1298904 09514twf3.doc/d 97-04-11 九、發明說明： 技術領域 本發明是有關於一種半導體製程，且特別是有關於一 種蝕刻沈積於半導體基底上之光阻層的方法。 發明背景 半導體兀件通常是經由重複各種不同之製程而製作於 例如是晶圓的半導體基底上。這些各種不同的製程包括成 月旲(Layering)製程、圖案化(patterning)/蝕刻⑽咖吨)製程、 ί参雜(Doping)製程與熱處理(jjeat Treatment)製程等。.圖案 化/蝕刻製程是一種很重要的半導體製程，其包括從半導體 基底的表面移除材料。亦即，圖案化/蝕刻製程之步驟至少 包括於半導體基底之表面上形成具有特定圖案之光阻層， 然後再從半導體基底之表面上選擇性蝕刻或移除材料。在 貪虫刻製中，半導體基底覆蓋有光阻層之部分會受到保 . 護，而半導體基底未覆蓋有光阻層之部分則會依照蝕刻製 程之型式與時間而蝕刻至設定程度。於是，在特定圖案中 ' 之未受到保護的材料會從半導體基底表面上移除。 目前業界常使用的兩種蝕刻製程包括濕式蝕刻製程與 乾式蝕刻製程。濕式飽刻製程係利用化學餓刻劑處理半導 體基底表面，使化學蝕刻劑與未受到保護之材料反應而形 成包含未受到保護之材料的水溶性產物，而此水溶性產物 再由溶劑帶走。乾式蝕刻製程則是利用氣體分子及/或離子 處理半導體基底表面，使氣體分子及/或離子與未受到保護 之材料產生反應（化學反應）或轟擊半導體基底之表面（物理 5 .1298904 09514twf3.doc/d 反應)以移除未受到保護之材料。乾式蝕刻製程通常被稱爲 電漿餽刻製程。 在蝕刻製程結束後，通常需要進行灰化(Ashing)製程以 移除殘留在半導體基底表面之光阻層。一種習知的灰化製 程係加入例如是氧氣之氣體，並使此氣體離子化形成電漿 後’利用此電漿作爲化學蝕刻劑或物質處理半導體基底表 面以移除光阻層。然後，利用有機溶劑或無機溶劑處理光 阻層’以破壞光阻層之結構並完全移除殘留之光阻層。因 爲’底層之導線不會改變，所以在習知的灰化製程之後會 進行濕式蝕刻製程，以更有效的移除光阻層。然而，灰化 製程有一個缺點就是在乾電漿處理製程時會產生很多缺 陷。而且，在後續的濕式蝕刻製程也無法移除這些缺陷。 就環境保護的考量而言，目前業界係利用臭氧化去離 子水處理光阻層以移除光阻層。然而，在噴灑旋轉處理器 (Sptay Spin Processor)中使用臭氧化去離子水處理蝕刻後 (Post-Etch)光阻層或低劑量植入(L〇w-Dose-Implant)深紫外 光(Deep Ultraviolet，DUV)型光阻層時，其光阻層之蝕刻速 率爲400 &/分I(A/min)至600埃/分鐘(A/min)。一^般而言， 利用臭執化去離子水處理光阻層之方法與目前製造程序所 使用之利用有機溶劑處理光阻層之方法相比較，利用臭氧 化去離子水處理光阻層之蝕刻速率是相當低的。 於是就需要一種能夠增加半導體基底之光阻層的蝕刻 速率的方法。 發明槪述 6 ^ 1298904 97-04-11 09514twf3.doc/d 有鑑於此，本發明提供一種蝕刻沈積於半導體基底上 之光阻層的方法，此方法係應用含氫離子反應性溶液處理 光阻層而使含氫離子反應性溶液與光阻層反應，接著應用 去離子水處理基底後，再應用臭氧化去離子水處理基底以 移除至少一部份之光阻層。含氫離子反應性溶液只要包含 氫離子’並包括一種以上之下列元素或化合物··氧、氧化 氫、過氧化氫、硫、硫酸鹽、二氧化硫、三氧化硫與硫酸。 本發明之特點在於可以更有效的進行光阻層移除製程，亦 即，舉例來說，在對蝕刻後或低劑量離子植入製程後的光 阻層進行濕式蝕刻剝離製程時，不需要進行灰化處理而且 也不會降低產能。 本發明另外提供一種蝕刻製程，此蝕刻製程係提供已 形成光阻材料之基底，導入硫酸溶液至反應室中，以使硫 酸溶液與光阻材料反應。然後，以臭氧化去離子水處理光 阻材料，以移除光阻材料。硫酸溶液係以導入或噴灑之方 式進入反應室，而且硫酸溶液進入反應室之時間爲10秒至 60秒左右。臭氧化去離子水至少包括60ppm之臭氧。 本發明又提供一種触刻沈積於半導體基底上之光阻層 的方法，此方法係將含氫離子反應性溶液噴灑於基底上10 秒至60秒左右後，將去離子水噴灑於基底上。此方法更包 括將溫度爲25°C之臭氧化去離子水噴灑至基底上或供給至 反應室中。然後，將溫度爲80°C至95°C左右之熱去離子水 噴灑至基底上或供給至反應室中。 在此，由上述內容、本說明書與習知技術者可明顯的 1298904 97-04-11 09514twf3.doc/d 看出任何結合所產生之特徵，在不互相矛盾的情況下，上 述之任何特徵或特徵之結合皆包含在本發明之範圍內。而 且，在此已經揭露了本發明之內容、部分觀點與特徵，當 然這些內容、部分觀點與特徵將會以本發明之實施例予以 具體化。而且，本發明之其他優點與特徵可明顯的由後附 之詳細內容與申請專利範圍看出。 爲讓本發明之上述和其他目的、特徵、和優點能更明 顯易懂，下文特舉一較佳實施例，並配合所附圖式，作詳 細說明如下： ’ 圖式之簡單說明： 第1圖爲繪示本發明較佳實施例之製程裝置側視圖； 以及 第2圖爲繪示本發明較佳實施例之蝕刻沈積於半導體 基底上之光阻層的方法流程圖。 圖式之標示說明： 100 :製程裝置 105 :基底 110 :反應室 110a :頂部 u〇b :底部 115 :旋轉台 12〇 :噴灑機構 125 :噴嘴 130 ··出口 8 1298904 09514twf3.doc/d 97-04-11 135 :晶圓匣 200、205、210、215、220、225、230、235 :步驟 實施例 以下請參照所附圖式’詳細說明本發明之較佳實施 例。在所附圖示中，盡量使用相同或相似的圖示標記表示 相同或相似的構件。而且’圖示所繪示的只是槪略圖並不 是精確的尺寸。在下述所揭露之內容中，爲了達到方便與 清楚之目的，所謂的方向術語如頂部、底部、左、右、上、 下、之上、高於、低於、之下、後面、前面等只是用於對 應所附圖示。這些方向術語並不是用以限定申請專利範圍 所界定之範圍。 在此所揭露之內容只是代表性的較佳實施例，需要明 白的是這些實施例只是代表實例而不是用以限制本發明。 而且，下述之詳細內容之目的，儘管只是解釋較佳實施例， 但是根據實施例所作之各種潤飾、取代與更動仍然屬於本 發明之保護範圍，因此本發明之範圍當視後附之申請專手I] 範圍所界定者爲準。此外，必須瞭解與體會的是在實施例 中所敘述之製程步驟與結構並沒有包含製作介層窗結構的 全部製造流程。本發明所揭露之方法可以與習知所使用的 不同積體電路製造技術整合在一起，而且在實施例中實行 的許多一般製程步驟只是用於提供實施本發明的一些必要 條件。一般而言，本發明係適用於半導體元件與製程之領 域中。於且，在下述的內容中，本發明係以相關的製程裝 置與於半導體基底上蝕刻光阻層之方法爲實例作說明。 9 1298904 09514twf3.doc/d 97-04-11 請參照第1圖，其繪示依照本發明較佳實施例之製程 裝置100側視圖。此製程裝置100可以快速且均一的對半 導體基底105進行化學及或物理處理。製程裝置100例如 是噴滴處理裝置(Spray Processor)。在本實施例中，製程裝 置100例如是由FSI International公司所製造的酸噴灑處理 裝置。此製程裝置100是由具有頂部110a與底部110b之 液體密封式處理反應室110、設置於反應室110之底部ll〇b 並用以旋轉基底105之旋轉台115、設置於反應室110之頂 部110a並用以供給流體(氣體或被體)於至少一個基底105~ 表面之噴灑機構120所構成。藉由使旋轉台115旋轉而可 以控制流體沈降於基底105表面及/或均勻的處理基底105 表面。此外，旋轉台115也可以用於旋乾基底105。噴灑機 構120具有複數個噴嘴125,其中每一個噴嘴連接至各種儲 槽(未圖示），且複數個噴嘴係設置於反應室110中，其用以 噴灑不同之流體，例如氮氣、含氫離子反應性溶液、臭氧 化去離子水、去離子水至基底1〇5表面。因此，可以同時 的或連續的使用不同之流體處理基底。 在一個實施例中，製程裝置100包括一個出口 13〇，此 出口 130連接一個抽取元件(未圖示），以抽取元件用以從反 應室110中移除所使用之流體。製程裝置11〇也包括設置 在反應室110中用以容納複數個堆疊在一起之基底的 晶圓匣135、用以上升與下降晶圓匣Π5之升降機(未圖示) 與用以從晶圓匣135移動基底1〇5至旋轉台115上之機械 手臂機構(未圖示）。而且，製程裝置110更包括一個用以將 10 -1298904 97-04-11 09514twD.doc/d 基底105固定在旋轉台115上之載具(未圖示）。製程裝置 100與其他習知的製程裝置可以用於執行本發明的方法。 