早期惡化之基板广理 裝置及處理方法。 处 用以欲解決課題之手段 為解決上述課題，本發明在於提供一種基板處理裝 置，其係以處理液將基板處理者，其特徵在於，該基板處 理裴置包含有被供給用於藉上述處理液處理之前述基板之 處理部，貯存上述處理液之貯液槽；將該貯液槽之處理液 供給至上述處理部，而於處理上述基板後返回上述貯液槽 之循環管路；及設於該循環管路，以將上述處理液所含2 201041030 氣體去除的除氣機構。 本發明在於提供一種基板處理方法，其係以處理液將 基板處理者，其賴在於，縣㈣理方法具有以下步驟： 將土板t、、、·。至處理部，將貯存於貯液槽之處理液供給至上 述處理。Ρ後目收至上述貯液槽；及去除從上述貯液槽供 給至上述處理部之上述處理液所含之氣體。 本發明在於提供一種基板處理裝置，其係以處理液將 0 I板處理者，其特徵在於，該基板處理裝置包含有被供給 用於藉上述處理液處理之上述基板之處理部；貯存上述處 理液之貯液槽；將該貯液槽之處理液供給至上述處理部， 而於處理上述基板後返回上述贿槽之第谈環管路；及第 2循環管路，該第2循環管路係具有將不對處理液反應之氣 冑作為細微氣泡而使其混人至處理液之氣泡產生機構，藉 將上述貯液槽之處理液供給至上述氣泡產生機構後返回上 述貯液槽，而以該處理液所含之細微氣泡使從上述處理部 〇 返回上述貯液槽之處理液所含的氣體去除者。 本發明在於提供一種基板處理方法，其係以處理液將 基板處理者，其特徵在於，該處理方法具有以下步驟：將 基板供給至處理部；將聍存於貯液槽之處理液供給至上述 處理部後，回收至上述貯液槽；將不對該處理液反應之氣 體作為細微氣泡，使其混入至上述貯液槽之處理液；及藉 使混入有細微氣泡之處理液返回上述貯液槽，而以該處理 液所含之細微氣泡去除從上述處理部回收至上述貯液槽之 處理液所含之氣體。 5 201041030 發明效果 根據本發明，使貯液槽之處理液循環’而用於基板之 處理之際，去除處理液所含之氣體。因此，由於即使大氣 中之氣體元素進入處理液，仍可去除該氣體元素’故可防 止處理液因大氣中所含之氣體元素，而早期惡化。 圖式簡單說明 第1圖係顯示此發明一實施形態之基板處理裝置之概 略結構圖。 第2圖係顯示用於上述處理裝置之除氣裝置之内部構 造的截面圖。 第3圖係顯示對純水賦與不同之4個條件時之經過時間 與溶氧濃度的關係之圖表。 第4圖係使業經除氣之純水於氣泡產生器反覆循環 時，測量純水之溶氧濃度之變化的圖表。 第5圖係顯示此發明第2實施形態之基板處理裝置之概 略結構圖。 第6圖係顯示此發明第3實施形態之基板處理裝置之概 略結構圖。 第7圖係顯示此發明第4實施形態之基板處理裝置之概 略結構圖。 第8圖係顯示在第3實施形態及第4實施形態中將細微 氣泡供給至貯液槽内之處理液時之經過時間與溶氧濃度的 關係之圖表。 【實施方式3 201041030 用以實施發明之形態 以下，一面參照第1圖至第4圖，一面說明此發明之一 實施形態。 第1圖顯示此發明之處理裝置之概略結構，此處理裝置 包含貯存有顯示液或剝離液等處理液L之貯液槽丨。於此貯 液槽1之底部連接有構成將處理液L供給至用以處理玻璃基 板或半導體晶圓等基板W之處理部2的處理液供給管路之 供液管3—端。 於上述供液管3之另一端連接有於設於上述處理部2之 喷淋官4。在噴淋管4，複數個噴嘴5以預定間隔、例如等間 隔而設。在上述喷淋管4之下方，由作為搬送上述基板1之 搬送機構的搬送輥構成之搬送輸送機6橫亙上述處理部2及 此處理部2之前後方向而設。此外，搬送機構亦可為鏈條輸 送機等。 上述基板W係藉由上述搬送輸送機6而被搬入至上述 處理部2 °上述噴淋管4係使長向與基板贾之搬送方向交叉 而配設。藉此，以搬送輸送機6在上述處理部2内搬送上述 基板W’而得以將處理液1供給至上面全體而處理。 於連接在上述貯液槽丨之上述供液管3—端部設有第1 循環栗11 ’於此第1循環泵11與上述貯液槽1間設有為用以 去除處理液L所含之氣體之除氣機構的除氣裝置12。 如第2圖所示，上述除氣裝置12具有一端形成有流入口 13 ’另一端形成有流出口 14之液密狀容器15。於此容器15 内之一端部與另—端部分別設有分隔板16。該等分隔板16 201041030 將上述容器15内區隔成連通於上述流入口 13之流入室17、 連通於上述流出口 14之流出室18、位於1對分隔板16間之減 壓室19。於此減壓室19配管連接有將内部氣壓減壓之減壓 泵2卜 於上述減壓室19設有一端液密地保持於其中一分隔板 16，另一端液密地保持於另一分隔板16之除氣構件22。此 除氣構件22係將以使氣體通過，不使液體通過之材料形成 之細微徑之許多筒狀中空線22a捆扎而構成，其一端連通上 述流入室17，另一端連通上述流出室18。 藉此，當上述第1循環泵11作動，上述貯液槽1内之處 理液L如第2圖箭號所示，從上述容器15之流入口 13供給至 流入室17時，該處理液L通過除氣構件22之中空線22a内 部，流至流出室18，而從流出口 14流出。 處理液L在上述除氣構件22之中空線22a流動時，上述 減壓室19以減壓泵21減壓至負壓，僅上述處理液L所含之氣 體通過中空線22a之周壁膜，而吸引至減壓室19。亦即，氣 體可從處理液L分離。然後，所分離之氣體得以以上述減壓 泵21排出至減壓室19之外部。 業經以上述除氣裝置12去除氣體之處理液L以上述第1 循環泵11之壓力供給至氣泡產生器24。從氣體供給部25將 不與處理液L反應之氣體、例如氮或氬等惰性氣體與處理液 L 一同加壓而供給至此氣泡產生器24。 此外，處理液L為顯像液時，不與處理液L反應之氣體 不為惰性氣體，而為氧亦可。 201041030 供給至上述氣泡產生器24之處理液L及惰性氣體以按 壓力差之不同速度一面在此氣泡產生器24之内部旋繞運 動，一面流動。藉此，由於因處理液L及惰性氣體之旋繞速 度之差，惰性氣體以處理液L而切變，故惰性氣體形成奈米 氣泡或微泡等細微氣泡，而含在處理液L中。 含有細微氣泡之處理液L在上述供液管3流動，而供給 至上述喷淋管4，從該喷淋管4朝以搬送輸送機6在處理部2 搬送之基板W上面喷射供給。 藉此，基板W之上面以處理液l，進行顯像或剝離等處 理。然後，業經處理基板W之處理液L經由與連接於處理部 2之上述供液管3形成循環管路之回收管28，回收至上述貯 液槽1。亦即，處理液L在供液管3及回收管28流動循環，而 反覆使用。 接著，就以上述結構之處理裝置處理基板…時之作用 作說明。 在處理基板w前，使第丨循環泵u及減壓泵21作動。藉 此，將貯液槽1内之處理液供給至除氣裝置12，從此除氣裝 置12之容器15之流入口 13流入，通過構成減壓室19之除氣 構件22之中空線22a的内部空間，從流出口 14流出’而流往 氣泡產生器24。 處理液L通過減壓室19之除氣構件22時，此減壓室19 以減壓泵21減壓，而可去除處理液L所含之氧或二氧化碳等 氣體。 藉此，由於從脱氣裝置12流出之處理液l未含有氣體， 9 201041030 故不致因處理液L所含之氣體’促進處理液L之惡化。舉例 言之，處理液L為顯像液時，二氧化碳與顯像液中和反應， 而促進顯像液之惡化’處理液為剝離液時，氧與剝離液氧 化反應’而促進剝離液之惡化，但由於已從處理液去除氧 或二氧化板寺氣體’故可防止處理液L因氣體而早期牵化。 如此進行，業經去除促進惡化之氣體之處理液L以上述 第1循環泵11加壓，而供給至氣泡產生器24。亦即，處理液 L不致因氧或二氧化碳等氣體而惡化，而供給至氣泡產生琴 24。將氣體供給部25之惰性氣體與處理液L—同加壓而供給 至此氣泡產生器24。 當將處理液L及惰性氣體供給至氣泡產生器24時，該等 形成旋繞流’而以不同之旋繞速度在内部流動，因該旋繞 速度之差’惰性氣體以處理液L切變，而產生奈米氣泡或微 泡等細微氣泡，該細微氣泡混入至處理液L。 細微氣泡混入之處理液L因第1循環泵1丨之壓力，在供 液管3流動’而到達噴淋管4 ’從設於此噴淋管4之複數個嗜 嘴5朝以搬送輸送機6在處理部2内搬送之基板W上面喷射。 藉此，基板W於處理液L為顯像液時，進行顯像處理， 為剝離液時，則剝離去除附著殘留於基板…之抗蝕劑。 處理液L從噴淋管4之噴嘴5朝基板W噴射時，由於處理 液L接觸大氣，故大氣中所含之二氧化碳或氧等氣體溶解， 而有導致惡化之虞。 然而，從喷淋管4之喷嘴5朝基板W噴射之處理液L含有 惰性氣體之細微氣泡。因此，從喷嘴5朝基板w喷射之處理 201041030 液L因該處理液L含有細微氣泡，大氣中之二氧化碳或氧等 氣體元素不易溶解。 亦即’虽以處理部2，將處理液L從噴嘴5朝基板W喷射 時，處理液L與大氣之接觸面積增大，而形成易溶解大氣中 之-氧化碳或氧等氣體元素之狀態，因處理液l含有細微氣 包大氣中之一氧化兔或氧不易溶解，故即使將處理液l 朝基板W喷射，亦不致惡化。 特別是使處理液L含有惰性氣體之細微氣泡至成飽和 狀態或接近飽和狀態為止時，由於大氣中之二氧化碳或氧更 不易洛解於該處理液L，故可更確實地防止處理液1之惡化。 再者，藉使處理液L含有惰性氣體之細微氣泡，當含有 細微氣泡之處理液L返回貯液槽丨時，可對積留於此貯液槽1 内之處理液以細微氣泡之起泡作用去除處理液[所含之大 氣中之二氧化碳或氧等。 因而，與惰性氣體之細微氣泡以飽和狀態或接觸飽和 狀態之狀態含在供給至處理部2之處理液L相配合，返回至 貯液槽1之處理液L不易含有大氣中之二氧化碳或氧等。 而且，藉以處理槽2將含有細微氣泡之處理液L供給至 基板W，從基板W去除之抗蝕劑等之電漿電位的塵埃以為 與基板W相同之電位之負電位的細微氣泡覆蓋。因此，於 基板W與塵埃間產生斥力，而可從基板冒去除塵埃，故可 防止業經去除之塵埃再附著於基板W。 處理液L為顯像液時，不僅因大氣中所含之二氧化碳之 接觸而惡化，於在供液管3循環之際，從第1循環泵u承受 11 201041030 熱犯，或以在供液管3流動時之流路阻力產生熱能時，因該熱 能，顯像液從最初所含之碳酸氫鉀或碳酸氫鈉熱分解，而產 生一氣化破，而有因該二氧化碳促進處理液[之惡化之情形。 然而，由於顯像液所含之二氧化碳以除氣裝置12去 除，故即使顯像液所含之碳酸氫鉀或碳酸氫鈉熱分解，而 產生二氧化碳’仍可防止顯像液早期惡化。 如此進行，業經處理基板W之處理液L反覆進行經由回 收管28，回收至貯液槽1後，以第丨循環泵丨〖在供液管3流動 而供給至處理部2之循環。 即，根據上述結構之處理裝置，由於處理液1所含之氣 體可以除氣裝置12去除，故可確實地防止處理液[因二氧化 碳或氧等氣體而早期惡化。 §業經除氣之處理液L從喷淋管4之喷嘴5喷射至基板 W時’ 4處理液L接觸大氣’故有將大氣所含之氣體溶解而惡 化之虞。然而，從喷嘴5噴射之處理液L含有#氣泡產生器24 以不與處理液L反應之惰性氣體等氣體而製作之細微氣泡。 因此，即使處理液L與大氣接觸，大氣中之二氧化碳或 氧等氣體不易溶解於已含有細微氣泡之處理液L，故藉此， 亦可防止處理液L早期惡化。 第3圖之曲線A〜D係將除氣後之純水所含之氧濃度變 化隨著時間經過測量之曲線。在第3圖中，曲線八係測量將 純水除氣，不循環，在此狀態下放置時之氧濃度變化的情 形，曲線B係測量進行循環15分後，混入氣泡，之後放置 時之氧濃度變化的情形。 12 201041030 曲線c係測量進行循環15分，混入c〇2氣泡，之後放置 夺之氧'農度的變化之情形。曲線D係測量進行循環15分，不 此入氣泡，之後放置時之氧濃度變化的情形。 從以上實驗可知即使將純水所含之氧除氣，藉如曲 線C D般循環’純水中之氧濃度增加，及如曲線b，即使 使’、先水循每’藉混入N2氣泡，仍可抑制氧濃度之增加。又， 亦可知如曲線A，除氣後，不循環，氧濃度便不致大幅增加。 0 第4圖係使以上述一實施形態所示之處理裝置使處理 液盾被時’測量處理液L之氧濃度變化的圖表。在此圖表， 才頁轴X1 - X 2之範圍係測量不於純水混入氣泡而循環時之氧 展度變化’ X2_X3、X3-X4及X4-X5之範圍係測量分別混入 A氣泡而循環時之氧濃度之變化。亦即，使純水每次循環 時混入N2氣泡。 