476986 A7 ___B7 五、發明説明（i ) 發明之領域 (請先閱讀背面之注意事項再填寫本頁) 本發明係關於淸潔陶瓷物件的方法。更特別是，本發 明乃關於由用於製造半導體器件之陶瓷物件移除粒子雜質 及化學雜質的方法。 發明之背景 半導體器件之製造，典型上需要使矽晶圓之表面受高 溫處理，例如擴散、氧化及澱積。在澱積作業中，介電材 料，例如多晶矽、氮化矽及二氧化矽乃澱積在矽晶圓之表 面上。在擴散作業中，材料乃經擴散而進入矽晶圓本體內 。在氧化作業.中，矽晶圓之表面被氧化而形成二氧化矽層 。此等作業之各作業典型上涉及把待處理之矽晶圓放置於 •一夾持器，還常稱爲''晶舟〃內。此晶舟典型上係由一陶 瓷材料所形成，且被建構成在一平行或垂直之定向內挾持 晶圓。一旦被裝載待處理之晶圓，晶舟乃被放置一電熱爐 或處理管內，然後將管內之環境改變以提供多式多樣之圍 氛，其溫度典型上介於由2 5 0°C至1 2 0 0 °C。 經濟部智慧財產局員工消費合作社印製 另一'共问之半導體作秦乃爲餓刻。俟光飽刻圖案殿積 在矽晶圓之表面上後，矽晶圓乃被載入一蝕刻器內。該蝕 刻器，其組件，典型上係製自陶瓷材料者，使用電漿蝕刻 技術以移除澱積在未受光蝕刻圖案保護之矽晶圓表面上的 材料。典型之蝕刻方法乃由矽晶圓表面移除氧化物，金屬 及/或聚合物。 雖然前述之各方法成功地把矽晶的表面發展成一有用 ^紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐) -4- 476986 A7 B7 五、發明説明（2 ) (請先閱讀背面之注意事項再填寫本頁) 之產物，但此方法終究會污染支承裝備之表面。舉例來說 ，在澱積作業期間，氮化物澱積法會把氮化矽塗覆層（澱 積層）遺留在晶圓上，亦遺留在支承晶圓之晶舟的表面上 。當該塗覆層變得太厚時，該塗覆層易於成片剝落，而以 粒子方式污染晶圓近傍。 在蝕刻方法中，由在製之晶圓上，審慎的移除各式各 樣材料層的結果會造成污染性粒子，例如待被澱積至蝕刻 器組件之表面上的二氧化矽、氮化物，以及氧化鋁。因爲 污染物會不利地影響待被此等組件處理之未來晶圓的處理 作業，污染法粒子必須由這些組件之表面上小心地予以淸 除。而於矽晶圓之遞減的線寬度，由這些組件之表面移除 亞微米尺寸的粒子（更特別是，具有不超過0 . 7微米寬 度之亞微米粒子）變得日益重要。 經濟部智慧財產局員工消費合作社印製 幾種用於淸潔已用過之晶舟的方法在先前技藝內乃爲 人所知。在一方法中，被一種澱積材料，例如氮化矽、多 晶矽或二氧化矽所塗覆之一已用過的組件乃遭受一種二步 驟式淸潔法，依此方法，先於類似於噴沙方法，使組件曝 露於硬九粒流，例如碳化矽九粒流中，再曝露於冷凍之二 氧化碳（C〇2 )九粒流中。另一步驟，稱之爲初步淸潔者 ，成功地由組件表面上脫去澱積之材料，同時遺留尺寸爲 微米級之碎片粒子，在第二步驟中，稱之爲主要淸潔者， C〇2九粒咸信造成微米級尺寸之碎片粒子冷凍，由而變得 易碎而破裂，進而使得破裂之粒子容易由表面被沖洗掉。 初步淸潔一般係藉將玻璃、氧化鋁、碳化矽、氧化駄 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） -5- 476986 A7 B7 五、發明説明（3 ) 、核桃殼粒子，或其他珠粒撞擊或 ''噴擊（blast ) 〃受淸 潔之部件而達成。典型上，珠粒乃被承載在空氣或其他氣 體之增壓流內。珠粒可爲球狀，或任何其他所需之形狀及 尺寸。一種慣用之珠粒材料爲9 8 %黑S i C細砂，珠粒 被引導至表面時之壓力乃取決於正在被淸潔之部件的組成 。當一種陶瓷部件待要被淸潔時，典型上該珠粒係於一氣 體內，以約2 0 — 3 5 p s 範圍內之壓力被施用。一旦 完全珠粒噴擊（即初步淸潔）後，緊接著即進行C 0 2淸潔 處理。C 0 2淸潔處理已被敘述於專利文獻內。見例如， U.S.Patent No.4,707,951, entitled Installation for the Projection of Particles of Dry Ice” ，and U. S. Patent No. 6，〇04,400， entitled 、、 Carbon Dioxide Cleaning Process ° 在淸潔被澱積層塗覆之已用過的晶舟的另一方法中， 製造業者推薦使用過之晶舟受一酸處理，宜使用一種強酸 例如H F，將之施以烘焙.。該H F處理會移除材料之澱積 層。 未於使用之半導體處理裝備的淸潔亦爲該領域內之一 眾所關心的議題。然而，就一未經使用的部件而言，該關 心之議題典型上爲金屬性污染，而非粒子性污染。在製造 S 1 C擴散組件之一傳統方法中，未經使用之S i C擴散 組件乃受一種弱酸之處理，然後再受烘焙。此方法之功用 在於由正受淸潔之部件中移除某些金屬性污染物及指紋。 在確保未經使用過之組件的淸潔的另一傳統方法中， 於將組件安置於一爐內以前，使組件受一種強酸之處理。 本紙張尺度適用中國國家標準（CNS ) A4規格（21〇Χ：297公釐） (請先閲讀背面之注意事項再填寫本頁)476986 A7 ___B7 V. Description of Invention (i) Field of Invention (Please read the precautions on the back before filling out this page) The present invention relates to the method of cleaning ceramic objects. More specifically, the present invention relates to a method for removing particulate impurities and chemical impurities from a ceramic article used for manufacturing a semiconductor device. BACKGROUND OF THE INVENTION The manufacture of semiconductor devices typically requires the surface of a silicon wafer to be subjected to high temperature processing, such as diffusion, oxidation, and deposition. During the deposition operation, dielectric materials such as polycrystalline silicon, silicon nitride, and silicon dioxide are deposited on the surface of a silicon wafer. In the diffusion operation, materials enter the silicon wafer body through diffusion. In the oxidation operation, the surface of the silicon wafer is oxidized to form a silicon dioxide layer. Each of these operations typically involves placing the silicon wafer to be processed in a holder, also often referred to as a `` crystal boat ''. The wafer boat is typically formed of a ceramic material and is constructed to hold wafers in a parallel or vertical orientation. Once the wafers to be processed are loaded, the wafer boat is placed in an electric furnace or processing tube, and then the environment in the tube is changed to provide a variety of atmospheres, the temperature of which is typically between 25 ° C To 1 2 0 0 ° C. Printed by the Consumer Cooperative of Intellectual Property Bureau of the Ministry of Economic Affairs. After the light-filled pattern is deposited on the surface of the silicon wafer, the silicon wafer is loaded into an etcher. The etcher, whose components are typically made of ceramic material, uses a plasma etching technique to remove material deposited on the surface of a silicon wafer that is not protected by a photo-etched pattern. A typical etching method is to remove oxides, metals and / or polymers from the surface of a silicon wafer. Although the foregoing methods have successfully developed the surface of the silicon crystal into a useful ^ paper size applicable to the Chinese National Standard (CNS) A4 specification (210X297 mm) -4- 476986 A7 B7 V. Description of the invention (2) (Please read the back first (Please fill in this page again), but this method will eventually pollute the surface of the supporting equipment. For example, during the deposition operation, the nitride deposition method leaves a silicon nitride coating (deposited layer) on the wafer and also on the surface of the wafer boat that supports the wafer. When the coating layer becomes too thick, the coating layer is liable to peel off in pieces, and the vicinity of the wafer is contaminated by particles. In the etching method, contamination particles such as silicon dioxide and nitride to be deposited on the surface of an etcher component can be caused by the deliberate removal of various layers of material on a fabricated wafer. , And alumina. Because contaminants can adversely affect the processing of future wafers to be processed by these components, contamination particles must be carefully removed from the surface of these components. With the decreasing line width of silicon wafers, it is becoming increasingly important to remove sub-micron-sized particles (more particularly, sub-micron particles having a width of no more than 0.7 microns) from the surface of these components. Printed by the Consumers' Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs Several methods used by Ji Jie have been used in the boat. In one method, a used component coated with a deposition material, such as silicon nitride, polycrystalline silicon, or silicon dioxide, is subjected to a two-step cleaning process. The sand method exposes the module to a hard nine-grain stream, such as a silicon carbide nine-grain stream, and then to a frozen carbon dioxide (C02) nine-grain stream. The other step, called the preliminary cleaner, successfully removes the deposited material