471053 A7 B7 五、發明説明（’） 相關之申請案 (請先閲讀背面之注意事項再填寫本頁) 本案係關於於西元1 9 9 9年1 2月2 2日提出申請 之專利申請案〇 9 / 4 7 0 , 5 1 0 ,發明名稱、、淸潔陶 瓷物件的方法〃，的部份追加案。 發明之領域 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 經濟部智慈財產局資工消費合作社印製 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圚本體內 。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250 °C至1 200 t。 另一共同之半導體作業乃爲蝕刻。俟光蝕刻圖案澱積 在矽晶圓之表面上後，矽晶圓乃被載入一蝕刻器內。該蝕 本紙張尺度適用中國國家標準（CNS ) A4規格（210X 297公釐） -4- 471053 A7 B7 五、發明説明（2 ) (請先閱讀背面之注意事項再填寫本頁) 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。典型之難刻方法乃由砂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圓的表面發展成一有 用之產物，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，亦遺留在支承晶圚之晶舟的表面 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。 經濟部智慧財產局員工消贫合作社印¾ 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。由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，具有不超過〇 . 7微米寬 度之亞微米粒子）變得日益重要。 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，被一種丨殿積材料，例如氮化砂、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。第一步驟，稱之爲初步淸潔者 本紙張尺度適用中國國家橾準（CNS ) A4規格（210X 297公釐） ' -5- 471053 Α7 Β7 五、發明説明（3 ) ，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， (請先閱讀背面之注意事項再填寫本頁) 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、氧化鈦 、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 1 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20-35ps1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.4,707,95 1, entitled Installation for the Projection of Particles of Dry Ice'" , and U.S.Patent No. 6，004,400，entitled '、Carbon Dioxide Cleaning Process'’ 。 經濟部智葸財產局資工消费合作社印%[ 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° 未經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 本紙張尺度適用中國國家標準（CNS ) Α4現格（210X 297公釐） -6- 471053 A7 B7 —-- 一 -^ 五、發明説明（4 ) s i C獷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埋。 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：於使用在一半導體壚內 之前，使未經使用之S i 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 之組件的傳統方法到涉及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U )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 半導體器件之製造需要使用帶高度表面純度水平的力口 工組件，而不論這些組件爲新穎者或該重新調理者。在某 本紙张尺度適用中國國家橾準（CNS ) A4規格（21GX297公缝)' ~—""〆 (請先閲讀背面之注意事項再填寫本頁) 裝·471053 A7 B7 V. Description of the invention (') Related applications (please read the notes on the back before filling this page) This case is a patent application filed on February 22nd, 1999. 9/4 7 0, 5 1 0, the name of the invention, the method of cleaning ceramic objects, and some additional cases. FIELD OF THE INVENTION The present invention relates to a method for cleaning ceramic articles. More specifically, the present invention relates to a method for removing particulate impurities and chemical impurities from a ceramic article used to manufacture a semiconductor device. Background of the Invention The manufacture of semiconductor devices printed by the Industrial and Consumer Cooperatives of the Intellectual Property Office of the Ministry of Economics typically requires that the surface of the silicon wafer 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, the material enters the silicon crystal body through diffusion. During 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 the environment in the tube is changed to provide a variety of atmospheres. The temperature is typically from 250 ° C to 1 200 t. Another common semiconductor operation is etching. After the calender etching pattern is deposited on the surface of the silicon wafer, the silicon wafer is loaded into an etcher. The scale of this etched paper is in accordance with Chinese National Standard (CNS) A4 (210X 297 mm) -4- 471053 A7 B7 V. Description of the invention (2) (Please read the precautions on the back before filling this page) Engraver, its components Typically, those made from ceramic materials use plasma etching technology to remove materials