TW200535998A - Substrate processing apparatus and method - Google Patents

Abstract

A method and apparatus for removing materials from a substrate contained in a closed, pressurized processing vessel. An exemplary method includes the steps of inserting a substrate to be processed into the processing vessel, closing the processing vessel gas-tight, and then pressurizing the processing vessel. A pressurized processing solution is introduced to the processing vessel while the processing vessel is maintained under pressure. The substrate is exposed to the processing solution, so that a processing step ensues and the desired material is removed from the substrate by reaction with the pressurized processing fluid. The processing is performed at greater than atmospheric pressure to maintain a high concentration of active components of the processing solution by increasing the solubility of active solution components, and to inhibit evaporation of volatile components of the processing solution.

Description

200535998 九、發明說明： 【發明所屬之技術領域】 本發明係關於基板處理。更明確地說，本發明係關於半 導體積體電路及元件的製造中所使用的清理、蝕刻以及剝 離方法及裝置。 【先前技術】 傳統積體電路係製造在半導體基板上。製造程序包括各 步驟’該等步驟包括形成光阻膜，其係在—微影姓刻處理 中用以定義積體電路之部分。在微影蝕刻處理之後，必須 移除（或「剝離」）一光阻膜，然後才可實行進一步的處理 已使用各種方法從一基板上剝離光阻臈。 在 得、，死方法中，在120至140。(：的溫度情況下將一種硫 酸（H2so4)及過氧化氫（H2〇2)溶液施加於光阻膜i。所得到 的ϋ氧單硫酉夂（H2S〇5)溶液為一種有效氧化溶液，並且因為 光阻膜為-種有機材料，所以Can)，s溶液用來氧化並移除光 阻膜。此方法之-缺點為邮04及&02為化學品，I可能對 個人及環境有害，尤其在高溫條件下。因為傳統處理容号 ’向大氣敞開，所以該等容器將煙氣排入處理工具二 :里系、’先k而需要收集並中和較大容量的污染氣 ==除去所得到的鹽分。此外，採用環境方面 之 除去化學廢品所需成本在不斷上升。此傳 並之另—缺點為移除速率較低。較低移除速率不合需 定情=在移除速率對通量具有直接及消極影響的製造設 92730.doc 200535998 美國專利第5,464,480號揭示—種替代傳統方法，其避免 以上化學品危險及其他與以上說明的剝離方法相關之問 題。此專利說明使用臭氧化水（即去離子水中吸收臭氧）以從 基板上移除有機材料，例如光阻膜。藉由將溶液維持在環 境溫度以下(例如在以與心的範圍以内)來增加溶液中 臭乳的濃度。雖然此方法可避免與先前說明的方法相關之 問題，但是其主要缺點之一者為移除速率亦較低。較低移 除速率可歸於藉由將氧化溶液維持在環境溫度以下所實現 的臭氧在水中之溶解性的有限增加，以及在低溫情況下進 订處理所導致的反應速率之減小。 在製造半導體元件_所使料—第二類魏式處理步 驟為從基板上移除無機材料。在一傳統#刻處理卜絲由 曝露於一含水氫氟酸（HF)溶液中，相對於—底層材料（例如 旬移除氧化石夕。職刻氧化層比姓刻其他材料（例如底層 快甚多。在此氧化物移除處理期間，hf的濃度可以改 變’尤其在高溫情況下’從而改變此濕式處理步驟所展現 的移除速率以及選擇性。與傳統濕式HF處理相關的—問題 為姓刻之不㈣性。例如，料可變得㈣於基板之表面， 從而阻塞局部區域中含水肝與基板之間的接觸。有時盘傳 統HF濕式處理相關的一第二問題為過高的氧化物 率攸而導致不均勻蝕刻以及表面粗糙。 、 、在製^ ί王序中所頻繁使用的一第三類型濕式處理為清理 ,、 圓之表面修改，其中從基板表面移除殘餘有機材 料' k粒以及金屬。_傳統清理順序有時稱為ΜΑ清洗方 92730.doc 200535998 法。此多步驟濕式處理使用一連串的五個互補化學洛以移 除殘餘有機材料、微粒以及金屬。在一第一步驟中，使基 板經受一加熱的Ηβ〇4及比〇2之水浴以移除殘餘有機材 料’例如剩餘在基板表面上的顯影光阻材料。在一第二步 驟中’在室溫情況下使基板經受一稀釋含水HF浴以移除氧 化層以及包含在裏面的雜質。在一第三步驟中，使基板經 受一加熱的氫氧化銨（NH4〇h)及H2〇z之水浴以移除微粒以 及其他污染物。在一第四步驟中，使基板經受一加熱的鹽 酸（HC1)及H2〇2之水浴以移除金屬。最終在第五步驟中，使 基板再次經受稀釋氫氟酸（HF)之浴以移除藉由先前步驟中 的氧化所形成的氧化層，從而釋放嵌入氧化層中的金屬污 染物並允許將其移除，而且致使晶圓表面具有疏水性。 如以上說明的H2S〇4/H2〇2有機剝離方法所述，RCA清洗 方法之一缺點為所使用的化學品（即h2S〇4、nh4〇H、H2〇2、 HC1以及HF)可能對個人及環境有害，並且安全收集、中和 以及除去的成本較高。此外，因為許多該等化學溶液為揮 發性或包含水相中的溶解揮發性氣體成分，而非在處理期 間包含在封閉容器中，所以在處理過程中可能會出現處理 /谷液中的濃度之變化，從而可能改變濕式處理之性能以及 通量。 在「合乎經濟發展要求的電子元件製造之以臭氧為基礎 的濕式處理」中，三菱電氣現代公司（Mitsubishi ADVANCE)的Kanegae建議採用臭氧化水以及包含少量hf 的臭氧化水，作為在以上說明的傳統RCA清洗方法中所使 92730.doc 200535998 用的該連串化學品之替代物。此方法在以下方面有利：其 減j/必須在處理期間使用並接著必須除去的可能危險化學 品之數量。然而，此方法在以下方面不合需要：其處理速 率並不快於與以上說明的傳統順序相關之速率。 在另類型濕式處理中’在高溫情況下採用有機溶劑 (例如二甲基亞颯（DMSO))與單甲醇胺（MEA)之混合物，來 剝離準備用作液晶顯示器（llquid crystal dlsplays ; lc卬之 面板的基板之表面。此濕式處理之應用會引起以上說明的 泞多相同問題。明確地說，必須以實質費用收集、處理以 及除去處理期間所產生的煙氣以及化學品廢液。此外，處 理化學品之揮發性成分可能會隨時間而損失，從而不合需 要地改變濕式處理化學品之成分，及其性能之均勻性、重 複性以及有效性。 根據以上情況，此項技術需要用以在製造半導體元件期 間實行濕式化學清理、剝離以及蝕刻步驟的改善方法及裝 【發明内容】 本發明係關於―種心在例如於半導體基板上製造積體 電路之程序期間從基板上移除材料的方法及裝置。 根據本發明從-基板之表面上移除—材料的方法之一且 體實施例，包括將包括該材料 〆刊行的孩基板***一敞開處理容 器中；將該處理容器封閉為尤、尸产 ]為不漏氣，並且將該處理容器增 壓至大於大氣壓力。將一厭a占 壓力處理溶液引入壓力處理容器 中以便將基板之一表面暖雲认—旷t 衣甶曝路於该壓力處理溶液中，並且處 92730.doc 200535998 理基板以藉由允許壓力處理流體與材料反應而從基板之該 表面移除材料。在將處理溶液引入處理容器期間以及在基 板之至j部分處理期間，將該溶液維持在高於大氣壓力的 壓力下。 乾燥基板的方法之一具體實施例包括將基板固定在一不 漏軋的處理容器中，並將該處理容器增壓至大於大氣壓 力。將壓力沖洗液體引入處理容器，該沖洗液體之一成分 或一壓力氣體之至少一者，包括集中在該沖洗溶液之一表 面上的一表面張力下降成分。將基板浸沒在沖洗液體内， 相對於沖洗液體移動處理基板，以便在以彎月面形式附於 基板表面的沖洗液體，與沖洗液體之剩餘分散部分之間建 立一表面張力梯度，該表面張力梯度將液體從基板表面汲 入分散沖洗液體。 用以依據本發明從一基板之表面上移除材料的一裝置之 一具體實施例，包括配置成在一不漏氣的密封環境中接收 並包含一基板之一處理容器；以及經由一入口閥與該處理 谷器進行流體通信的一壓力處理溶液之一來源。一排汽閥 使處理容器之流體可與一排洩口通信。一壓力保持容器係 配置成維持一壓力處理溶液，其成分之濃度大於大氣壓力 情況下溶液中可用的成分之濃度。一控制閥係耦合在處理 谷器與保持容器之間，以控制從保持容器至處理容器的處 理溶液之流量。 要從基板上移除的材料之特性將依據特定應用而改變。 在一應用中，要移除的材料可包括一有機材料（例如光阻）， 92730.doc 200535998 而處理命液可包括在高濃度情況下於一酸性溶液中所吸收 的臭氧。因為―麼力溶液中氣體的溶解性得到增加，以及 因為臭氧從封閉系統中釋氣得到禁止，所以吸入溶液中的 臭氧湲度大於可在大氣麼力以及相同溫度情況下出現的濃 度。在-給定溫度情況下，處理溶液中臭氧的較高漢度的 處理速率快於採料統方法達到的處理速率。200535998 IX. Description of the invention: [Technical field to which the invention belongs] The present invention relates to substrate processing. More specifically, the present invention relates to a cleaning, etching, and peeling method and apparatus used in the manufacture of semiconductor volume circuits and components. [Prior Art] Traditional integrated circuits are manufactured on semiconductor substrates. The manufacturing process includes various steps. These steps include forming a photoresist film, which is used to define the integrated circuit in the lithography process. After the lithographic etching process, a photoresist film must be removed (or "peeled") before further processing can be performed. Various methods have been used to remove photoresist from a substrate. In the method of dying, it is between 120 and 140. (: A solution of sulfuric acid (H2so4) and hydrogen peroxide (H2O2) is applied to the photoresist film i at the temperature of (.). The obtained solution of H2SO5 is an effective oxidation solution. And because the photoresist film is an organic material, Can), s solution is used to oxidize and remove the photoresist film. The disadvantage of this method is that Post 04 and & 02 are chemicals. I may be harmful to individuals and the environment, especially under high temperature conditions. Because the traditional processing capacity number is open to the atmosphere, these containers discharge the flue gas into the processing tool II: lining, ‘k first, and need to collect and neutralize a large volume of polluted gas == remove the salt obtained. In addition, the cost of environmentally friendly chemical waste removal is increasing. This transfer is another—the disadvantage is the lower removal rate. Undesirable lower removal rate = manufacturing facility with direct and negative effects on flux at removal rate 92730.doc 200535998 US Patent No. 5,464,480 reveals an alternative traditional method that avoids the dangers of the above chemicals and other Problems related to the peeling method described above. This patent describes the use of ozonated water (that is, the absorption of ozone in deionized water) to remove organic materials, such as photoresist films, from a substrate. By maintaining the solution below the ambient temperature (e.g., within the range of ambiguity), the concentration of malodor in the solution is increased. Although this method avoids the problems associated with the previously described method, one of its main disadvantages is its low removal rate. The lower removal rate can be attributed to the limited increase in the solubility of ozone in water achieved by maintaining the oxidizing solution below ambient temperature, as well as the decrease in the reaction rate caused by ordering treatments at low temperatures. The second type of Wei-type processing step in manufacturing semiconductor components is to remove inorganic materials from the substrate. In a traditional #etching process, the wire is exposed to an aqueous hydrofluoric acid (HF) solution, as opposed to-the underlying material (for example, the oxide stone is removed. The oxide layer is engraved faster than the other materials (such as the bottom layer). Many. During this oxide removal process, the concentration of hf can be changed 'especially at high temperatures' thereby altering the removal rate and selectivity exhibited by this wet processing step. Related to conventional wet HF processing—problems For example, the material can become trapped on the surface of the substrate, thereby blocking the contact between the water-containing liver and the substrate in a local area. Sometimes a second problem associated with traditional HF wet processing is excessive. High oxide rate leads to uneven etching and rough surface. A third type of wet treatment frequently used in the manufacturing process is cleaning, round surface modification, where residual organics are removed from the substrate surface. Materials' k-grains and metals. _ The traditional cleaning sequence is sometimes referred to as the MA cleaning method 92730.doc 200535998. This multi-step wet process uses a series of five complementary chemistries to remove residual organic Materials, particles, and metals. In a first step, the substrate is subjected to a heated water bath of ββ4 and ratio 02 to remove residual organic materials, such as a developing photoresist material remaining on the substrate surface. In two steps, the substrate was subjected to a dilute aqueous HF bath at room temperature to remove the oxide layer and impurities contained therein. In a third step, the substrate was subjected to a heated ammonium hydroxide (NH4oh) And H2Oz water bath to remove particles and other contaminants. In a fourth step, the substrate is subjected to a heated hydrochloric acid (HC1) and H2O2 water bath to remove metal. Finally in the fifth step, Subjecting the substrate to a bath of diluted hydrofluoric acid (HF) again to remove the oxide layer formed by the oxidation in the previous step, thereby releasing and allowing the metal contaminants embedded in the oxide layer to be removed, and causing the wafer The surface is hydrophobic. As described in the H2S04 / H2O2 organic stripping method described above, one of the disadvantages of the RCA cleaning method is the chemicals used (ie h2S04, nh4〇H, H2 02, HC1, and HF) may be personal and environmental And the cost of safe collection, neutralization, and removal is high. In addition, because many of these chemical solutions are volatile or contain dissolved volatile gas components in the aqueous phase, rather than being contained in closed containers during processing, During the process, there may be changes in the concentration of the treatment / valley, which may change the performance and flux of the wet treatment. In "Ozone-based wet treatment of electronic components manufactured in accordance with economic development requirements", Kanegae of Mitsubishi ADVANCE recommends the use of ozonated water and ozonated water containing a small amount of hf as a substitute for the series of chemicals used in the traditional RCA cleaning method 92730.doc 200535998 described above . This method is advantageous in that it reduces j / number of potentially hazardous chemicals that must be used during processing and then must be removed. However, this method is undesirable in that it does not process faster than the rate associated with the traditional sequence described above. In another type of wet process, a mixture of an organic solvent (such as dimethylsulfinium (DMSO)) and monomethanolamine (MEA) is used at high temperature to peel and prepare for use as a liquid crystal display (llquid crystal dlsplays; lc 卬The surface of the substrate of the panel. The application of this wet process causes many of the same problems described above. Specifically, the smoke and chemical waste liquid generated during the process must be collected, processed, and removed at a substantial cost. In addition The volatile components of processing chemicals may be lost over time, thereby undesirably changing the composition of wet processing chemicals, and the uniformity, repeatability and effectiveness of their performance. According to the above situation, this technology requires the use of Improved method and device for performing wet chemical cleaning, peeling and etching steps during semiconductor device manufacturing [Summary of the Invention] The present invention relates to-removing a seed core from a substrate during a process of manufacturing an integrated circuit on a semiconductor substrate, for example Method and device for material One of the methods for removing material from the surface of a substrate according to the present invention For example, including inserting a child substrate including the publication of this material into an open processing container; closing the processing container to a cadaver] is airtight, and pressurizing the processing container to a pressure greater than atmospheric pressure. A pressure treatment solution is introduced into the pressure treatment container to warm one surface of the substrate. The clothing is exposed to the pressure treatment solution, and the substrate is treated at 92730.doc 200535998 to allow the pressure to process fluids and materials. The material is removed from the surface of the substrate by the reaction. The solution is maintained at a pressure higher than the atmospheric pressure during the introduction of the processing solution into the processing container and during the processing of the substrate through part j. One method of drying the substrate is specifically implemented Examples include fixing a substrate in a non-missing processing container, and pressurizing the processing container to a pressure greater than atmospheric pressure. Introducing a pressure flushing liquid into the processing container, at least one of a component of the flushing liquid or a pressure gas, It includes a surface tension reducing component concentrated on one of the surfaces of the rinsing solution. The substrate is immersed in the rinsing liquid relative to the rinsing solution. The liquid moves the substrate so as to establish a surface tension gradient between the rinse liquid attached to the substrate surface in the form of a meniscus and the remaining dispersed portion of the rinse liquid, the surface tension gradient drawing liquid from the substrate surface into the dispersed rinse liquid. A specific embodiment of an apparatus for removing material from the surface of a substrate according to the present invention includes a processing container configured to receive and contain a substrate in a hermetically sealed environment; and via an inlet valve A source of a pressure treatment solution in fluid communication with the treatment trough. A steam valve allows the fluid in the treatment vessel to communicate with a drain. A pressure holding vessel is configured to maintain a pressure treatment solution with a concentration of its components. The concentration of components available in the solution under conditions of greater than atmospheric pressure. A control valve is coupled between the processing trough and the holding container to control the flow of the processing solution from the holding container to the processing container. The characteristics of the material to be removed from the substrate will vary depending on the particular application. In an application, the material to be removed may include an organic material (eg, photoresist), 92730.doc 200535998, and the treatment solution may include ozone absorbed in an acidic solution at a high concentration. Because the solubility of the gas in the solution is increased, and because the release of ozone from the closed system is prohibited, the degree of ozone in the inhaled solution is greater than the concentration that can occur at atmospheric force and at the same temperature. At a given temperature, the higher treatment rate of ozone in the treatment solution is faster than the treatment rate achieved by the feedstock method.