請同時參照第1圖與第2圖，蝕刻沈積於基底1〇5上 之光阻層的方法係先將已經預先在表面形成一層光阻層之 基底105放置於反應室110中（步驟200)。然後，使用周知 的技術圖案化基底105表面之光阻層，使其具有設定之圖 案形狀。此光阻層之厚度例如是5〇00埃至15〇00埃左右之 範圍內。光阻層例如是任何型式之光阻或者光阻之組合， 其中光阻例如是正光阻、負光阻、深紫外光光阻等。對於 光阻而言，以具有碳鏈結構之光阻爲佳。當光阻層已經設 置在基底105上後，使用濕式蝕刻製程或乾式蝕刻製程蝕 刻基底105，然後再以下述之製程移除光阻層。 在步驟205時，經由複數個噴嘴125之其中的一個或 多個導入含氫離子反應性溶液至反應室110中，而使含氫 離子反應性溶液沈稹在基底105的光阻層上。導入反應室 110之含氫離子反應性溶液的流率例如是600 seem至3000 seem (標準立方公分/分鐘)左右。 使用或噴灑含氫離子反應性溶液處理光阻層表面之時 間例如是1〇秒至60秒左右。當在使用含氫離子反應性溶 液處理光阻層時，同時使旋轉台115上之基底105旋轉以 確保含氫離子反應性溶液塗層完全的或均一的覆蓋住光阻 層。當然也可以在使用含氫離子反應性溶液處理光阻層之 後，再使旋轉台115上之基底105旋轉以使含氫離子反應 性溶液均一的分佈於光阻層上。含氫離子反應性溶液例如 1298904 09514twD.doc/d 97-04-11 是包含氫離子，並包括一種以上之下列元素或化合物之流 體：氧、氧化氫、過氧化氫、硫、硫酸鹽、二氧化硫、三 氧化硫與硫酸。在本實施例中，含氫離子反應性溶液例如 是強化硫酸水溶液（Spike Sulfuric Acid Solution)。在其他實 施例中含氫離子反應性溶液例如是強化過氧化氫水溶液。 含氫離子反應性溶液也可以例如是強化硫酸水溶液與過氧 化氫之混和溶液(h2so4/h2o2)，其中強化硫酸水溶液與過氧 化氫之體積比例如是2 : 1至10 : 1左右。 含氫離子反應性溶液與至少一部份的光阻層反應，並 且改變光阻層之性質，而使得光阻層在後續的旋轉噴灑製 程(步驟215以後）中能夠有效的與臭氧化去離子水反應。尤 其是在本實施例中，含氫離子反應性溶液使光阻層中之碳 鏈由單鍵轉換成雙鍵。由於此種化學結構之改變使得光阻 層更容易且更快的與臭氧化去離子水反應，因此可以增加 光阻層之蝕刻速率。在使用含氫離子反應性溶液處理光阻 層之後，延遲30秒左右以使含氫離子反應性溶液與光阻層 產生反應，再應用去離子水處理基底（步驟210)。在本實施 例中，藉由使光阻與含氫離子反應性溶液反應之後，光阻 層之蝕刻速率可以增加至1000埃/分鐘至1300埃/分鐘左 右。因此，可以縮短基底105之製造週期時間，而且不需 要執行會產生很多缺陷之灰化製程。 此外，含氫離子反應性溶液也會使光阻層全部的或部 分的從晶圓上剝離。在後續的清洗製程進行之前，含氫離 子反應性溶液蝕刻光阻之速率是與含氫離子反應性溶液的 12 1298904 09514twG.doc/d 97-04-11 化學組成及含氫離子反應性溶液留在基底上之總時間有 關。在一實施例中，光阻層之蝕刻速率與含氫離子反應性 溶液留在光阻上之總時間成正比。在本實施例中，含氫離 子反應性溶液會使部分的光阻層從晶圓上剝離。 在步驟210時，經由複數個噴嘴125之其中的一個或 多個導入去離子水至反應室110中，而將去離子水應用於 或噴灑在基底105表面。去離子水以流率例如是125〇SCcm 至8000 seem (標準立方公分/分鐘）左右導入反應室11〇 中，以清洗基底1〇5。其中，清洗基底之時間例如是120 秒左右。在一實施例中，去離子水會留在光阻層表面一段 時間以便於進行後續的製程。此外，去離子水也會從基底 105表面洗去或移除含氫離子反應性溶液。去離子水之溫度 例如是20°c至95°c。 在步驟215時，經由複數個噴嘴1；25之其中的一個或 多個導入臭氧化去離子水至反應室110中，而應用臭氧化 去離子水處理光阻層以部分的或完全的移除（剝離）光阻 層。臭氧化去離子水以流率例如是3000sccm(標準立方公分 /分鐘)左右導入反應室110中，以處理光阻層1〇5。其中， 處理光阻層之時間例如是12〇秒至3000秒左右。臭氧化去 離子水包括60ppm至ll5ppm之臭氧。在—實施例中，溶 解在去離子水中之臭氧例如是60ppm左右。在本實施例 中，臭氧化去離子水之溫度例如是25°C (室溫）。 由於光阻層在先前的步驟中已經過含氫離子反應性溶 液處理’因此光阻層之移除速率(亦即，触刻速率)會增加。 13 1298904 〇9514twC.doc/d 97-04-11 具體而言，含氫離子反應性溶液會改變光阻層之化學特性 (例如：鍵結)及/或機械特性(例如：脫落），於是當應用臭氧 化去離子水處理光阻層時，臭氧化去離子水會與光阻層產 生較大的反應，結果使得光阻層之移除速率加快。在步驟 215中，臭氧會從臭氧化去離子水中逸散出來並幫助移除光 阻層。在一實施例中，可以縮小或省去步驟210，而直接使 用臭氧化去離子水洗去基底105表面上之含氫離子反應性 溶液。 在步驟220中，經由複數個噴嘴125之其中的一個或 多個導入熱去離子水至反應室110中，而使用熱去離子水 處理基底105表面以使基底105之溫度上升。在一實施例 中，基底105例如時上升至85°C。在本實施例中，熱去離 子水之溫度例如是80°C至95°C左右，並以流率例如是 3000sCCm(標準立方公分/分鐘)左右導入(噴灑）晶圓表面。其 中，導入(噴灑）晶圓表面之時間例如是1秒至3000秒左右。 進行導入熱去離子水之步驟（步驟220)可以增加反應。而 且，此步驟可以在導入臭氧化去離子水之步驟（步驟215)之 前、同時或導入臭氧化去離子水之步驟（步驟215)之後進 行。在本實施例中，熱去離子水是在導入臭氧化去離子水 之步驟(步驟215)之後或同時進行。 在步驟225中，使用製程裝置100測量光阻層是否已 經完全移除。量測光阻層是否完全移除之方法例如是反射 式測量法。如果光阻層還沒有完全移除，則重複開始本方 法之步驟205。然後，依序重複進行步驟205、步驟210、 14 1298904 09514twf3.doc/d 97-04-11 步驟215、步驟220。任何習知此技藝者應可領會上述實施 例中之一個或多個步驟經過修改、省略或重複仍然是屬於 本發明之精神與範疇內。此外，實施例中之上述步驟的重 新排列亦屬於本發明之精神與範疇內。本發明之方法可以 使用於從基底的半導體層或金屬內連線層上移除光阻層。 當光阻層已經完全移除，則繼續進行步驟230。 在步驟23〇中，經由複數個噴嘴125之其中的一個或 多個導入去離子水至反應室110中，而使用去離子水處理 基底105表面。以去離子水處理基底1()5表面可以清洗基 底105並移除在蝕刻製程中所留下之殘留粒子。在步驟235 中’舉例來說，藉由使旋轉台115旋轉而對基底1〇5進行 乾燥製程。在一個實例中，旋轉台115例如是以500rpm之 轉速旋轉480秒左右。 雖然本發明已以一較佳實施例揭露如上，然其並非用 以限定本發明。對任何熟習此技藝者而言，根據上述之內 容，而在彼此不互相矛盾之情況下，當可對上述實施例作 各種之更動與潤飾。例如含氫離子反應性溶液可以包括很 多種之兀素或化合物，但其仍然不脫離本發明之精神和範 圍內。此外，習知技藝者根據在此所揭露之內容，所做的 其他組合、刪除、取代和修改等都是很明顯的，因此本發 明之保護範圍當視後附之申請專利範圍所界定者爲準。