200822195 九、發明說明： 【發明所屬之技術領域】 本發明係有關一種半導體生產過程中清洗基板或晶圓 的方法，更明確言之，係有關產生一種共沸混合物的方法 並使用匕來清洗基板。 【先前技術】 積體電路的性能、可靠度、及產能受到生產過程中所 使用的晶圓之影響，或是受到生產過程後留在元件表面上 的不必要物理/化學雜質之影響。 备一種元件的最低線寬變小，足以達到微米以下的境 界時，在氧化作用及形成圖案之前清楚清洗晶圓表面的技 術更形重要。清洗半導體晶圓表面的技術大略分為濕化學 清洗法、乾燥清洗法、蒸氣法等，其中濕化學清洗法最常 被使用。在濕化學清洗法中，一種包含標準清洗丨（sc〇 及標準清洗2 (SC - 2)的RCA《青洗法最受廣泛使用。一般而 言，矽晶圓濕清洗的執行方式是將約5〇—1〇〇片晶圓一起浸 入-種清洗液中，例如SC一USC—2，並在去離子水⑼= )中沖洗它們。然@，將晶圓―起浸入清洗液的過程有一 個問題，由於過程需仰賴水流流經間歇待沖洗的晶圓，故 緩慢是不可避免的。 因此，更快速清洗及沖洗晶圓的需求日益增加，因為 需要較短的時間來製作半導體積體電路。 ’ 因此’美國專利申請號碼嶋2，130揭露一種改善晶圓沖洗 的方法，是在一種裝置中清洗罝一 “ _ 200822195 晶圓被暴露在一種清洗液中’以高速旋轉，然後施加或噴 麗一種去離子水到旋轉的晶圓上，用來去除晶圓上的清洗 液。旋轉晶圓的離心力可進一步改善晶圓沖洗。 然而，即使當晶圓以高速旋轉時，去離子水仍在晶圓 中央隆起，這是因為離心力弱以及去離子水的表面張力所 致’且因為離心力故去離子水膜在晶圓周圍較薄。 此時，高濃度化學製品極快速擴散在去離子水中；因 此，雖然在沖洗過程開始時使用去離子水沖洗具有成效， 但隨著時間流逝，擴散率將降低，且在晶圓中央隆起的去 離子水仍然存在。 為了解決上述問題’美國專利申請號碼〇9/892,13〇提出 一種方法，在施加化學製品與/或施加去離子水之後，施 加一種表面張力低於水的表面張力的溶液（不論是液體或 氣體形式）到晶圓上，例如異丙醇（IpA)。按照此方法，在 沖洗的最初階段是由一種具有高溶解度的去離子水來去除 化學製品，而在沖洗的最後階段則是由IpA來降低在晶圓 中央隆起的去離子水層，藉此加速擴散。 另一個實施例揭露一種方法，在施加化學製品之後以 及在施加去離子水作沖洗之前喷麗一種異丙醇蒸氣或液體 。另-個實施例揭露-種方法，透過—個喷嘴在晶圓的一 個點施加-種異丙醇液體，同時透過另一個喷嘴在晶圓的 另一個點施加去離子水。 其亦揭露一種方法，古Λ、 Ν於至溫的溫度加熱去離子水 ，例如60-70 °C，藉由供雍刼处t l /、w “、、肖b到去離子水來加速化學製品 200822195 擴散。 其亦揭露-種方法，以高於晶圓沖洗期間的速度來旋 轉晶圓，或是在沖洗之後施加氮氣到晶圓，來使晶圓乾燥 〇 然而，雖然先前工藝已經揭露使用去離子水與一種表 面張力低於水的表面張力的液體（例如異丙醇）來清洗基 板的方法，卻尚未發表當以室溫清洗基板時，藉由適當調 整去離子水與異丙醇的混合比率來簡化乾燥過程的方法。 在這方面，本發明人已發現：清洗、沖洗、及乾燥基 板的過程可以在室溫下更有效率地進行，方式是在清洗基 板的過程中使用一種共沸混合物，該共沸混合物是藉由混 合一種去離子水與一種表面張力低於水的表面張力的液體 (尤其是異丙醇）來產生。 因此’本發明提供一種產生共沸混合物的方法，以適 當比率混合一種在清洗半導體過程中所施加的去離子水以 及一種表面張力低於水的表面張力的液體，並使用所產生 的共沸混合物在室溫下更有效率地清洗基板。 【發明内容】 【技術問題】 本發明的目的是要提供一種產生共沸混合物的方法， 該共沸混合物可在低於去離子水與異丙醇蒸發溫度的溫度 下輕易蒸發，方式是適當調整一種用來清洗半導體的去離 子水與一種表面張力低於水的表面張力的液體之混合比率 ’以及提供一種使用該共沸混合物來有效清洗基板的方法 7 200822195 本發明的另一目的是要提供一種產生共沸混合物的方 法’該共沸混合物是由一種具有固定組成比率的去離子水 與一種表面張力低於水的表面張力的液體所組成，方式是 使用一台附著於半導體清洗裝置的施加器上的同軸靜態混 合器，並使用該共沸混合物來有效清洗基板。 【技術解答】 為了達成上述目的，本發明提供一種產生共沸混合物 的方法，該共沸混合物可輕易在室溫下蒸發，方式是適當 調整一種去離子水與一種表面張力低於水的表面張力的液 體之混合比率，以便在清洗時用來沖洗基板表面。再者， 本發明進一步提供一種清洗晶圓的方法，方式是施加上述 共沸混合物到晶圓。 依據本發明的基板清洗法包含下列步驟：旋轉基板； 施加一種清洗液到旋轉基板的表面；產生一種共沸混合物 ’方式是混合一種去離子水與一種表面張力低於水的表面 張力的液體；以及施加該共沸混合物到旋轉基板的表面， 其中該共沸混合物的沸點低於即將混合的去離子水與液體 之沸點。 依據本發明的基板清洗法最好進一步包含在施加共沸 混合物的步驟之後，使用一種氣體來吹拂旋轉基板的中央 ’或是施加一種表面張力低於水的表面張力的液體之蒸氣 到旋轉的基板之步驟。 依據本發明的基板清洗法最好進一步包含在施加共沸 200822195 混合物的步驟之後，同時施加一種氣體與一種表面張力低 於水的表面張力的液體之蒸氣到旋轉的基板之步驟。 依據本發明的基板清洗法所施加的共沸混合物最好是 由一台同軸靜態混合器來產生與提供。 依據本發明的基板清洗法最好可由一種氮氣薄膜來阻止房 間外部的雜質湧入，該氮氣薄膜的形成方式是從執行基板 - 清洗的房間内部空間周圍的房間上方提供氮氣。 【優點】 本發明使用一種可在相對低於去離子水與液體蒸發溫 度的溫度下輕易蒸發的共沸混合物，可有效清洗晶圓，該 共沸混合物是藉由適當調整一種用來清洗基板的去離子水 與一種表面張力低於水的表面張力的液體之組成比率來產 生。 本發明使用一種由具有固定組成比率的去離子水與一 種表面張力低於水的表面張力的液體所組成的共沸混合物 ，可有效清洗晶圓，該共沸混合物是藉由一台附著於半導 體清洗裝置的施加器上的同軸靜態混合器來產生。 200822195 【實施方式】 下文將參照附圖詳細說明本發明的更佳實施例。 圖1是依據本發明的基板清洗法所使用的單一基板清 洗裝置的一個實施例之剖面圖。 如圖1所示，依據本發明的基板清洗法所使用的基板 清洗裝置10包含：一個基板固定裝置100 (又名「卡盤」） ，用來固定上方的基板102並旋轉它；施加器1〇4 、1〇6 ，用來施加清洗液、沖洗用的去離子水等到旋轉基板的表 面上；一台同轴靜態混合器（1〇8)，其連接到施加器1〇6 ， 用來混合即將施加到基板102表面的液體（例如去離子水 與異丙醇）以產生共沸混合物；流速計11〇 、114 ，其連 接到同軸靜態混合器，用來調節流入同軸靜態混合器的液 體之流速；短脈衝幫浦112 、116 ，用來提供液體到同軸 靜態混合器；以及一個與外界環境分隔的房間12〇 ，用來 執行基板清洗。 再者，從執行基板清洗的房間12〇内部周圍的房間 120上方提供氮氣來形成一道氮氣薄膜簾幕，藉此阻止房 間外部的雜質湧入。 下文將參照圖2說明依據本發明的基板清洗裝置所 使用的基板固定裝置1〇〇的一個實施例。 圖2是依據本發明的基板清洗裝置所使用的基板固定 裴置的一個實施例之剖面圖。 如圖2所示，依據本發明的一個實施例，基板固定裝 置忉〇 (卡盤）包含：一個上板21，其包含一個多孔板23， 200822195 上面有數個孔作不規則且均勻的分佈；一個下板22，其連 接到上板21的底端，用來形成一個氣體貯藏區扔，從卡盤 100的外部透過一個心軸流入的氣體被貯藏在裡面；一個 晶圓支架24，藉由緊密附著到基板側邊的方式，用來固定 基板；以及一個感測元件，包含一個感測器，用來感測晶 圓的存在以及晶圓在多孔板23中央的大略位置，其中的多 孔板23為圓形’並且位於上板21的中央。 當氣體，例如氮氣，從位於上板21與下板22之間的氣 體貯藏區透過多孔板23的數個孔往外流向基板時，附著在 上板21頂端的基板因外流氣體的壓力而往上漂浮，而漂浮 基板的側邊則由基板支架24固定住。 再者，如圖2所示，多孔板23上面所形成的數個孔以 不規則且均勻的方式分佈，如同泡沫海綿的形狀。多孔板 23是由一種呈現最卓越化學抗性的高功能塑膠所構成，即 一種聚四氟乙烯（PTFE)，一般稱作「鐵氟龍」；故其不會 與處理晶圓所使用的化學製品起反應，並且不會產生任何 雜質。 多孔板23上面所形成的孔的尺寸與數目可加以調整； 孔的尺寸最好是5-800州，而體積最好是多孔板23體積的 5-90%。再者’透過孔往外流出的氣體是以不規則方向喷灑 到晶圓上。 在本實施例中，上板21僅包含一個圓形多孔板23，但 多孔板23可採取任何形狀，例如多邊形等，再者，可以相 對於卡盤10中央的點對稱形式來安排多個多孔板。 200822195 依據本發明的基板清洗法，使用上述卡盤1〇〇讓氮氣 透過多孔板23往外流出，使得基板102往上漂浮並且旋轉 ° SC-1與SC-2通常作為半導體清洗液使用，這些液體被喷 灑到旋轉基板102的表面，以便沖洗該表面。依據本發明 的基板清洗法，施加清洗液到基板1〇2的過程以及沖洗基 板的過程是在相同裝置1〇進行。 依據本發明的基板清洗法的一個實施例，為了沖洗基 板102 ，藉由一台施加器ι〇6將一種處於共沸混合物狀態 的去離子水（DIW)與異丙醇（IPA)的混合溶液施加到基板1〇2 的表面，同時由卡盤100轉動被喷灑上S(>1與sc—2等清洗 液的基板102。 一般而言’去離子水在離子污染物中具有高溶解度， 且購買與處理成本不高，同時它在消除污染物方面具有成 效，因為在沖洗的最初步驟，仍留在基板上的高濃度化學 製品快速散佈在去離子水中並且減少。