從此可知，藉於純水混入&氣泡而循環，可使溶氧濃 度減少。認為溶氧濃度減少之理由係因藉使純水反覆循 ◎ ί哀純水所含之&氣泡量逐漸增加。亦即，認為係因藉純 水所含之Ns氣泡量增加，大氣之氧不易進入之故。 第5圖係顯示此發明第2實施形態之處理裝置之結構 圖。此外，與第1圖所示之處理裝置相同之部份附上相同記 號’而省略詳細說明。 在此實施形態中，貯存於貯液槽丨之處理液L以除氣裝 置12將氣體除氣後，供給至氣泡產生器24。當以此氣泡產 生器24於處理液L混入細微氣泡後，該處理液l以供液管3 返回至貯液槽1貯存。貯存於貯液槽丨之處理液L反覆進行從 13 201041030 此貯液槽1過過除氣裝置12及氣泡產生器24,而返回貯液槽 1之循環。 另一方面’貯液槽1及喷淋管4以構成於中途部設有第2 循％栗31之循環管路之供液管3a連接。於處理基板w時， 藉使上述第2循環泵31作動，而從貯液槽1將含有細微氣泡 之處理液L供給至上述喷淋管4 ’而從此噴淋管4之喷嘴5喷 射至基板W。 然後，供給至基板W之處理液L反覆進行以回收管28回 收至貯液槽1，從此貯液槽1通過除氣裝置12及氣泡產生器 24 ’而返回至貯液槽1之循環。 根據此種結構，即使不以處理部2處理基板霣時，仍可 使貯液槽1内之處理液L在氣泡產生器24、貯液槽丨及除氣裝 置12間循環，將業經充分在處理槽1内除氣之處理液L預先 貯存。因此，於處理基板W之際，可將業經除氣、且混入 細微氣泡，貯存於貯液槽丨之處理液L迅速地供給至基板w。 而且，供給至基板w前，反覆進行將處理液L從貯液槽 1通過除氣裝置12及氣泡產生器24，返回至貯液槽丨之循 環，而可使處理液L所含之溶氧濃度降低。 此外，於使處理液L所含之溶氧濃度降低時，以氣泡產 生器24使N2氣泡混入至處理液[。 第6圖係顯示此發明第3實施形態之處理裝置之結構 圖。此外，與第1圖所示之處理裝置相同之部份附上同一標 號，而省略詳細說明。 此第3實％开〉態係第5圖所示之第2實施形態之變形 14 201041030 例，貯存於貯液槽1之處理液L可以第1循環泵u直接供給至 氣泡產生器24。亦即，在第3實施形態中，相對於上述第2 實施形態，在去除了設於供液管3之除氣裝置12之點不同。 此外，在第3實施形態中，將貯液槽丨之處理液1之一部 份供給至處理部2後，返回至貯液槽1之路徑作為第丨循環管 路，將貯液槽1之處理液L之一部份供給至氣泡產生器24 後，返回貯液槽1之路徑作為第2循環管路。 根據此種結構，以處理部2從噴淋管4供給至基板％之 處理液L進行以第1循環管路溶解二氧化碳或氧等氣體，以 回收管28返回貯液槽1之循環。 另一方面，貯液槽1之處理液[進行以第2循環管路與氣 體供給部25之惰性氣體一同供給至氣泡產生器24，混入奈 米氣泡或微泡等細微氣泡，而返回貯液槽丨之循環。 當以氣泡產生器24含有細微氣泡之處理液l返回至貯 液槽1時，與於此貯液槽1含有從處理部2返回之氧或二氧化 碳等溶氣之處理液L混合。 藉此，由於於溶解有從處理部2返回之二氧化碳或氧等 氣體之處理液L混合以氣泡產生器24含有細微氣泡，並以第2 循環管路在貯液槽丨與氣泡產生器24間循環之處理液^，故可 以氣泡產生器24之處理液L所含之細微氣泡之起泡作用，去 除溶解於來自處理部2之處理液1之二氧化碳或氧等氣體。 亦即，藉使以氣泡產生器24混入有細微氣泡之處理液L 以第2循環管路循環至貯液槽卜即使不使用第1、第2實施 形態所含之除氣裝置12，亦可去除原本含在以第丨循環管路 15 201041030 從處理部2返回至貯液槽丨之處理液L，或藉將處理液l供給 至基板W而含有之二氧化碳或氧等氣體。 又，即使不以處理部2處理基板w時，亦可使貯液槽1 内之處理液L在氣泡產生器24與貯液槽丨間循環，而可於處 理槽1内預先貯存已充分除氣之處理液L。因此’處理基板 W之際，可將業經除氣，且混入細微氣泡，而貯存於貯液 槽1之處理液L迅速地供給至基板w。 第7圖係顯示第6圖所示之第3實施形態之變形例的第4 貫把形態，在此第4實施形態中，將貯存於貯液槽丨之處理 液L之供液管3、及供給氣體供給部25之惰性氣體之供氣管 25a連接於第丨循環泵丨丨之吸引側。然後，以上述第丨循環泵 1將處理液L及惰性氣體預先混合後，供給至氣泡產生器24。 藉此，將預先混合之處理液L及惰性氣體—面在氣泡產 生器24内部旋繞，一面流動而授拌，惰性氣體形成細微氣 泡’故可以良好效率使細微氣泡混合於處理液L。 此外，在第4實施形態中’亦與第3實施形態同樣地， 將貯液槽1之處理液L之一部份供給至處理部2後，返回至貯 液槽1之路徑作為第1循環管路，將貯液槽丨之處理液1之一 部份供給至氣泡產生器24後’返回貯液槽1之路徑作為第2 循環管路。 此種結構亦與第6圖所示之第3實施形態同樣地，可於 溶解有以第1循環管路從處理部2返回至貯液槽1之二氧化 碳或氧等氣體之處理液L混合以第2循環管路在氣泡產生器 24與貯液槽1循環之處理液L所含之細微氣泡。 201041030 藉此，即使以處理部2將二氧化碳或氧等氣體溶解於處 理液L，該氣體可以在第2循環管路循環，返回至貯液槽】 之處理液所含之細微氣泡的起泡作用有效地去除。 第8圖係顯示將細微氣泡供給至處理液時之經過時門 與處理液所含之溶氧量的關係之圖表。此圖表在第3、第4 實施形態中，以第1循環管路使氧溶解於處理液，液解開始 後，在氧量達約35mgA之約14分後，於以第2循環管路循環 之處理液開始細微氣泡之供給時，確認了在開始細微氣泡 之供給後約ό分之後的經過時間、約20分後，貯液槽丨之處 理液中之溶氧量大幅降低。 此外，在上述各實施形態，處理部係舉了將基板一面 以搬送輸送機搬送，一面處理之例來說明，處理部亦可為 使基板一面旋轉，一面供給處理液之所謂旋轉處理裝置。 又，氣泡產生器不限於上述各實施形態所舉之結構 者，舉例言之，亦可為藉將氣體加壓而通過過濾器，而使 液體中產生氣泡之所謂加壓方式等其他結構。Further, the developing solution contains potassium hydrogencarbonate (KHC〇3) or sodium hydrogencarbonate (NaH c〇3). Then, when the developing solution is pressurized by a circulation pump, the thermal energy generated by the above-mentioned potassium bicarbonate or sodium hydrogencarbonate due to the circulation path resistance or the like is applied to the circulation path, and the thermal energy is decomposed to generate ―The situation of rolling carbon. Therefore, this situation also causes the early deterioration of the treatment liquid. Γ ^ 明 ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ method. Means for Solving the Problems In order to solve the above problems, the present invention provides a substrate processing apparatus that processes a substrate with a processing liquid, wherein the substrate processing apparatus includes a supply processing unit for supplying the processing a processing unit of the substrate for liquid treatment, storing a liquid storage tank of the processing liquid; supplying the processing liquid of the liquid storage tank to the processing unit, and returning to the circulation line of the liquid storage tank after processing the substrate; In the circulation line, a deaeration mechanism for removing 2 201041030 gas contained in the above treatment liquid. The present invention provides a substrate processing method in which a substrate is processed by a processing liquid, and the method according to the county (four) method has the following steps: The earth plate t, , , . The treatment liquid stored in the liquid storage tank is supplied to the treatment unit to the above treatment. Thereafter, the liquid is collected into the liquid storage tank; and the gas contained in the processing liquid supplied from the liquid storage tank to the processing unit is removed. The present invention provides a substrate processing apparatus that processes a processor with a processing liquid, wherein the substrate processing apparatus includes a processing unit that is supplied with the substrate for processing by the processing liquid; and stores the processing a liquid storage tank; the treatment liquid of the liquid storage tank is supplied to the processing unit, and after returning to the substrate, the circuit returns to the first loop of the bribe trough; and the second circulation line, the second circulation line And a bubble generating mechanism that mixes the gas which does not react with the treatment liquid as a fine bubble and mixes it with the treatment liquid, and supplies the treatment liquid of the