在本么月之另-應用巾，要從基板上移除的材料可包括 -無機材料’例如一金屬或介電質。在此類具體實施例中， 地冷液可包括其壓力大於大氣壓力的一酸性或鹼性溶 液。可將壓力溶液中所得到的酸或驗之濃度維持在較高溫 度下，從而增強反應並增加移除速率。因為依據本發明之 具體實施例的濕式處理所使用的系統之封閉性質，所以會 出現增加的移除速率’無不會經由與傳統較高溫度濕式處 理糸統相關的蒸發或釋氣而相應地損失揮發性溶液成分。 在本發明之另一可能庫用由 —.,4. W應用中，可清理一基板之表面以移In another application of this month, the material to be removed from the substrate may include-an inorganic material 'such as a metal or a dielectric. In such specific embodiments, the ground cooling liquid may include an acidic or alkaline solution having a pressure greater than atmospheric pressure. The acid or assay concentration obtained in the pressure solution can be maintained at a higher temperature to enhance the reaction and increase the removal rate. Because of the closed nature of the system used for wet processing in accordance with a specific embodiment of the present invention, there will be an increased removal rate 'all without evaporation or outgassing associated with traditional higher temperature wet processing systems. The volatile solution components are correspondingly lost. In another possible application of the present invention, the surface of a substrate can be cleaned to remove

除不同類型的材料(例如金屬、有機以及無機污染物)之微量 組^在此類清理應用中’多連串的互補濕式處理化學品 可加加於晶圓表面。某些或所有步驟可出現在相同處理容 器中’並且某些或所有該等步驟可發生在高溫或壓力輪庵 情況下。 可實現本文揭示的本 參考說明書以及附圖之剩餘部分 發明之性質及優點的進一步瞭解。 【實施方式】 A裝置 92730.doc 10 200535998 圖1顯示依據本發明之一呈 一也η Μ例的一處理裝置10。處 :g括—昼力處理容器_，在該處理容器100令處 板⑺2或一基板船⑽中的複數個基板。基板船或固 持副可包括一旋轉機制，其用以旋轉晶圓以增強所出現 的濕式處理之均勻性及有效性。 在圖1所示的特定具體實施例中，基板1〇2係完全浸沒在 一處理溶液1G6中，如以下更詳細地解釋，該溶液可包括溶 解在3水或酸性或驗性溶液或者有機溶劑中的—高濃度 氧化劑。藉由在將處理溶液引人處理容請物間或之後將 該溶液維持在星力條件下’可防止溶解氧化劑或酸或驗從 處理溶液106中釋氣或蒸發。如本專利中請案中所使用，術 語「壓力條件下」意味著低於大氣壓力的任一壓力。一排 洩閥108控制處理容器1〇〇中的處理溶液1〇6之數量；而氣相 閥110及132則藉由調節分別從第―及第：氣體來源⑴及 133流入容器1〇〇的氣體而控制處理容器1〇〇中的氣體壓 力。氣體來源111及1 3 3或包含一惰性氣體，或包括一或多 個尋求併入處理溶液的成分之一氣體，或惰性氣體與活性 氣體之一組合。 濕式處理裝置可視需要進一步包括一循環迴路丨12，其具 有入口 112a、出口 U2b、幫浦114、過濾器116以及其他結 構例如液體流ΐ汁。幫浦114經由循環迴路112抽送處理 溶液106，以便處理溶液1〇6在處理期間經受動態流程。圖i 所示的濕式處理裝置之具體實施例，可藉由操作磁性驅動 攪拌器結構1 3 0，或者由一旋轉軸所直接驅動的一攪拌器或 92730.doc 200535998 以及 其他結構，進一步達到處理室1〇〇中的一所需混合位準 流體移動。 雖然圖1所示的具體實施例包括一循環迴路，但是本發明 亚不需要此點。可用於依據本發明之濕式處理的其他容哭 架構之範例包括靜態罐；溢流罐，其包括用以接收容器溢 流的堪式結構；以及快速傾卸沖洗（qulck dump d㈣叫； QDR)罐，其具有致動流體從沖洗罐迅速地排出之可移動底 板或門，從而使流體得到再循環或除去。 控刀軋體以及壓力 雖然圖1之具體實施例顯示接 處理溶液的相同容器，但是本發明亦不需要此點。依據本 發明之替代具體實施例可使用由一第一材料製成的一不漏 氣外殼，其容納採用一不同材料形成的一液體處理容器。 此類具體實施例之一範例可以為一裝置，其中一石英产理 容器因其極低可濾去污染特性而最好包含處理液體。然 而，石英為一相對易碎材料，並且可能不會經受住高施加 氣體壓力。因此，可將此類石英處理容器固定在一不漏氣 封包内，該封包包括不銹鋼或另一能包含高施加壓力的剛 性材料。 圖1所示裝置亦包括經由閥151與容器1〇〇通信的一真空 幫浦15〇。真空幫浦15〇可允許在將自氣體來源U1及/或133 的一氣體引入壓力容器100之前，從封閉容器100中抽空空 氣。此抽空可確保在將壓力處理溶液引入容器之前容器中 具有均勻的氣體環境，亦可允許在抽空條件下利用一承載 室（load lock)或類似結構，將處理基板傳送至容器ι〇〇中以 92730.doc 12 200535998 及從中將基板傳送出來。 圖1之裝置進一步包括一溫度控制結構11 8，其與處理溶 液106之壓力流進行熱通信以調節處理溶液之溫度。藉由控 制壓力處理溶液之溫度，結構118可實現各種所需處理結 果。例如，在將溫度控制結構118配置成增加處理溶液之壓 力流的溫度情況下，可增強濕式化學反應之速率。處理時 間之一對應減少會增加處理通量並降低操作成本，而無與 傳統高溫處理相關的揮發性處理溶液成分之釋氣或蒸發及 損失。可用於依據本發明之具體實施例的處理之高溫的範 圍可達約200° C或更高，取決於一特定應用之需要。 相反，可將溫度控制結構118配置成減小處理溶液之壓力 流的溫度。在此類替代具體實施例中，壓力處理溶液之減 小溫度可抑制不必要的赭I只庙士： clIn addition to trace types of different types of materials (such as metal, organic, and inorganic contaminants), in such cleaning applications, a series of complementary wet processing chemicals can be added to the wafer surface. Some or all of the steps may occur in the same processing vessel ' and some or all of these steps may occur under high temperature or pressure wheels. Further understanding of the nature and advantages of the invention disclosed in this reference specification and the remainder of the drawings can be achieved. [Embodiment] A device 92730.doc 10 200535998 Fig. 1 shows a processing device 10 according to one example of the present invention. Where: g includes-day force processing container_, in the processing container 100 order plate 2 or a plurality of substrates in a substrate boat. The substrate boat or holding pair may include a rotation mechanism to rotate the wafer to enhance the uniformity and effectiveness of the wet processing that occurs. In the specific embodiment shown in FIG. 1, the substrate 102 is completely immersed in a processing solution 1G6. As explained in more detail below, the solution may include a solution dissolved in 3 water or an acidic or test solution or an organic solvent. Medium-high concentration of oxidant. By maintaining the solution under a star condition during or after introducing the treatment solution into the treatment container, it is possible to prevent dissolution of the oxidizing agent or acid or release of gas from the treatment solution 106 or evaporation. As used in this patent application, the term "under pressure" means any pressure below atmospheric pressure. An exhaust valve 108 controls the amount of the processing solution 106 in the processing container 100, and the gas phase valves 110 and 132 adjust the gas flowing into the container 100 from the first and the third gas sources, 133 and 133, respectively. The gas pressure in the processing vessel 100 is controlled. The gas sources 111 and 133 may include an inert gas, or a gas including one or more ingredients sought to be incorporated into the processing solution, or a combination of an inert gas and an active gas. The wet processing device may further include a circulation circuit 12 as required, which has an inlet 112a, an outlet U2b, a pump 114, a filter 116, and other structures such as liquid flow. The pump 114 pumps the processing solution 106 via the circulation circuit 112 so that the processing solution 106 undergoes a dynamic flow during processing. The specific embodiment of the wet processing device shown in FIG. I can be further achieved by operating a magnetically driven agitator structure 130, or a stirrer directly driven by a rotating shaft or 92730.doc 200535998 and other structures. A desired mixing level fluid in the processing chamber 100 moves. Although the specific embodiment shown in Fig. 1 includes a loop circuit, this is not required in the present invention. Examples of other cryogenic structures that can be used for wet processing in accordance with the present invention include static tanks; overflow tanks including Kansas structures to receive container overflow; and qulck dump d howl; QDR) A tank having a movable bottom plate or door that actuates fluid to be quickly discharged from the flush tank, thereby recirculating or removing the fluid. Controlled rolling body and pressure Although the embodiment of Figure 1 shows the same container for the processing solution, this is not required in the present invention. An alternative embodiment according to the present invention may use an airtight enclosure made of a first material that houses a liquid processing container formed of a different material. An example of such a specific embodiment may be an apparatus in which a quartz container is preferred to include a treatment liquid due to its extremely low filterable contamination characteristics. However, quartz is a relatively fragile material and may not withstand high applied gas pressures. Therefore, such quartz processing vessels can be fixed in an airtight package, which includes stainless steel or another rigid material capable of containing high applied pressure. The apparatus shown in FIG. 1 also includes a vacuum pump 15 for communicating with the container 100 via a valve 151. The vacuum pump 15 may allow the air to be evacuated from the closed vessel 100 before introducing a gas from the gas source U1 and / or 133 into the pressure vessel 100. This evacuation ensures a uniform gas environment in the container before the pressure processing solution is introduced into the container, and also allows a processing chamber (load lock) or similar structure to be used to transfer the processing substrate to the container under vacuum conditions. 92730.doc 12 200535998 and transfer the substrate from it. The apparatus of Fig. 1 further includes a temperature control structure 118, which is in thermal communication with the pressure flow of the processing solution 106 to regulate the temperature of the processing solution. By controlling the temperature of the pressure treatment solution, the structure 118 can achieve various desired treatment results. For example, where the temperature control structure 118 is configured to increase the temperature of the pressure flow of the processing solution, the rate of the wet chemical reaction may be enhanced. A corresponding reduction in processing time increases processing throughput and reduces operating costs without outgassing or evaporation and loss of volatile processing solution components associated with traditional high temperature processing. The range of high temperatures that can be used for processing in accordance with specific embodiments of the present invention can reach about 200 ° C or higher, depending on the needs of a particular application. Instead, the temperature control structure 118 may be configured to reduce the temperature of the pressure flow of the processing solution. In such alternative embodiments, the reduced temperature of the pressure treatment solution can suppress unnecessary temples: cl

可將一 變化溫度輪廓用 、外狂朋间，不 92730.doc 200535998 以最大化處理之有效性，取決於一特定應用之特徵及需要。 在圖1之特定具體實施例中，將溫度控制結構固定在循環 迴路112中。然而在替代具體實施例中，例如在沒有一循環 迴路之特徵的一裝置中，溫度控制結構可直接與處理容器 100進行熱通信。然而，雖然圖1顯示負責對處理溶液之壓 力流進行加熱以及冷卻的一單一溫度控制結構（即一帕爾 貼（Peltier·)加熱器/冷卻器），但是本發明亦不需要此點。依 據替代具體實施例，可將分離的加熱及冷卻結構用以控制 處理溶液之溫度。 此外，σ亥虞置可包括一超音波震盈（megas〇nic)單元， 其與處理容器進行聲音通信。從超音波震盪單元12〇傳達至 谷态中所含物質之聲音能量，可辅助橫跨呈現在一浸沒基 板之表面上的液體動力邊界層而傳送處理溶液成分，從而 增強反應性並減少處理次數。基板處理中的超音波震盪清 理之使耗詳細地說明在美國專利第5,279,3 16號中，其名 稱為「半導體晶圓之多處理聲波浴系統」，其係與本申請案 共同讓渡並基於所有目的而以引用的方式併人本文中。在 一特定具財施财，將處理溶液之—壓力流施加於一封 閉處理容器可導致容器的充分增塵，以實現本發明之高濃 度以及迅速移除速率。 圖1之虞置進一 #包括、經由氣體間138與處理容器通 L的廢棄/排除單元136。廢棄/排除單元136慮及在將 自容器⑽流出的廢物排人環境中之前，將該廢物破壞。 見在 > 考圖2’其顯不—臭氧化裝置Μ之—範例性具體實 92730.doc 200535998 施例，可將該裝置用以依據本發明之一具體實施例產生一 壓力、南丨辰度臭氧（〇3)〉谷液。將氧氣（〇2)從氧氣來源2〇1經 由一入口 202引入臭氧產生器200。臭氧產生器200接收氧氣 流並隨後在出口 204處產生包含大量臭氧之一氣體，該出口· 係經由一氣體過濾器及氣相臭氧感應器與文氏注射器2〇8 之入口 2 0 6輕合。將含臭氧氣體引入置放在一壓力臭氧化迴 路210中的文氏注射器208。文氏注射器208用以提高速度並 降低經過的液體溶液之壓力。一準真空因此係建立在文氏 噴頭208中間的液體溶液中’並將含臭氧氣體從臭氧產生器 200導入流經臭氧化迴路2 1 〇的液體中，從而形成一臭氧化 溶液。臭氧化溶液從文氏注射器208之出口 212排出，並引 入一衝擊容器216之一入口214。在引入臭氧化溶液之前， 將衝擊容器216部分填充脫離子（DI)水。雖然將最普遍地使 用DI水作為液體材料，但亦可使用其他溶劑，取決於特定 應用。例如，在依據本發明之一替代具體實施例中，可使 用非水溶液或酸性或鹼性含水溶液。雖然圖2所示的結構包 括一臭氧化迴路，但是本發明並不需要此點。在一替代具 體實施例中，臭氧產生裝置可與流人處理容器並接著排出 而不再加以循環的一水流進行流體通信。在另一替代具體 實％例巾，用力本發明之一臭氧產生裝置可簡單地提供含 臭虱虱體之一 * 口，、給包含處理溶液的一容器之頂部空間。 衝擊容器2⑽維持在壓力條件下，並用以將臭氧化溶液 -液體之表面上的氣相分離。臭氧化迴路21〇亦係維持在壓 力條件下。臭氧化溶液利用_幫浦218圍繞迴路21〇循環，A change in temperature profile can be used between the outsiders and friends, not 92730.doc 200535998 to maximize the effectiveness of processing, depending on the characteristics and needs of a particular application. In the specific embodiment of FIG. 1, the temperature control structure is fixed in the circulation loop 112. However, in alternative embodiments, such as in a device that does not have the characteristics of a loop circuit, the temperature control structure may be in thermal communication with the processing vessel 100 directly. However, although Fig. 1 shows a single temperature control structure (i.e., a Peltier heater / cooler) responsible for heating and cooling the pressure flow of the processing solution, this point is not required in the present invention. According to alternative embodiments, separate heating and cooling structures can be used to control the temperature of the processing solution. In addition, the sigma set may include an ultrasonic megasonic unit that communicates acoustically with the processing container. The sound energy transmitted from the ultrasonic oscillating unit 12 to the substance contained in the valley state can assist in transferring the processing solution components across the hydrodynamic boundary layer present on the surface of an immersed substrate, thereby enhancing reactivity and reducing the number of processing times. . The cost of ultrasonic vibration cleaning in substrate processing is described in detail in US Patent No. 5,279,3 16, which is entitled "Multi-Processing Acoustic Bath System for Semiconductor Wafers", which is jointly transferred and merged with this application. It is incorporated herein by reference for all purposes. Applying a pressure flow of the processing solution to a closed processing container can result in sufficient dusting of the container to achieve the high concentration and rapid removal rate of the present invention. FIG. 1 Yu Zhi Jin Yi # includes a disposal / removal unit 136 that communicates with a processing container via a gas chamber 138. The disposal / removal unit 136 takes into consideration the destruction of waste discharged from the container ⑽ before it is discharged into the environment. See > Fig. 2 'Its display-ozonation device M-Exemplary specific example 92730.doc 200535998 embodiment, the device can be used to generate a pressure, south according to a specific embodiment of the present invention Degree ozone (〇3)> Valley fluid. Oxygen (〇2) is introduced into the ozone generator 200 from an oxygen source 201 through an inlet 202. The ozone generator 200 receives the oxygen stream and then generates a gas containing a large amount of ozone at the outlet 204. The outlet is lightly connected through a gas filter and a gas-phase ozone sensor to the inlet 2 of the Wen's syringe 208. . An ozone-containing gas is introduced into a Venturi syringe 208 placed in a pressure ozonation circuit 210. The Venturi syringe 208 is used to increase the speed and reduce the pressure of the passing liquid solution. A quasi-vacuum is thus established in the liquid solution in the middle of the Venturi nozzle 208 'and the ozone-containing gas is introduced from the ozone generator 200 into the liquid flowing through the ozonization circuit 2 10 to form an ozonated solution. The ozonated solution is discharged from the outlet 212 of the Venturi syringe 208 and is introduced into an inlet 214 of an impact container 216. Prior to the introduction of the ozonation solution, the shock container 216 was partially filled with deionized (DI) water. Although DI water will most commonly be used as the liquid material, other solvents may be used, depending on the particular application. For example, in an alternative embodiment according to the present invention, a non-aqueous solution or an acidic or alkaline aqueous solution may be used. Although the structure shown in Fig. 2 includes an ozonation circuit, this is not required in the present invention. In an alternative specific embodiment, the ozone-generating device may be in fluid communication with a stream of water flowing into a processing vessel and then discharged without being circulated. In another alternative embodiment, using one of the ozone generating devices of the present invention can simply provide a mouthpiece containing a sting lice, giving head space to a container containing a treatment solution. The shock container 2⑽ is maintained under pressure and is used to separate the gas phase on the surface of the ozonation solution-liquid. The ozonation circuit 21o is also maintained under pressure. The ozonation solution uses _pupu 218 to circulate around the circuit 21o,