基於此理由，基板 的清洗過程廣泛使用去離子水。 % 然而，當施加去離子水到已被塗上清洗液或蝕刻液等 的基板以便作沖洗時，旋轉基板所產生的離心力在基板的 周圍變得較強，因而在基板表面上所形成的去離子水膜在 周圍較薄；然而，基板中央的離心力相對較弱，這就是去 離子水膜在中央隆起的原因。亦即旋轉基板的離心力使得 去離子水膜在基板周圍較薄，而離心力弱的基板中央則因 去離子水的表面張力而隆起。 如上文所述，隨著時間流逝，污染物散佈在去離子水 12 200822195 中的情形將逐漸減少，而去離子水將在基板中央隆起。因 此，為了更有效沖洗及乾燥基板，有必要降低去離子水在 基板中央所形成的隆起部分。 依據本發明的基板清洗法，以適當比率混合去離子水 液體（1)與異丙醇（IPA: (CH3)2CH0H)液體（1)來配製一種共 /弗此a物並將這種共彿混合物施加到基板的表面，以便 沖洗基板。 雖然異丙醇在離子污染物中的溶解度比水低，但其表 面張力低於水的表面張力；因此，當異丙醇與去離子水混 合時，混合物的整體表面張力比水低，如此便可降低去離 子水在基板中央所形成的隆起部分。 再者，異丙醇可產生一種無法藉由蒸餾法消除水分來 轉成純粹產品的共沸混合物。共沸混合物是指一種處於溶 液狀態並且可產生共沸的液體混合物。一般而言，與混合 了二種液體成分的溶液處於同等狀態的蒸氣，其組成不同 於溶液本身的組成。在將液體混合物溶液蒸餾成每種成分 液體時便應用到此事實。當蒸餾一種溶液時，蒸氣的組成 通常不同於原始溶液的組成，且一種成分超過另一種成分 。因此，關於溶液本身的組成，另一種成分的濃度逐漸增 加，而溶液沸點則因此持續提高。 然而，具有某種組成的溶液呈現純粹液體的特性；亦 即在瘵餾期間，溶液的組成與蒸氣的組成相同，因此構 成浴液的成分維持不變，繼續在特定溫度沸騰。同樣地， 在液體混合物溶液的情況中，發生在某個溫度且不改變組 13 200822195 成的沸騰稱作「共沸」，而發生共沸的溫度（沸點）則稱 作「共沸點」。 如前文所述，具有特定組成且可產生共沸的液體混合 物溶液稱作「共沸混合物」，此共沸混合物分為「最低共 沸混合物」，其共沸發生在溶液系統的最低沸點，以及Γ 最高共沸混合物」，其共沸發生在最高沸點。 依據本發明，以異丙醇液體對去離子水的混合比率來 產生一種共沸混合物’其中的混合比率介於10—:gQ—10 ; 當異丙醇液體對去離子水的比率大約是95· 6 ·· 4· 4時，在J 個大氣壓力下，共沸發生在8〇·4 t時，其沸點低於水的沸 點（99· 97 °C )以及異丙醇的沸點（82· ，而這是去離子 水與異丙醇的最低共沸混合物。 因此，藉由施加異丙醇與去離子水的共沸混合物到旋 轉的基板，清洗基板的過程，尤其是沖洗與乾燥，因為以 下三種作用而可獲大幅改善。明確言之，首先，基板表面 所形成的去離子水與異丙醇液體的薄膜由於旋轉基板的離 心力故在基板周圍變得較薄。 接下來，異丙醇的表面張力低於水的表面張力，造成 去離子水與異丙醇混合物的整體表面張力降低；結果去離 子水與異丙醇在基板表面所形成的薄膜比只有去離子水所 形成的薄膜還要薄，特別是可降低出現在基板中央的薄膜 5部分的厚度°再者’當去離子水以適當比率與異丙醇 混合時，可產生具有較低沸點的共沸混合物，因此可更容 易發生室溫下的蒸發作用。結果清洗基板的沖洗與乾燥過 200822195 程可以進一步獲得改善。 再者’依據本發明的基板清洗法，只使用到少量異丙 醇’故可選擇有點昂貴的異丙醇。 再者’依據本發明的基板清洗法，使用少量異丙醇便 可有效防止水印留在基板上。 如圖1所示’在施加去離子水與異丙醇的共沸混合物 到基板102表面的步驟之後，本發明的基板清洗法最好可 進一步包含藉由一台施加器1〇4吹出氮氣到基板1〇2中央 的步驟。吹出氮氣可增加物理應力到基板的隆起部分，因 此可減少基板中央隆起部分的厚度，以及與去離子水混合 的異丙醇液體。 再者，在施加去離子水與異丙醇的共沸混合物到基板 102的表面之後，最好可藉由一台施加器1〇4添加異丙醇 的蒸氣到基板102中央，以便降低基板中央所形成的隆起 部分的厚度。此時，添加到基板1〇2中央的異丙醇溶解在 去離子水中，藉此降低表面張力，結果減少基板表面中央 的厚度。 再者，在施加去離子水與異丙醇的共沸混合物到基板 102的表面之後，最好可藉由一台施加器1〇4同時添加氮 氣與異丙醇的蒸氣到基板1〇2中央，以便降低基板中央所 形成的隆起部分的厚度。 圖3是單一基板清洗裝置用來混合去離子水與異丙醇 以產生共沸混合物的同軸靜態混合器的一個實施例之剖面 圖0 15 200822195 如圖3所示，同軸靜態混合器1〇8是一種用來產生共 沸混合物的裝置，方式是接收由一個短脈衝幫浦112供應 且流速受到一個流速計11〇控制的異丙醇液體（IPA (1))， 以及由一個短脈衝幫浦116供應且流速受到一個流速計 114控制的去離子水（DIW (1))，並將二者混合。 在採用預先混合系統並且從裝置外部供應去離子水與 異丙醇混合物的情形下，需要較大尺寸的裝置，並且隨著 在裝置的混合槽中的時間流逝，去離子水的蒸氣壓力變得 不同於異丙醇的蒸氣壓力；因此，去離子水與異丙醇的組 成比率將改變。 結果是不能維持去離子水與異丙醇的最佳組成比率， 因而無法產生具有最低沸點的共沸混合物。 因此’如圖1所示，本發明的基板清洗法所使用的裝 置10配備了 一台同軸靜態混合器1〇8 ，用來在裝置中混 合去離子水與異丙醇。 般而δ ’同軸靜態混合器1〇8裡面有數個元件302 ，在管内從右到左連續固定，對經過的流體產生連續混合 動作同時將層流流體轉換成紊流流體，以便有效混合二 種或多種流體、氣體、及粉狀體。同轴靜態混合器扮演三 種角色’即區分、倒轉方向、及混合，方式是區分流體流 動、倒轉其方向並在管内傳送期間變換之，藉此達成良好 的此合。因此，使用同轴靜態混合器1〇8可幫助改善生產 =，因為在達成較佳混合效果的同時，它也透過簡化、連 、.只及降低時間以及減少生產成本（例如藉由節省能源） 200822195 ，讓整體混合過程的管理更輕鬆。並且不論同軸靜態混合 器附著在何處，皆可達到效果。 藉由採用上述同軸靜態混合器，依據本發明的基板清 洗法可藉由她加共沸混合物到基板表面更有效地清洗基板 ，同時維持去離子水與異丙醇的共沸混合物的組成比率固 定不變，不管時間如何流逝。 以上所提供的實施例說明可讓熟悉此工藝的人自由實 踐本發明。對於熟悉此工藝的人而言，那些實施例的各種 變化將是顯而易見的，並且可將本文所定義的一般原則應 用在其他K軛例上，而不超出本發明的想法與範圍。因此 入本發月並未文限於本文所揭露的實施例，而是將所有符 口本發明所揭露的原則與創新特色的同等物均包含在内。 17 200822195 【圖式間早說明】 圖是依據本發明的基板清洗法所使用的單一基板清 洗裝置的一個實施例之剖面圖。 圖2是依據本發明的基板请洗法所使用的基板固定裝 置的一個實施例之剖面圖。 異丙醇 之剖面 圖3疋單一基板清洗裝置用來混合去離子水與 以產生共/弗混合物的同轴靜態混合器的一個實施例 圖0 【主要元件符號說明】 100 :基板固定裝置 102 :基板（或晶圓） 104 、106 :施加器 108 :同軸靜態混合器 110、114 :流速計 112、116 :短脈衝幫浦 120 :房間 18200822195 IX. Description of the Invention: [Technical Field] The present invention relates to a method for cleaning a substrate or a wafer in a semiconductor manufacturing process, and more specifically, a method for producing an azeotrope and using a crucible to clean a substrate . [Prior Art] The performance, reliability, and throughput of an integrated circuit are affected by the wafer used in the production process or by unnecessary physical/chemical impurities remaining on the surface of the component after the production process. When the minimum line width of an element is reduced to a level below micron, it is more important to clearly clean the surface of the wafer prior to oxidation and patterning. The technique for cleaning the surface of a semiconductor wafer is roughly classified into a wet chemical cleaning method, a dry cleaning method, a vapor method, and the like, and a wet chemical cleaning method is most often used. In the wet chemical cleaning method, an RCA "greenwashing