liquid storage tank to the bubble generation mechanism, and returns to the liquid storage tank to The fine bubbles contained in the treatment liquid remove the gas contained in the treatment liquid returned from the treatment unit to the liquid storage tank. The present invention provides a substrate processing method for processing a substrate with a processing liquid, characterized in that the processing method has the steps of: supplying a substrate to a processing portion; and supplying the processing liquid stored in the liquid storage tank to the above After the treatment unit, the liquid is recovered in the liquid storage tank; the gas that does not react with the treatment liquid is used as a fine bubble, and is mixed into the treatment liquid of the liquid storage tank; and the treatment liquid mixed with the fine air bubbles is returned to the liquid storage tank. The fine gas contained in the treatment liquid removes the gas contained in the treatment liquid recovered from the treatment unit to the storage tank. 5 201041030 EFFECT OF THE INVENTION According to the present invention, when the treatment liquid of the liquid storage tank is circulated and used for the treatment of the substrate, the gas contained in the treatment liquid is removed. Therefore, even if a gas element in the atmosphere enters the treatment liquid, the gas element can be removed, so that the treatment liquid can be prevented from being deteriorated early due to the gas element contained in the atmosphere. BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a schematic block diagram showing a substrate processing apparatus according to an embodiment of the present invention. Fig. 2 is a cross-sectional view showing the internal structure of the deaerator used in the above processing apparatus. Fig. 3 is a graph showing the relationship between the elapsed time and the dissolved oxygen concentration when four different conditions are assigned to pure water. Fig. 4 is a graph showing the change in the dissolved oxygen concentration of pure water when the degassed pure water is repeatedly circulated in the bubble generator. Fig. 5 is a schematic block diagram showing a substrate processing apparatus according to a second embodiment of the present invention. Fig. 6 is a schematic block diagram showing a substrate processing apparatus according to a third embodiment of the present invention. Fig. 7 is a schematic block diagram showing a substrate processing apparatus according to a fourth embodiment of the present invention. Fig. 8 is a graph showing the relationship between the elapsed time and the dissolved oxygen concentration when the fine bubbles are supplied to the treatment liquid in the storage tank in the third embodiment and the fourth embodiment. [Embodiment 3] 201041030 Embodiment for carrying out the invention Hereinafter, an embodiment of the invention will be described with reference to Figs. 1 to 4 . Fig. 1 shows a schematic configuration of a processing apparatus of the present invention, which comprises a liquid storage tank 贮存 in which a treatment liquid L such as a display liquid or a peeling liquid is stored. A liquid supply pipe 3 end which constitutes a processing liquid supply line for supplying the processing liquid L to the processing unit 2 for processing the substrate W such as a glass substrate or a semiconductor wafer is connected to the bottom of the reservoir 1. The shower head 4 provided in the processing unit 2 is connected to the other end of the liquid supply tube 3. In the shower pipe 4, a plurality of nozzles 5 are provided at predetermined intervals, for example, at equal intervals. Below the shower pipe 4, a transport conveyor 6 composed of a transport roller that transports the transport mechanism of the substrate 1 is disposed across the processing unit 2 and the processing unit 2 in a front-rear direction. Further, the conveying mechanism may be a chain conveyor or the like. The substrate W is carried into the processing unit by the transport conveyor 6. The shower tube 4 is disposed such that the longitudinal direction intersects the transport direction of the substrate. Thereby, the substrate W' is transported by the transport conveyor 6 in the processing unit 2, and the processing liquid 1 is supplied to the entire upper surface for processing. The first circulating pump 11' is disposed at the end of the liquid supply tube 3 connected to the liquid storage tank, and the first circulating pump 11 and the liquid storage tank 1 are provided between the first circulating pump 11 and the liquid storage tank 1 for removing the processing liquid L. The degassing device 12 of the gas deaeration mechanism. As shown in Fig. 2, the deaerator 12 has a liquid-tight container 15 having an inlet port 13' formed at one end and an outlet port 14 formed at the other end. A partition plate 16 is provided at one end and the other end of the container 15 respectively. The partitioning plate 16 201041030 partitions the inside of the container 15 into an inflow chamber 17 communicating with