BACKGROUND OF THE INVENTION 1. Field of the Invention This invention relates to a semiconductor process, and more particularly to a method of etching a photoresist layer deposited on a semiconductor substrate. BACKGROUND OF THE INVENTION Semiconductor devices are typically fabricated on a semiconductor substrate, such as a wafer, by repeating various processes. These various processes include the Layering process, the patterning/etching (10) coffee process, the Doping process, and the jjeat treatment process. The patterning/etching process is an important semiconductor process that involves removing material from the surface of the semiconductor substrate. That is, the step of patterning/etching includes at least forming a photoresist layer having a specific pattern on the surface of the semiconductor substrate, and then selectively etching or removing the material from the surface of the semiconductor substrate. In the etching process, the portion of the semiconductor substrate covered with the photoresist layer is protected, and the portion of the semiconductor substrate not covered with the photoresist layer is etched to a set degree in accordance with the pattern and time of the etching process. Thus, the unprotected material in the particular pattern is removed from the surface of the semiconductor substrate. The two etching processes currently used in the industry include wet etching processes and dry etching processes. The wet saturation process utilizes a chemical etchant to treat the surface of the semiconductor substrate, reacting the chemical etchant with the unprotected material to form a water-soluble product comprising the unprotected material, which is then carried away by the solvent. . The dry etching process uses gas molecules and/or ions to treat the surface of the semiconductor substrate to react (chemically react) gas molecules and/or ions with the unprotected material or bombard the surface of the semiconductor substrate (physical 5. 1298904 09514twf3.doc /d Reaction) to remove unprotected material. Dry etching processes are often referred to as plasma feed processes. After the end of the etching process, an ashing process is usually required to remove the photoresist layer remaining on the surface of the semiconductor substrate. A conventional ashing process incorporates a gas such as oxygen and ionizes the gas to form a plasma. The plasma is treated as a chemical etchant or substance to treat the surface of the semiconductor substrate to remove the photoresist layer. Then, the photoresist layer is treated with an organic solvent or an inorganic solvent to break the structure of the photoresist layer and completely remove the residual photoresist layer. Since the underlying wires do not change, a wet etch process is performed after the conventional ashing process to remove the photoresist layer more effectively. However, one disadvantage of the ashing process is that many defects occur during the dry plasma processing process. Moreover, these defects cannot be removed in subsequent wet etching processes. In terms of environmental protection considerations, the industry currently uses ozonized deionized water to treat the photoresist layer to remove the photoresist layer. However, post-etch (Post-Etch) photoresist layer or low-dose implant (L〇w-Dose-Implant) deep ultraviolet light (Deep Ultraviolet) is treated with ozonized deionized water in a Sptay Spin Processor. When the DUV) type photoresist layer is used, the etching rate of the photoresist layer is 400 & /min I (A / min) to 600 angstrom / minute (A / min). Generally, the method of treating the photoresist layer by using deodorized deionized water is compared with the method of treating the photoresist layer by using an organic solvent in the current manufacturing process, and etching the photoresist layer by ozonized deionized water. The rate is quite low. There is thus a need for a method that increases the etch rate of a photoresist layer of a semiconductor substrate. SUMMARY OF THE INVENTION 6 ^ 1298904 97-04-11 09514twf3.doc/d In view of the above, the present invention provides a method of etching a photoresist layer deposited on a semiconductor substrate by using a hydrogen ion-containing reactive solution to treat the photoresist