from the surface of the component, while leaving micron-sized debris particles. In the second step, it is called the main cleaner, C 〇2 Nine grains of salt cause micron-sized debris particles to freeze, thereby becoming brittle and broken, which in turn makes the broken particles easily washed away from the surface. The preliminary cleaning is generally based on the use of glass, aluminum oxide, silicon carbide, and silicon oxide. The paper size applies the Chinese National Standard (CNS) A4 specification (210X297 mm) -5- 476986 A7 B7 5. Description of the invention (3), walnut shell particles , Or other beads hit or blasted by the cleaned parts. Typically, the beads are carried in a pressurized stream of air or other gas. Beads can be spherical or any other desired shape and size. A commonly used bead material is 98% black Si C fine sand. The pressure at which the beads are guided to the surface depends on the composition of the parts being cleaned. When a ceramic component is to be cleaned, the beads are typically tied to a gas and applied at a pressure in the range of about 20 to 35 ps. Once the beads are completely sprayed (ie, preliminary cleaning), the C 0 2 cleaning process is immediately followed. The C 0 2 cleaning process has been described in the patent literature. See, for example, US Patent No. 4,707,951, entitled Installation for the Projection of Particles of Dry Ice ", and US Patent No. 6,00,400, entitled, Carbon Dioxide Cleaning Process ° In another method of used wafer boat, the manufacturer recommends that the used wafer boat be treated with an acid, and a strong acid such as HF should be used for baking. The HF treatment will remove the deposited layer of the material. The cleanliness of the semiconductor processing equipment used is also a topic of concern in this field. However, for an unused component, the topic of concern is typically metallic pollution, not particulate pollution. In one traditional method of manufacturing S 1 C diffusion components, unused S i C diffusion components are treated with a weak acid and then baked. The function of this method is to remove a certain part from the cleaned part Metal contaminants and fingerprints. In another conventional method of ensuring the cleanliness of unused components, the components are exposed to a strong acid before they are placed in a furnace. Handle. This paper size is in accordance with Chinese National Standard (CNS) A4 specification (21〇 ×: 297mm) (Please read the precautions on the back before filling this page)
、1T 經濟部智慧財產局員工消費合作社印製 -6- 476986 Α7 Β7 五、發明説明（4) (請先閲讀背面之注意事項再填寫本頁) 類似地，熱H C 1淸潔曾被使用在半導體擴散組件上。舉 例來說，在 UK Patent Application No. GB 2,130,192 中， 硏討者揭示下述之一種製造步驟：於使用在一半導體爐內 之前，使未經使用之S 1 C組件受一種熱H C 1處理。 在某些場合中，H F處理本身曾被認爲足以淸潔未經 使用之晶舟（以減少金屬污染）以及已用過之晶舟（以化 學方式剝去於半導體加工處理期間澱積之塗層）。雖然如 此，單獨使用H F並不能移除於此類處理後仍可能存在之 成問題的粒子狀碎片。 綜上所言，提供淸潔之未經使用的半導體組件的傳統 方法涉及以酸進行淸潔以移除金屬性污染，而淸潔已用過 之組件的待流方法到涉及i )先行珠粒噴擊，緊接著行 C〇2淸潔以移除少量碎片粒子之機械剝去澱積之塗層的二 步驟方法，或ϋ )熱強酸淸潔以移除由澱積之材料所造成 的塗層。 . 發明之梗槪 經濟部智慧財產局員工涓費合作社印製 半導體器件之製造需要使用帶高度表面純度水平的加 工組件，而不論這些組件爲新穎者或該重新調理者。在某 些工作內，例如在處理期間用於定位及維持半導體晶圓之 陶瓷晶舟內，晶圓制動槽之長深度及狹間距乃界定晶舟之 幾何形狀，該幾何形狀帶一被劃定輪廓之表面，該表面之 縱橫地會防止珠子噴擊足夠地除去來自這些槽之較深部份 的塗覆物。特別是，大於約4 : 1之繼續比（即槽深度對 本紙張尺度適用中國國家標準（CNS ) Α4規格（21〇Χ297公釐） 476986 A7 ______B7__ 五、發明説明（5 ) (請先閲讀背面之注意事項再填寫本頁) 槽寬度之比）典型上超出待流之淸潔方法的能力。本發明 乃藉由提供一種製程來呈獻克服該及其他缺點的方法，在 該製程中，半導體製造組件之無機表面乃先後受化學淸除 及C ◦ 2淸潔作業所淸潔。在一體現中，化學淸除係藉用一 種含強酸的溶劑來達成。在一更安定的體現中，化學淸除 係藉用一種含至少1 V / 〇之一種選自下列群體之酸來達 成：H F，具有p K a小於約1之酸，及其混合物。如本 文所用者，'' v / 〇 〃一詞係代表容量百分比，而''強酸 〃則代表具有至少1 v / 〇之酸的一溶液，該酸之p K a 小於約1者。 C〇2淸潔步驟乃應用乾冰之粒子，它們被投射至正被 淸潔之表面上。化學淸潔及C 0 2淸潔步驟的組合已被發現 能成功地由工件之表面移除粒狀及金屬污染物。 經濟部智慧財產局員工消費合作社印製 使用本發明方法而受淸潔之工件業已發現其表面上粒 子尺寸大於約0 · 3 // m者之污染物粒子密度不超過約 〇· 4粒子，且宜不超過約0 · 2粒子/每平方公分，此 類工件業已被發現其表面金屬性污染物濃度不超過約 6〇〇p p m (係藉由S I M S法，.將約1 〇 n m深度處 上測量）。於應用本發明淸潔方法於處理典型之工件後， 測得知在表面金屬性污染中，不多於約4 〇 〇 p p m金屬 性污染物（鹼金屬及鹼土金屬乃除外）及不多於約2 2 5 p p m餓（二者係依S I M S法，於約1 〇 ΙΊ m深處測得 )仍存留。 本發明之一方法乃依據下列之認知··於H F處理後， 本紙張尺度適用中國國家標準（CNS ) Α4規格（210Χ297公釐） --— - 8- 476986 Α7 Β7 五、發明説明（6) (請先閱讀背面之注意事項再填寫本頁) 造成問題之碎片粒子仍會存在，C〇2淸潔步驟固然會移除 粒狀污染物，但不能移除非粒子狀表面金屬污染物。迄今 ，相關之技藝仍未有任何有關本發明之建議，即，採用 HF處理來移除表面金屬，接著，藉由C〇2淸潔步驟來移 除任何存留之碎片粒子。C〇2淸潔步驟及H F處理二者之 組合的特異性乃在於：傳統上C〇2淸潔步驟僅於一用過之 工件遭受會產生碎片粒子之機械法淸除後才被使用。 本發明亦關於工件，例如應用於半導體加工處理中之 陶瓷舟，它已藉由使用本發明之方法而予以淸潔者。生成 之工件的特異性乃在於其金屬性及粒子狀表面污染之水平 遠低於可用內行人士所知之方法而先前可獲得的工件的表 面污染水平。 發明之詳述 經濟部智慧財產局8工消費合作社印製 本發明提供一種用於供應陶瓷工件的方法，此類工件 乃例如應用於半導體製造之陶瓷晶舟，其金屬性及粒子狀 表面污染的水平低於先前可獲得者。詳言之，雖然使用酸 淸潔爲此藝人士所知，且雖然綜合使用珠子噴擊及C〇2淸 潔亦爲此藝所知，但迄今，在此藝尙未有如下之建議：將 一酸淸潔步驟與C〇2淸潔步驟組合來淸潔未經使用或已使 用過之塗覆的陶瓷工件。酸淸潔步驟可與C 0 2淸潔步驟組 合之認知乃產生一種適合用於淸潔來用過或已用過之塗覆 工件的淸潔方法。 如前所述，使用本發明方法之結果乃提供具有下列性 本紙張尺度適用中國國家標準（CNS ) Α4規格（210X297公釐） -9- 476986 A7 ___B7_ 五、發明説明（7 ) (請先閱讀背面之注意事項再填寫本頁) 質之工件：此工件之表面上微子尺寸大於約0 · 3 // m者 之污染物密度不超過約0.4粒子/每平方公分，且其表 面金屬污染物濃度不超過約6 0 0 p P m (依S I M S法 ，於約1 0 n m深度測得）。 傳統上，當使用者由製造者接收到一未用過陶瓷晶舟 時，會使工件接受淸潔作業，俾移除於製造，包裝，裝運 期間澱積在工件表面上之任何金屬污染物。在某些場合中 ，已用過之塗覆工件可藉由化學淸潔步驟，使用一強酸而 加以淸潔。如同淸洗未用過之工件者，酸淸潔步驟乃提供 一種令人滿意的手段以供由工件之表面移除金屬性污染物 〇 經濟部智慧財產局員工涓費合作社印製 雖然酸淸潔作業所提供之表面，其金屬性污染物降低 到令人滿意的水平，此步驟卻未能提供粒子狀污染到達足 夠低水平之表面。事實上，某些能證實化學淸除步驟確實 促成粒子狀污染的證據已存在。吾人固然不希望受囿於任 何特別之理論，但在淸潔工件，例如用過之陶瓷舟內，藉 由使用H F，以化學方式淸除塗層而得之被淸潔的工件仍 有高水平之粒子狀污染，蓋因淸除作業會遺留粒子狀污染 物於陶瓷表面上。 又，粒子狀污染並非單獨起因於化學淸除步驟以及後 加工步驟。更正確地說，在未用過之工件的場合中，吾人 咸信：用機器製造組件，例如S 1 C晶舟的結果，會產生 澱積在組件之表面上的粒子。當然，粒子亦可能澱積在未 用過之組件上，蓋因此類組件暴露於不淸淨之屋環境之故 本紙張尺度適用中國國家標準（CNS ) Α4規格（210X 297公釐） -10- 476986 經濟部智慧財產局員工消費合作社印製 A7 B7 五、發明説明（8) 。必須提及的是：在未用過或已用過之組件，以及先處理 ，處理或後一處理步驟之場合中，粒子之形成在工件上的 許多機制可能存在，而本發明是不企求受限於任何特別之 粒子形成或澱積機制。 如前所提及，c 〇 2淸潔步驟傳統上業已與初步淸潔步 驟，例如珠粒噴擊組合使用。珠粒噴擊與C 0 2淸潔步驟之 組合通常來當應用在未用過的工件，但已被應用在已用過 之工件上，該工件在半導體處理期間，帶有C V D塗層》 積在其表面上，雖然該方法已被發現在移除粒子狀污染物 上令人滿意，但它卻缺乏對發生在未用過及已用過之工件 上之金屬性污染物的能力。 本發明乃認知到：在身爲未用過之組件或被化學方式 淸除之組份的工件受到最終之C〇2淸潔歩驟以前，需要由 組件之表面被移除之問題性亞微米粒子仍然存在。移除此 類粒子狀污染物之需要以及達成此類移除之方式既未被察 知亦未被執行於傳統之方法中。 再者，當與藉由淸潔方法（該方法係使C〇2淸潔已用 過之有塗層的工件）而被處理二修正產物作比較時，由本 發明方法獲致之產物，顯出較優之金屬純度水平。如前所 提及者，傳統方法係以機械方式，由一用過之組件，例如 晶舟，經由珠粒噴擊，淸除塗層，然後使用C〇2淸潔作業 來完全淸潔步驟。固然不希望受囿於任何特別之理論，但 在用過之晶舟的場合中，傳統之瞭解是：表面之金屬性污 染並不是一個問題。相反地，即使表面之金屬性污染引起 本紙張尺度適用中國國家標準（CNS ) A4規格（210 X 297公釐） (請先閲讀背面之注意事項再填寫本頁) 、11 -11 - 476986 A7 ____B7 五、發明説明（9 ) 問題，將此類問題假定可藉由應用先前技藝.中已知之技術 即能充分地加以消除是錯誤的。 (請先閱讀背面之注意事項再填寫本頁) 相較之下，雖然證據建議珠粒噴擊步驟確實有在工件 之表面處增加金屬性雜質之濃度的作用。該非所欲之效果 可能爲使用不純淨之噴擊介質的結果。 本發明之方法優於傳統之珠粒噴擊/ C〇2淸潔作業之 處乃在於它不會導致被消除之工件表面的金屬性污染。事 實上，本發明方法具有減少表面處之金屬濃度的作用力。 