deposited on the surface of the silicon wafer that is not protected by the photo-etching pattern. A typical difficult method is to remove oxides, metals and / or polymers from the surface of the sand wafer. Although the foregoing methods have successfully developed the surface of the silicon wafer into a useful product, this method will eventually contaminate 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 be peeled off in pieces, and the vicinity of the wafer is contaminated by particles. Printed by the Anti-Poverty Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs ¾ In the etching method, the careful removal of a variety of material layers on the manufactured wafer can cause contaminating particles, such as being deposited on an etcher Silicon dioxide, nitride, and aluminum oxide on the surface of the component. 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. Due to the decreasing line width of silicon wafers, the removal of 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 has become increasingly important. Several methods have been used in the clean boat that Jiu Jie has used in the prior art. In one method, a used component coated with a substrate material, such as nitrided sand, polycrystalline silicon, or silicon dioxide, is subjected to a two-step cleaning process. The sandblasting 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 first step is called preliminary cleaning. This paper size is applicable to China National Standards (CNS) A4 (210X 297 mm) '-5- 471053 Α7 Β7 5. Description of the invention (3), successfully from the component surface Remove the deposited material and leave the micron-sized debris particles at the same time. In the second step, it is called the main cleaner. (Please read the precautions on the back before filling this page) Xianxin caused micron-sized fragments to freeze, which made them fragile and ruptured, thereby making it easy for the broken particles to be washed away from the surface. Initial cleaning is generally achieved by hitting or blasting glass, alumina, silicon carbide, titanium oxide, walnut shell particles, or other beads against 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 S 1 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 20-35 ps1. 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, U.S. Patent No. 4,707,95 1, entitled Installation for the Projection of Particles of Dry Ice '", and U.S. Patent No. 6,004,400, entitled', Carbon Dioxide Cleaning Process ''. Printed by the Ministry of Economic Affairs, Intellectual Property, Industrial and Industrial Cooperatives, [In another method of the used wafer boat coated by the deposited layer, the manufacturer recommends that the used wafer boat be treated with an acid. Strong acids, such as HF, are baked. The H F process will remove the deposited layer of materials. The cleanliness of unused semiconductor processing equipment is also a topic of concern in this field. However, in the case of an unused component, the topic of concern is typically metallic pollution rather than particulate pollution. In the manufacture of this paper, the Chinese National Standard (CNS) A4 is now applicable (210X 297 mm) -6- 471053 A7 B7 ----one-^ five, description of the invention (4) one of the traditional methods of si C loose components Unused si C diffusion components are treated with a weak acid and then baked. The function of this method is to remove certain metallic contaminants and fingerprints from the parts being cleaned. In another conventional method of ensuring the cleanliness of unused components, the components are buried in a strong acid before they are placed in a furnace. Similarly, thermal H C 1 cleaning has been used on semiconductor diffusion devices. 