the inflow port 13, an outflow chamber 18 communicating with the outflow port 14, and a decompression chamber 19 located between the pair of partition plates 16. . The decompression chamber 19 is connected to a decompression pump 2 for decompressing the internal air pressure. The decompression chamber 19 is provided with one end liquid-tightly held in one of the partition plates 16, and the other end is liquid-tightly held in the other. The deaeration member 22 of the partition plate 16. The deaeration member 22 is formed by bundling a plurality of cylindrical hollow wires 22a having a fine diameter formed by passing a gas without passing the liquid, and one end thereof communicates with the inflow chamber 17, and the other end communicates with the outflow chamber 18. When the first circulation pump 11 is actuated, the treatment liquid L in the liquid storage tank 1 is supplied from the inlet 13 of the container 15 to the inflow chamber 17 as indicated by the arrow in FIG. 2, and the treatment liquid L is supplied. The inside of the hollow wire 22a of the deaeration member 22 flows to the outflow chamber 18, and flows out from the outflow port 14. When the treatment liquid L flows through the hollow wire 22a of the deaeration member 22, the decompression chamber 19 is depressurized to a negative pressure by the decompression pump 21, and only the gas contained in the treatment liquid L passes through the peripheral wall membrane of the hollow wire 22a. Attracted to the decompression chamber 19. That is, the gas can be separated from the treatment liquid L. Then, the separated gas is discharged to the outside of the decompression chamber 19 by the above-described decompression pump 21. The treatment liquid L from which the gas is removed by the above-described deaerator 12 is supplied to the bubble generator 24 at the pressure of the first circulation pump 11. A gas which does not react with the treatment liquid L, an inert gas such as nitrogen or argon, is pressurized from the gas supply unit 25 together with the treatment liquid L, and is supplied to the bubble generator 24. Further, when the treatment liquid L is a developing liquid, the gas which does not react with the treatment liquid L is not an inert gas but may be oxygen. 201041030 The treatment liquid L and the inert gas supplied to the bubble generator 24 flow while being swirled inside the bubble generator 24 at different speeds of the pressure difference. As a result, the inert gas is sheared by the treatment liquid L due to the difference in the winding speed of the treatment liquid L and the inert gas. Therefore, the inert gas forms fine bubbles such as nanobubbles or microbubbles, and is contained in the treatment liquid L. The treatment liquid L containing the fine bubbles flows into the liquid supply pipe 3, and is supplied to the shower pipe 4, and is ejected from the shower pipe 4 to the upper surface of the substrate W conveyed by the conveyance conveyor 6 on the processing unit 2. Thereby, the upper surface of the substrate W is subjected to processing such as development or peeling with the treatment liquid 1. Then, the treatment liquid L of the treated substrate W is recovered into the storage tank 1 via a recovery pipe 28 which forms a circulation line with the above-described liquid supply pipe 3 connected to the processing unit 2. That is, the treatment liquid L flows and circulates in the liquid supply pipe 3 and the recovery pipe 28, and is used repeatedly. Next, the operation when the substrate is processed by the processing apparatus of the above configuration will be described. Before the substrate w is processed, the second circulation pump u and the pressure reducing pump 21 are actuated. Thereby, the treatment liquid in the liquid storage tank 1 is supplied to the deaerator 12, and the inflow port 13 of the container 15 of the deaeration device 12 flows in, and passes through the inside of the hollow wire 22a of the deaeration member 22 constituting the decompression chamber 19. The space flows out of the outflow port 14 and flows to the bubble generator 24. When the treatment liquid L passes through the deaeration member 22 of the decompression chamber 19, the decompression chamber 19 is depressurized by the decompression pump 21, and gas such as oxygen or carbon dioxide contained in the treatment liquid L can be removed. As a result, the treatment liquid 1 flowing out of the deaerator 12 does not contain gas, and 9 201041030 does not cause the deterioration of the treatment liquid L due to the gas contained in the treatment liquid L. For example, when the treatment liquid L is a developing solution, carbon dioxide neutralizes the reaction liquid to promote the deterioration of the developing liquid. When the treatment liquid is a stripping liquid, oxygen and the stripping liquid are oxidized to promote the deterioration of the stripping liquid. However, since the oxygen or the dioxide gas is removed from the treatment liquid, the treatment liquid L can be prevented from being earlyly corroded by the gas. In