同樣地，對未用過之工件，例如未用過之s 1 C晶舟 而言，表面金屬雜質之一般認知是這樣的：H F或熱 H C 1淸潔作業僅能提供臨界之實用性，蓋因其功用只能 逐漸地減少在組件之表面處的金屬濃度至稍微低於形成工 件之主體材料表面的金屬濃度水平（對S i C而言金屬濃 度爲1 一 1 0 p p m )，以及對主體材料佔有之該相對純 度優勢將隨著時間而消失，，蓋因於高溫環境下，隨後之使 用會促進主體金屬擴散進入組份之表面區域內。因此，該 技藝並未於所有之情況中要求進行H F淸潔作業。 經濟部智慧財產局8工消費合作社印製 代表未用過之S i C組件的材料，其表面業已藉由一 傳統方法（X -射線光電光譜分析法，簡稱X P S )以及 另一方法（繼發性離子質量光譜分析法，簡稱S I M S ) 予以分析。傳統之X P S分析乃在大約3 n m深度處提供 資料，且具有約0 . 1 - 1 · 0 %敏感應度，該敏感度範 圍乃取決於有關聯之元素。相對地，S I M S分析乃在約 1〇n m深度處提供資料，且具有約〇 . 2 — 3 · 〇 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） -12- 476986 A7 _____B7 五、發明説明（1〇) (請先閱讀背面之注意事項再填寫本頁) P P m敏感度。爲於此理由，S I M S試驗提供一更正確 之方法於測量半導體處理組件內之金屬表面濃度。業已發 現：在X P S未能偵測任何金屬（且因此未能提供上升之 表面金屬濃度的特徵）的場合中，S I M S試驗在1〇 n m深度處報導大約2 0 0 0 p p m金屬存在。在高溫半 導體加工之領域中，這些表面濃度水平顯然屬不理想者。 因此，S I M S分析之結果證實未用過之陶瓷組件之表面 需要，宜用一種化學淸除步驟予以淸潔，以減少存在·於半 導體處理組件表面處之金屬性污染物的高表面水平。必須 瞭解的是，在本發明之一體現中，表面爲一CVD表面， 它業已隨意受機械製造或其他後處理步驟。 經濟部智慧財產局員工消費合作社印製 詳言之，必須瞭解的是：本發明之方法係企圖被應用 於多種無機表面，此等無機表面係被半導體處理組件所採 用者。此類表面典型上包含陶瓷材料，例如，通常被用於 半導體製造之陶瓷表面，然而，該方法可應用於非陶瓷表 面，例如矽及鑽石。如此，討論之重點固然主要在於半導 體加工組件，例如陶瓷晶舟，以及特別是由S i C所形成 之組件，但必須瞭解的是：本發明並非企求受限於此方式 。正確的說，本發明乃企求適用任何具有與半導體晶圓加 工技術有關聯之無機表面的半導體加工組件。這些表面包 括，但不限於矽（S i )，碳化矽（S i C )，氮化矽（ S i 3 N 4 )，鑽石，氧化釔，氧化鉻（Z r〇2 )，氮化 鋁（A 1 N )，氧化鋁（A 1 2〇3 ),石墨以及多晶形成 熔凝石英。 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） - 13- 476986 A 7 B7 五、發明説明（μ) (請先閱讀背面之注意事項再填寫本頁) 表面可藉由蒸氣-澱積而形成，且如前所討論，可用 C V D技術予以澱積而形成。此類表面包括，但不限於多 晶形成其他 CVD Si., C V D SiC，CVD S 1 〇 2 , CVD Si3N4以及CVD鑽石表面。當然 ，必須瞭解的是：本發明固然可應用於帶有塗層在上之表 面，本發明方法亦可應用於未帶有塗層之無機表面上。 在論及S i C工件時，幾種工件乃被應用於此領域內 。在一體現中，簡單由S i C形成之工件乃被使用。在另 一體現中，工件乃包含孔隙度減少之S i C ,它係藉由使 S 1 C結構之孔隙裝載S i而形成。由於S i易於由孔隙 逃出，此類工件往往被設置以C V D S i C層。詳言之 ，此等組件典型上係由一種多孔性α - S i C主體所形成 ，該α - S i C主體帶有塡滿孔隙之S i 。爲欲防止S i 逃出，非常純淨之石一 S 1 C層乃藉由使c v D方法而被 澱積在組件之表面上。該j - S 1 C層係企求封合表面， 並抑制接近工件表面之S 1的損失。 經濟部智慧財產局員工消費合作社印製 必須瞭解的是：澱積在工件上以防止S i逃出之-S i C材料並非企求藉由本發明方法予以移除。 正確的說，當於本說明書中提到由用過之工件移除塗 層時，主題塗層乃指於工件應用於半導體加工期間，業已 被源積在工件上之塗層而言。由此，未用過之被塗覆工件 乃指新穎被製造而帶有所欲之塗層形成在表面上之工件， 而已用過，被塗覆之工件乃指帶有一非所欲之塗層的工件 ，該非所欲之塗層係於半導體處理期間被澱積者。當然， 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公楚) -14- 476986 A7 B7 五、發明説明（12) 於應用時，未用過之被塗層的工件會獲得一頟外，非所欲 之塗層，而該塗層之移除乃形成本發B月之一體現。 雖然可用於（淸潔）垂直式框架，但必須明白的是： 採用一強酸淸潔，緊接著施以C 0 2淸潔之本發明方法不僅 對垂直式框架提供意想不到之（淸潔）裨益，而且對任何 形狀之半導體處理裝備亦然。用於可被本發明施用之單晶 圓處理內的半導體處理組件，其例包括，但不限於鐘罩， 靜電卡盤，聚焦環，影像環，室，基座，提升桿，拱頂， 端操縱裝置，襯裏，支架，噴嘴通道，壓力計通道，晶圓 插入通道，歸板，施熱器，以及真空卡盤。用於可被本發 明施用之分批處理內之半導體處理組件，其例包括，但不 限於攪拌棒，作業管，晶片舟，襯裏，軸架，長晶舟；以 及模擬晶圓。用於可被本發明施用之化學機械拋光（ c Μ P )內之半導體處理組件，其例包括，但不限於，調 理用襯墊以及晶圓支持器。 •最後，吾人咸信：本發明乃爲最先提供現成安裝之產 物，即，可在使用者之工廠內可安全地而防護性運裝袋內 取出，而直接被安裝在半導體爐內而不須使用者進一步進 行淸潔之產品，該產物是所以能予獲致係因爲此類組件藉 由表面處理而帶有最低可能量之表面金屬及粒子。 詳言之，在本發明之一方位中，於立即完全C〇2淸潔 步驟後，立即將淸潔過之工件安裝在一用於處理半導體晶 圓之爐內，或放入用於運裝及貯存淸潔過之半導體處理組 件之袋子內。在前者作業中，工件乃直接由C 0 2淸潔步驟 ^紙張尺度適用中國國家標準（CMS > A4規格（210X297公釐） (請先閱讀背面之注意事項再填寫本頁) «· 訂 經濟部智慧財產局員工消費合作社印製 -15- 476986 A7 —__ _B7 五、發明説明（13) 轉移至爐內而不需進一步之淸潔步驟。在後者作業中，工 件乃於受C 0 2淸潔後，直接被包裝，即，被裝入袋中而不 需進一步之淸潔步驟。於該後者作業之場合中，該由包裝 體取出工件後，直接將工件安裝於用於處理半導體晶圓之 一爐內而不需進一步之淸潔步驟。不同於領域內已知的方 法（此方法需要在由包裝體取出工件以及將工件安裝於爐 內之間，提供額外之淸潔步驟）的是：使用本發明方法被 淸潔之組件可於由其包裝體取出後，立即安裝於爐內。此 作業之優點在於：此作業省掉額外之處理步驟，該步驟可 能造成污染，尤其是粒子狀污染水平之增加。 固然有幾種先前技藝之淸潔規律，優點以及缺點已述 及於前，於此技藝內所知者未有提供下述表面之能力：此 表面具有可由本文內述及之發明方法獲致之低金屬及粒子 污染水平。於一種強酸溶液，例如含有H F或其他具有 p K a小於約1之酸的溶液內進行淸洗的結果乃提供一種 具有不令人滿意之粒子污染物水平的表面。或者，於一弱 酸溶液內進行淸洗，接著進行珠粒噴擊之結果乃導致理想 性更差之金屬污染物水平。在本發明（進行強酸淸洗後， 緊接著進行C 0 2淸潔步驟）問世以前，人們從未能獲得金 屬性及粒子性污染之可接受的水平。 在本發明之另一體現中，化學淸潔及C 0 2淸潔步驟乃 與一改良型珠粒噴擊步驟偶合。詳言之，於此體現中，本 發明乃包括使用綠色s i C粒子對工件之表面施以珠粒噴 擊的步驟。然後，使表面與帶有至少1 v / 〇之一種酸的 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） ’ ' "" (請先閲讀背面之注意事項再填寫本頁j 訂 經濟部智慧財產局員工消費合作社印製 -16- 476986 A7 __B7 五、發明説明（14) (請先閲讀背面之注意事項再填寫本頁) 溶劑接觸，該酸係選自下列之群體：H F，具有p K a小 於1之酸，及其混合體。繼之，使用.C〇2淸潔作業來處理 該表面。在珠粒噴擊中，使用S i C之特異性乃在於：迄 今，只有黑色S i C已被用於供珠粒噴擊處理。於本發明 中，據發現：使用綠色S i C珠粒進行噴擊之結果乃提供 污染物之水平顯著較低的表面。咸信此乃由於黑色S i C 珠粒對綠色S i C珠粒之組成的結果。前者包含含有約 9 8 % S i C之細砂（以及約2 %之雜質水平），而後者 則含有介於約1 0 0 0 - 2 0 0 〇份/每百萬水平之雜質 (即，0 · 1 — 0 · 2 %雜質水平）。 在本發明之另一體現中，強酸淸潔步驟可予以消除而 代之以前述使用綠色S i C珠粒之珠粒噴擊步驟。因此， 此方法乃採用以綠色S i C進行之珠粒噴擊，接著進行 C〇2淸潔之步驟。 經濟部智慧財產局員工消費合作社印製 在另一體現中，當淸潔某些組件時，酸淸潔步驟之使 用可予省略。詳言之，如前所述，某些工件可予裝設以塗 層。此類塗層可藉由多種方法予以裝設，包括化學蒸氣澱 積法，濺鍍澱積法以及噴灑塗覆法。舉例來說，製自α -S i C之工件可予裝設以C V D澱積之0 - S i C塗層以 形成一非常純淨之表面。同樣地，厚度至多達5 0 0微米 之厚C V D澱積之S i C膜通常並不需要額外之機械製造 步驟，因此會避免金屬性污染之重要來源。或者，由其他 陶瓷材製成之工件可以是這樣的：這些工件不需要某些處 理步驟，例如會將金屬性雜質引導至陶瓷表面上之砂噴擊 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） '—一 -17- 476986 A7 B7 五、發明説明（15) (請先閲讀背面之注意事項再填寫本頁) 。這些工件亦具有金屬性污染物低的表面。具有此類被塗 覆或純淨之表面之新工件相對上不含有金屬性污染物。當 然，前述之任何表面將包括某些低水平不能避免之雜質， 然而，此類雜質水平顯著地低於藉由機械製造步驟，例如 砂噴擊而被引入之雜質的水平。這些工件可藉由僅用C〇2 作業而直接予以淸潔或直接予以安裝入一爐可立即予以包 裝而無需額外之淸潔步驟。同樣地，此類型被包裝之工件 可由具包裝體內取出，且立即安裝於一爐內而無需額外之 淸潔步驟。如此，先前技藝雖然包括使用C 0 2作業而無酸 淸潔步驟之方法，但這些方法沒有一個是就前述型態之未 曾用過的工件.而使用者。藉由消除某些未用過之工件所需 的酸淸潔步驟，淸潔時間及作業之複雜性可予減少到最低 程度。 必須提及的是：採用前述綠色S i C之各體現中， 經濟部智慧財產局員工消費合作社印m C〇2淸潔步驟可採用此藝內所周知之技術及裝置。令人滿 意之C〇2方法及輸送系統中之一例乃爲敘述於U.S .Patent Application Senal Number 08 /890,1 1 6 內，發明名稱 '、 Carbon Dioxide Cleaning Process "者，其教不乃藉由爹考 方式予以列入本文中。 進一步之改良包括於C〇2淸潔步驟內使用高純度 C〇2以及應用本發明方法至可能於一淸潔室環境內之程度 〇 無需說的是：於圍繞工件之環境內，於淸潔期間或後 ，任何減少雜質之行爲最終將導致一較淸潔之工件。 本紙張尺度適用中國國家標準（CNS ) A4規格（210X29*7公釐） -18- A7 ------- B7 五、發明説明（16) 就使用於本發明方法之步驟之幾個試驗而言，所得$ ，結果乃予列示於後。於表1內，業已受機械製造（例如濕 武或乾式砂噴擊）之受C V D S i C塗覆的元件，乃就 其雜質物加以分析。這些樣品係直接於受砂噴擊後，於後 噴擊弱酸處理後，或於樣品已受本發明方法（H F / C 〇 2 )後砂噴擊較予以測量者。本發明方法提供之改良之 金屬（尤其是鐵）移除能力可見於表內。 11 —金屬性雜以p p m計 siE業 N a. A 1 Τι V C r F e N i S 6 54 3 0.5 14 115 2 W s sP酸 6 33 1 0.1 8 38 0.8 w s i發明 2 17 .1 0.05 6 28 2 D S 136 98 60 10 4 1441 18 D S 弱酸 132 60 39 7 3 381 8 D S 本發明 7 107 20 3 4 211 4 W S =濕式砂噴擊 D S =乾式砂噴擊 係藉S I M S法，於低於表面約1 0 n m處測得之結果。 本紙張尺度適用中國國家榡準（CNS ) A4規格（210X297公釐） (請先閲讀背面之注意事項再填寫本I) 訂 經濟部智慧財產局員工消費合作社印製 -19- 476986 經濟部智慧財產局員工消費合作社印製 A7 B7 五、發明説明（17) 表2乃列示不帶有C V D塗覆表面之非機械製造樣品 上的粒子狀雑質。樣品1 一 6係受傳統之工件淸潔步驟處 理，而樣品7 — 1 〇則用本發明方法加以淸潔。粒子狀雜 質數目乃予列示於各樣品之二側面。Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs-6-476986 Α7 Β7 V. Description of the Invention (4) (Please read the notes on the back before filling this page) Similarly, the hot HC 1 淸 Jie has been used in Semiconductor diffusion components. For example, in UK Patent Application No. GB 2,130,192, a reviewer disclosed one of the following manufacturing steps: before use in a semiconductor furnace, an unused S 1 C component is subjected to a thermal H C 1 treatment. In some cases, the HF process itself was considered sufficient to clean unused wafer boats (to reduce metal contamination) and used wafer boats (chemically peel off coatings deposited during semiconductor processing) Floor). Nonetheless, the use of H F alone cannot remove the problematic particulate debris that may still exist after such treatments. In summary, the traditional method of providing cleaned unused semiconductor components involves cleaning with an acid to remove metallic contamination, while the clean-up method of cleaned components already used involves i) advanced beads Spraying, followed by a two-step method of mechanically stripping the deposited coating with CO2 cleaning to remove a small amount of debris particles, or 热) hot acid cleaning to remove the coating caused by the deposited material Floor. The Scourge of Invention The manufacturing of semiconductor devices by employees of the Intellectual Property Office of the Ministry of Economic Affairs printed on cooperatives requires the use of processing components with a high level of surface purity, regardless of whether the components are novel or the reconditioner. In some work, for example, in a ceramic wafer boat used to position and maintain semiconductor wafers during processing, the long depth and narrow pitch of the wafer braking grooves define the geometry of the wafer boat. Contoured surface, the crosswise aspect of the surface prevents the bead blasting from sufficiently removing the coating from the deeper portions of the grooves. In particular, the continuous ratio greater than about 4: 1 (that is, the groove depth applies the Chinese National Standard (CNS) A4 specification (21〇 × 297 mm) to the paper size. 476986 A7 ______B7__ 5. Description of the invention (5) (Please read the back Please fill in this page again) The ratio of the slot width) is typically beyond the capacity of the cleaning method to be flowed. The present invention presents a method to overcome these and other shortcomings by providing a process in which the inorganic surfaces of semiconductor manufacturing components are cleaned by chemical removal and C 2 cleaning operations. In one embodiment, chemical elimination is accomplished by using a solvent containing a strong acid. In a more stable embodiment, chemical elimination is accomplished by borrowing an acid containing at least 1 V / 0 from an acid selected from the group consisting of: H F, an acid having a p K a of less than about 1, and mixtures thereof. As used herein, the term `` v / 〇 〃 '' represents a percentage of capacity, and `` strong acid 〃 '' represents a solution with an acid having at least 1 v / 〇, the acid having a pKa less than about 1. The Co2 cleaning step uses dry ice particles that are projected onto the surface being cleaned. The combination of chemical cleaning and C 0 2 cleaning steps has been found to successfully remove granular and metallic contaminants from the surface of a workpiece. Printed by the Consumers' Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs and using the method of the present invention, workpieces that have been subjected to cleaning have found that the particle size of the pollutants whose particle size on the surface is greater than about 0 · 3 // m does not exceed about 0.4 particles, It should not exceed about 0.2 particles per square centimeter. Such workpieces have been found to have a surface metal contaminant concentration of not more than about 600 ppm (by SIMS method. Measured at a depth of about 10 nm ). After applying the cleaning method of the present invention to a typical workpiece, it was found that in the surface metallic contamination, not more than about 400 ppm metallic pollutants (except alkali metals and alkaline earth metals) and not more than about 2 2 5 ppm starvation (both measured at a depth of about 100 μm according to the SIMS method) is still present. One of the methods of the present invention is based on the following knowledge ... After HF treatment, this paper size applies the Chinese National Standard (CNS) A4 specification (210 × 297 mm)-8-476986 Α7 B7 V. Description of the invention (6) (Please read the precautions on the back before filling out this page) The debris particles that caused the problem will still exist. Although the CO2 cleaning step will remove particulate pollutants, it cannot remove non-particle surface metal pollutants. So far, the related art has not made any suggestion about the present invention, that is, the surface metal is removed by HF treatment, and then any remaining debris particles are removed by a CO2 cleaning step. The specificity of the combination of the C02 cleaning step and the HF treatment is that, traditionally, the C02 cleaning step is used only after a used workpiece has been mechanically removed which will generate debris particles. The present invention also relates to workpieces, such as ceramic boats used in semiconductor processing, which have been cleaned by using the method of the present invention. The specificity of the resulting workpiece is that the level of metallic and particulate surface contamination is much lower than the level of surface contamination of previously available workpieces that can be obtained using methods known to those skilled in the art. Detailed description of the invention Printed by the 8th Industrial Cooperative of the Intellectual Property Bureau of the Ministry of Economics The present invention provides a method for supplying ceramic workpieces, such workpieces are, for example, ceramic wafer boats used in semiconductor manufacturing. The level is lower than previously available. In detail, although the use of acid cleaning is known to those in the art, and although the comprehensive use of bead blasting and C02 cleaning is also known to the art, so far, there is no suggestion in this art: An acid cleaning step is combined with a CO2 cleaning step to clean unused or used coated ceramic workpieces. The recognition that the acid cleaning step can be combined with the C 0 2 cleaning step is to produce a cleaning method suitable for cleaning used or used coated workpieces. As mentioned above, the result of using the method of the present invention is to provide the following characteristics: The paper size is applicable to the Chinese National Standard (CNS) A4 specification (210X297 mm) -9-476986 A7 ___B7_ V. Description of the invention (7) (Please read first Note on the back, please fill in this page again) Quality workpiece: The surface of this workpiece has a neutrino size greater than about 0 · 3 // m. The pollutant density does not exceed about 0.4 particles per square centimeter, and the surface has metal contamination. The concentration does not exceed about 600 p P m (measured at a depth of about 10 nm according to the SIMS method). Traditionally, when a user receives an unused ceramic wafer boat from the manufacturer, the workpiece is subjected to cleaning operations, and any metal contaminants deposited on the surface of the workpiece during manufacturing, packaging, and shipping are removed. In some cases, used coated workpieces can be cleaned by a chemical cleaning step using a strong acid. Like those who clean unused workpieces, the acid cleaning step provides a satisfactory method for removing metallic contaminants from the surface of the workpiece. The employees of the Intellectual Property Bureau of the Ministry of Economic Affairs have printed them to the cooperative, although the acid cleaning The surface provided by the operation has reduced its metallic contamination to a satisfactory level, but this step has failed to provide a surface with sufficiently low levels of particulate contamination. In fact, there is some evidence that the chemical elimination step actually contributed to particulate contamination. Although I do n’t want to suffer from any particular theory, in cleaned workpieces, such as used ceramic boats, by using HF to chemically remove the coating, the cleaned workpieces still have a high level. Particle contamination, the Gein removal operation will leave particulate contamination on the ceramic surface. In addition, the particulate contamination is not caused solely by the chemical elimination step and the post-processing step. To be more precise, in the case of unused workpieces, I believe that the result of using a machine to manufacture a component, such as an S 1 C wafer boat, will produce particles deposited on the surface of the component. Of course, particles may also be deposited on unused components, so that such components are exposed to unclean house environments. This paper size applies the Chinese National Standard (CNS) A4 specification (210X 297 mm) -10- 476986 A7 B7 printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 5. Description of Invention (8). It must be mentioned that in the case of unused or used components, and in the case of first processing, processing or subsequent processing steps, many mechanisms for the formation of particles on the workpiece may exist, and the present invention is not intended to be affected. Limited to any particular particle formation or deposition mechanism. As mentioned earlier, the c02 cleaning step has traditionally been used in combination with preliminary cleaning steps, such as bead blasting. The combination of bead blasting and C 0 2 cleaning step is usually used when it is applied to an unused workpiece, but it has been applied to a used workpiece, which has a CVD coating during semiconductor processing. On its surface, although this method has been found to be satisfactory in removing particulate contaminants, it lacks the ability to prevent metallic contaminants from occurring on unused and used workpieces. The present invention recognizes that problematic sub-microns that need to be removed from the surface of a component before a workpiece that is an unused component or chemically removed component undergoes the final C02 cleaning step. The particles are still there. The need to remove such particulate contaminants, and the manner in which such removals are achieved, are neither known nor implemented in traditional methods. Furthermore, when compared with the second modified product by the cleaning method (the method is to use the coated workpiece of Co2 cleaning), the product obtained by the method of the present invention shows a relatively Excellent metal purity level. As mentioned earlier, the traditional method is to mechanically remove a coating from a used component, such as a wafer boat, by spraying with beads, and then use a CO2 cleaning operation to complete the cleaning step. Although I do not want to be bound by any particular theory, in the case of used crystal boats, the traditional understanding is that metallic contamination on the surface is not a problem. Conversely, even if the metal contamination on the surface causes the paper size to apply the Chinese National Standard (CNS) A4 (210 X 297 mm) (please read the precautions on the back before filling this page), 11 -11-476986 A7 ____B7 5. Description of Invention (9) It is a mistake to assume that such problems can be sufficiently eliminated by applying the techniques known in the prior art. (Please read the notes on the back before filling this page.) In contrast, although evidence suggests that the bead blasting step does increase the concentration of metallic impurities at the surface of the workpiece. This unwanted effect may be the result of the use of impure spray media. The advantage of the method of the present invention over the conventional bead blasting / C02 cleaning operation is that it does not cause metallic contamination on the surface of the workpiece to be eliminated. In fact, the method of the invention has the effect of reducing the metal concentration at the surface. Similarly, for unused workpieces, such as unused s 1 C wafer boats, the general recognition of surface metal impurities is as follows: HF or hot HC 1 cleaning operations can only provide critical practicality, cover Because of its function, it can only gradually reduce the metal concentration at the surface of the component to a level slightly lower than that of the surface of the body material forming the workpiece (the metal concentration is 1 to 10 ppm for Si C), and to the body The relative purity advantage possessed by the material will disappear with time. Due to the high temperature environment, subsequent use will promote the diffusion of the host metal into the surface area of the component. Therefore, this technique does not require H F cleaning