method" containing standard cleaning cartridges (sc〇 and standard cleaning 2 (SC-2) is most widely used. In general, the wet cleaning of tantalum wafers is performed in a manner 5〇—1 wafers are immersed together in a cleaning solution, such as SC-USC-2, and rinsed in deionized water (9) = ). However, there is a problem with the process of immersing the wafer into the cleaning solution. Since the process depends on the flow of water through the intermittent wafer to be rinsed, slowness is inevitable. Therefore, there is an increasing demand for faster cleaning and rinsing of wafers because it takes less time to fabricate semiconductor integrated circuits. Thus, U.S. Patent Application Serial No. 2,130 discloses a method of improving wafer rinsing by cleaning a device in a device that is exposed to a cleaning fluid at a high speed and then applied or sprayed. A deionized water is applied to the rotating wafer to remove the cleaning liquid from the wafer. The centrifugal force of the rotating wafer can further improve the wafer flushing. However, even when the wafer is rotated at a high speed, the deionized water is still crystallized. The central bulge of the circle is due to the weak centrifugal force and the surface tension of the deionized water. And because of the centrifugal force, the ionized water film is thin around the wafer. At this time, the high concentration of the chemical is extremely rapidly diffused in the deionized water; therefore, Although it is effective to use deionized water at the beginning of the rinsing process, the diffusion rate will decrease over time, and deionized water still bulging in the center of the wafer will still exist. In order to solve the above problem, 'US Patent Application No. 〇9/ 892, 13 〇 propose a method of applying a surface tension lower than water after applying chemicals and/or applying deionized water a solution of tension (whether in liquid or gaseous form) onto a wafer, such as isopropanol (IpA). In this way, the chemical is removed from a highly soluble deionized water during the initial stages of rinsing. The final stage of rinsing is to reduce the layer of deionized water in the center of the wafer by IpA, thereby accelerating diffusion. Another embodiment discloses a method that sprays after applying the chemical and before applying deionized water for rinsing An isopropanol vapor or liquid. Another embodiment discloses a method of applying an isopropanol liquid at one point of a wafer through a nozzle while applying another point on the wafer through another nozzle. Ionic water. It also discloses a method in which deuterated water is heated at a temperature of, for example, 60-70 ° C, by means of a supply of tl /, w ", , b b to deionized water. Accelerate the diffusion of chemicals 200822195. It also discloses a method of rotating the wafer at a higher speed than during wafer rinsing, or applying nitrogen to the wafer after rinsing to dry the wafer, although previous processes have disclosed the use of deionized water and A method of cleaning a substrate with a liquid having a surface tension lower than the surface tension of water (for example, isopropyl alcohol) has not been published. When the substrate is washed at room temperature, it is simplified by appropriately adjusting the mixing ratio of deionized water and isopropyl alcohol. The method of the drying process. In this regard, the inventors have discovered that the process of cleaning, rinsing, and drying the substrate can be carried out more efficiently at room temperature by using an azeotrope during the cleaning of the substrate, which is aborted It is produced by mixing a deionized water with a liquid having a surface tension lower than the surface tension of water (especially isopropanol). Thus, the present invention provides a method of producing an azeotrope in which a deionized water applied during cleaning of a semiconductor and a liquid having a surface tension lower than that of water are mixed at an appropriate ratio, and the resulting azeotrope is used. The substrate is more efficiently cleaned at