this manner, the treatment liquid L for removing the gas which promotes deterioration is pressurized by the first circulation pump 11 and supplied to the bubble generator 24. That is, the treatment liquid L is not deteriorated by a gas such as oxygen or carbon dioxide, but is supplied to the bubble to generate the piano 24. The inert gas of the gas supply unit 25 is pressurized together with the treatment liquid L to be supplied to the bubble generator 24. When the treatment liquid L and the inert gas are supplied to the bubble generator 24, the swirling flow is formed to flow internally at different winding speeds, and the inert gas is sheared by the treatment liquid L due to the difference in the winding speed. Fine bubbles such as nanobubbles or microbubbles which are mixed into the treatment liquid L. The treatment liquid L in which the fine bubbles are mixed is flowed in the liquid supply pipe 3 due to the pressure of the first circulation pump 1 and reaches the shower pipe 4'. From the plurality of nozzles 5 provided in the shower pipe 4, the conveyor is conveyed. 6 is sprayed on the upper surface of the substrate W conveyed in the processing unit 2. Thereby, the substrate W is subjected to development processing when the processing liquid L is a developing liquid, and when it is a peeling liquid, the resist remaining on the substrate is peeled off and removed. When the treatment liquid L is ejected from the nozzle 5 of the shower pipe 4 toward the substrate W, the treatment liquid L is exposed to the atmosphere, so that a gas such as carbon dioxide or oxygen contained in the atmosphere is dissolved, which may cause deterioration. However, the treatment liquid L sprayed from the nozzle 5 of the shower pipe 4 toward the substrate W contains fine bubbles of an inert gas. Therefore, the process of ejecting from the nozzle 5 toward the substrate w 201041030 The liquid L contains fine bubbles in the treatment liquid L, and the gaseous elements such as carbon dioxide or oxygen in the atmosphere are not easily dissolved. In other words, when the processing liquid 2 ejects the processing liquid L from the nozzle 5 toward the substrate W, the contact area between the processing liquid L and the atmosphere increases, and a state in which a gas element such as carbon monoxide or oxygen is easily dissolved in the atmosphere is formed. Since the treatment liquid 1 contains one of the oxidized rabbits in the atmosphere of the fine air bag or the oxygen is not easily dissolved, even if the treatment liquid l is sprayed toward the substrate W, it does not deteriorate. In particular, when the treatment liquid L contains the fine bubbles of the inert gas until it is saturated or nearly saturated, since the carbon dioxide or oxygen in the atmosphere is less likely to be dissolved in the treatment liquid L, the treatment liquid 1 can be more reliably prevented. deterioration. Further, if the treatment liquid L contains fine bubbles of an inert gas, when the treatment liquid L containing the fine bubbles is returned to the storage tank, the treatment liquid accumulated in the storage tank 1 can be bubbled with fine bubbles. It removes the treatment liquid [carbon dioxide or oxygen in the atmosphere contained in it. Therefore, the fine liquid bubbles of the inert gas are contained in the state of the saturated state or the contact saturated state, and are contained in the treatment liquid L supplied to the treatment unit 2, and the treatment liquid L returned to the liquid storage tank 1 does not easily contain carbon dioxide or oxygen in the atmosphere. . In addition, the treatment liquid L containing fine bubbles is supplied to the substrate W by the treatment tank 2, and the dust of the plasma potential of the resist or the like removed from the substrate W is covered with fine bubbles of a negative potential of the same potential as the substrate W. Therefore, a repulsive force is generated between the substrate W and the dust, and dust can be removed from the substrate, so that the removed dust can be prevented from adhering to the substrate W. When the treatment liquid L is a development liquid, it is not only deteriorated by the contact of carbon dioxide contained in the atmosphere, but also when the liquid supply pipe 3 is circulated, the first circulation pump u receives the heat of the 201041030, or the liquid supply pipe. (3) When the flow resistance at the time of flow generates heat energy, the thermal liquid is thermally decomposed from the originally contained potassium hydrogencarbonate or sodium hydrogencarbonate, thereby causing a gasification break, and the carbon dioxide promotes the treatment liquid [deterioration] The situation. However, since the carbon dioxide contained in the developing liquid is removed by the deaerator 12, even if the potassium hydrogencarbonate or sodium hydrogencarbonate contained in the developing solution is thermally decomposed to generate carbon dioxide, the early deterioration of the developing liquid can be prevented. In this manner, the treatment liquid L of