92730.dOC 200535998 邊幫浦經由一選用過濾器2 83從衝擊容器2 1 6之一出口 220 接收溶液。亦可將一選用溫度控制結構2 1 9置於迴路2 1 〇中 以對臭氧化溶液進行加熱或冷卻。隨著圍繞臭氧化迴路2 i 〇 抽送溶液並導出更多臭氧，溶解在臭氧化溶液中的臭氧之 濃度會增加。明確地說，隨著臭氧化溶液經由臭氧化迴路 2 1 0從衝擊容為2 1 6開始循環並返回至衝擊容器2丨6中，並且 隨著藉由文氏注射器208之運作將更多臭氧導入溶液中，溶 液實際上吸收具有一峰值濃度的臭氧。在一給定溫度情況 下，此峰值濃度高於在入口氣體流中的臭氧濃度相同之大 氣壓力情況下運作的一系統所能達到的濃度。 臭氧化迴路210進一步包括注射器2〇8下游的靜態混合結 構280。靜態混合結構28〇增強氣相臭氧與液體處理溶液之 間的互動，從而導致將額外數量的臭氧引入溶液中。臭氧 化迴路2H)亦包括固定在靜態混合器下游的一接觸器結構 282，其增強液體處理溶液與臭氧氣體接觸的駐留時間，從 而進-步增強液相中臭氧的溶解，以便達到具有溶解臭氧 ㈣液之飽和的條件。雖然圖2所示的具體實施例包括一靜 態混合器以及一接觸器結構，伸 疋本發明對兩者均不需 要’並且可省略一或兩者而裝置 竹保持在本發明之範疇内。 如以下結合本發明提供的優點 π 4、，、田靖述，在某些應用 中可月匕不貝成壓力處理溶液包含氣 乳相材枓（例如臭氧）之教 泡。因此在圖1所示的具體實施例中H ) ^ ^ J Υ 臭虱化迴路210進一 步包括固定在接觸器282之下游 ^〆 的虱方疋除氣器/分離器 284。虱紋除氣器284用來移除 八液體處理溶液中的氣 92730.doc -16 - 200535998 泡’其係作為剛才實行的注射、混合以及接觸處理之一結 果。在氣體係溶解於屡力處理溶液令而無氣泡之形成㈣ 况下本毛月之替代具體實施例可以不需要此類釋氣結 構。例如，在依據本發明之某些具體實施例中，可以橫跨 利用-隔膜氣化器結構的一隔膜將臭氧引入處理溶液。不 像圖1所示的文氏注射器結構—樣，在利i㈣氣化㈣ -替代具體實施例中，並非將臭氧之氣泡引人溶液以需要 後來在對氣泡敏感的應用中分離/移除該等氣泡。 圖3顯示依據本發明之一裝置的另一具體實施例，該裝置 將圖1之壓力處理容器與圖2之臭氧化襄置整合。當一濕式 處理階段完結時’可將處理溶液1〇6從處理容器⑽傳送至 保持在充分低於處理容器1〇〇的壓力之壓力下的一保持容 器300中’從而允許實行處理流體之傳送。在圖场示的呈 體實施例中，保持容器可包括圖2所示的臭氧化裝置之衝擊 容器。然、而’在替代具體實施例中，保持容器可包括維 持在足夠壓力下的-分離及獨立保持容器’以確保處理溶 液之南濃度特徵。 間310、3U以及110控制處理容器1〇〇與保持容器之間 的相對壓力’以實行經由閥311對保持容器3〇〇的處理流體 ，傳送。雖然、未在圖3中顯示_或多個幫浦，但是可使㈣ 等-或多個f浦來實現或輔助處理容器與保持容器之間的 流體傳送。例如’可將保持容器中的壓力維持在高於或低 於處理容器中的壓力。 在圖3所示的具體實施例中，保持容器μ _ 92730.doc 200535998 經由閥網路340與處理容器1〇〇之 在此具體實施例中，處理容#伴样/間進仃氣體通信。 片 处夺為仗保持槽3〇〇接收壓力含臭氧 氣體之一氣體流，以便在渴$卢裡如 &自童"人心七 、、处J間氣體環境保持濃縮 的六、乳，攸而方便氣體臭氧溶解於處理溶液中 將間網路34〇關閉並將處理溶崎處二 t至保持容器_中。在已將處理溶液106傳送至保持容 副中之後’可排空處理容器並且可從處理容器⑽中移 除基板1〇2。採用所說明的方式，可將處理溶液之臭氧及立 他成分維持在溶液中以備後來使用，而無需除去或排㈣ 等溶液成分。或者，可在一第二臭氧產生器與處理容器之 間進行直接連接以供應一新鮮含臭氧氣體流。 雖然圖3所示的具體實施例包括一單_保持容器，但是依 據本發明之-替代具體實施例可㈣二或多個保持容器， 以與處理容器進行選擇性流體通信。此類組態將在實行依 據本發明之具體實施例的多步驟濕式處理中尤其有價值， 其中將-基板曝露於一序列互補處理溶液中。以下結合圖8 及9論述此類多步驟濕式處理之範例。 依據本發明t其他具體實施例可利用A流量來實現濕式 處理。依據本發明之另一替代具體實施例，圖4顯示一範例 性處理裝置4G之-示意性解說，該裝置包括_壓力處理容 器400,其内處理一基板402或基板固持器4〇4中的複數個基 板402。可抽空處理容器4〇〇以將壓力減小為低壓，接著僅 採用一惰性氣體重新增壓，該氣體如氮氣，或可包含一反 應氣體（例如臭氧），或可包含氣體（例如c〇2)與臭氧之一組 92730.doc -18- 200535998 合。容器亦可包含類似於以上解釋的—液體處理溶液， 以便可將基板402與該液體處理溶液接觸，該接觸係藉由採 用液體小滴或薄霧喷射基板所導致的全部沈浸、部分沈浸 或潤濕。將-或多個喷嘴4〇6置放於處理容器4〇〇中並配置 該等喷嘴’以便其朝要處理的基板4G2之表面引導（即喷射） 一處理溶液。將噴嘴406與一處理溶液供應線路4〇8耦合。 雖然圖4所示的具體實施例包括喷嘴，但是依據本發明之替 代具體實她例可續單地包括孔或洞，處理溶液即經由該等 孔或洞而得以喷射。 處理溶液供應線路408經由一處理溶液線路入口 /出口 410而進入/退出處理容器4〇〇。一處理溶液控制閥412經由 供應線路408及喷嘴406控制處理溶液之流量。一壓力控制 閥414亦係與處理容器4〇〇耦合，以控制處理容器4〇〇中的氣 體/液體壓力。而且一排洩閥41 8係與處理容器4〇〇之底部耦 合，以控制液體（例如處理溶液或用以清理處理容器4〇〇的 溶劑）從處理容器400中排出。 圖4所不的裝置可利用大液體流量，以增強基板上出現的 處理之速率及/或效率。例如，可將湍流給予流經供應線路 的流體，以便容器内的液體展現出充分的湍流以促進基板 表面與處理溶液之間的互動。在剝離等應用中需要此類湍 流。 在此高流速具體實施例中，亦可利用喷射臭氧化液體流 與晶圓表面之間的壓力下降來促使更迅速及有效的處理。 例如’可藉由實體約束限制由圖2之臭氧產生器產生的氣體 92730.doc -19- 200535998 氧之百 ’可實 例如， 即出現 的氣泡 不僅在 臭氧之 最初產 臭氧氣 使臭氧 :臭乳：量。然而，當出現壓力下降時氣體中的臭 或取、、、处壓力處理溶液中釋氣所得的臭氧濃度 質上超過，含在最初產生氣體中的百分比或濃度。 在強制臭虱化處理溶液之一溶液流經由一喷嘴時， 此c力下降’從而導致釋氣及包含_增強臭氧濃度 之形成° #用所指示的方式從溶液中釋出的臭氧， 又又基板4提阿可傳遞至基板表面附近的氣泡中的 /辰度而且可將處理容器令的氣相濃度增加至超過 生氣體中臭氧之濃度。接近於晶圓之表面的此濃縮 才&七、另機制，用以因剝離、钱刻或清理目的而 與晶圓表面接觸。 在依據本發明之其他替代具體實施例中，不必將晶圓沈 浸在處理溶液中。採用—替代方法，可將一基板懸浮於二 處理溶液上，以便覆蓋液體的汽相與基板互動並處理基 板依據另替代方法，可以液體小滴之形式將一處理溶 液喷射至晶圓表面上。可將噴嘴配置成產生相對較大滴， 以便藉由較大滴之衝擊而傳送至晶圓之表面上的動量，進 一步促進晶圓表面上的材料與處理溶液之間的互動，從而 增強濕式處理。或者，可因此目的而使用一脈動淋浴噴射。 在基板包括可受到液體之撞擊的損壞之易碎結構的情況 下，最好使用僅產生低動量傳送的一細微薄霧。在並非將 基板元王沈 >文在處理流體中的情況下，若在壓力處理流體 進入喷嘴之前該流體充分接近於飽和，則由強制流體經由 喷嘴所引起的壓力下降可導致處理容器中氣相之一增強臭 92730.doc -20- 200535998 氧漠度，從而引起更迅速的基板處理。一特定應用之特定 需求將決定本發明之此方面。 依據本發明之具體實施例可在處理期間進一步利用基板 之旋轉以增強處理。處理期間的基板旋轉可實行許多有用 功能。基板之旋轉可減小呈現在—浸沒晶圓之表面上的液 體動力或聲音邊界層的厚度，從而促進質量傳送以及處理 流體及其成分與基板之間的其他互動。對於處理非浸沒基 板而言’基板之旋轉可減小該厚度並增加呈現在晶圓表面 上的液體層之均勻《，從而促進從氣相至晶圓表面的一成 分之質量傳送。旋轉晶圓亦致動能量處理（例如噴射）之均勻 分配，或者將超聲波或超音波震盪能量施加於在一浸沒或 非浸沒狀態中得到處理的一基板之整個表面上。 依據本發明之其他替代具體實施例可利用處理容器内壓 力處理流體之-層流或塞流’而非滿流’以達到浸沒半導 體晶圓或基板的濕式處理。此類具體實施例將尤其適合於 清理基板，該清理係藉由均勻地帶走少量的污染物，其具 有最少的混合物或可能再吸收至基板表面上。採用此類層 流具體實施例的濕式處理之增強，將與處理溶液成分之高 >辰度以及由增壓致動的高處理溫度相關。 B方法 亨利㈣㈣定律講授：溶解於液相中的一成分氣體之濃 度隨著該成分之濃度在液體上的氣相中增加而增加，並隨 著溫度降低而增加。因此，隨著增加氣相中臭氧的濃度， 溶解於液相中的臭氧在一給定溫度及壓力情況下會增加。 92730.doc 200535998 在一給定壓力及氣相濃度情況下 >谷解的臭氧含置。此係顯示在圖5 ’降低溫度會增加液相 中，其繪製在三種不同 中 壓 力情況下一 含水溶液之溶解臭氧濃度對 溫度：在一接近恆 定氣相臭氧濃度情況下溫度為〇 ης彳σ 1/t ^ . 又句 υ Psig、14.7 psig 以及 29.4 psig。 道爾頓（Dahon)定律講授··溶解於一液體中的—氣體之濃 度隨著氣相中總氣體壓力的增加而增加。在理想條件下， 此增加係直接成比例。目此，若在某一氣相臭氧濃度情況 下於20°C及大氣壓力（1大氣壓=〇 psig)情況下，溶解於以 水中的100 ppm臭氧飽和出現，則藉由將氣體壓力提高至 〜14.7 pS1g (其比氣相中的臭氧濃度相同之大氣壓力約大 一大氣壓力），可在液體中達到接近二倍的臭氧濃度之增加 (即200 ppm)。若更進一步將壓力提高至〜29 4 ，則臭 氧濃度將增加至約300 ppm並以此類推。該等數字僅為範例 性，而且該等數字並非意味著精確地指示在任一特定組的 處理條件之情況下的飽和濃度，而係基於一理想氣體之特 性，因而僅為近似值。較大臭氧濃度將隨著更進一步地增 加壓力而出現。然而實際上，壓力與濃度之間一對一的比 例丨生與理想情況有偏差。因此，為最大化液相中的溶解臭 氧濃度，應最大化系統壓力及氣相濃度。此特徵亦係反映 在圖5中’其中即使由臭氧產生器所產生的氣相中的臭氧之 濃度實質上保持恆定，溶解臭氧之濃度仍隨著壓力的增加 而增加。 依據本發明之方法的具體實施例利用壓力、溫度與溶解 92730.doc 200535998 ΐ玍之間的關係 , 柯出仗向施情況下實 仃濕式處理，可維持處理溶液中活性成分的溶解性，從而 可最佳化如移除速率及選擇性之類濕式處理參數。 明確地說，可將以上纟士人m 、，口。圖1至4所顯示及說明的處理裝 置用於許多濕式處理應用中， 匕括但不限於剝離有機材料 (例如已顯影的光阻膜），以乃 他± 及攸基板上移除殘餘有機或無機 破粒。在此類應用中，處理 处理岭，夜可包括溶解於脫離子水中 二高濃度氧化劑(例如臭氧)，例如由圖2之裝置所產生的 臭氧化溶液。 亦可將圖1至4之處理梦罟1Λ 、 又置0用以從基板上姓 料，例如矽、二氧化矽或金 …機材 乂 i屬在此類型應用中，處理溶 液可包括用以姓刻一氧化物的—酸性溶液( 移除金屬的HC1，或可包括用以移除無 ，一)。該等溶液之任一者亦可視需要而包：二 濃度氧化劑，例如臭氧。 ^ 物僅Ar㈣ i 乂上5兄明的處理溶液之可能候選 物僅為犯例性，因此不應視為限制性。可使用其 nr°)純基板上移除的㈣。❹，處理溶液可包 ==光阻材料、光阻顯影劑材料、或半導體元 件之1&中所利用的另一類型有機物質。 在以上說明的具體實施财，在將處理溶液引入處理容 器期間以及至少在虛捜且七从* 奋 在處理基板的部分時間期 維持在壓力條件下。然 』』在1備處理溶液期間以 在將液引入處理室之前，將該溶液维持在愿力條件 下。因為不允許處理溶液與大氣愿力平衡，所以可將來自 92730.doc -23- 200535998 氣相的高濃度成分維持在氧化劑溶液中，而保持非氧化劑 溶液中的揮發性成分並防止該成分經由釋氣而損失。此 外，亦防止因其他成分之蒸發而引起的損失。 現在參考圖6,其顯示依據本發明—具體實施例之處理美 板之一範例性方法60，該方法採用（例如）圖3之裝置3〇。^ 初，在步驟600中將基板1〇2置於處理容器1〇〇中。接著在= 驟中，將容器刚封閉為不漏氣。在選用步雜3(由2 線方塊選擇性指示）中，可在以下步驟中引人壓力氣體之前 抽空容器1〇0。在步驟604中’在壓力條件下將一惰性氣體 (例如氮氣）或-非惰性氣體（例如氧氣或臭氧）引入封閉處 理容器中。作為進入封閉容器的此氣體流入之結果，容器 100變得具有壓力。 ° 可施加達到約六十個大氣壓力或更高壓力。60 ATM的上 限壓力僅為範例性，而且本發明並不受限於在任一特定壓 力範圍内運作。在決定本發明之運作的壓力中要考量的因 素包括但不限於特定處理溶液中活性成分的溶解性，以及 製造、操作以及維護濕式處理設施之預期成本。@為後者 因素，所以施加相對較高壓力（例如10 ATM以上）可能會實 質上增加安全並有效地將處理溶液維持在壓力條件下所需 要的結構之成本。 雖然圖6顯示其中在處理期間將塵力處理溶液維持在壓 力條件下的一具體實施例，伯曰并π $立 員抛例但疋並不需要此高壓力保持恆 定。根據一特定應用之需要，可在一濕式處理步驟的過程 期間施加一變化壓力輪廊。在某些具體實施例中，一變化 92730.doc -24- 200535998 ，力輪廓可根據/谷解溶液成分之溶解性特徵來最佳化處理 芩數、。在其他具體實施例中，一變化壓力輪靡可最佳地慮 及’合液成刀之補充’因為該等成分在處理期間得到消耗。 同樣亦可使用溫度梯度來增強處理。 在步驟606中，在對處理容器⑽增壓之後，在塵力條件 字处里/今液1 〇6 (例如）從圖3所示的保持罐/衝擊容器中 引入容II1GG。在將基板維持㈣力條件下的同時，接著在 步驟608中處理_ , 暴板102達一必要時間，以從基板102上移除 不必要的材料。 在已處理基板1〇2之後，在步驟61〇中可將處理溶液⑽ 維持在壓力條件下並使之流入一壓力保持罐，然後從容器 100中移除基板1G2。此允許重新使用處理溶液1()6以處理後 來-批基板。或者，可經由一㈣閥從處理容器中移除處 理溶液106。 在以下選用步驟612中，-旦已從處理室中移除麼力處理 溶液’則可採㈣水沖洗基板1()2以從晶圓上以及從處理室 中移除任何殘餘材料。彳洗步驟612為選用步驟，其中使用 -稀釋處理溶液，或其中期望僅會有較低位準的污染。 進一步視需要而定，在步驟614中可依據本發明之具體實 施例烘乾晶圓。例如，已傳統上烘乾處理晶圓，該洪乾係 藉由在包括形成於基板表面上的f月面之流體的表面張 力，與液相中的分散流體之表面張力之間建立或開發一微 分或表面張力梯度。隨著將基板從液體移入氣相，將附著 於f月Φ之區$中基板表面上的流體拖回至分散流體中。 92730.doc -25 - 200535998 一般而言，實行此點已藉由將一溶劑蒸汽引入液體上的氣 相，從而覆蓋基板。隨著溶劑開始一般進八液體表面之流 體以及彎月面之流體的溶液中，該成分之局部濃度會增加 並減小該流體與液體氣體介面處的晶圓之間的局部表面張 力。因為彎月面之流體的容積很小，所以在彎月面區域中 會出現比在分散流體之表面上更迅速的濃度增加。局部增 加的濃度引起受影響流體與基板表面之間表面張力的局部 減小。從分散流體中提取出晶圓，或從基板排出流體。因 此’流體之局部表面張力的微分導致流體從彎月面區域得 以沒入分散流體中。 依據本發明之具體實施例，此烘乾處理可發生在高壓力 情況下。依據本發明之具體實施例在高壓力情況下進行烘 乾，可改變基板與處理溶液之間的介面處之表面張力參 數。例如，高壓力可驅動較大濃度的表面張力下降成分進 入處理溶液，從而增強梯度之範圍及/或形成梯度所用的速 又或者依據本發明之具體實施例的壓力烘乾，在大氣 壓力情況下無可用濃度的情況下，可允許使用要呈現在處 理流體中以及在周圍氣相中的表面張力下降材料之變化及 組合。該等表Φ張力τ降成分可使基板烘乾可採用在環境 壓力情況下不可能採用的速度以及效率而發生。或者，可 將具有大為減小的表面張力之一第二溶液（例如酒精）置於 沖洗流體的表面上。可將二種流體之間的表面張力 梯度用以烘乾。 在一最終步驟616中，準備裝置及基板以進行額外處理。 92730.doc 200535998 在剛才說明的濕式處理步驟為一連串互補濕式或乾式處理 步驟之一部分的情況下’基板102可保持在容器令以等待重 新增屢並重新開始曝露於魔力處理溶;夜令，額外供 乾處理步驟之情況下#露於反應麼力氣體中”戈者，、可將 基板i02傳送至另—處理容器中以進行額外濕式及/或乾式 處理。 可採用許多方法實行將處理基板傳送至處理容器中並從 中傳送該等基板。在-範例性方法中’將基板1〇2從處理溶 液106移入與容器丨00耦合的一承載室（圖中未顯示）中。一旦 從容器100中密封並進行壓力分離，接著可從承載室中移除 基板102。或者在處理之後，可採用_第二氣體增加壓力並 且排出流體以實行基板之烘乾。或者在已處理基板之後， 可釋放壓力並在大氣壓力情況下從處理容器中移除基板， 同時容器繼續保持處理溶液。接著可將基板移入一分離的 烘乾結構中以便若有必須則移除殘餘流體。 在一範例性應用中，可將迄今說明的處理裝置用以從基 板表面上剝離一有機材料，例如利用包括臭氧的一壓力含 水溶液及一有機酸（例如醋酸），或簡單地利用以水溶液中 的臭氧。圖7顯示用以實行此範例性應用的一方法7〇。 在方法70之最初步驟700中，將基板1〇2傳送至圖4之處理 容器400中。在步驟701中，將容器4〇〇密封為不漏氣。在選 用步驟702中，從容器中抽空空氣。在選用步驟7〇3中，可 將富臭氧氣體引入處理容器中，從而將壓力提高至大氣壓 力以上。此壓力氣體可直接來自一臭氧產生器，或可來自 92730.doc -27- 200535998 可將一壓力處理液體引 例如’可在100 psig情 可在25 pSlg情況下開始 另一容器中的釋氣。在步驟7〇4中， 入容器400中以便出現一壓力下降（ 況下抽送處理流體，並且處理容界 並達到50 pSlg或更高，從而導致臭氧釋氣以及氣相中容器 之增強臭氧濃度。可視需要從容器中排出所得到的部分耗 盡液體或回收以備再用，並且可繼續引入具有高臭氧漢度 的新鮮壓力處理流體。 在步驟705中’經由採用一液體薄膜潤濕晶圓表面的喷嘴 來繼續引入壓力溶液。在此處理步驟之前或在此步驟期 間，可在將晶圓保持在一水平或垂直方向的情況下，視需 要而旋轉晶圓或使之自》，從而使形成於基板表面上的溶 液層變薄。在處理步驟7〇5中，氣相中高臭氧氣體濃度以及 一較薄、咼度臭氧化液體層之條件，可能會導致實質上增 強臭氧擴散至基板表面上，從而增加反應速率。方法之 處理步驟705可發生在咼溫情況下以增強反應速率；發生在 低溫度情況下以增強溶液成分之溶解濃度；或在環境溫度 情況下以減輕處理。亦可使用隨著時間變化的溫度輪廓。 因為在處理步驟705期間的高壓力，所以較高溶解臭氧之濃 度可能會呈現在水層中，而且更多高度濃縮數量的臭氧可 旎會呈現在氣相中，從而與大氣壓力情況下的傳統處理相 比，增強濕式處理性能。或者，在此具體實施例中可使用 除臭氧以外的氣體或氣體之混合物。例如，依據本發明之 具體實施例可使用二氧化碳或二氧化碳與臭氧的一混合 物’以形成一壓力處理溶液。 92730.doc -28- 200535998 結合圖7顯示並說明的處理流程可推斷額外溶液傳送、晶 圓沖洗、曰曰曰圓烘乾、以及晶圓傳送步驟，如先前已說明。 依據本發明之方法及裝置的另一可能應用為晶圓清理。 此類清理處理可包括（例如）從基板表面移除有機材料、微粒 以及來自先岫蝕刻或剝離步驟的金屬殘餘物。可將圖i 至4之處理裝置中所示的 一處理容器用以實行清理方法。在 任一情況下，處理將類似於圖6及7所說明的個別方法。在 將處理裝置10用以實行一後剝離清理處理之情況下，圖8 顯示採用此範例性多順序清理處理⑼所實行的數個步驟之 一總體圖。 在一第一連串步驟82中，可施加包括一壓力臭氧化含水 硫酸HdO4之一第一處理溶液，以移除殘餘有機污染物以及 某些金屬〉可染物。在一第二連串步驟84中，可施加包括壓 力臭氧化含水稀釋氫氟酸（HF)之一第二處理溶液，以移除 氧化物以及併入該氧化物中的金屬污染物。在一第三連串 步驟86中，可施加包括壓力含水臭氧化氫氧化銨之一第三 處理浴液，以移除無機微粒。在一第四連串步驟88中，可 施加包括壓力含水臭氧化鹽酸（HC1)之一第四處理溶液，以 移除額外金屬污染物。最終在一第五連串步驟中，可施 加包括壓力含水臭氧化稀釋氫氟酸（HF)之一第五處理溶 液，以移除在第四連串步驟中形成的氧化物，以及移除額 外金屬污染物。 圖8所解說的處理流程顯示按順序將基板曝露於相同容 器内的不同處理化學品中。為方便利用一種類型以上的化 92730.doc -29- 200535998 學品按順序進行濕式處理’可在處理階段之間沖洗及/或烘 乾呈現的基板及封裝該等基板的處理容器，以便移除殘餘 >可染物並防止交又污染。 、圖8所解况的處理流程顯示按順序將基板曝露於相 同容器内的不同處理化學品中，但是本發明並不需要此 =。依據本發明之具體實施例的一方法，可在專用於一特 疋处里化子口口之施加的不同壓力處理容器之間使用一或多 個基板傳运步驟，從而最小化不同壓力化學溶液之間交又 卞的風險。此外，雖然圖8顯示實行之一連串的塵力濕式 處理步驟，但是亦不需要此點，並且可在大氣壓力條件下 按順序實行某些處理步驟。 而且雖然圖8所解$沾走田、六 _ 、 况的處理^程顯示其中將基板曝露於 連續濕式處理化® 1:7 ΑΑ β u 化予。口中的一多步驟處理，但是本發明亦不 需要此點。可在處理容器内採用濕式處理步驟按順序實行 或夕個烘乾處理步驟，並且該方法將保 •内。例如，在一濕式處 之車巳 处段芡騍之後，可在缺乏一液體處 理溶液的情況下將-基板曝露於—壓力戰體流中。在此 烘乾處理步驟之結束時’可在壓力條件下使基板經受—第 二濕式處理步驟。 此外，雖然圖8所解說的處理流程解說以-特定順序施加 五種不同的處理化學品’但是本發明並不受限於此數量的 處理化學品’或受限於此特定步驟順序。取決於-特定應 而要依據本發明之替代具體實施例可利用以—不同 順序把加於基板的所有、某些或額外處理化學品。例如， 92730.doc -30- 200535998 可依據本發明之具體實施例而利用為處理溶液之成分的無 機酸，包括但不限於HF、HC卜H2S〇4、h2C〇3、HN〇3、 Η3ΡΟ#、王水、鉻酸與硫酸混合物、硫酸與過硫酸銨混合物 及其各種組合。可依據本發明之具體實施例而利用為處理 浴液之成分的有機酸之範例，包括但不限於醋酸、蟻酸、 丁酸、丙酸、擰檬酸以及磺酸。可依據本發明之具體實施 例而利用為處理溶液之成分的氧化劑之範例，包括但不限 於氧氣、臭氧、過氧化氫以及其他過氧化物。其他可能的 氧化劑包括經由將臭氧或氧氣曝露於一放電或uv輻射而 產生於臭氧或氧氣的氧基以及氫氧基。可依據本發明之具 體實施例而利用為處理溶液之成分的鹼之範例，包括但不 限於 NH4〇H、NaOH 以及 KOH。 圖9顯示依據本發明之一多步驟清理方法900的一替代具 體實施例之一簡化流程圖，該方法避免使用及隨之需要除 去圖8之許多危險化學品。明確地說，簡化RCA清洗方法之 此取代處理係顯示在圖9中，並利用壓力臭氧化水以及包含 少量取代剛才說明的多清理化學品之氫氟酸的壓力臭氧化 水。在此替代多步驟清洗方法之第一步驟9〇2中，一臭氧化 水溶液移除並氧化殘餘有機物。在第二步驟9〇4中，包含少 量HF的一臭氧化水溶液移除併入其中的氧化層以及污染 物。在一第三步驟9〇6中，可啟動具有超音波震盪能量的臭 氧化水並將其用以移除微粒。在一第四步驟9〇8中，臭氧化 水HF溶液移除金屬以及新氧化層。 雖然結合圖8及9說明及解說的多順序清理處理利用鹼 92730.doc -31 - 200535998 性、酸性以及氧化成分，但是依據本發明之具體實施例的 處理方法及裝置並不受限於該等類型的處理溶液成分。依 據本發明之其他具體實施例，可施加壓力以將一還原劑（例 如氫氣）之高濃度或反應維持在一處理溶液内，以引起所兩 表面變化。此還原劑可用來鈍化或改變一基板之表面= 性，例如藉由最小化一氧化層的形成，或採用疏水“Η取代 疏水S i Ο鍵結層。92730.dOC 200535998 The side pump receives the solution from an outlet 220 of one of the shock containers 2 1 6 via an optional filter 2 83. An optional temperature control structure 2 19 can also be placed in the circuit 2 10 to heat or cool the ozonation solution. As the solution is pumped around the ozonation circuit 2 i 0 and more ozone is derived, the concentration of ozone dissolved in the ozonation solution will increase. Specifically, as the ozonation solution circulates from the impact volume to 2 1 6 through the ozonization circuit 2 1 0 and returns to the impact container 2 6, and more ozone will be provided by the operation of the Venturi syringe 208 Introduced into the solution, the solution actually absorbs ozone with a peak concentration. At a given temperature, this peak concentration is higher than can be achieved by a system operating at the same atmospheric pressure as the ozone concentration in the inlet gas stream. The ozonation circuit 210 further includes a static mixing structure 280 downstream of the syringe 208. The static mixing structure 280 enhances the interaction between the gas phase ozone and the liquid treatment solution, resulting in the introduction of an additional amount of ozone into the solution. The ozonation circuit 2H) also includes a contactor structure 282 fixed downstream of the static mixer, which enhances the residence time of the liquid treatment solution in contact with the ozone gas, thereby further enhancing the dissolution of ozone in the liquid phase in order to achieve dissolved ozone Saturated conditions. Although the specific embodiment shown in FIG. 2 includes a static mixer and a contactor structure, the present invention does not require both, and one or both can be omitted and the device can be kept within the scope of the present invention. As described below in combination with the advantages provided by the present invention, in some applications, the pressure treatment solution may be used in certain applications to contain the teachings of the gas phase material (such as ozone). Therefore, in the specific embodiment shown in FIG. 1 H) ^ ^ J Υ lice loop 210 further includes a lice square deaerator / separator 284 fixed downstream of the contactor 282. The lice deaerator 284 is used to remove the gas from the eight-liquid treatment solution 92730.doc -16-200535998 The bubble 'is a result of the injection, mixing, and contact treatment just performed. Such an outgassing structure may not be required in the alternative embodiment of the present invention in the case where the gas system is dissolved in the repeated treatment solution so that no bubbles are formed. For example, in some embodiments according to the present invention, ozone may be introduced into the treatment solution across a diaphragm of a utilization-diaphragm gasifier structure. Unlike the Venturi syringe structure shown in FIG. 1-in the specific embodiment, instead of introducing bubbles of ozone into the solution to require later separation / removal of the bubbles in applications sensitive to bubbles Wait for bubbles. Fig. 3 shows another embodiment of an apparatus according to the present invention, which integrates the pressure treatment vessel of Fig. 1 with the ozonation chamber of Fig. 2. When a wet processing stage is completed, 'the processing solution 106 can be transferred from the processing container 至 to a holding container 300 maintained at a pressure sufficiently lower than the pressure of the processing container 100', thereby allowing the implementation of the processing fluid. Send. In the embodiment shown in the figure, the holding container may include an impact container of the ozonation device shown in FIG. 2. However, in an alternative embodiment, the holding container may include a -separation and independent holding container maintained at a sufficient pressure to ensure the south concentration characteristics of the processing solution. The rooms 310, 3U, and 110 control the relative pressure between the processing container 100 and the holding container 'to carry out the transfer of the processing fluid of the holding container 300 through the valve 311. Although one or more pumps are not shown in FIG. 3, it is possible to use ㈣ or more pumps to realize or assist the fluid transfer between the processing container and the holding container. For example, ' the pressure in the holding vessel can be maintained above or below the pressure in the processing vessel. In the specific embodiment shown in FIG. 3, the holding container μ_92730.doc 200535998 is communicated with the processing container 100 via the valve network 340. In this specific embodiment, the processing volume #accompanying sample / into the gas communication. The film captures a gas holding tank 300 to receive one of the pressure-containing gas streams of ozone, in order to maintain a concentrated gas environment in the thirsty Luliu & Zitong " Renxin Qi, Qi, and J. Conveniently, the gaseous ozone is dissolved in the processing solution, the inter-network 34 is closed, and the processing solution is placed in a holding container. After the processing solution 106 has been transferred to the holding container, the processing container can be emptied and the substrate 102 can be removed from the processing container ⑽. In the manner described, the ozone and other components of the treatment solution can be maintained in the solution for later use, without the need to remove or eliminate the solution components such as polonium. Alternatively, a direct connection may be made between a second ozone generator and the processing vessel to supply a fresh ozone-containing gas stream. Although the specific embodiment shown in FIG. 3 includes a single-retaining container, according to an alternative embodiment of the present invention, there may be two or more retaining containers for selective fluid communication with the processing container. Such a configuration would be particularly valuable in implementing a multi-step wet process according to a specific embodiment of the invention, in which the substrate is exposed to a sequence of complementary processing solutions. Examples of such multi-step wet processing are discussed below with reference to FIGS. 8 and 9. According to other specific embodiments of the present invention, the A flow rate can be used to achieve wet processing. According to another alternative embodiment of the present invention, FIG. 4 shows an exemplary processing device 4G-a schematic illustration, the device includes a pressure processing container 400, which processes a substrate 402 or a substrate holder 400 A plurality of substrates 402. The processing vessel 400 may be evacuated to reduce the pressure to a low pressure, and then repressurized with only an inert gas, such as nitrogen, or may contain a reactive gas (such as ozone), or may contain a gas (such as c02 ) And one of the ozone group 92730.doc -18- 200535998. The container may also contain a liquid processing solution similar to that explained above, so that the substrate 402 can be contacted with the liquid processing solution, the contact being the total immersion, partial immersion, or wetting caused by spraying the substrate with liquid droplets or mist wet. -Or multiple nozzles 406 are placed in the processing container 400 and these nozzles' are arranged so that they guide (i.e., spray) a processing solution toward the surface of the substrate 4G2 to be processed. The nozzle 406 is coupled to a processing solution supply line 408. Although the specific embodiment shown in FIG. 4 includes a nozzle, according to an alternative embodiment of the present invention, it is possible to continue to include holes or holes, and the treatment solution is sprayed through the holes or holes. The processing solution supply line 408 enters / exits the processing container 400 via a processing solution line inlet / outlet 410. A treatment solution control valve 412 controls the flow rate of the treatment solution through the supply line 408 and the nozzle 406. A pressure control valve 414 is also coupled to the processing vessel 400 to control the gas / liquid pressure in the processing vessel 400. Moreover, a drain valve 418 is coupled to the bottom of the processing container 400 to control the liquid (such as a processing solution or a solvent for cleaning the processing container 400) from being discharged from the processing container 400. The device shown in FIG. 4 may utilize large liquid flow rates to enhance the rate and / or efficiency of processing occurring on the substrate. For example, turbulence can be given to the fluid flowing through the supply line so that the liquid in the container exhibits sufficient turbulence to promote the interaction between the substrate surface and the processing solution. Such turbulence is required in applications such as peeling. In this high flow rate embodiment, the pressure drop between the jetted ozonizing liquid stream and the wafer surface can also be used to facilitate faster and more efficient processing. For example, 'the gas produced by the ozone generator of Fig. 2 can be restricted by physical constraints 92730.doc -19- 200535998 hundred of oxygen' can be exemplified as: the bubbles appear not only in the first ozone gas production of ozone to make ozone: smelly milk :the amount. However, when a pressure drop occurs, the odor in the gas or the ozone concentration obtained by releasing the gas from the pressure treatment solution is substantially higher than the percentage or concentration contained in the initially generated gas. When a solution of the forced lice treatment solution flows through a nozzle, this c force decreases, resulting in outgassing and formation of enhanced ozone concentrations. # The ozone released from the solution in the manner indicated, and again The substrate 4 can be transferred to the air bubbles in the vicinity of the substrate surface, and can increase the gas phase concentration of the processing container to exceed the ozone concentration in the raw gas. This concentration is close to the surface of the wafer. Seventh, another mechanism is used to contact the wafer surface for peeling, engraving, or cleaning purposes. In other alternative embodiments according to the present invention, it is not necessary to immerse the wafer in a processing solution. Adopting an alternative method, a substrate can be suspended on the second processing solution so that the vapor phase of the covering liquid interacts with the substrate and processes the substrate. According to another alternative method, a processing solution can be sprayed onto the wafer surface in the form of liquid droplets. The nozzle can be configured to generate relatively large drops, so that the momentum transmitted to the surface of the wafer by the impact of the larger drops further promotes the interaction between the material on the wafer surface and the processing solution, thereby enhancing wet deal with. Alternatively, a pulsating shower spray can be used for this purpose. In the case where the substrate includes a fragile structure which can be damaged by the impact of liquid, it is preferable to use a fine mist which generates only a low momentum transfer. In the case where the substrate Wang Shen is not in the processing fluid, if the fluid is sufficiently close to saturation before the pressure processing fluid enters the nozzle, the pressure drop caused by the forced fluid through the nozzle can cause gas in the processing vessel. One of the phases enhances the odor of 92730.doc -20- 200535998, resulting in faster substrate processing. The specific needs of a particular application will determine this aspect of the invention. A specific embodiment according to the present invention may further utilize the rotation of the substrate during processing to enhance processing. Substrate rotation during processing can perform many useful functions. Rotation of the substrate reduces the thickness of the hydrodynamic or acoustic boundary layer present on the surface of the immersion wafer, thereby facilitating mass transfer and other interactions between the processing fluid and its components and the substrate. For processing non-immersed substrates, the rotation of the substrate can reduce this thickness and increase the uniformity of the liquid layer present on the wafer surface, thereby facilitating a mass transfer from the gas phase to the wafer surface. Rotating a wafer also initiates an even distribution of energy processing (such as spraying), or applies ultrasonic or ultrasonic oscillating energy to the entire surface of a substrate that is processed in an immersed or non-immersed state. According to other alternative embodiments of the present invention, the pressure in the processing vessel may be used to treat the laminar or plug flow of the fluid 'instead of a full flow' to achieve wet processing of immersed semiconductor wafers or substrates. Such a specific embodiment would be particularly suitable for cleaning a substrate by uniformly removing a small amount of contaminants with a minimal mixture or possibly reabsorption onto the surface of the substrate. The enhancement of wet processing using such a laminar flow embodiment will be related to the high > degree of composition of the processing solution and the high processing temperature which is actuated by pressurization. Method B. Henry's Law teaches that the concentration of a component gas dissolved in the liquid phase increases as the concentration of the component increases in the gas phase above the liquid, and increases as the temperature decreases. Therefore, as the concentration of ozone in the gas phase increases, the ozone dissolved in the liquid phase increases at a given temperature and pressure. 