in all cases. The material representing the unused Si C component printed by the 8th Industrial Cooperative Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs has been surfaced by a traditional method (X-ray photoelectron spectroscopy, XPS) and another method (secondary Analysis of ionic mass spectrometry (abbreviated as SIMS). The traditional XPS analysis provides data at a depth of about 3 nm and has a sensitivity of about 0.1-1.0%, which depends on the related elements. In contrast, SIMS analysis provides data at a depth of about 10 nm, and has about 0.2-3 · 〇 This paper size applies the Chinese National Standard (CNS) A4 specification (210X297 mm) -12- 476986 A7 _____B7 5 Description of the invention (1〇) (Please read the precautions on the back before filling this page) PP m sensitivity. For this reason, the SI M S test provides a more accurate method for measuring the metal surface concentration in a semiconductor processing device. It has been found that in cases where XPS fails to detect any metal (and therefore does not provide a characterization of rising surface metal concentrations), the SI M S test reports the presence of approximately 2000 p pm metal at a depth of 10 nm. In the field of high temperature semiconductor processing, these surface concentration levels are clearly not ideal. Therefore, the results of the SI M S analysis confirm the surface requirements of unused ceramic components and should be cleaned with a chemical removal step to reduce the high surface levels of metallic contaminants present on the surface of semiconductor-treated components. It must be understood that, in one embodiment of the invention, the surface is a CVD surface, which has been subjected to mechanical manufacturing or other post-processing steps at will. Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economics In detail, it must be understood that the method of the present invention is intended to be applied to a variety of inorganic surfaces that are used by semiconductor processing components. Such surfaces typically include ceramic materials, for example, ceramic surfaces commonly used in semiconductor manufacturing, however, the method can be applied to non-ceramic surfaces such as silicon and diamond. In this way, the focus of the discussion is of course on semiconductor processing components, such as ceramic wafer boats, and components formed especially by SiC, but it must be understood that the present invention is not intended to be limited to this approach. Rather, the present invention seeks to apply any semiconductor processing component having an inorganic surface associated with semiconductor wafer processing technology. These surfaces include, but are not limited to, silicon (Si), silicon carbide (Sic), silicon nitride (Si3N4), diamond, yttrium oxide, chromium oxide (ZrO2), aluminum nitride ( A 1 N), alumina (A 1 2 03), graphite and polycrystalline form fused quartz. This paper size applies Chinese National Standard (CNS) A4 specification (210X297 mm)-13- 476986 A 7 B7 V. Description of the invention (μ) (Please read the precautions on the back before filling this page) The surface can be made of steam- It is formed by deposition, and as previously discussed, it can be formed by CVD. Such surfaces include, but are not limited to, polycrystalline formation of other CVD Si., C V D SiC, CVD S 102, CVD Si3N4, and CVD diamond surfaces. Of course, it must be understood that although the present invention can be applied to a surface with a coating on it, the method of the present invention can also be applied to an inorganic surface without a coating. When it comes to S i C artifacts, several artifacts are used in this field. In one embodiment, a workpiece simply formed of Si C is used. In another embodiment, the workpiece contains S i C with reduced porosity, which is formed by loading Si with pores in the S 1 C structure. Since S i easily escapes from the pores, such workpieces are often provided with a C V D S i C layer. In detail, these components are typically formed of a porous α-S i C body with the Si filled with pores. In order to prevent Si from escaping, a very pure stone-S1C layer is deposited on the surface of the module by using the cvD method. This j-S 1 C layer seeks to seal the surface and suppress the loss of S 1 close to the surface of the workpiece. Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs. It must be understood that the Si-C material deposited on the workpiece to prevent Si from escaping is not intended to be removed by the method of the present invention. To be precise, when it is mentioned in this specification that the coating is removed from the used workpiece, the subject coating refers to the coating that has been deposited on the workpiece during the application of the workpiece to semiconductor processing. Therefore, an unused coated workpiece refers to a workpiece that is newly manufactured and has a desired coating formed on the surface, while a used, coated workpiece refers to an undesired coating The undesired coating is deposited during semiconductor processing. Of course, this paper size applies to the Chinese National Standard (CNS) A4 specification (210X297 Gongchu) -14-476986 A7 B7 V. Description of the invention (12) In the application, unused uncoated workpieces will get extra , The undesired coating, and the removal of this coating is an embodiment of this month. Although it can be used for (淸 洁) vertical frame, it must be understood that: The method of the present invention using a strong acid clean, followed by C 0 2 淸 clean not only provides unexpected (淸 洁) benefits to the vertical frame , And also for semiconductor processing equipment of any shape. Examples of semiconductor processing components used in single wafer processing that can be applied by the present invention include, but are not limited to, bell jars, electrostatic chucks, focusing rings, image rings, chambers, bases, lifters, vaults, ends Manipulator, lining, holder, nozzle channel, pressure channel, wafer insertion channel, return plate, heater, and vacuum chuck. Examples of semiconductor processing components used in batch processes that can be applied by the present invention include, but are not limited