The layer is reacted with a hydrogen ion-reactive solution and a photoresist layer, and then the substrate is treated with deionized water, and then the substrate is treated with ozonized deionized water to remove at least a portion of the photoresist layer. The hydrogen ion-containing reactive solution contains only hydrogen ions and includes one or more of the following elements or compounds: oxygen, hydrogen peroxide, hydrogen peroxide, sulfur, sulfate, sulfur dioxide, sulfur trioxide, and sulfuric acid. The invention is characterized in that the photoresist layer removing process can be performed more effectively, that is, for example, when the photoresist layer after the etching or the low-dose ion implantation process is subjected to the wet etching stripping process, it is not required Ashing is done without reducing production capacity. The present invention further provides an etching process for providing a substrate on which a photoresist material has been formed, introducing a sulfuric acid solution into the reaction chamber to react the sulfuric acid solution with the photoresist material. The photoresist is then treated with ozonated deionized water to remove the photoresist. The sulfuric acid solution enters the reaction chamber by introduction or spraying, and the time for the sulfuric acid solution to enter the reaction chamber is about 10 seconds to 60 seconds. Ozonated deionized water includes at least 60 ppm of ozone. The present invention further provides a method of etching a photoresist layer deposited on a semiconductor substrate by spraying a hydrogen ion-containing reactive solution onto the substrate for about 10 seconds to 60 seconds to spray deionized water onto the substrate. The method further comprises spraying ozonated deionized water at a temperature of 25 ° C onto the substrate or into the reaction chamber. Then, hot deionized water having a temperature of about 80 ° C to 95 ° C is sprayed onto the substrate or supplied to the reaction chamber. Here, any feature described above may be seen from the above, the description and the well-known ones of the prior art, 1298904 97-04-11 09514twf3.doc/d, without any contradiction, any of the above features or Combinations of features are included within the scope of the invention. The content, the aspects, and the features of the present invention are disclosed herein. Furthermore, other advantages and features of the invention will be apparent from the appended claims and appended claims. The above and other objects, features, and advantages of the present invention will become more apparent and understood. The drawing shows a side view of a process device according to a preferred embodiment of the present invention; and FIG. 2 is a flow chart showing a method of etching a photoresist layer deposited on a semiconductor substrate in accordance with a preferred embodiment of the present invention. Description of the drawings: 100: Process device 105: Base 110: Reaction chamber 110a: Top u〇b: Bottom 115: Rotary table 12: Spray mechanism 125: Nozzle 130 · · Exit 8 1298904 09514twf3.doc/d 97- 04-11 135: Wafers 200, 205, 210, 215, 220, 225, 230, 235: Steps of Embodiment Hereinafter, preferred embodiments of the present invention will be described in detail with reference to the accompanying drawings. Where the same or similar reference numerals are used, the same or similar components are used in the attached drawings. Moreover, the illustrations are only schematic and not exact dimensions. In the following disclosure, for the purpose of convenience and clarity, the so-called directional terms such as top, bottom, left, right, up, down, above, above, below, below, behind, front, etc. are only Used