92730.doc 200535998 At a given pressure and gas phase concentration > Dissolved ozone content. This series is shown in Figure 5 'Reducing the temperature will increase the liquid phase, which is plotted against the dissolved ozone concentration of the aqueous solution versus temperature under three different medium pressure conditions: the temperature is 0ης 彳 σ in the case of a near constant gas phase ozone concentration 1 / t ^. Also υ Psig, 14.7 psig, and 29.4 psig. Dahon's law teaches that · the concentration of a gas dissolved in a liquid increases as the total gas pressure in the gas phase increases. Under ideal conditions, this increase is directly proportional. For this reason, if at a certain ozone concentration in the gas phase at 20 ° C and atmospheric pressure (1 atmosphere = 0 psig), 100 ppm ozone dissolved in water appears saturated, then the gas pressure is increased to ~ 14.7 pS1g (which is about one atmosphere pressure higher than the atmospheric pressure with the same ozone concentration in the gas phase) can achieve nearly twice the increase in ozone concentration (i.e. 200 ppm) in the liquid. If the pressure is further increased to ~ 29 4, the ozone concentration will increase to about 300 ppm and so on. These numbers are exemplary only, and they are not meant to accurately indicate the saturation concentration under any particular set of processing conditions, but are based on the characteristics of an ideal gas and are therefore approximate values only. Larger ozone concentrations will occur as the pressure increases further. However, in practice, the one-to-one ratio between pressure and concentration is different from the ideal situation. Therefore, to maximize the dissolved ozone concentration in the liquid phase, the system pressure and gas phase concentration should be maximized. This feature is also reflected in Fig. 5 ', wherein even if the concentration of ozone in the gas phase generated by the ozone generator remains substantially constant, the concentration of dissolved ozone still increases as the pressure increases. The specific embodiment of the method according to the present invention makes use of the relationship between pressure, temperature, and dissolution 92730.doc 200535998 ΐ 玍, Ke Chuanzhan wet treatment can be used to maintain the solubility of active ingredients in the treatment solution, This allows optimization of wet processing parameters such as removal rate and selectivity. To be clear, the above-mentioned warriors m,, mouth can be described. The processing devices shown and illustrated in Figures 1 to 4 are used in many wet processing applications, including but not limited to stripping organic materials (such as developed photoresist films) to remove residual organic materials from substrates and substrates. Or inorganic particles. In such applications, treating the ridge may include dissolving two highly concentrated oxidants (e.g., ozone) in deionized water, such as the ozonation solution produced by the apparatus of FIG. It is also possible to set the processing nightmare 1Λ of Figures 1 to 4 and set it to 0 for surnames from the substrate, such as silicon, silicon dioxide, or gold ... The machine material is in this type of application. The treatment solution may include a surname Etching an oxide-acidic solution (to remove metal HC1, or may include to remove none, a). Any of these solutions may also be packaged as required: two concentrations of oxidant, such as ozone. ^ Only possible candidates for the treatment solution of 5 兄 on Ar㈣ i 仅为 are only examples and should not be considered limiting. Plutonium removed from its nr °) pure substrate can be used. Alas, the treatment solution may include == photoresist material, photoresist developer material, or another type of organic substance used in 1 & of the semiconductor device. In the specific implementation described above, the pressure conditions are maintained during the introduction of the processing solution into the processing container and at least during the time period during which the substrate is processed. However, during the preparation of the processing solution, the solution was maintained under the desired conditions before the solution was introduced into the processing chamber. Because the treatment solution is not allowed to equilibrate with the atmosphere, high-concentration components from the gas phase of 92730.doc -23- 200535998 can be maintained in the oxidant solution, while the volatile components in the non-oxidant solution are maintained and the components are prevented from being released through Lost in anger. In addition, losses due to evaporation of other ingredients are also prevented. Reference is now made to Fig. 6, which shows an exemplary method 60 of processing a beauty panel in accordance with the present invention, a specific embodiment, which uses, for example, the apparatus 30 of Fig. 3. ^ Initially, the substrate 102 is placed in the processing container 100 in step 600. Then in step =, the container has just been closed so that it does not leak. In the optional step 3 (optionally indicated by the 2-line box), the container 100 can be evacuated before introducing the pressurized gas in the following steps. In step 604 'an inert gas (e.g. nitrogen) or a -non-inert gas (e.g. oxygen or ozone) is introduced into the closed processing vessel under pressure. As a result of this inflow of gas into the closed container, the container 100 becomes pressured. ° Can be applied up to about sixty atmospheric pressure or higher. The upper limit of 60 ATM is exemplary only, and the invention is not limited to operating in any particular pressure range. Factors to be considered in determining the operating pressure of the present invention include, but are not limited to, the solubility of the active ingredients in a particular processing solution, and the expected costs of manufacturing, operating, and maintaining a wet processing facility. @ Is the latter factor, so applying relatively high pressure (for example, above 10 ATM) may actually increase the cost of the structure required to safely and effectively maintain the processing solution under pressure. Although Fig. 6 shows a specific embodiment in which the dust treatment solution is maintained under pressure during the process, a π $ member is thrown, but this high pressure is not required to remain constant. Depending on the needs of a particular application, a varying pressure profile may be applied during the course of a wet processing step. In some specific embodiments, with a change of 92730.doc -24-200535998, the force profile can be optimized based on the solubility characteristics of the / solution solution components. In other embodiments, a varying pressure cycle may best take into account the 'supplement of hydration into a knife' because these components are consumed during processing. Temperature gradients can also be used to enhance processing. In step 606, after pressurizing the treatment container, the volume II1GG is introduced in the dust condition word / present liquid 106 (for example) from the holding tank / impact container shown in FIG. While the substrate is maintained under a force condition, then in step 608, the substrate 102 is processed for a necessary time to remove unnecessary material from the substrate 102. After the substrate 10 has been processed, the processing solution ⑽ may be maintained under pressure and flowed into a pressure holding tank in step 61, and then the substrate 1G2 may be removed from the container 100. This allows reuse of the processing solution 1 () 6 to process the subsequent-batch substrates. Alternatively, the processing solution 106 may be removed from the processing container via a poppet valve. In the following optional step 612, once the Moli processing solution has been removed from the processing chamber, the substrate 1 () 2 can be rinsed with water to remove any residual material from the wafer and from the processing chamber. The rinsing step 612 is an optional step in which a -dilute treatment solution is used, or in which only a lower level of contamination is expected. Further as needed, the wafer may be dried in step 614 according to a specific embodiment of the present invention. For example, wafers have traditionally been bake-processed by establishing or developing a system between the surface tension of the fluid including the f-plane formed on the substrate surface and the surface tension of the dispersed fluid in the liquid phase. Differential or surface tension gradient. As the substrate is moved from the liquid to the gas phase, the fluid adhering to the surface of the substrate in the region $ fΦ is pulled back into the dispersed fluid. 92730.doc -25-200535998 Generally speaking, this has been achieved by introducing a solvent vapor into the gas phase of the liquid, thereby covering the substrate. As the solvent generally enters the solution of the fluid on the surface of the liquid and the fluid on the meniscus, the local concentration of the component increases and reduces the local surface tension between the fluid and the wafer at the liquid-gas interface. Because the volume of the meniscus fluid is small, a more rapid concentration increase occurs in the meniscus region than on the surface of the dispersed fluid. The locally increased concentration causes a local decrease in surface tension between the affected fluid and the substrate surface. The wafer is extracted from the dispersion fluid, or the fluid is discharged from the substrate. Therefore, the differentiation of the local surface tension of the 'fluid causes the fluid to sink from the meniscus area into the dispersed fluid. According to a specific embodiment of the present invention, this drying process may occur under high pressure conditions. According to a specific embodiment of the present invention, drying under high pressure conditions can change the surface tension parameter at the interface between the substrate and the processing solution. For example, high pressure can drive a larger concentration of surface tension-reducing components into the processing solution, thereby enhancing the range of the gradient and / or the speed at which the gradient is formed, or pressure drying according to a specific embodiment of the present invention, under atmospheric pressure In the absence of a usable concentration, variations and combinations of surface tension reducing materials to be present in the treatment fluid and in the surrounding gas phase may be allowed. These table Φ tension τ drop components enable substrate drying to occur at speeds and efficiencies that are not possible under ambient pressure conditions. Alternatively, a second solution (such as alcohol) with a greatly reduced surface tension can be placed on the surface of the rinsing fluid. The surface tension gradient between the two fluids can be used for drying. In a final step 616, the device and substrate are prepared for additional processing. 92730.doc 200535998 In the case where the wet processing step just described is part of a series of complementary wet or dry processing steps, the substrate 102 can be kept in a container order to wait for re-increment and restart exposure to magic processing solution; In the case of additional exposure to dry processing steps, "exposed in the reaction gas", the substrate i02 can be transferred to another processing container for additional wet and / or dry processing. Many methods can be used to implement The processing substrate is transferred to and from the processing container. In an exemplary method, 'the substrate 102 is moved from the processing solution 106 into a carrier chamber (not shown) coupled to the container 00. Once The substrate 102 is sealed and pressure separated from the container 100, and then the substrate 102 can be removed from the carrier chamber. Or, after processing, a second gas can be used to increase the pressure and discharge the fluid to dry the substrate. Or after the substrate has been processed , The pressure can be released and the substrate can be removed from the processing container under atmospheric pressure while the container continues to hold the processing solution. The substrate can then be moved into a Separate drying structure to remove residual fluid if necessary. In an exemplary application, the processing apparatus described so far can be used to strip an organic material from the surface of a substrate, for example, using a pressurized aqueous solution including ozone And an organic acid (such as acetic acid), or simply using ozone in an aqueous solution. Figure 7 shows a method 70 for performing this exemplary application. In the initial step 700 of method 70, the substrate 102 is transferred Go to the processing container 400 in Fig. 4. In step 701, the container 400 is sealed to be airtight. In the selection step 702, air is evacuated from the container. In the selection step 703, the ozone-rich gas may be Into the processing vessel to increase the pressure above atmospheric pressure. This pressure gas can come directly from an ozone generator, or can be from 92730.doc -27- 200535998 A pressure processing liquid can be introduced, for example, 'can be at 100 psig At 25 pSlg, outgassing in another container is started. In step 704, the container 400 is introduced so that a pressure drop occurs (in this case, the processing fluid is pumped, and the processing volume and To 50 pSlg or higher, which results in ozone outgassing and enhanced ozone concentration in the gas phase container. The resulting partially depleted liquid can be discharged from the container or recycled for reuse as needed, and can continue to be introduced with high ozone Fresh pressure processing fluid. In step 705, the introduction of the pressure solution is continued via a nozzle that wets the surface of the wafer with a liquid film. Prior to or during this step, the wafer may be held at a level In the vertical direction, if necessary, rotate the wafer or make it thinner, so that the solution layer formed on the substrate surface becomes thinner. In processing step 705, the high ozone gas concentration in the gas phase and a thinner layer 3. The conditions of the ozonized liquid layer may cause substantially enhanced ozone diffusion to the surface of the substrate, thereby increasing the reaction rate. The processing step 705 of the method may occur at a high temperature to enhance the reaction rate; it occurs at a low temperature to enhance the dissolved concentration of the solution components; or at an ambient temperature to reduce the processing. It is also possible to use temperature profiles that change over time. Due to the high pressure during the processing step 705, a higher concentration of dissolved ozone may be present in the water layer, and more highly concentrated amounts of ozone may be present in the gas phase, thus being inconsistent with the traditional conditions of atmospheric pressure. Compared with the treatment, the wet processing performance is enhanced. Alternatively, a gas or a mixture of gases other than ozone may be used in this embodiment. For example, according to a specific embodiment of the present invention, carbon dioxide or a mixture of carbon dioxide and ozone 'can be used to form a pressure treatment solution. 92730.doc -28- 200535998 In conjunction with the process flow shown and illustrated in Figure 7, extra solution transfer, wafer rinse, wafer drying, and wafer transfer steps can be inferred, as previously described. Another possible application of the method and apparatus according to the present invention is wafer cleaning. Such cleaning processes may include, for example, removing organic materials, particulates, and metal residues from a prior etching or stripping step from the substrate surface. A processing container shown in the processing apparatus of Figs. I to 4 can be used to carry out the cleaning method. In either case, the process will be similar to the individual methods illustrated in Figs. In the case where the processing device 10 is used to perform a post-peel cleaning process, FIG. 8 shows an overall diagram of several steps performed using this exemplary multi-sequence cleaning process. In a first series of steps 82, a first treatment solution including a pressure ozonated aqueous sulfuric acid HdO4 may be applied to remove residual organic pollutants and certain metals> dyeables. In a second series of steps 84, a second treatment solution including pressure ozonization of aqueous dilute hydrofluoric acid (HF) may be applied to remove the oxide and metal contaminants incorporated into the oxide. In a third series of steps 86, a third treatment bath including a pressured aqueous ozonated ammonium hydroxide may be applied to remove the inorganic particles. In a fourth series of steps 88, a fourth treatment solution including pressurized aqueous ozonated hydrochloric acid (HC1) may be applied to remove additional metal contaminants. Finally, in a fifth series of steps, a fifth treatment solution including pressure aqueous ozonation to dilute hydrofluoric acid (HF) may be applied to remove oxides formed in the fourth series of steps, and to remove additional Metal contaminants. The process flow illustrated in Figure 8 shows sequentially exposing the substrate to different processing chemicals in the same container. In order to facilitate the use of more than one type of chemical 92730.doc -29- 200535998, the samples are subjected to wet processing in order. Remove residues > Dyes and prevent cross-contamination. The processing flow illustrated in FIG. 8 shows that the substrates are sequentially exposed to different processing chemicals in the same container, but this is not required in the present invention. According to a method according to a specific embodiment of the present invention, one or more substrate transfer steps can be used between different pressure processing containers dedicated to the application of a spout, thereby minimizing different pressure chemical solutions. Risk of reciprocity. In addition, although FIG. 8 shows that a series of dust wet processing steps are performed, this is not necessary, and some processing steps may be performed sequentially under the condition of atmospheric pressure. Moreover, although the processing steps shown in FIG. 8 are shown in FIG. 8, the substrate is exposed to the continuous wet processing method 1: 7 ΑΑ β u. A multi-step process in the mouth, but this is not required in the present invention. Wet processing steps can be carried out sequentially in the processing container or a drying process step can be carried out, and the method will guarantee the inside. For example, after a car is in a wet place, the substrate can be exposed to a pressure war stream in the absence of a liquid processing solution. At the end of this drying process step, the substrate can be subjected to a pressure condition-a second wet processing step. In addition, although the process flow illustrated in FIG. 8 illustrates that five different processing chemicals are applied in a specific order ', the present invention is not limited to this number of processing chemicals' or is limited by this specific step sequence. Depending on the specific embodiment, alternative embodiments according to the present invention may be utilized to apply all, some or additional processing chemicals to the substrate in a different order. For example, 92730.doc -30-200535998 can utilize inorganic acids that are components of the processing solution according to specific embodiments of the present invention, including but not limited to HF, HC, H2S〇4, h2C〇3, HN〇3, Η3ΡΟ # , Aqua regia, a mixture of chromic acid and sulfuric acid, a mixture of sulfuric acid and ammonium persulfate, and various combinations thereof. Examples of organic acids that can be used as components of the treatment bath according to specific embodiments of the present invention include, but are not limited to, acetic acid, formic acid, butyric acid, propionic acid, citric acid, and sulfonic acid. Examples of oxidants that can be used as a component of the processing solution according to specific embodiments of the present invention include, but are not limited to, oxygen, ozone, hydrogen peroxide, and other peroxides. Other possible oxidants include oxygen and hydroxyl groups generated from ozone or oxygen by exposing ozone or oxygen to a discharge or UV radiation. Examples of bases that can be used as a component of the processing solution according to specific embodiments of the present invention include, but are not limited to, NH4OH, NaOH, and KOH. FIG. 9 shows a simplified flowchart of an alternative specific embodiment of a multi-step cleaning method 900 according to the present invention. This method avoids the use and subsequently requires the removal of many of the hazardous chemicals of FIG. Specifically, this replacement treatment for the simplified RCA cleaning method is shown in Fig. 9 and uses pressure ozonized water and pressure ozonated water containing a small amount of hydrofluoric acid instead of the multi-cleaning chemical just described. In the first step 902 of this alternative multi-step cleaning method, an ozonated aqueous solution removes and oxidizes residual organics. In a second step 904, an ozonated aqueous solution containing a small amount of HF removes the oxide layer and contaminants incorporated therein. In a third step 906, odorous oxidized water with ultrasonic vibration energy can be activated and used to remove particles. In a fourth step 908, the ozonated water HF solution removes metals and new oxide layers. Although the multi-sequence cleaning process described and explained with reference to FIGS. 8 and 9 utilizes alkali 92730.doc -31-200535998, the processing method and apparatus according to specific embodiments of the present invention are not limited to these Type of processing solution ingredients. According to other embodiments of the present invention, pressure may be applied to maintain a high concentration or reaction of a reducing agent (e.g., hydrogen) in a processing solution to cause changes in both surfaces. This reducing agent can be used to passivate or change the surface properties of a substrate, for example, by minimizing the formation of an oxide layer, or replacing the hydrophobic S i 0 bonding layer with a hydrophobic "Η".