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 stack, an unused S i 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 clean unused semiconductor components involves cleaning with an acid to remove metallic contamination, and the traditional method of cleaning used components involves i) advanced bead 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 U) hot acid cleaning to remove the coating caused by the deposited material . The stumbling block of the invention The manufacture of semiconductor devices requires the use of power components with a high level of surface purity, regardless of whether they are new or reconditioned. In a certain paper standard, the Chinese National Standard (CNS) A4 specification (21GX297 common stitching) is used ~~ " " 〆 (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钍印製 471053 A7 B7 五、發明説明（5 ) 些工件內，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，該幾何形狀帶有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之縱橫比（即槽深度 對槽寬度之比）典型上超出傳統之淸潔方法的能力。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 0 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/o之一種選自下列群體之酸來達成：HF，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。 或者，化學淸潔可藉用多種酸之任何其一來造成。舉 例來說，在一體現中，化學淸除係藉用氯化之酸來達成。 特別是，一種氯化之酸，例如H C丨，可於進行C〇2淸潔 步驟以前，被施加至待受淸潔之表面上。H C 1固然由於 高解離水平而成爲理想者，但其他酸氯化物，包括但不限 於氯乙酸，氯丙酸及氯苯甲酸等亦可加以使用。於增溫， 即，大約8 5 °C以上使用此類酸之結果（雖然該等增溫並 不需要），會導致生成改良之表面純度。 當然，本發明並非企求受限於氯化酸或鹵化酸。更正 本紙張尺度適用中國國家標準（CNS )八4規格（210X297公釐） (請先閲讀背面之注意事項再填寫本頁) 裝· 訂 經濟部智慧財1局員工消費合作社印製 -8- 471053 經濟部智惡財產局員工消費合作社印^ A7 _____B7_五、發明説明（6 ) 確地說_，本發明乃企求使用幾乎任一種能由基底表面淸除 污染物的酸。雖非一必要的條件，但在增溫下使用此類酸 之事實咸信乃爲導致改良之表面純度的原因。 在另一體現中，液體酸處理可被氣相淸除劑所置換。 舉例來說，於進行C 0 2淸潔步驟前，待受淸潔之表面可受 一種鹵素氣體或一種會鹵化之化合物之氣體的處理。如此 ，化學淸潔步驟可藉由使表面暴露於氣相氣化之化合物， 例如s i C 1 4而達成。氣相鹵化之化合物亦可加以使用。 此等化合物包括，但不限於1，1，1 一三氯乙烷（ TCA)及1，2_反式—二氯乙烯（DCE)。 在另一體現中，超臨界流體之用作化學淸除劑亦爲吾 人所企求。超臨界流體乃爲在超過臨界溫度時仍維持原狀 之致密氣體（上述之臨界溫度乃指當超過某一溫度時，氣 體不能因受壓而液化）.。因爲超臨界流體較液體少黏滯， 且更易於擴散，它們被期待在化學淸除應用上提供優越之 效果。 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。 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 0.4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 ^紙张尺度適用^國國家櫺準（CNS ) Μ規格（2ΪΟΧ297公釐） (請先閣讀背面之注意事項再填寫本頁) -裝· *1Τ 線 -9 - 471053 經濟部智慧財產局8工消費合作社印製 A7 B7 ___五、發明説明（7 ) 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 Ο Ο P P rn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 Ο n m深處測得） 仍存留。 本發明之一方法乃依據下列之認知：於化學淸除後， 造成問題之碎片粒子仍會存在，C 0 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，採用化 學淸除來移除表面金屬，接著，藉由C 0 2淸潔步驟來移除 任何存留之碎片粒子。C 0 2淸潔步驟乃化學淸除步驟二者 之組合的特異性乃在於：傳統上C 0 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。 在本發明之另一體現中，除了 C 0 2淸潔步驟以外之方 法可用於由工件表面移除粒子狀碎片。舉例來說，淸潔可 藉由使用聲波能量代替（：〇2淸潔步驟來達成，或藉由使用 聲波能量加上C 0 2淸潔步驟來達成。聲波能量可以超音波 或以兆赫音波能量方式加以施用。兆赫音波淸潔步驟與超 音波淸潔步驟相關連之處在於前者係在淸潔作業中使用音 波，然而，不同於在超音波淸潔步驟內所採用之頻率（大 約5 0 — 2 5 0 k Η z )，兆赫音波淸潔步驟係採用介於 約了〇〇一1 0〇〇k Η ζ間之頻率。 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 本紙張尺度適用中國國家樣準（CNS ) Α4規格（2丨0X297公釐1 ^ -- -10- (請先閲讀背面之注意事項再填寫本頁) •裝- 訂 ·線 471053 A7 B7 五、發明説明（8 ) (請先閱讀背面之注意事項再填寫本頁) 之工件韵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。 發明之詳沭 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 0 2淸 潔亦爲此藝所知，但迄今，在此藝尙未有如下之建議：將 一化學消除步驟與c 0 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。化學淸潔步驟可與C 0 2淸潔步 驟組合之認知乃產生一種適合用於淸潔未用過或已用過之 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 質之工件：|此工件之表面上粒子尺寸大於約〇 . 3 β m者 經濟部智慧財產局員工消費合作社印製 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 pm (依S I MS法 ，於約1 Ο 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，會使工件接受酸淸潔作業，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 本ϋ尺度適用中國國家標準(CNS ) A4規格（210X 297公釐1 "11 - 471053 A7 B7 經濟部智慧財產局員工消资合作钍印製 五、發明説明（9 ) 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。 雖然化學淸除步驟所提供之表面，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， 藉由使用化學淸除作業人移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，粒子亦可能丨殿積在未 用過之組件上，蓋因此類組件暴露於不淸淨之屋環境之故 。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 粒子形成或殿積機制。 