room temperature. SUMMARY OF THE INVENTION [Technical Problem] An object of the present invention is to provide a method for producing an azeotrope which can be easily evaporated at a temperature lower than a temperature at which deionized water and isopropanol evaporate, by appropriately adjusting A mixing ratio of deionized water for cleaning a semiconductor to a liquid having a surface tension lower than the surface tension of water' and a method for effectively cleaning the substrate using the azeotrope 7 200822195 Another object of the present invention is to provide A method of producing an azeotrope mixture consisting of a liquid having a fixed composition ratio of deionized water and a surface tension having a surface tension lower than that of water by using an application attached to a semiconductor cleaning apparatus. A coaxial static mixer on the vessel and using the azeotrope to effectively clean the substrate. [Technical Solution] In order to achieve the above object, the present invention provides a method for producing an azeotrope which can be easily evaporated at room temperature by appropriately adjusting a deionized water and a surface tension lower than that of water. The mixing ratio of the liquids is used to rinse the surface of the substrate during cleaning. Furthermore, the present invention further provides a method of cleaning a wafer by applying the azeotrope to the wafer. The substrate cleaning method according to the present invention comprises the steps of: rotating a substrate; applying a cleaning liquid to the surface of the rotating substrate; producing an azeotrope mixture by mixing a deionized water with a liquid having a surface tension lower than that of water; And applying the azeotrope to the surface of the rotating substrate, wherein the boiling point of the azeotrope is lower than the boiling point of the deionized water to be mixed with the liquid. The substrate cleaning method according to the present invention preferably further comprises, after the step of applying the azeotrope, using a gas to blow the center of the rotating substrate or applying a vapor of a liquid having a surface tension lower than the surface tension of the water to the rotating substrate. The steps. The substrate cleaning method according to the present invention preferably further comprises the step of simultaneously applying a gas and a vapor of a liquid having a surface tension lower than the surface tension of water to the rotating substrate after the step of applying the azeotrope 200822195 mixture. The azeotrope applied by the substrate cleaning method in accordance with the present invention is preferably produced and provided by a coaxial static mixer. The substrate cleaning method according to the present invention preferably employs a nitrogen film to prevent the influx of impurities outside the room, which is formed by supplying nitrogen gas from above the room surrounding the substrate-cleaning room interior. [Advantages] The present invention can effectively clean a wafer by using an azeotropic mixture which can be easily evaporated at a temperature relatively lower than the temperature at which the deionized water and the liquid evaporate, and the azeotrope is appropriately adjusted to clean the substrate. Deionized water is produced as a composition ratio of a liquid having a surface tension lower than the surface tension of water. The invention uses an azeotropic mixture composed of deionized water having a fixed composition ratio and a liquid having a surface tension lower than the surface tension of water, which can effectively clean the wafer, and the azeotrope is attached to the semiconductor by one A coaxial static mixer on the applicator of the cleaning device is produced. [Embodiment] Hereinafter, a more preferred embodiment of the present invention will be described in detail with reference to the accompanying drawings. BRIEF DESCRIPTION OF THE DRAWINGS Figure 1 is a cross-sectional view showing an embodiment of a single substrate cleaning apparatus used in a substrate cleaning method in