用於依據本發明之具體實施例的一處理溶液之另一可能 種類的成分’為抑制不合需要的副作用之一添加劑。表面 活性劑及潤濕劑代表可用於本發明之具體實施例的一處理 溶液之另一類別成分。此類潤濕劑及表面活性劑用來降低 與基板表面的介面處流體之表面張力。表面張力的減小可 方便處理溶液與呈現在基板之不同地形内的污染物之間的 互動。除允許將潤濕劑及表面活性劑維持在一高濃度以 外’與依據本發明之方法及裝置相關的高壓力亦可直接方 便濕式處理本身。例如，在大氣壓力情況下潤濕劑或表面 活性劑之南濃度可導致過多的泡沫，但是可在依據本發明 之具體實施例進行處理的高壓力條件下最小化或減少該泡 沫’從而導致更均勻及有效的濕式處理。 利用除增壓以外的技術，可進一步增加依據本發明之具 體實施例的壓力處理溶液之反應性，並因此增加材料之移 除的速率。例如’於在壓力條件下施加處理溶液之前、期 間或之後’從一超音波震盪單元將聲音能量加入處理溶液 之一壓力流可導致增強濕式處理。 92730.doc -32- 200535998 =用本^明之具體實施例增加溶解於DI水溶液中的臭氧 …又可3加攸一基板之表面上移除有機光阻材料的速 率例女在如用一傳統正光阻塗佈一矽晶圓的情況下， f 一 =靜止罐中於5°C及大氣壓力情況下，包含80Ppm臭 虱的臭虱化含水處理流體以400至50〇A/mm之範圍的速 率移除光阻。藉由在代情況下利用㈣力提高至正好超過 b psig來將處理溶;夜中的臭氧濃度增加至⑽，光阻移 除速率&加至約8GG至lGGGA/min之間。如本發明說明之別 處所詳細論述’藉由抑制不合需要的競爭反應及反應機 制，一壓力處理溶液之溫度的降低亦可增強處理。 將處理〉谷液維持在環境溫度以上亦可增強濕式處理。 例如，包含溶解於一相對靜止罐之〇1水中約8〇卯瓜臭氧 的、大虱壓力及5°C之濕式處理條件，導致在約4〇〇至 A/min之間的一光阻移除速率。在大氣壓力情況下將溶 液溫度提高至20〇C，導致在約700至80〇A/min之間的一光阻 移除速率。 依據本發明之其他替代具體實施例，藉由增加處理溶液 之流量’亦可增強壓力處理溶液之反應性，並因此增加材 料移除速率。此外，當依據本發明之具體實施例在高壓力 情况下進行濕式處理時，溫度及流量之組合影響可提供一 累積利益。例如，增壓至18 atm並維持在7〇。〇情況下的_ 地里’谷液流包含接近65 ppm的溶解臭氧。在一溶液流具有 4 2〇〇,00〇或更大雷諾（Reyn〇ld)數之相同條件下，此壓力溶 液之施加導致在約2000至4000A/min之間的光阻剝離速 92730.doc -33 - 200535998 率’而在不同條件τ可導致更高剝離速率。例％，可採用 不同於非植入阻抗材料的速率移除植入離子的顯影光阻材 料°而且’可採用不同速率移除不同阻抗材料。 c優點 鹼性、氧化以及其他活性溶液成分的增加濃度，可增強處 理命液與呈現在晶圓表面上的材料之間的反應之範圍及/ 或速度。 依據本發明之方法及裝置的具體實施例可提供傳統溪式 化學處理技術所沒有的許多優點。一可能重要優點為高壓 力允許將處理溶液之活性揮發性成分的較高遭度維持在溶 液中’其中該等成分可用以與晶圓上的材料反應。例如， 和用依據本發明之具體實施例，在約書C與鹰乂之間的 溫度範圍情況下，處理溶液之_成分的濃度可以在約0」盘 5_ Ppm的範圍内。依據本發明之高麼力所導致的酸性、、 由依據本發明之方法及裝置所授予的一第〔可能優點 為’密封環境允許處理發生在高溫或低溫情況下，從而進 -步增強處理的有效性及/或速度。明確地說，處理溶液之 某些成分為揮發性並可藉由在高溫情況下濕式處理期間來 自-敞開處理容器的蒸發而損失，或可釋氣並損失。例如， 依據本發明之具體實施例利用的一處理溶液可包括揮發性 有機成分，例如DMSO、MEA、n_甲基峨π各烧嗣（NMp)、兒 茶盼及其他成分。藉由在-密封環境中實行濕式處理，即 使當濕式處理反應係發生在一高溫情況下時，該等揮發性 成分仍係保持在液體中並因此可用以與一基板反應。可保 92730.doc -34- 200535998 壓力條件下的處理溶液之其他揮發性成分的範例，包 於^臭氧、二氧化碳、^Ha、F2、cl2、NH3 以及其他可溶解及不可溶解氣體。 依據本發明之呈艚音 -體貫轭例的方法及裝置之一第三 點，係關於建立並利用# 一月“良 液成分之比率的二：!=可用於環境M力情況下的溶 ".、式處理洛液之能力。例如，依據本發明 之一壓力處理溶液的—具體實施例利用臭氧及HF之-含水 混合物。在此處理溶液中，hf用作—種酸以溶解曝露的氧Another possible kind of ingredient 'for a treatment solution according to a specific embodiment of the present invention is one of additives which suppresses undesirable side effects. Surfactants and wetting agents represent another class of ingredients that can be used in a treatment solution of a particular embodiment of the invention. Such wetting agents and surfactants are used to reduce the surface tension of the fluid at the interface with the substrate surface. The reduction in surface tension facilitates the interaction between the processing solution and the contaminants present in the different terrains of the substrate. In addition to allowing wetting agents and surfactants to be maintained at a high concentration ', the high pressures associated with the method and apparatus according to the present invention can also directly facilitate wet processing itself. For example, the south concentration of wetting agents or surfactants under atmospheric pressure may cause excessive foaming, but the foaming may be minimized or reduced under high pressure conditions that are processed in accordance with specific embodiments of the present invention, thereby leading to more Uniform and effective wet processing. Using techniques other than pressurization, the reactivity of the pressure treatment solution according to a specific embodiment of the present invention can be further increased, and thus the rate of material removal can be increased. For example, 'before, during, or after application of the treatment solution under pressure', the addition of sound energy from a supersonic oscillation unit to a pressure stream of the treatment solution may result in enhanced wet processing. 92730.doc -32- 200535998 = Increase the ozone dissolved in the DI aqueous solution using the specific embodiment of the present invention ... and the rate at which the organic photoresist material can be removed from the surface of the substrate. In the case of resist coating a silicon wafer, f a = flea-containing aqueous treatment fluid containing 80Ppm stink flies at a rate of 400 to 50 A / mm in a still tank at 5 ° C and atmospheric pressure Remove the photoresist. The treatment was dissolved by increasing the krypton force to just over b psig in the case of generation; the ozone concentration at night was increased to krypton, and the photoresist removal rate was increased to about 8GG to 1GGGA / min. As discussed in detail elsewhere in the present invention ', by suppressing undesired competitive reactions and reaction mechanisms, a reduction in the temperature of a pressure treatment solution can also enhance the treatment. Maintaining treatment> Valley fluid above ambient temperature can also enhance wet processing. For example, wet treatment conditions that contain about 80% of the ozone in 001 water in a relatively still tank of water, big lice pressure, and 5 ° C, result in a photoresist between about 400 to A / min. Remove rate. Increasing the solution temperature to 20 ° C under atmospheric pressure results in a photoresist removal rate between about 700 and 80 ° A / min. According to other alternative embodiments of the present invention, the reactivity of the pressure treatment solution can also be enhanced by increasing the flow rate of the treatment solution ', and thus the material removal rate can be increased. In addition, when wet processing is performed under high pressure conditions according to a specific embodiment of the present invention, the combined effects of temperature and flow can provide a cumulative benefit. For example, pressurize to 18 atm and maintain it at 70. In the case of _ 地 里 ’valley stream contains approximately 65 ppm dissolved ozone. Under the same conditions of a solution stream having a Reynolds number of 420,000, or greater, the application of this pressure solution resulted in a photoresistance peel rate between about 2000 and 4000 A / min. 92730.doc -33-200535998 rate 'under different conditions τ can lead to higher peel rates. For example, the developing photoresist material implanted with ions can be removed at a rate different from that of the non-implanted impedance material, and different impedance materials can be removed at different rates. c Advantages Increasing the concentration of alkaline, oxidation, and other active solution components can increase the range and / or speed of the reaction between the processing fluid and the material present on the wafer surface. Embodiments of the method and apparatus according to the present invention can provide many advantages not found in conventional stream chemical processing techniques. One potentially important advantage is that high pressure allows to maintain a higher degree of active volatile components of the processing solution in the solution ', where these components can be used to react with materials on the wafer. For example, and in accordance with a specific embodiment of the present invention, the concentration of the component in the processing solution may be in the range of about 0 "disc 5_Ppm in the temperature range between Joss C and Eagle. The acidity caused by the high force according to the present invention, and a first [possible advantage granted by the method and device according to the present invention are that the 'sealed environment allows processing to take place at high or low temperatures, thereby further enhancing the processing Effectiveness and / or speed. In particular, some components of the treatment solution are volatile and can be lost by evaporation from an open treatment container during wet processing at high temperatures, or can be outgassed and lost. For example, a treatment solution utilized in accordance with a specific embodiment of the present invention may include volatile organic components, such as DMSO, MEA, n-methylpyridine (NMp), catechin, and other components. By carrying out the wet processing in a sealed environment, even when the wet processing reaction takes place at a high temperature, the volatile components remain in the liquid and can therefore be used to react with a substrate. Examples of other volatile components that can protect 92730.doc -34- 200535998 under pressure conditions include ^ ozone, carbon dioxide, ^ Ha, F2, cl2, NH3, and other soluble and insoluble gases. The third point of the method and device for presenting the example of the rales-through penetrating yoke according to the present invention is related to the establishment and use of # 一月 "The ratio of the components of the good liquid:! = Can be used in the case of environmental M force. ". The ability to treat Luo liquid by formula. For example, a specific embodiment of a pressure treatment solution according to the present invention utilizes an aqueous mixture of ozone and HF. In this treatment solution, hf is used as an acid to dissolve the exposure Oxygen