to correspond to the attached illustration. These directional terms are not intended to limit the scope defined by the scope of the patent application. The disclosure of the present invention is intended to be representative of the preferred embodiments. Moreover, for the purpose of the following detailed description, although the preferred embodiments are merely explained, the various modifications, substitutions and changes made in accordance with the embodiments are still within the scope of the present invention, and therefore the scope of the present invention is attached to the application. The scope defined by the scope of the hand I] shall prevail. In addition, it must be understood and understood that the process steps and structures described in the examples do not include the entire manufacturing process for making the via structure. The method disclosed herein can be integrated with conventional integrated circuit fabrication techniques as are conventionally used, and many of the general process steps performed in the embodiments are merely provided to provide some of the necessary conditions for practicing the invention. In general, the present invention is applicable to the field of semiconductor devices and processes. Further, in the following, the present invention is described by way of an example of a related process device and a method of etching a photoresist layer on a semiconductor substrate. 9 1298904 09514twf3.doc/d 97-04-11 Referring to Figure 1, a side view of a process apparatus 100 in accordance with a preferred embodiment of the present invention is shown. The process device 100 can chemically or physically process the semiconductor substrate 105 quickly and uniformly. The process device 100 is, for example, a spray processor. In the present embodiment, the process unit 100 is, for example, an acid spray treatment device manufactured by FSI International. The process device 100 is composed of a liquid-sealed reaction chamber 110 having a top portion 110a and a bottom portion 110b, a rotating table 115 disposed at a bottom portion 〇b of the reaction chamber 110 for rotating the substrate 105, and a top portion 110a disposed on the reaction chamber 110. The spray mechanism 120 is configured to supply a fluid (gas or body) to at least one substrate 105~ surface. The fluid can be controlled to settle on the surface of the substrate 105 and/or the surface of the uniform processing substrate 105 by rotating the rotating table 115. Additionally, the rotary table 115 can also be used to spin dry the substrate 105. The spray mechanism 120 has a plurality of nozzles 125, each of which is connected to various reservoirs (not shown), and a plurality of nozzles are disposed in the reaction chamber 110 for spraying different fluids, such as nitrogen and hydrogen ions. The reactive solution, ozonated deionized water, deionized water to the surface of the substrate 1〇5. Thus, the substrate can be treated with different fluids simultaneously or continuously. In one embodiment, process unit 100 includes an outlet 13 that is coupled to an extraction element (not shown) for extracting elements for removal of fluid from reaction chamber 110. The process device 11A also includes a wafer cassette 135 disposed in the reaction chamber 110 for accommodating a plurality of stacked substrates, an elevator (not shown) for raising and lowering the wafer cassette 5, and a slave wafer The crucible 135 moves the substrate 1〇5 to a robot arm mechanism (not shown) on the rotary table 115. Moreover, the process unit 110 further includes a carrier (not shown) for securing the 10-1298904 97-04-11 09514 twD.doc/d substrate 105 to the rotating stage 115. Process device 100 and