the treated substrate W is repeatedly returned to the storage tank 1 via the recovery pipe 28, and then circulated by the third circulation pump 供给 in the liquid supply pipe 3 and supplied to the treatment unit 2. In other words, according to the processing apparatus of the above configuration, since the gas contained in the processing liquid 1 can be removed by the deaerator 12, it is possible to reliably prevent the processing liquid from being deteriorated early due to a gas such as carbon dioxide or oxygen. When the degassing treatment liquid L is ejected from the nozzle 5 of the shower tube 4 to the substrate W, the treatment liquid L is in contact with the atmosphere, so that the gas contained in the atmosphere is dissolved and deteriorated. However, the treatment liquid L sprayed from the nozzle 5 contains fine bubbles formed by the # bubble generator 24 so as to be a gas such as an inert gas that does not react with the treatment liquid L. Therefore, even if the treatment liquid L comes into contact with the atmosphere, the gas such as carbon dioxide or oxygen in the atmosphere is not easily dissolved in the treatment liquid L containing the fine bubbles, so that the treatment liquid L can be prevented from being deteriorated in the early stage. Curves A to D in Fig. 3 are graphs showing changes in the oxygen concentration contained in the pure water after degassing over time. In Fig. 3, the curve eight system measures the degassing of pure water, does not circulate, and the oxygen concentration changes when placed in this state. Curve B measures the oxygen after mixing for 15 minutes, then mixes the bubbles. The situation in which the concentration changes. 12 201041030 Curve c is measured and cycled for 15 minutes, mixed with c〇2 bubbles, and then placed in the case of oxygen change. Curve D measures the case where the circulation is 15 minutes, the bubble is not entered, and the oxygen concentration at the time of the change is changed. It can be seen from the above experiments that even if the oxygen contained in the pure water is degassed, the oxygen concentration in the pure water is increased by the curve CD, and as the curve b, even if the water is circulated into the N2 bubble, It can suppress the increase of oxygen concentration. Further, it can be seen that, as in the curve A, after degassing, the oxygen concentration does not increase significantly without circulation. Fig. 4 is a graph showing the change in the oxygen concentration of the treatment liquid L when the treatment liquid shield is treated by the processing apparatus shown in the above embodiment. In this chart, the range of the page axis X1 - X 2 is measured by the difference in the oxygen spread when the pure water is mixed into the bubble, and the range of X2_X3, X3-X4, and X4-X5 is measured by mixing into the A bubble and circulating. The change in oxygen concentration. That is, the pure water is mixed with N2 bubbles every time it is circulated. From this, it can be seen that by circulating pure water mixed with & bubbles, the dissolved oxygen concentration can be reduced. The reason for the decrease in dissolved oxygen concentration is that the amount of & bubbles contained in pure water is gradually increased by the passage of pure water. That is to say, it is considered that the amount of Ns bubbles contained in the pure water is increased, and the oxygen in the atmosphere is not easily entered. Fig. 5 is a view showing the configuration of a processing apparatus according to a second embodiment of the present invention. Incidentally, the same portions as those of the processing device shown in Fig. 1 are denoted by the same reference numerals, and detailed description thereof will be omitted. In this embodiment, the treatment liquid L stored in the reservoir tank is degassed by the deaerator 12 and then supplied to the bubble generator 24. When the bubble generation device 24 mixes the fine bubbles in the treatment liquid L, the treatment liquid 1 is returned to the reservoir 1 for storage by the liquid supply tube 3. The treatment liquid L stored in the liquid storage tank is repeatedly subjected to a cycle of returning from the deaerator 12 and the bubble generator 24 through the deaerator 12 and the bubble generator 24 from 13 201041030. On the other hand, the liquid storage tank 1 and the shower pipe 4 are connected to a liquid supply pipe 3a which is formed in a circulation line in which the second circumstance 31 is provided in the middle portion. When the substrate w is processed, the processing liquid L containing the fine bubbles is supplied from the reservoir 1 to the shower tube 4' by the second circulation pump 31, and is ejected from the nozzle 5 of the shower tube 4 to the substrate. W. Then, the treatment liquid L supplied to the substrate W is repeatedly returned to the liquid storage tank 1 by the recovery pipe 28, and the liquid storage tank 1 is returned to the circulation of the liquid storage tank 1 through the deaerator 12 and the bubble generator 24'. According to this configuration, even