相反貞氧成分用作一種氧化劑以採用曝露的石夕產 f氧切。對於在大氣壓力情況下進行的傳統濕式處理而 —難乂將’合液申的臭氧維持在足夠濃度以匹配藉由HF的 ，化物之移除的速率。然而依據本發明之具體實施例，在 尚壓力情況下可將足夠數量的臭氧引入溶液中，以便藉由 即處理溶液成分的氧化物移除之速率，接近匹配由臭氧處 理溶液成分形成氧化物的速率。建立迄今包括溶液成分之Conversely, the oxygen component is used as an oxidant to produce f-oxygen cuts from the exposed stone. For conventional wet processing under atmospheric pressure, it is difficult to maintain the ozone of the 'synthetic solution at a sufficient concentration to match the rate of removal of compounds by HF. However, according to a specific embodiment of the present invention, a sufficient amount of ozone can be introduced into the solution under pressure, so that the oxide removal rate of the solution component is close to match the oxide formed by the ozone treatment solution component. rate. Established to date including solution ingredients

可接取比率的濕式處理溶液之能力，為濕式處理技術增 添靈活性以及新能力。 由依據本發明之方法及裝置的具體實施例所授予的一第 四可此優點為，在處理期間控制氣泡的位準之能力。氣泡 可形成於一基板之表面上，從而導致在一特定製造程序步 驟期間形成氣體。例如，在實行包括但不限於電鍍或電化 子蝕刻、剝離以及採用HF的氧化矽之移除的各處理步驟期 間’氣泡的呈現會有害。 在濕式處理期間，氣泡可禁止將來自液體或氣相（氣泡） 92730.doc -35 - 200535998 的活性成分傳送至基板。此抑制傳送可導致非均勾處理。 在此情況下，氣泡的形成為不合需要並且最好加以禁止或 抑制。作為一進-步的解說’在基板清理應用t ,目的係 使處理溶液接觸基板的整個表面區域，從而使處理溶液盘 少量污染物反應並移除該等污染物。然而，氣泡可容μ 表面特徵（例如高縱橫比槽溝）内，從而致使處理溶液不可接 取該等區域。此外’搜尋要移除的雜質可聚積在氣泡之液 體/氣體介面上，而非藉由處理溶液從晶圓之表面帶走，從 而禁止採用處理溶液移除污染物，或增加污染物重新附著 於基板表面上的趨勢。在其他應用中，氣泡的呈現為不合 需要，因為其具有可壓縮性並且趨於吸收並浪費來自希= 用以增強清理之超音波震盪單元的聲音能量。 在其他某些濕式處理應用+，可能會需要氣泡的形成。 例如，在光阻剝除應用中，氣泡的形成、接合、塌陷以及 純粹呈現可促進處理流體與光阻層之間的物理及化學互 動’從而導致光阻的增強移除。此行動之一可能機制為建 立局部混合流或湍流，其可辅助移動基板表面上的膜或微 粒，或辅助最小化化學濃度輪廓。從個別反應動力而言， 刀政在液相中的細分氣泡可包含一活性氣相成分，其濃度 比出現在液相中的活性成分之濃度高甚多。藉由使活性成 刀之較小氣泡的濃度接近於基板表面，活性成分可更輕易 地擴散在鄰近於基板表面的剩餘相對較薄流體層上，從而 允夺更多的活性成分終於與基板表面接觸並可用於反應。 有利的係，依據本發明之方法及裝置的具體實施例可禁 92730.doc -36- 200535998 止或促進處理溶液中氣泡的局部形成。明確地說，依據本 發明在處理期間使㈣高壓力心有效地估計處理溶液及 :、成刀的沸點，或者即使當形成氣泡時，氣泡仍趨於變小 並且壽命縮短’從而導致較高的處理有效性。在局部產生 氣泡的情況下’增加的壓力引起更多的析出/形成氣體得以 溶解或再溶解於液體中，從而延遲穩定氣泡形成的開始。 此外’-旦因溶液之局部壓力微分或攻擊㈣而形成氣 泡，當氣泡再曝露於分散流體壓力時，可更迅速地再吸收 所得到的氣泡。 在有利的情況下，藉由在處理設施中引入局部壓力下 降，氣泡可形成於飽和或接近飽和的壓力處理流體中。例 =，此可允許形成包含高於呈現在流體上氣體空間中的臭 氧^度之臭氧濃度的氣泡。如以上所論述，該等氣泡中活 性溶液成分之高濃度可導致增強的質量傳送以及增強的處 理速率。 由依據本發明之方法及裝置的具體實施例所授予的一第 五可能優點為，資源與環境相容性的有效消耗。在傳統濕 式處理期間，溶解於處理溶液中的臭氧^^%、hf&及其他 成分釋氣，並必須以所消耗的先驅材料之形式的實質努力 及成本繼續在浴液中加以補充。額外費用係與所得到的排 出物之處理及排除以允許其得以安全地釋入環境中相關。 相反，在一實質封閉系統中實行依據本發明之具體實施 例的晶圓之濕式化學處理。將處理溶液維持在壓力條件 下，因此臭氧及其他可能揮發性溶液成分保持溶解於溶液 92730.doc -37- 200535998 中以與基板反應，而無需值定補充及除去。因此在圖3所示 的衣置卜將處理溶液維持在M力條件下實質上會減小經 ’睪孔或，，、、t的揮發性成分之損失，從而無需收集並排除 損失的材料。 此外@然在某些具體實施例中將系㈣力減小至大氣 壓力以方便從處理容器中移除基板，但是本發明並不需要 此點。在替代具體實施例中，在處理停止之後，可抽空容 器並將處理晶圓料至另—Μ室巾㈣續濕式或乾式處 理。在此類具體實施例中，可輕易地保持臭氧及其他揮發 性溶液成分與環境空氣隔離，從而允許在_最大濃度點情 況下進行處理。相卩敞開容器中的大氣麼力處理可能 會需要昂貴及複雜的設施，來捕獲變得與環境空氣混合 的在處理順序期間釋放的揮發性煙氣，從而增加重要設 施的開支並提高動行成本。 D另外替代具體實施例 雖然以上已顯示並說明本發明之特定具體實施例，但是 應瞭解本發明並不受限於該等特定具體實施例。該等具體 貫％例的變更將保持在本文表述的發明概念之範轉内。 例如，雖然迄今已結合用以利用含水溶液的剝離、清理 以及#刻應用之壓力濕式處理說明依據本發明之具體實施 例’但是可使用其他液體。亦可使用例如氣化、氟化以及 其他非水溶劑或其組合之液體。即使係不能混合的液體之 組合，仍可加以有利地處理，該處理係利用溫度、壓力以 及混合參數之適當組合，以確保基板表面與處理流體的液 92730.doc -38- 200535998 體之間的互動。在依據本發明之一替代具體實施例中，液 體可包括〇3細水中的c〇2之—混合物。從溶解瓜所得到 的碳酸會降低職，從而促㈣氧的溶㈣並允許更多的 臭乳可讀於溶液t，或將已溶解的臭氧穩定於溶液中。 溶解於依據本發明之具體實施例的—壓力處理溶液中的 ⑶2,亦可利用超臨界或接近超臨界流體或條件致動濕式處 理。在此超臨界《近超臨界應用中，普遍利用在⑽編 與100 ATM之間的壓力。 而且’耗以上已結合經由施加—壓力氣體流對一封閉 處理容器進行增壓，來說明依據發明之方法的具體實施 例，但是本發明並不受限於此特定步驟。依據本發明之替 代具體實施例，將-壓力處理溶液單獨引人—封閉處理溶 液中m促使包含-溶解氣體成分之一重要飽和程度 的壓力溶：之容器的增壓。在此壓力液體處理溶液之流入 期間施加高溫可進一步加速處理容器的增壓。 依據本發明之其他具體實施例，可從處理容器完全或部 刀排出展現出減少或耗盡成分的處理溶液，而不會溢出濃 縮的釋氣成分。可採用富壓力處理溶液成分之—二入物取 代所移除的耗盡處理溶液。利用不漏氣而非不漏液的一處 理容器可進一步致動此耗盡材料的取代之循環。 可抽空一處理容器 刖採用一或多種氣 ’或可包含希望吸 、氟、co2、nh3或 依據本發明之其他替代具體實施例， 内的二氣’接著在引入壓力處理流體之 體取代空氣。取代氣體可以為惰性氣體 入處理溶液中的活性化學物種，例如氣 92730.doc -39- 200535998 臭氧。亦可將一連串不同氣體或不同氣體之一組合引入抽 空至中，以準備在壓力條件下引入處理溶液。或者，可分 離地引入烴氣，或將其與其他氣體組合。 依據本發明之其他替代具體實施例，處理溶液可包括一 有機溶劑。可用於本發明的有機溶劑之範例包括但不限於 PR、PR顯影劑、二氧化矽、丙酮、二甲苯、斯托達德（st〇ddard) 溶劑、η-丁基醋酸鹽、乙氧基乙烷基醋酸鹽、2_甲氧基乙烷 基、ΝΜΡ、ΤΜΑΗ、ΙΡΑ、氣化溶劑、氟化溶劑、烴溶劑、 磺酸以及酚類有機剝離劑。 以上淪述已集中在因施加高壓力而利用包含一溶解氣體 成分之高濃度的一壓力處理溶液。然而，依據本發明之替 代具體實施例亦可包含可與一基板表面互動並處理該基板 表面的未洛解氣體之濃度。湍流及其他物理現象可促進將 未〉谷解氣體引入處理流體中，以及未溶解氣體與基板表面 之間的互動。 雖然迄今說明的本發明之具體實施例係關於，在製造半 導體元件期間基板（例如包括所命名的少數之石夕、SiGe、The ability to access a ratio of wet processing solutions adds flexibility and new capabilities to wet processing technology. A fourth advantage afforded by a specific embodiment of the method and apparatus according to the present invention is the ability to control the level of bubbles during processing. Bubbles can form on the surface of a substrate, causing gas to form during a particular manufacturing process step. For example, the appearance of 'bubbles' during various processing steps including, but not limited to, plating or electrochemical etching, stripping, and removal of silicon oxide using HF can be detrimental. During wet processing, bubbles prevent the transfer of active ingredients from the liquid or gas phase (bubbles) 92730.doc -35-200535998 to the substrate. This suppressed transfer can lead to non-uniform hook processing. In this case, the formation of bubbles is undesirable and is preferably prohibited or suppressed. As a step-by-step explanation, in the substrate cleaning application t, the purpose is to make the processing solution contact the entire surface area of the substrate, so that a small amount of pollutants from the processing solution tray react and remove these pollutants. However, air bubbles can hold μ surface features (such as high aspect ratio grooves), making the area inaccessible to the processing solution. In addition, 'search for impurities to be removed can accumulate on the liquid / gas interface of the bubbles, instead of being taken away from the surface of the wafer by the processing solution, thereby prohibiting the use of the processing solution to remove the contaminants or increasing the reattachment of the contaminants to Trend on the substrate surface. In other applications, the presentation of bubbles is undesirable because it is compressible and tends to absorb and waste sound energy from Greek = ultrasonic vibration units used to enhance cleanup. In some other wet processing applications, bubble formation may be required. For example, in photoresist stripping applications, the formation, bonding, collapse, and pure appearance of bubbles can promote physical and chemical interactions between the processing fluid and the photoresist layer ', resulting in enhanced removal of the photoresist. One possible mechanism for this action is to establish a local mixed flow or turbulence, which can assist in moving membranes or particles on the substrate surface, or to help minimize chemical concentration profiles. From the perspective of individual reaction kinetics, the finely divided bubbles in the liquid phase of the knife can contain an active gas phase component whose concentration is much higher than the concentration of the active component present in the liquid phase. By making the concentration of the smaller bubbles of the active knife close to the substrate surface, the active ingredient can be more easily diffused on the remaining relatively thin fluid layer adjacent to the substrate surface, thereby allowing more active ingredients to finally reach the substrate surface Contact and available for reaction. Advantageously, specific embodiments of the method and apparatus according to the present invention can inhibit or promote the local formation of bubbles in the processing solution. Specifically, according to the present invention, the high pressure center is used to effectively estimate the processing solution and the boiling point of the knife during processing, or even when bubbles are formed, the bubbles tend to become smaller and the life is shortened, thereby leading to a higher Processing effectiveness. In the case where bubbles are locally generated, the increased pressure causes more precipitation / formation gas to be dissolved or re-dissolved in the liquid, thereby delaying the start of stable bubble formation. In addition, air bubbles are formed due to local pressure differential of the solution or attack of radon. When the air bubbles are re-exposed to the pressure of the dispersion fluid, the obtained air bubbles can be reabsorbed more quickly. In advantageous cases, by introducing a local pressure drop in the processing facility, bubbles can be formed in a saturated or near-saturated pressure processing fluid. For example, this allows the formation of bubbles containing ozone concentrations higher than the ozone levels present in the gaseous space above the fluid. As discussed above, the high concentration of active solution components in these bubbles can lead to enhanced mass transfer and enhanced processing rates. A fifth possible advantage conferred by a specific embodiment of the method and device according to the present invention is the efficient consumption of resources and environmental compatibility. During traditional wet processing, ozone, hf & and other components dissolved in the processing solution are outgassed and must be replenished in the bath with substantial effort and cost in the form of consumed precursor materials. Additional costs are related to the disposal and exclusion of the resulting emissions to allow their safe release into the environment. Instead, a wet chemical treatment of a wafer according to a specific embodiment of the invention is performed in a substantially closed system. The treatment solution is maintained under pressure, so ozone and other potentially volatile solution components remain dissolved in the solution 92730.doc -37- 200535998 to react with the substrate without the need for replenishment and removal. Therefore, maintaining the treatment solution at the condition of M force as shown in Fig. 3 will substantially reduce the loss of volatile components through the pores, holes ,, and t, thereby eliminating the need to collect and exclude the lost material. In addition, in some embodiments, the coupling force is reduced to atmospheric pressure to facilitate the removal of the substrate from the processing container, but this is not required by the present invention. In an alternative embodiment, after the processing is stopped, the container may be evacuated and the processed wafers may be transferred to another M chamber towel for continuous wet or dry processing. In such specific embodiments, ozone and other volatile solution components can be easily kept isolated from the ambient air, allowing processing at the maximum concentration point. Relative atmospheric processing in open containers may require expensive and complex facilities to capture volatile fumes released during the processing sequence that become mixed with ambient air, increasing the cost of critical facilities and increasing operating costs . DAlternative Specific Embodiments Although specific specific embodiments of the invention have been shown and described above, it should be understood that the invention is not limited to these specific specific embodiments. These specific changes will remain within the scope of the inventive concepts described herein. For example, although a specific embodiment according to the present invention 'has been described so far in connection with peeling, cleaning, and pressure wet processing using an aqueous solution, other liquids may be used. Liquids such as gasification, fluorination, and other non-aqueous solvents or combinations thereof can also be used. Even if it is a combination of liquids that cannot be mixed, it can still be advantageously processed. This treatment uses a suitable combination of temperature, pressure, and mixing parameters to ensure that the surface of the substrate and the liquid of the processing fluid are 92730.doc -38- 200535998 interactive. In an alternative embodiment according to the present invention, the liquid may include a mixture of CO2 in fine water. The carbonic acid obtained from dissolving melon will reduce the duty, thereby promoting the dissolution of oxygen and allowing more stinky milk to be read in the solution t, or to stabilize the dissolved ozone in the solution. ⑶2 dissolved in a pressure treatment solution according to a specific embodiment of the present invention can also use supercritical or near supercritical fluids or conditions to initiate wet processing. In this supercritical near-critical application, the pressure between knitting and 100 ATM is commonly used. Furthermore, the above embodiment has been described with reference to a specific embodiment of the method according to the invention by pressurizing a closed processing vessel via an application-pressure gas flow, but the invention is not limited to this specific step. According to an alternative embodiment of the present invention, the pressure treatment solution is separately introduced into the closed treatment solution. The m in the closed treatment solution promotes the pressure dissolution of the container containing an important saturation level of the dissolved gas component: the pressure of the container. Applying high temperature during the inflow of this pressure liquid treatment solution can further accelerate the pressurization of the treatment vessel. According to other specific embodiments of the present invention, the processing solution exhibiting reduced or depleted components can be completely or partially discharged from the processing container without overflowing the concentrated outgassing components. The depleted treatment solution that is removed may be replaced with a binary of the components of the pressure-enriched treatment solution. The use of a gas-tight rather than liquid-tight processing vessel can further actuate the cycle of replacement of this depleted material. A processing vessel may be evacuated (i.e., one or more gases may be used) or may contain desirably, fluorine, co2, nh3, or other alternative embodiments according to the present invention, and the internal two gases are then replaced with air in the body where the pressure treatment fluid is introduced. The replacement gas may be an active chemical species that is an inert gas into the processing solution, such as gas 92730.doc -39- 200535998 ozone. A series of different gases or a combination of different gases may also be introduced into the evacuation chamber to prepare for the introduction of the treatment solution under pressure. Alternatively, the hydrocarbon gas may be introduced separately or combined with other gases. According to other alternative embodiments of the present invention, the processing solution may include an organic solvent. Examples of organic solvents that can be used in the present invention include, but are not limited to, PR, PR developer, silicon dioxide, acetone, xylene, stoddard solvent, η-butyl acetate, ethoxyethyl Alkyl acetate, 2-methoxyethane, NMP, TMA, IPA, gasification solvent, fluorinated solvent, hydrocarbon solvent, sulfonic acid and phenolic organic stripping agent. The foregoing description has focused on the use of a pressure treatment solution containing a high concentration of a dissolved gas component due to the application of high pressure. However, alternative embodiments according to the present invention may also include a concentration of non-protonated gas that can interact with a substrate surface and process the substrate surface. Turbulence and other physical phenomena can promote the introduction of undissolved gas into the processing fluid and the interaction between undissolved gas and the substrate surface. Although the specific embodiments of the present invention described so far relate to substrates (such as the named minority stone, SiGe,