other conventional process devices can be used to perform the methods of the present invention. Referring to FIG. 1 and FIG. 2 simultaneously, the method of etching the photoresist layer deposited on the substrate 1 〇 5 is to first place the substrate 105 which has previously formed a photoresist layer on the surface in the reaction chamber 110 (step 200). . The photoresist layer on the surface of substrate 105 is then patterned using well-known techniques to have a patterned pattern. The thickness of the photoresist layer is, for example, in the range of from about 50,000 angstroms to about 15 angstroms. The photoresist layer is, for example, any type of photoresist or combination of photoresists, wherein the photoresist is, for example, a positive photoresist, a negative photoresist, a deep ultraviolet photoresist, or the like. For the photoresist, a photoresist having a carbon chain structure is preferred. After the photoresist layer has been disposed on the substrate 105, the substrate 105 is etched using a wet etching process or a dry etching process, and then the photoresist layer is removed by the following process. At step 205, the hydrogen ion-containing reactive solution is introduced into the reaction chamber 110 via one or more of the plurality of nozzles 125, and the hydrogen-containing ion-reactive solution is deposited on the photoresist layer of the substrate 105. The flow rate of the hydrogen ion-containing reactive solution introduced into the reaction chamber 110 is, for example, about 600 seem to 3000 seem (standard cubic centimeters per minute). The time for treating the surface of the photoresist layer using or spraying a hydrogen ion-containing reactive solution is, for example, about 1 second to 60 seconds. When the photoresist layer is treated with a hydrogen ion-containing reactive solution, the substrate 105 on the rotating stage 115 is simultaneously rotated to ensure that the hydrogen ion-containing reactive solution coating completely or uniformly covers the photoresist layer. It is of course also possible to rotate the substrate 105 on the rotating stage 115 after the photoresist layer is treated with the hydrogen ion-containing reactive solution to uniformly distribute the hydrogen-containing reactive solution on the photoresist layer. A hydrogen ion-containing reactive solution such as 1298904 09514 twD.doc/d 97-04-11 is a fluid comprising hydrogen ions and comprising more than one of the following elements or compounds: oxygen, hydrogen peroxide, hydrogen peroxide, sulfur, sulfate, sulfur dioxide. , sulfur trioxide and sulfuric acid. In the present embodiment, the hydrogen ion-containing reactive solution is, for example, a sulphuric acid solution (Spike Sulfuric Acid Solution). In other embodiments, the hydrogen ion-containing reactive solution is, for example, a fortified aqueous hydrogen peroxide solution. The hydrogen ion-containing reactive solution may also be, for example, a mixed solution of an aqueous solution of sulfuric acid and hydrogen peroxide (h2so4/h2o2), wherein the volume ratio of the aqueous sulfuric acid solution to the hydrogen peroxide is, for example, about 2:1 to 10:1. The hydrogen ion-containing reactive solution reacts with at least a portion of the photoresist layer and changes the properties of the photoresist layer, so that the photoresist layer can be effectively deionized and deionized in a subsequent spin-spraying process (after step 215) Water reaction. Particularly in the present embodiment, the hydrogen ion-containing reactive solution converts the carbon chain in the photoresist layer from a single bond to a double bond. Since the change in the chemical structure makes the photoresist layer easier and