when the substrate 霣 is not processed by the processing unit 2, the processing liquid L in the sump 1 can be circulated between the bubble generator 24, the sump, and the deaerator 12, and it is sufficient The treatment liquid L for degassing in the treatment tank 1 is stored in advance. Therefore, when the substrate W is processed, the treatment liquid L which has been degassed and mixed with fine bubbles and stored in the reservoir tank can be quickly supplied to the substrate w. Further, before being supplied to the substrate w, the circulation of the treatment liquid L from the sump 1 through the deaerator 12 and the bubble generator 24 to the sump is repeated, and the dissolved oxygen contained in the treatment liquid L can be made. The concentration is lowered. Further, when the dissolved oxygen concentration contained in the treatment liquid L is lowered, the bubble generator 24 causes the N2 bubbles to be mixed into the treatment liquid [. Fig. 6 is a view showing the configuration of a processing apparatus according to a third embodiment of the present invention. In addition, the same portions as those of the processing device shown in Fig. 1 are denoted by the same reference numerals, and the detailed description is omitted. This third embodiment is a modification of the second embodiment shown in Fig. 5. In the example of the first embodiment, the processing liquid L stored in the liquid storage tank 1 can be directly supplied to the bubble generator 24 by the first circulation pump u. In other words, in the third embodiment, the second embodiment is different in that the deaerator 12 provided in the liquid supply pipe 3 is removed. Further, in the third embodiment, a part of the treatment liquid 1 of the liquid storage tank is supplied to the treatment unit 2, and then the path to the liquid storage tank 1 is used as the second circulation line, and the liquid storage tank 1 is After a part of the treatment liquid L is supplied to the bubble generator 24, the path of the liquid storage tank 1 is returned to the second circulation line. According to this configuration, the treatment liquid L supplied from the shower unit 4 to the substrate % by the treatment unit 2 dissolves a gas such as carbon dioxide or oxygen in the first circulation line, and the circulation of the recovery pipe 28 to the sump 1 is performed. On the other hand, the treatment liquid of the liquid storage tank 1 is supplied to the bubble generator 24 together with the inert gas of the gas supply unit 25 in the second circulation line, and fine bubbles such as nanobubbles or microbubbles are mixed and returned to the storage liquid. The cycle of the tank. When the treatment liquid 1 containing the fine bubbles in the bubble generator 24 is returned to the reservoir 1, the reservoir 1 contains the treatment liquid L which is a dissolved gas such as oxygen or carbon dioxide which is returned from the treatment unit 2. As a result, the treatment liquid L in which the gas such as carbon dioxide or oxygen returned from the treatment unit 2 is dissolved is mixed with the bubble generator 24 to contain fine bubbles, and the second circulation line is between the reservoir tank and the bubble generator 24. By circulating the treatment liquid, the gas bubbles such as carbon dioxide or oxygen dissolved in the treatment liquid 1 from the treatment unit 2 can be removed by the foaming action of the fine bubbles contained in the treatment liquid L of the bubble generator 24. In other words, the treatment liquid L in which the fine bubbles are mixed by the bubble generator 24 is circulated to the liquid storage tank in the second circulation line, and the deaerator 12 included in the first and second embodiments can be used. The treatment liquid L originally contained in the second circulation line 15 201041030 from the processing unit 2 to the liquid storage tank is removed, or a gas such as carbon dioxide or oxygen contained in the processing liquid 1 is supplied to the substrate W. Further, even when the substrate w is not processed by the processing unit 2, the processing liquid L in the liquid storage tank 1 can be circulated between the bubble generator 24 and the liquid storage tank, and can be sufficiently stored in the processing tank 1 in advance. Gas treatment liquid L. Therefore, when the substrate W is processed, the treatment liquid L stored in the liquid storage tank 1 can be quickly supplied to the substrate w by degassing and mixing fine bubbles. Fig. 7 is a view showing a fourth embodiment of a modification of the third embodiment shown in Fig. 6. In the fourth embodiment, the liquid supply tube 3 of the treatment liquid L stored in the reservoir tank, The gas supply pipe 25a of the inert gas supplied to the gas supply unit 25 is connected to the suction side of the second circulation pump. Then, the treatment liquid L and the inert gas are mixed in advance by the second circulation pump 1, and then supplied to the bubble generator 24. As a result, the pre-mixed treatment liquid L and the inert gas-surface