accordance with the present invention. As shown in FIG. 1, the substrate cleaning apparatus 10 used in the substrate cleaning method according to the present invention comprises: a substrate fixing device 100 (also referred to as "chuck") for fixing the upper substrate 102 and rotating it; the applicator 1 〇4,1〇6, for applying cleaning liquid, deionized water for rinsing, etc. onto the surface of the rotating substrate; a coaxial static mixer (1〇8) connected to the applicator 1〇6 for The liquid to be applied to the surface of the substrate 102 (for example, deionized water and isopropanol) is mixed to produce an azeotrope; the flow meter 11〇, 114 is connected to a coaxial static mixer for regulating the liquid flowing into the coaxial static mixer. The flow rate; the short pulse pumps 112, 116 are used to provide a liquid to the coaxial static mixer; and a room 12 分隔 separate from the external environment for performing substrate cleaning. Further, nitrogen gas was supplied from above the room 120 around the inside of the room 12 where the substrate cleaning was performed to form a nitrogen film curtain, thereby preventing the intrusion of impurities outside the room. An embodiment of the substrate holding device 1A used in the substrate cleaning apparatus according to the present invention will be described below with reference to FIG. Fig. 2 is a cross-sectional view showing an embodiment of a substrate fixing device used in the substrate cleaning apparatus according to the present invention. As shown in FIG. 2, according to an embodiment of the present invention, a substrate fixing device (chuck) includes: an upper plate 21 including a perforated plate 23, and a plurality of holes on the 200822195 for irregular and uniform distribution; a lower plate 22 connected to the bottom end of the upper plate 21 for forming a gas storage area to be thrown, and gas flowing in from the outside of the chuck 100 through a mandrel is stored therein; a wafer holder 24, by a method of closely adhering to the side of the substrate for fixing the substrate; and a sensing element including a sensor for sensing the presence of the wafer and a general position of the wafer in the center of the perforated plate 23, wherein the perforated plate 23 is a circle 'and is located at the center of the upper plate 21. When a gas such as nitrogen gas flows from the gas storage region between the upper plate 21 and the lower plate 22 through the plurality of holes of the perforated plate 23 to the substrate, the substrate attached to the top end of the upper plate 21 is lifted by the pressure of the outflow gas. Floating, while the sides of the floating substrate are held by the substrate holder 24. Further, as shown in Fig. 2, a plurality of holes formed on the perforated plate 23 are distributed in an irregular and uniform manner like the shape of a foam sponge. The perforated plate 23 is composed of a highly functional plastic that exhibits the most superior chemical resistance, namely a polytetrafluoroethylene (PTFE), commonly referred to as "Teflon"; therefore, it does not interact with the chemistry used to process the wafer. The product reacts and does not produce any impurities. The size and number of the holes formed in the perforated plate 23 can be adjusted; the size of the holes is preferably from 5 to 800, and the volume is preferably from 5 to 90% of the volume of the perforated plate 23. Furthermore, the gas flowing out through the holes is sprayed onto the wafer in an irregular direction. In the present embodiment, the upper plate 21 contains only one circular perforated plate 23, but the perforated plate 23 may take any shape such as a polygon or the like, and further, a plurality of perforations may be arranged in a point symmetrical form with respect to the center of the chuck 10. board. 