to, stirring rods, working tubes, wafer boats, linings, cradles, wafer boats; and simulated wafers. Examples of semiconductor processing components used in chemical mechanical polishing (CMP) that can be applied by the present invention include, but are not limited to, conditioning pads and wafer holders. • Finally, I believe that the present invention is the first to provide ready-to-install products, that is, it can be safely and protectively removed from the user's factory in a shipping bag and directly installed in a semiconductor furnace without It is necessary for the user to further clean the product. The product can be obtained because such components have the lowest possible amount of surface metals and particles through surface treatment. In detail, in one aspect of the present invention, immediately after the CO2 cleaning step is completely completed, the cleaned workpiece is immediately installed in a furnace for processing semiconductor wafers, or placed in a furnace for shipment. And in a bag containing cleaned semiconductor processing components. In the former operation, the workpiece is directly cleaned by C 0 2 ^ The paper size applies the Chinese national standard (CMS > A4 size (210X297 mm) (Please read the precautions on the back before filling in this page) «· Order economy Printed by the Consumer Cooperatives of the Ministry of Intellectual Property Bureau -15-476986 A7 —__ _B7 V. Description of the invention (13) Transfer to the furnace without further cleaning steps. In the latter operation, the workpiece is subject to C 0 2 淸After cleaning, it is directly packaged, that is, packed into a bag without further cleaning steps. In the latter operation, after the workpiece is taken out of the package, the workpiece is directly mounted on the semiconductor wafer for processing. In a furnace without further cleaning steps. Unlike the methods known in the art (this method requires an additional cleaning step between removing the workpiece from the package and installing the workpiece in the furnace) : The components cleaned by using the method of the present invention can be installed in the furnace immediately after being removed from its packaging body. The advantage of this operation is that this operation saves additional processing steps, which may cause pollution, especially It is an increase in the level of particulate pollution. Although there are several previous techniques of cleaning, the advantages and disadvantages have been mentioned previously, those skilled in the art do not have the ability to provide the following surface: this surface has the ability to Low levels of metal and particle contamination resulting from the invented method. The result of rinsing in a strong acid solution, such as a solution containing HF or another acid with a p K a of less than about 1, provides an unsatisfactory result. Surface with a level of particulate contamination. Alternatively, rinsing in a weak acid solution followed by bead blasting results in a less ideal level of metal contaminants. In the present invention (after strong acid rinsing, the Next, the C 0 2 cleaning step) before the advent of it, people have never achieved acceptable levels of metallic and particulate pollution. In another embodiment of the present invention, the chemical cleaning and C 0 2 cleaning steps are related to A modified bead spraying step is coupled. In detail, in this embodiment, the present invention includes the step of applying bead spraying to the surface of the workpiece using green si C particles. Then, The size of this paper with an acid of at least 1 v / 〇 applies to the Chinese National Standard (CNS) A4 specification (210X297 mm) '' " " (Please read the precautions on the back before filling in this page. J Order Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs-16- 476986 A7 __B7 V. Description of the invention (14) (Please read the notes on the back before filling this page) Solvent contact, the acid is selected from the following groups: HF Acids with p K a less than 1, and mixtures thereof. Next, the surface was treated with .CO2 cleaning. In bead spraying, the specificity of using S i C is that, to date, only Black Si C has been used for bead blasting. In the present invention, it has been found that the result of spraying with green SiC beads is to provide a surface with significantly lower levels of contaminants. This is believed to be the result of the composition of black S i C beads to green S i C beads. The former contains fine sand with about 98% SiC (and an impurity level of about 2%), while the latter contains impurities between about 100-200 parts per million levels (i.e., 0 · 1 — 0 · 2% impurity level). In another embodiment of the present invention, the strong acid scouring step may be eliminated and replaced by the aforementioned bead spraying step using green S i C beads. Therefore, this method uses the bead spraying with green SiC, followed by the C02 cleaning step. Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs. In another embodiment, the use of the acid cleaning step can be omitted when cleaning certain components. In detail, as mentioned earlier, some workpieces can be installed with coatings. Such coatings can be installed by a variety of methods, including chemical vapor deposition, sputtering deposition, and spray coating. For example, a workpiece made from α-S i C can be provided with a 0-S i C coating deposited by C V D to form a very pure surface. Similarly, C V D deposited Si films with a thickness of up to 500 micrometers usually do not require additional mechanical manufacturing steps and therefore avoid important sources of metallic contamination. Alternatively, workpieces made of other ceramic materials may be such that these workpieces do not require certain processing steps, such as sand blasting that guides metallic impurities to the ceramic surface. This paper is compliant with Chinese National Standards (CNS) A4 Specifications (210X297mm) '— 一 -17- 476986 A7 B7 V. Description of the invention (15) (Please read the precautions on the back before filling this page). These workpieces also have surfaces with low metallic contamination. New workpieces with such coated or pure surfaces are relatively