GaAs、Si、GaAs、GalnP以及GaN的基板）之濕式化學處理。 然而，本發明並不受限於此特定應用，並且可在壓力條件 處理其他材料。利用本發明的濕式處理之候選物的範例包 括但不限於，硬磁碟及硬碟基板、光學元件（例如反射鏡、 透鏡或波導）、以及用於微電機系統（micro-electncal mechamcai systems ; MEMS)及液晶顯示器元件的製造之基 板0 92730.doc -40- 200535998 此外，雖然以上已主要結合其中在壓力條件下將一成分 引入一處理溶液中的濕式處理應用而說明依據本發明之具 體貫施例，但是本發明並不需要此點。依據本發明之替代 具體實施例，可在依據本發明之高壓力情況下將一濕式處 理溶液簡單地維持在處理容器中，從而避免溶液成分可能 經由釋氣或蒸發而不必要地損失。 雖然已根據較佳方法及結構說明本發明，但是熟習此項 技術者應瞭解可對揭示的具體實施例進行許多修改及更改 而不脫離本發明。因此’希望將該等修改及變更視為在由 所附申請專利範圍定義的本發明之精神及範疇内。 【圖式簡單說明】 圖1為依據本發明之一處理裝置的一具體實施例之一簡 化示意圖。 圖2為依據本發明之一具體實施例的一範例性臭氧化裝 置之-簡化示意圖’該裝置可用以產生一壓力、高濃度臭 虱洛液並可用於圖1所示的處理裝置。 立圖3為依據本發明之一裝置的一具體實施例之一簡化示 ::/亥裝置包括一保持容器及-處理容器(例如圖1所示 二^唯二可用以在從該處理容器中移除處理溶液_^^ 液維持在壓力條件下。 簡化示 立圖4為依據本發明之-裝置的-具體實施例之_ “圖其顯不經由喷嘴將處理流體引入一處理 圖5繪製右二從 氧之濃度對^同壓力條件^含水溶液中溶解的臭 92730.doc 200535998 圖6為解說依據本發明之—處理方法的— 之 一簡化流程圖丨 ’該方法可用以採用圖1所示的處理裝置來處 理基板。 圖7為解說依據本發明之一虛理大 — 又Θ 羼理方法的一具體實施例之 間化流程圖， 其顯示「壓力」臭氧處理順序。 圖8為解說一 多順序基板清理程序之一具體實施例的一 簡化流程圖。 圖9為解說一 多順序基板清理程序之一替代具體實施例 的—簡化流程圖 〇 【主要元件符號說明】 10 處理裝置 20 臭氧化裝置 30 裝置 4〇 處理裝置 60 方法 7〇 方法 8〇 清理處理 1〇〇 處理容器 1〇2 基板 1〇4 基板固持器 1〇6 處理溶液 1〇8 排洩閥 110 氣相閥 Hi 第一氣體來源 92730. docGaAs, Si, GaAs, GalnP, and GaN substrates). However, the invention is not limited to this particular application, and other materials can be processed under pressure conditions. Examples of candidates for wet processing using the present invention include, but are not limited to, hard disks and hard disk substrates, optical components (such as mirrors, lenses, or waveguides), and micro-electncal mechamcai systems; MEMS) and substrates for the manufacture of liquid crystal display elements 0 92730.doc -40- 200535998 In addition, although the above has been mainly described in conjunction with wet processing applications in which a component is introduced into a processing solution under pressure, the specifics according to the present invention are described The examples are implemented, but the invention does not need this. According to an alternative embodiment of the present invention, a wet processing solution can be simply maintained in a processing container under high pressure conditions according to the present invention, thereby avoiding unnecessary loss of solution components through outgassing or evaporation. Although the invention has been described in terms of preferred methods and structures, those skilled in the art will appreciate that many modifications and changes can be made to the specific embodiments disclosed without departing from the invention. Therefore, 'It is intended that such modifications and changes shall be deemed to be within the spirit and scope of the present invention as defined by the scope of the appended claims. [Brief description of the drawings] FIG. 1 is a simplified schematic diagram of a specific embodiment of a processing device according to the present invention. FIG. 2 is a simplified schematic diagram of an exemplary ozonation device according to a specific embodiment of the present invention. The device can be used to generate a high-pressure, high-concentration bed bug liquid and can be used in the processing device shown in FIG. FIG. 3 is a simplified illustration of a specific embodiment of a device according to the present invention: The device includes a holding container and a processing container (e.g., as shown in FIG. 1 and only two can be used to remove the container from the processing container). Remove the processing solution _ ^^ The liquid is maintained under pressure. Simplified illustration of Figure 4 is a-specific embodiment of the device according to the present invention. "Figure shows the introduction of processing fluid through a nozzle into a process. Figure 5 draws right Two from the concentration of oxygen ^ the same pressure conditions ^ dissolved odor in aqueous solution 92730.doc 200535998 Figure 6 is a simplified flowchart illustrating one of the-processing method according to the present invention 丨 'The method can be used as shown in Figure 1 FIG. 7 is a flowchart illustrating a specific embodiment of a virtual theorem-theta cleavage method according to one embodiment of the present invention, which shows a “pressure” ozone treatment sequence. A simplified flowchart of a specific embodiment of a sequential substrate cleaning program. FIG. 9 is a simplified flowchart illustrating an alternative to the specific embodiment of a multi-sequence substrate cleaning program— [simplified flowchart of main component symbols] 10 Processing device 20 Ozone device 30 Device 40 Processing device 60 Method 70 Method 80 Cleaning treatment 100 Processing container 10 Substrate 1 04 Substrate holder 1 06 Processing solution 108 Purge valve 110 Gas phase valve Hi First Gas Source 92730.doc