200822195 According to the substrate cleaning method of the present invention, the above-mentioned chuck 1 is used to allow nitrogen gas to flow out through the porous plate 23, so that the substrate 102 floats upward and rotates. SC-1 and SC-2 are generally used as semiconductor cleaning liquids. It is sprayed onto the surface of the rotating substrate 102 to rinse the surface. According to the substrate cleaning method of the present invention, the process of applying the cleaning liquid to the substrate 1 2 and the process of rinsing the substrate are carried out in the same apparatus. According to an embodiment of the substrate cleaning method of the present invention, in order to rinse the substrate 102, a mixed solution of deionized water (DIW) and isopropanol (IPA) in an azeotropic mixture state is applied by an applicator ι6. It is applied to the surface of the substrate 1〇2 while being rotated by the chuck 100 to be sprayed with the substrate 102 of S (>1 and sc-2 cleaning liquid. Generally, the deionized water has high solubility in ionic contaminants. And the cost of purchasing and processing is not high, and it is effective in eliminating contaminants because in the initial step of rinsing, the high concentration of chemicals remaining on the substrate is rapidly dispersed in the deionized water and reduced. For this reason, the substrate Deionized water is widely used in the cleaning process. However, when deionized water is applied to a substrate to which a cleaning liquid or an etching liquid or the like has been applied for rinsing, the centrifugal force generated by rotating the substrate becomes stronger around the substrate. Therefore, the deionized water film formed on the surface of the substrate is thinner around; however, the centrifugal force in the center of the substrate is relatively weak, which is the reason why the deionized water film is raised in the center. The centrifugal force of the rotating substrate causes the deionized water film to be thinner around the substrate, while the center of the substrate with weak centrifugal force is raised due to the surface tension of the deionized water. As described above, the contaminant is dispersed in the deionized water as time passes. The situation in 200822195 will gradually decrease, and the deionized water will bulge in the center of the substrate. Therefore, in order to more effectively rinse and dry the substrate, it is necessary to reduce the bulging portion formed by deionized water in the center of the substrate. Mixing the deionized water liquid (1) with the isopropanol (IPA: (CH3)2CH0H) liquid (1) at an appropriate ratio to formulate a co-/a mixture and applying the co-bud mixture to the surface of the substrate, In order to rinse the substrate. Although isopropanol has a lower solubility in ionic contaminants than water, its surface tension is lower than the surface tension of water; therefore, when isopropyl alcohol is mixed with deionized water, the overall surface tension of the mixture is higher than that of water. Low, this can reduce the bulging part of the deionized water formed in the center of the substrate. Furthermore, isopropyl alcohol can produce a kind of water that cannot be removed by distillation to convert An azeotrope of a product. An azeotrope is a mixture of liquids that is in a solution state and can produce azeotropy. In general, a vapor in the same state as a solution in which two liquid components are mixed is different in composition from the solution itself. The composition is applied to the fact that the liquid mixture solution is distilled into each component liquid. When one solution is distilled, the composition of the vapor is usually different from the composition of the original solution, and one component exceeds the other component. The composition of the other component gradually increases the concentration of the other component, and the boiling point of the solution thus continues to increase. However, the solution having a certain composition exhibits a pure liquid characteristic; that is, during the retorting, the composition of the solution is the same as the composition of the vapor. Therefore, the constituents constituting the bath remain unchanged and continue to boil at a specific temperature. Similarly, in the case of the liquid mixture solution, the