are swirled inside the bubble generator 24, and the mixture is flowed and mixed, and the inert gas forms fine bubbles. Therefore, the fine bubbles can be mixed with the treatment liquid L with good efficiency. In the fourth embodiment, as in the third embodiment, a part of the treatment liquid L of the liquid storage tank 1 is supplied to the treatment unit 2, and the path to the liquid storage tank 1 is returned as the first cycle. In the piping, a part of the treatment liquid 1 of the liquid storage tank is supplied to the bubble generator 24, and the path of the return liquid storage tank 1 is taken as the second circulation line. In the same manner as in the third embodiment shown in FIG. 6, the structure can be mixed with the treatment liquid L in which the gas such as carbon dioxide or oxygen which is returned from the treatment unit 2 to the reservoir tank 1 in the first circulation line is dissolved. The fine bubbles contained in the treatment liquid L circulating in the bubble generator 24 and the reservoir 1 in the second circulation line. According to 201041030, even if the processing unit 2 dissolves a gas such as carbon dioxide or oxygen in the treatment liquid L, the gas can be circulated in the second circulation line, and the foaming action of the fine bubbles contained in the treatment liquid returned to the storage tank can be performed. Effectively removed. Fig. 8 is a graph showing the relationship between the time gate and the amount of dissolved oxygen contained in the treatment liquid when the fine bubbles are supplied to the treatment liquid. In the third and fourth embodiments, the oxygen is dissolved in the treatment liquid in the first circulation line, and after the liquid solution is started, after the oxygen amount reaches about 14 minutes in about 35 mgA, the circulation is performed in the second circulation line. When the supply of the fine bubbles was started, it was confirmed that the amount of dissolved oxygen in the treatment liquid of the liquid storage tank was largely lowered after about 20 minutes after the start of the supply of the fine bubbles. In the above-described embodiments, the processing unit is described as an example in which the substrate is conveyed by the transport conveyor, and the processing unit may be a so-called rotary processing device that supplies the processing liquid while rotating the substrate. Further, the bubble generator is not limited to the structure exemplified in each of the above embodiments, and may be another structure such as a so-called pressurization method in which a gas is passed through a filter by pressurizing the gas to generate bubbles in the liquid.
I：圖式簡單説明J 第1圖係顯示此發明一實施形態之基板處理裝置之概 略結構圖。 第2圖係顯示用於上述處理裝置之除氣裝置之内部構 造的戴面圖。 第3圖係顯示對純水賦與不同之4個條件時之經過時間 與溶氧濃度的關係之圖表。 第4圖係使業經除氣之純水於氣泡產生器反覆循環 17 201041030 時，測量純水之溶氧濃度之變化的圖表。 第5圖係顯示此發明第2實施形態之基板處理裝置之概 略結構圖。 第6圖係顯示此發明第3實施形態之基板處理裝置之概 略結構圖。 第7圖係顯示此發明第4實施形態之基板處理裝置之概 略結構圖。 第8圖係顯示在第3實施形態及第4實施形態中將細微 氣泡供給至貯液槽内之處理液時之經過時間與溶氧濃度的 關係之圖表。 【主要元件符號說明】 1...貯液槽 18...流出室 2...處理部 19...減壓室 3,3a...供液管 21...減壓泵 4...喷淋管 22...除氣構件 5...喷嘴 22a...中空線 6...搬送輸送機 24...氣泡產生器 11...第1循環泵 25...氣體供給部 12...除氣裝置 25a...供氣管 13".流入口 28...回收管 14…流出口 31...第2循環泵 15...容器 A-D...曲線 16...分隔板 L...處理液 17...流入室 W...基板 18I. BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a schematic block diagram showing a substrate processing apparatus according to an embodiment of the present invention. Fig. 2 is a perspective view showing the internal structure of the deaerator used in the above processing apparatus. Fig. 3 is a graph showing the relationship between the elapsed time and the dissolved oxygen concentration when four different conditions are assigned to pure water. Figure 4 is a graph showing the change in dissolved oxygen concentration of pure water when the degassed pure water is repeatedly circulated in the bubble generator 17 201041030. Fig. 5 is a schematic block diagram showing a substrate processing apparatus according to a second embodiment of the present invention. Fig. 6 is a schematic block diagram showing a substrate processing apparatus according to a third embodiment of the present invention. Fig. 7 is a schematic block diagram showing a substrate processing apparatus according to a fourth embodiment of the present invention. Fig. 8 is a graph showing the relationship between the elapsed time and the dissolved oxygen concentration when the fine bubbles are supplied to the treatment liquid in the storage tank in the third embodiment and the fourth embodiment. [Description of main component symbols] 1...Liquid tank 18...Outflow chamber 2...Processing unit 19...Decompression chamber 3, 3a...Supply pipe 21...Decompression pump 4. .. spray pipe 22...degassing member 5...nozzle 22a...hollow line 6...transport conveyor 24...bubble generator 11...first circulation pump 25...gas Supply unit 12...degassing device 25a...air supply pipe 13".inlet 28...recovery pipe 14...outlet 31...second circulation pump 15...container AD...curve 16. .. partition plate L... treatment liquid 17... inflow chamber W... substrate 18