faster to react with the ozonated deionized water, the etching rate of the photoresist layer can be increased. After treating the photoresist layer with the hydrogen ion-containing reactive solution, the reaction is delayed by about 30 seconds to react the hydrogen-containing ion-reactive solution with the photoresist layer, and the substrate is treated with deionized water (step 210). In this embodiment, the etching rate of the photoresist layer can be increased to about 1000 Å/min to 1300 Å/min by reacting the photoresist with the hydrogen ion-containing reactive solution. Therefore, the manufacturing cycle time of the substrate 105 can be shortened, and the ashing process which causes many defects is not required to be performed. In addition, the hydrogen ion-containing reactive solution also strips all or part of the photoresist layer from the wafer. Before the subsequent cleaning process, the rate of etching the photoresist with the hydrogen ion-reactive solution is 12 1298904 09514 twG.doc/d 97-04-11 chemical composition and hydrogen ion-reactive solution remaining with the hydrogen ion-containing reactive solution. It is related to the total time on the substrate. In one embodiment, the etch rate of the photoresist layer is proportional to the total time that the hydrogen ion-containing reactive solution remains on the photoresist. In this embodiment, the hydrogen-containing ion reactive solution causes a portion of the photoresist layer to be stripped from the wafer. At step 210, deionized water is introduced into the reaction chamber 110 via one or more of a plurality of nozzles 125, and deionized water is applied or sprayed onto the surface of the substrate 105. The deionized water is introduced into the reaction chamber 11A at a flow rate of, for example, 125 〇SCcm to 8000 seem (standard cubic centimeters/minute) to clean the substrate 1〇5. Among them, the time for cleaning the substrate is, for example, about 120 seconds. In one embodiment, the deionized water will remain on the surface of the photoresist layer for a period of time to facilitate subsequent processing. In addition, deionized water also washes away or removes the hydrogen ion-containing reactive solution from the surface of the substrate 105. The temperature of the deionized water is, for example, 20 ° C to 95 ° C. At step 215, ozonated deionized water is introduced into the reaction chamber 110 via one or more of the plurality of nozzles 1; 25, and the photoresist layer is treated with ozonized deionized water for partial or complete removal. (Peeling) the photoresist layer. The ozonated deionized water is introduced into the reaction chamber 110 at a flow rate of, for example, 3000 sccm (standard cubic centimeters per minute) to treat the photoresist layer 1〇5. The time for processing the photoresist layer is, for example, about 12 sec to 3,000 sec. Ozonated deionized water includes from 60 ppm to ll5 ppm of ozone. In the embodiment, the ozone dissolved in the deionized water is, for example, about 60 ppm. In the present embodiment, the temperature of the ozonated deionized water is, for example, 25 ° C (room temperature). Since the photoresist layer has been subjected to hydrogen ion-reactive solution treatment in the previous step, the removal rate of the photoresist layer (i.e., the etch rate) may increase. 