boiling occurs at a certain temperature and does not change the group 13 200822195, which is called "azeotropic". The azeotropic temperature (boiling point) is called "azeotropic point". As mentioned above, a liquid mixture solution having a specific composition and capable of generating an azeotrope is referred to as an "azeotropic mixture", and the azeotrope is classified as a "minimum azeotrope", the azeotropy occurring at the lowest boiling point of the solution system, and最高 The highest azeotrope, its azeotropy occurs at the highest boiling point. According to the present invention, a mixing ratio of isopropyl alcohol liquid to deionized water is used to produce an azeotrope mixture wherein the mixing ratio is between 10::gQ-10; when the ratio of isopropanol liquid to deionized water is about 95 · 6 ·· 4 · 4, at a total of J atmospheric pressure, azeotropy occurs at 8 〇 · 4 t, its boiling point is lower than the boiling point of water (99 · 97 ° C) and the boiling point of isopropanol (82 · And this is the lowest azeotropic mixture of deionized water and isopropanol. Therefore, by applying an azeotropic mixture of isopropanol and deionized water to the rotating substrate, the process of cleaning the substrate, especially rinsing and drying, because The following three effects can be greatly improved. Specifically, first, the film of deionized water and isopropyl alcohol liquid formed on the surface of the substrate becomes thinner around the substrate due to the centrifugal force of the rotating substrate. Next, isopropanol The surface tension is lower than the surface tension of water, resulting in a decrease in the overall surface tension of the mixture of deionized water and isopropanol; as a result, the film formed on the surface of the substrate by deionized water and isopropanol is more than the film formed only by deionized water. To be thin In particular, the thickness of the portion of the film 5 present in the center of the substrate can be lowered. Further, when deionized water is mixed with isopropyl alcohol at an appropriate ratio, an azeotropic mixture having a lower boiling point can be produced, so that room temperature can be more easily generated. The evaporation underneath. As a result, the rinsing and drying of the cleaning substrate can be further improved through the process of 200822195. Further, according to the substrate cleaning method of the present invention, only a small amount of isopropyl alcohol is used, so that a somewhat expensive isopropanol can be selected. According to the substrate cleaning method of the present invention, the use of a small amount of isopropyl alcohol can effectively prevent the watermark from remaining on the substrate. As shown in FIG. 1 'the step of applying an azeotropic mixture of deionized water and isopropyl alcohol to the surface of the substrate 102 Thereafter, the substrate cleaning method of the present invention preferably further comprises the step of blowing nitrogen gas into the center of the substrate 1〇2 by an applicator 1〇4. The nitrogen gas is blown to increase the physical stress to the raised portion of the substrate, thereby reducing the center of the substrate. The thickness of the raised portion, and the isopropanol liquid mixed with deionized water. Further, an azeotropic mixture of deionized water and isopropanol is applied to the substrate. After the surface of 102, it is preferable to add the vapor of isopropyl alcohol to the center of the substrate 102 by means of an applicator 1〇4 in order to reduce the thickness of the raised portion formed in the center of the substrate. At this time, it is added to the center of the substrate 1〇2. The isopropyl alcohol is dissolved in deionized water, thereby lowering the surface tension, and as a result, reducing the thickness in the center of the surface of the substrate. Further, after applying an azeotropic mixture of deionized water and isopropyl alcohol to the surface of the substrate 102, it is preferred. Simultaneously adding a vapor of nitrogen and isopropanol to the center of the substrate 1〇2 by means of an applicator 1〇4 to reduce the thickness of the raised portion formed in the center of the substrate. Fig. 3 is a single substrate cleaning device for mixing deionized water Cross-sectional view of one embodiment of a coaxial static mixer with isopropanol to produce an azeotrope. 