-42- 200535998 112 循環迴路 112a 入口 112b 出口 114 幫浦 116 過濾器 118 溫度控制結構 120 超音波震盪單元 130 攪拌器結構 132 氣相閥 133 第二氣體來源 136 廢棄/排除單元 138 氣體閥 150 真空幫浦 151 閥 200 臭氧產生器 201 氧氣來源 202 入口 204 出口 206 入口 208 文氏注射器 210 臭氧化迴路 212 出口 214 入口 216 衝擊容器 92730.doc -43 - 200535998 218 幫浦 219 溫度控制結構 220 出口 280 靜態混合結構 282 接觸器結構 283 過濾器 284 氣旋除氣器 300 保持罐 310 閥 311 閥 340 閥網路 400 處理容器 402 基板 404 基板固持器 406 噴嘴 408 供應線路 410 入口 /出口 412 控制閥 418 排茂閥 900 多步驟清理方法 92730.doc -44--42- 200535998 112 Circulation circuit 112a Inlet 112b Outlet 114 Pump 116 Filter 118 Temperature control structure 120 Ultrasonic vibration unit 130 Stirrer structure 132 Gas phase valve 133 Second gas source 136 Disposal / exclusion unit 138 Gas valve 150 Vacuum help Pu 151 Valve 200 Ozone generator 201 Oxygen source 202 Inlet 204 Outlet 206 Inlet 208 Venturi syringe 210 Ozone circuit 212 Outlet 214 Inlet 216 Shock container 92730.doc -43-200535998 218 Pump 219 Temperature control structure 220 Outlet 280 Static mixing Structure 282 Contactor structure 283 Filter 284 Cyclone deaerator 300 Holding tank 310 Valve 311 Valve 340 Valve network 400 Processing container 402 Substrate 404 Substrate holder 406 Nozzle 408 Supply line 410 Inlet / outlet 412 Control valve 418 Exhaust valve 900 Multi-step cleaning method 92730.doc -44-

Claims (1)

200535998 十、申請專利範圍： 1. 一種修改一基板之一表面的方法，該方法包括： 將該基板***一處理容器中； 將該處理容器增壓至大於大氣壓力；將一壓力處理节 體引入該壓力處理容器中，以便將該基板的一表面之至 少一部分曝露於該壓力處理流體中；以及 處理該基板以在該壓力處理流體與該表面之間引起一 反應，該反應包括從該基板表面上移除材料、將材料添 加至该基板表面上、以及修改一基板表面之至少一者， 其中在將該處理溶液引入該處理容器期間以及在該基板 的處理之至少一部分期間，將該處理溶液維持在高於大 氣壓力之一壓力。 2·如申請專利範圍第1項之方法，其進一步包括在處理期間 施加聲能、電磁能以及微波之至少一者。 3·如申請專利範圍第1項之方法，其進一步包括在該基板與 該處理溶液之間藉由振動該基板、旋轉該基板之至少一 者給予相對運動，給予一湍流至該處理溶液中，以及給 予一層流至該處理溶液中。 4·如申請專利範圍第1項之方法，其進一步包括： 從該處理容器中移除該處理流體； 將一第二處理流體引入該壓力處理容器中以與該基板 接觸；以及 藉由允許該第二處理流體與該基板表面反應來處理該 基板’其中在將該第二處理流體引入該處理容器中之前 92730.doc 200535998 、在將該第二處理流體引入該處理容器期間、以及在該 基板的處理之至少一部分期間，將該第二處理流體維持 在局於大氣壓力之一壓力。 5 ·如申請專利範圍第1項之方法，其中·· 該處理溶液包括一酸性溶液、一鹼性溶液以及一有機 溶劑之至少一者；以及 該成分包括臭氧、過氧化氫以及一氫氧基之至少一者 〇 6·如申請專利範圍第1項之方法，其中將該處理溶液增壓至 約50 ATM或更低。 7.如申請專利範圍第1項之方法，其進一步包括在該處理步 驟之後將該處理溶液傳送至一保持罐，同時將該處理溶 液維持在壓力條件下。 8·如申請專利範圍第1項之方法，其中在將該壓力處理溶液 引入該壓力處理容器中之後，該壓力處理溶液經歷一壓 力下降’以便出現一溶液成分的釋氣。 9 ·如申請專利範圍第1項之方法，其中該處理步驟包括增強 該處理溶液中的氣泡形成，以及抑制該處理溶液中的氣 泡形成之至少一者。 I 0 ·如申#專利範圍第1項之方法，其進一步包括藉由在引入 該壓力處理溶液之前引入一氣體流，在對該抽空處理室 增壓之前抽空該密封處理容器。 II ·如申請專利範圍第1項之方法，其進一步包括在以下處理 步驟之後烘乾該基板··隨著相對於該壓力處理溶液移動 92730.doc 200535998 該基板，藉由在該基板表面上該處理溶液之一彎月面與 該處理溶液的一剩餘分散部分之間，產生一表面張力梯 度。 12. 13. 14. 如申請專利範圍第11項之方法，其中該處理容器内的壓 力引起包括一氣體、一液體以及一蒸汽之至少一者的一 表面張力下降成分集中在該彎月面中，以產生該表面張 力梯度。 一種用以藉由從一基板表面上移除材料、將材料添加至 該基板表面上、以及修改一基板表面之至少一者來修改 該基板之該表面的裝置，該裝置包括： 處理谷器，其係配置成在一不漏氣密封環境中接收 並包含一基板； 一壓力處理溶液來源，其係經由一入口閥與該處理容 器進行流體通信，該壓力處理溶液來源係配置成包含一 壓力處理溶液，其具有大於在大氣壓力情況下該溶液中 可用者之一成分之一濃度；以及 -排沒閥，其使該處理容器可與—㈣口進行流體通 信。 如申請專利範圍第13項之裝置，其進一步包括·· —壓力保持容器，其係配置成當並未在該處理容器中 使用-壓力處理溶液時將該溶液維持在壓力條件下；以 及 -耦合在該處理容器與該保持容器之間的控制閥，直 用以控制從該保持容器至該處理容器的該處理溶液之一 92730.doc 200535998 流量。 15.如申請專利範圍第丨3項之裝置，其進一 、 ^ 步包括一超音波 震盪單元，該超音波震盪單元與該處理空 处里谷為進行聲音通 信並係配置成施加聲能於該處理容器中。 步包括一臭氧化 進行流體通信並 得以溶解，該臭 1 6·如申請專利範圍第丨3項之裝置，其進_ 裝置，該臭氧化裝置與該壓力處理容器 係配置成引起臭氧在該壓力處理溶液中 氧化裝置包括： 一氧氣來源； 臭氧產生器’其與该氧氣來源進行流體通信；以及 一注射器結構，其與該臭氧產生器進行流體通信，該 /主射器結構係配置成從該臭氧產生器之一出口接收一含 臭氧氣體之一氣體流，並引起來自該含臭氧氣體之臭氧 在該壓力處理流體之一流内得以溶解。 17.如申請專利範圍第13項之裝置，其進一步包括一嗜嘴， 該喷嘴係配置成引導一處理溶液之一壓力流與呈現在該 處理容器内的一基板接觸。 18·如申睛專利範圍第13項之裝置，其進一步包括一電位來 源’該電位來源與該處理容器進行電氣通信並係配置成 產生直流電及交流電之至少一者，以引起該處理容器内 的一電化學反應。 1 9 · 一種烘乾一基板之方法，其包括： 將一基板固定於一不漏氣處理容器内； 將該處理容器增壓至大於大氣壓力； 92730.doc 200535998 將一壓力沖洗液體弓I入該處理容器中以浸沒該基板’ 該沖洗液體包括集中在該沖洗溶液之一表面處的一表面 張力下降成分；以及 相對於該沖洗液體移動該處理基板，以便在該基板表 面上的一彎月面與該沖洗液體之一剩餘分散部分之間建 立一表面張力梯度，該表面張力梯度將液體從該基板表 面汲入剩餘分散沖洗液體中。 20. —種採用一處理液體處理一基板之方法，該方法包括· 製備在一第一壓力情況下具有一成分之—第—濃产的 一溶液； 減小該溶液之一壓力以引起該成分之釋氣，從而濃縮 一氣相中該成分之一濃度；以及 將該基板曝露於該釋氣成分中。 92730.doc200535998 10. Scope of patent application: 1. A method for modifying a surface of a substrate, the method comprising: inserting the substrate into a processing container; pressurizing the processing container to a pressure greater than atmospheric pressure; introducing a pressure processing joint The pressure processing container to expose at least a portion of a surface of the substrate to the pressure processing fluid; and processing the substrate to cause a reaction between the pressure processing fluid and the surface, the reaction including from the surface of the substrate Removing, adding material to the substrate surface, and modifying at least one of a substrate surface, wherein the processing solution is introduced into the processing container during the processing solution and during at least a portion of the processing of the substrate, Maintained at a pressure above atmospheric pressure. 2. The method of claim 1, further comprising applying at least one of acoustic energy, electromagnetic energy, and microwave during processing. 3. The method according to item 1 of the patent application scope, further comprising giving relative motion between the substrate and the processing solution by vibrating the substrate and rotating at least one of the substrates, and giving a turbulence to the processing solution, And give a layer of flow to the treatment solution. 4. The method of claim 1, further comprising: removing the processing fluid from the processing container; introducing a second processing fluid into the pressure processing container to contact the substrate; and by allowing the A second processing fluid reacts with the surface of the substrate to process the substrate ', where before the second processing fluid is introduced into the processing container 92730.doc 200535998, during the second processing fluid is introduced into the processing container, and at the substrate The second processing fluid is maintained at a pressure that is one of atmospheric pressure during at least a portion of the processing of. 5. The method of claim 1 in the scope of patent application, wherein the treatment solution includes at least one of an acidic solution, an alkaline solution, and an organic solvent; and the component includes ozone, hydrogen peroxide, and a hydroxyl group At least one of the methods of claim 1, wherein the treatment solution is pressurized to about 50 ATM or lower. 7. The method of claim 1, further comprising transferring the processing solution to a holding tank after the processing step, while maintaining the processing solution under pressure. 8. A method as claimed in claim 1 in which after the pressure treatment solution is introduced into the pressure treatment container, the pressure treatment solution undergoes a pressure drop 'so that outgassing of a solution component occurs. 9. The method of claim 1, wherein the processing step includes at least one of enhancing the formation of bubbles in the processing solution and suppressing the formation of bubbles in the processing solution. I 0 · The method of item # 1 of the patent scope, further comprising evacuating the sealed processing container before introducing the gaseous processing solution before pressurizing the evacuated processing chamber. II. The method of claim 1 in the scope of patent application, which further comprises drying the substrate after the following processing steps. As the substrate is moved relative to the pressure treatment solution, 92730.doc 200535998, the substrate is A surface tension gradient is created between a meniscus of the treatment solution and a remaining dispersed portion of the treatment solution. 12. 13. 14. The method of claim 11 in which the pressure in the processing vessel causes a surface tension-reducing component including at least one of a gas, a liquid, and a vapor to be concentrated in the meniscus To produce this surface tension gradient. A device for modifying the surface of a substrate by removing material from a substrate surface, adding material to the substrate surface, and modifying at least one of the substrate surface, the device includes: a valley processor, It is configured to receive and contain a substrate in a hermetically sealed environment; a source of pressure processing solution is in fluid communication with the processing container via an inlet valve, and the source of pressure processing solution is configured to include a pressure treatment A solution having a concentration greater than one of the components available in the solution at atmospheric pressure; and a drain valve which enables the processing vessel to fluidly communicate with the mouthpiece. If the device of the scope of application for item 13 of the patent application further comprises a pressure holding vessel configured to maintain the solution under pressure when the pressure treating solution is not used in the processing vessel; and-coupling The control valve between the processing container and the holding container is directly used to control the flow of one of the processing solutions from the holding container to the processing container 92730.doc 200535998. 15. The device according to item 3 of the scope of patent application, further comprising an ultrasonic oscillating unit, the ultrasonic oscillating unit and the processing space are configured for sound communication and are configured to apply acoustic energy to the processing Container. The steps include an ozonation for fluid communication and dissolution. The odor 16. As in the device of the scope of patent application No. 3, its inlet device, the ozonation device and the pressure treatment container are configured to cause ozone at the pressure The oxidizing device in the processing solution includes: an oxygen source; an ozone generator 'which is in fluid communication with the oxygen source; and a syringe structure which is in fluid communication with the ozone generator, and the / main injector structure is configured to be driven from the An outlet of the ozone generator receives a gas stream of ozone-containing gas and causes the ozone from the ozone-containing gas to be dissolved in a stream of the pressure treatment fluid. 17. The device of claim 13 further comprising a mouthpiece configured to direct a pressure flow of a processing solution into contact with a substrate present in the processing container. 18. The device of claim 13 in the patent scope, further comprising a potential source 'the potential source is in electrical communication with the processing container and is configured to generate at least one of direct current and alternating current to cause the An electrochemical reaction. 19 · A method of drying a substrate, comprising: fixing a substrate in an airtight processing container; pressurizing the processing container to a pressure greater than atmospheric pressure; 92730.doc 200535998 pouring a pressure flushing liquid into The processing container is immersed in the substrate. The rinsing liquid includes a surface tension reducing component concentrated at one surface of the rinsing solution; and the processing substrate is moved relative to the rinsing liquid to form a meniscus on the surface of the substrate. A surface tension gradient is established between the surface and one of the remaining dispersed portions of the rinse liquid, and the surface tension gradient draws liquid from the surface of the substrate into the remaining dispersed rinse liquid. 20. A method for processing a substrate by using a processing liquid, the method comprising: preparing a solution having a component in a first pressure—the first concentrated production; reducing a pressure in the solution to cause the component Outgassing, thereby concentrating a concentration of the component in a gas phase; and exposing the substrate to the outgassing component. 92730.doc