13 1298904 〇9514twC.doc/d 97-04-11 Specifically, a hydrogen ion-containing reactive solution changes the chemical properties (eg, bonding) and/or mechanical properties (eg, shedding) of the photoresist layer, so When the photoresist layer is treated with ozonized deionized water, the ozonated deionized water will react with the photoresist layer to a large extent, and as a result, the removal rate of the photoresist layer is accelerated. In step 215, ozone will escape from the ozonated deionized water and help remove the photoresist layer. In one embodiment, step 210 can be reduced or omitted, and the hydrogen ion-containing reactive solution on the surface of substrate 105 can be washed directly with ozonated deionized water. In step 220, hot deionized water is introduced into the reaction chamber 110 via one or more of a plurality of nozzles 125, and the surface of the substrate 105 is treated with hot deionized water to raise the temperature of the substrate 105. In one embodiment, substrate 105 rises to 85 ° C, for example. In the present embodiment, the temperature of the thermally deionized water is, for example, about 80 ° C to 95 ° C, and is introduced (sprayed) onto the surface of the wafer at a flow rate of, for example, 3000 sCCm (standard cubic centimeters per minute). Among them, the time for introducing (spraying) the surface of the wafer is, for example, about 1 second to 3000 seconds. The step of introducing hot deionized water (step 220) can increase the reaction. Moreover, this step can be carried out before the step of introducing ozonated deionized water (step 215), simultaneously or after the step of introducing ozonized deionized water (step 215). In this embodiment, the hot deionized water is carried out after or simultaneously with the step of introducing ozonated deionized water (step 215). In step 225, process unit 100 is used to measure whether the photoresist layer has been completely removed. A method of measuring whether the photoresist layer is completely removed is, for example, a reflective measurement method. If the photoresist layer has not been completely removed, then step 205 of the method is repeated. Then, step 205, step 210, 14 1298904 09514twf3.doc/d 97-04-11 step 215, step 220 are repeated in sequence. Any person skilled in the art should appreciate that one or more of the above-described embodiments may be modified, omitted or repeated within the spirit and scope of the present invention. Further, the re-arrangement of the above steps in the embodiments is also within the spirit and scope of the present invention. The method of the present invention can be used to remove a photoresist layer from a semiconductor layer or a metal interconnect layer of a substrate. When the photoresist layer has been completely removed, proceed to step 230. In step 23, the deionized water is introduced into the reaction chamber 110 via one or more of the plurality of nozzles 125, and the surface of the substrate 105 is treated with deionized water. Treating the surface of the substrate 1 () 5 with deionized water can clean the substrate 105 and remove residual particles left in the etching process. In step 235, for example, the substrate 1〇5 is subjected to a drying process by rotating the rotary table 115. In one example, the rotary table 115 is rotated, for example, at a speed of 500 rpm for about 480 seconds. Although the invention has been described above in terms of a preferred embodiment, it is not intended to limit the invention. For those skilled in the art, various modifications and refinements can be made to the above-described embodiments in light of the above, without contradicting each other. For example, a hydrogen ion-containing reactive solution can include a wide variety of halogens or compounds, but still does not depart from the spirit and scope of the present invention. In addition, other combinations, deletions, substitutions, and modifications of the present invention will be apparent to those skilled in the art, and the scope of the present invention is defined by the scope of the appended claims. quasi.