0 15 200822195 As shown in Figure 3, a coaxial static mixer 1〇8 is a device for producing an azeotrope by means of Receiving an isopropanol liquid (IPA (1)) supplied by a short pulse pump 112 and having a flow rate controlled by a flow meter 11〇, and supplied by a short pulse pump 116 and the flow rate is subjected to a flow Speedometer 114 controls deionized water (DIW (1)) and mixes the two. In the case where a pre-mixing system is employed and a mixture of deionized water and isopropyl alcohol is supplied from the outside of the apparatus, a larger-sized device is required, and as time passes in the mixing tank of the apparatus, the vapor pressure of the deionized water becomes Unlike the vapor pressure of isopropanol; therefore, the composition ratio of deionized water to isopropanol will vary. As a result, the optimum composition ratio of deionized water to isopropyl alcohol cannot be maintained, and thus an azeotropic mixture having the lowest boiling point cannot be produced. Thus, as shown in Fig. 1, the apparatus 10 used in the substrate cleaning method of the present invention is equipped with a coaxial static mixer 1 〇 8 for mixing deionized water and isopropyl alcohol in the apparatus. The δ 'coaxial static mixer 1 〇 8 has a plurality of elements 302 therein, which are continuously fixed from right to left in the tube, and continuously compresses the passing fluid while converting the laminar fluid into a turbulent fluid, so as to effectively mix the two kinds. Or a variety of fluids, gases, and powders. Coaxial static mixers play three roles of distinguishing, reversing, and mixing by distinguishing fluid flow, reversing its direction, and transforming it during tube transfer, thereby achieving a good fit. Therefore, the use of a coaxial static mixer 1 〇 8 can help improve production = because it achieves better mixing results, while also simplifying, connecting, reducing time and reducing production costs (for example, by saving energy) 200822195, making the management of the overall mixing process easier. And no matter where the coaxial static mixer is attached, the effect can be achieved. By using the above-described coaxial static mixer, the substrate cleaning method according to the present invention can more effectively clean the substrate by adding an azeotrope to the surface of the substrate while maintaining the composition ratio of the azeotropic mixture of deionized water and isopropyl alcohol. No change, no matter how time passes. The examples provided above are illustrative of the practice of the invention by those skilled in the art. Various changes to those embodiments will be apparent to those skilled in the art, and the general principles defined herein may be applied to other K yokes without departing from the spirit and scope of the invention. Therefore, the present disclosure is not limited to the embodiments disclosed herein, but all the principles disclosed in the present invention and the equivalents of the innovative features are included. 17 200822195 [Brief Description of the Drawings] Fig. 1 is a cross-sectional view showing an embodiment of a single substrate cleaning apparatus used in the substrate cleaning method according to the present invention. Fig. 2 is a cross-sectional view showing an embodiment of a substrate fixing device used in the substrate cleaning method according to the present invention. Sectional view of isopropyl alcohol Figure 3 is an embodiment of a single substrate cleaning apparatus for mixing a deionized water with a coaxial static mixer for producing a co-precipitate mixture. Figure 0 [Main component symbol description] 100: Substrate fixing device 102: Substrate (or wafer) 104, 106: applicator 108: coaxial static mixer 110, 114: flow meter 112, 116: short pulse pump 120: room 18