free of metallic contaminants. Of course, any of the foregoing surfaces will include certain low levels of unavoidable impurities, however, the level of such impurities is significantly lower than the level of impurities introduced through mechanical manufacturing steps such as sand blasting. These parts can be cleaned directly by using only CO2 or installed directly into a furnace and can be immediately packed without additional cleaning steps. Similarly, this type of packaged workpiece can be removed from the packaged body and immediately installed in a furnace without additional cleaning steps. Thus, although the prior art includes a method using C 0 2 operation without acid cleaning steps, none of these methods is an unused workpiece of the aforementioned type and the user. By eliminating the acid cleaning steps required for some unused parts, cleaning time and operation complexity can be minimized. It must be mentioned that in adopting the above-mentioned embodiments of the green S i C, the cleaning steps of the consumer co-operatives of the Intellectual Property Bureau of the Ministry of Economic Affairs of the consumer co-operatives can adopt technologies and devices well known in the art. An example of a satisfactory CO2 method and conveying system is described in US. Patent Application Senal Number 08/890, 1 1 6 and the name of the invention, 'Carbon Dioxide Cleaning Process " It is included in this article by Dao test method. Further improvements include the use of high purity CO 2 in the CO 2 cleaning step and the application of the method of the present invention to the extent possible in a clean room environment. Needless to say: in the environment surrounding the workpiece, During or after, any action to reduce impurities will eventually lead to a cleaner workpiece. This paper size applies Chinese National Standard (CNS) A4 specification (210X29 * 7mm) -18- A7 ------- B7 V. Description of the invention (16) Several tests on the steps used in the method of the present invention In the case of $, the results are shown later. In Table 1, C V D S i C coated components that have been manufactured by machinery (such as wet or dry sand blasting) are analyzed for impurities. These samples were measured directly after being subjected to sand blasting, after being subjected to weak acid treatment by post blasting, or after the sample has been subjected to the method of the present invention (H F / Co 2). The improved metal (especially iron) removal ability provided by the method of the present invention can be seen in the table. 11 — Metallic impurities in ppm siE industry N a. A 1 T VC r F e N i S 6 54 3 0.5 14 115 2 W s sP acid 6 33 1 0.1 8 38 0.8 wsi invention 2 17.1 0.05 6 28 2 DS 136 98 60 10 4 1441 18 DS Weak acid 132 60 39 7 3 381 8 DS Inventive 7 107 20 3 4 211 4 WS = Wet sand blasting DS = Dry sand blasting Results measured at about 10 nm. This paper size is applicable to China National Standards (CNS) A4 (210X297 mm) (Please read the notes on the back before filling in this I) Printed by the Consumer Cooperative of the Bureau A7 B7 V. Description of Invention (17) Table 2 shows the particulate matter on non-mechanical manufacturing samples without CVD-coated surfaces. Samples 1 to 6 were processed by the conventional workpiece cleaning step, while samples 7 to 10 were cleaned by the method of the present invention. The number of particulate impurities is listed on the two sides of each sample.
表2 -粒子狀雜質I I ------1--—_ 1 —--- 樣品 作業 側面1 側面2 1 傳統 0.98 1.12 2 傳統 0 . 8 〇.6 7 3 傳統 0.77 0.78 4 傳統 0.99 0.86 5 傳統 1.34 1.23 6 傳統 0.79 0.86 7 C 〇 2 0.03 0.17 8 C 0 2 · 0.14 0.12 9 C 〇 2 0.05 0.03 1〇 C 0 2 0.04 0.12 表3乃列示於受前述C 0 2作業之處理前及後之樣品的 粒子狀雑質資料。於樣品A、B及C中，樣品係機械製造 .之S i C，它不帶有一 d V D塗層在其表面上。樣品D係 一非機械製造之樣品，它帶有一 C V D S i C表面。由 表3可見，C 0 2淸潔作業之使用導致粒子狀污染物之量顯 著地減少。 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） (請先閲讀背面之注意事項再填寫本頁)Table 2 -Particulate impurities II ------ 1 ----_ 1 ----- Sample operation Side 1 Side 2 1 Traditional 0.98 1.12 2 Traditional 0.8 0.8 0.6 3 Traditional 0.77 0.78 4 Traditional 0.99 0.86 5 Conventional 1.34 1.23 6 Conventional 0.79 0.86 7 C 〇2 0.03 0.17 8 C 0 2 · 0.14 0.12 9 C 〇2 0.05 0.03 1 〇C 0 2 0.04 0.12 Subsequent samples of granular carcass data. In samples A, B and C, the samples are mechanically manufactured Si C, which does not have a d V D coating on its surface. Sample D is a non-mechanical sample with a C V D S i C surface. It can be seen from Table 3 that the use of C 0 2 cleaning operations results in a significant reduction in the amount of particulate pollutants. This paper size applies to China National Standard (CNS) A4 (210X297 mm) (Please read the precautions on the back before filling this page)
-20 - 476986 A7 __B7 五、發明説明（18) 等效體 由對本發明之特定體現所作之如前詳述，顯而易見的 統上但。及代 系且 ，圍神取 穎，明範精之 新述說利明樣 之詳以專發各 用以加請本式 物加伊申離各 染中施之脫作 污文實屬不下 性本之附在況 子在的下可情 粒已目如明的 及現明制發圍 性體說限本範 屬之作來期之 金別供用預定 除特僅求乃界 移然由企者所 件固藉非明圍 。 工。已並發範飾 瓷述業例本利修 陶敘實施，專及 由被事實之請變 : 已之等言申改 是業述此詳如 ， (請先閲讀背面之注意事項再填寫本頁} 經濟部智慧財產局員工消費合作社印製 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） -21 --20-476986 A7 __B7 V. Description of the invention (18) Equivalents The detailed description of the specific embodiment of the present invention is as described in detail above, and it is obvious that it is the same as above. And the generations, and surrounded by God, Ming Fanjing's new description of Lee Mingming in detail to issue each to add this form of Gai Shen from the defiled insults in each dye is really attached to the nature of In the case of the situation, the situation is clear and the system of the hair style is limited. The future gold is available for reservation. In addition to the special requirements, only the boundary is removed, and it is fixed by the company. By non-Ming Wai. work. Fan Li Po Porcelain Case Study has been implemented concurrently, and it has been implemented by Li Li Tao Tao, specifically and changed by the facts: Already stated that the application of the amendment is described in detail, (Please read the precautions on the back before filling in this page} Printed by the Consumers' Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs, the paper size applies to the Chinese National Standard (CNS) A4 specification (210X297 mm) -21-