如前所提及，C 0 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〇2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塗層殿 積在其表面上，雖然該方法已被發現在移除粒子狀污染物 (請先閲讀背面之注意事項再填寫本頁) •裝_ 訂 )·線 本紙乐尺度適用中國國家揉準（CNS〉Μ規格（210X297公釐） -12- 471053 A7 B7_ 五、發明説明（1〇 ) 上令人滿意，但它卻缺乏移除發生在未用過及已用過之工 件上之金屬性污染的能力。 (請先閲讀背面之注意事項再填寫本頁) 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 0 2淸潔步驟以前，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來淸潔已 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 0 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。 經濟部智慧財產局員工消费合作社印製 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 0 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 L C晶舟 本紙張尺度適用中國國家標準（CNS ) A4現格（210X297公釐） -13- 471053 經濟部智慧財產局員工消費合作社印製 A7 B7__五、發明説明（Μ ) 而言，表面金屬雜質之一般認知是這樣的：H F或熱 H C i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 — 1 Ο ρ Ρ πί )，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化學淸除。 代表未用過之s 1 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，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 . 0 Ρ 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 nm深度處報導大約2 〇 〇 〇 p pm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。 医1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 本紙張尺度適用中國國家標準（CNS ) Α4規格（210X297公釐） (請先閱讀背面之注意事項再填寫本頁) -裝. 訂 I·線 -14 - 471053 經濟部智慧財產局員工消費合作社印¾ A7 ____B7_____五、發明説明（12 ) 瞭解的是，在本發明之一體現中，表面爲一 c V D表面， 它業已隨意受機械製造或其他後處理步驟。 如先前所扼要敘述者，化學淸除步驟可採用各式各樣 化學淸除劑。特別是，它可爲一種酸而具有至少1 V / 〇 之一種選自如下群體的酸：H F，具有P K a小於約；[之 酸，以及其混合體。在一合宜之體現中，化學淸除劑係選 自氯化酸類。尤其是，一種氯化酸，例如H C 1可予以使 用。固然H C 1由於其高解離水平而爲理想者，但其他酸 氯化物，包括但不限於氯乙酸，氯丙酸以及氯苯甲酸亦可 加以使用。在一合宜之體現中，化學淸除步驟係於溫度， 即，約8 5 °C以上進行，此類溫度業已被發現能導致改良 之表面純度。 亦予提及的是，化學消除步驟可藉由使用氣相化學淸 除劑來進行。示範性氣相化學淸除劑包括鹵素氣體以及含 有鹵化之化合物的氣體。由此，化學淸除步驟可藉由使用 氣相氯，氟，溴，碘等，或氣相氯化之化合物，例如 S 1 C 1 4來進行。氣相鹵化之有機化合物亦可加以使用。 如前所述及者，此類·化合物包括，但不限於1， 1， 1 — 三氯乙院（TCA)及1， 2 —反式二氯乙婦（DCE) 〇 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 本紙張尺度適用中國國家標準（CNS) Μ規格（210X297公釐） (請先閱讀背面之注意事項再填寫本頁) 裝 -訂 線 -15- 471053 A7 B7 五、發明説明（13 ) (請先閱讀背面之注意事項再填寫本頁) 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 ，但不限於砂（S i )，碳化砂（s i C )，氮化5夕（ S i a N 4 )，鑽石，氧化釔，氧化锆（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。、 1T Consumption cooperation with employees of the Intellectual Property Bureau of the Ministry of Economic Affairs, printed 471053 A7 B7 V. Description of the invention (5) In some workpieces, for example, in the ceramic wafer boat for positioning and maintaining semiconductor wafers during processing, The long depth and narrow pitch define the geometry of the wafer boat, which has a contoured surface whose vertical and horizontal orientation prevents the bead blast from removing the coating from the deeper portions of these grooves sufficiently . In particular, an aspect ratio greater than about 4: 1 (i.e., the ratio of groove depth to groove width) typically exceeds the capabilities of conventional cleaning methods. The present invention proposes a method for overcoming this disadvantage by providing a process in which the inorganic surface of a semiconductor manufacturing component is successively cleaned by chemical removal and C 0 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 using an acid containing at least 1 v / o selected from the group consisting of HF, an acid having a pKa of less than about 1, and mixtures thereof. As used herein, the term 'v / 〇〃' represents a percentage of capacity, while `` strong acid '' represents a solution of an acid having at least 1 v / 〇, the pKa of the acid being less than about 1. Alternatively, chemical cleaning can be done by using any of a variety of acids. For example, in one embodiment, chemical elimination is accomplished by using a chlorinated acid. In particular, a chlorinated acid, such as HCI, may be applied to the surface to be cleaned before the Co2 cleaning step is performed. Although H C 1 is ideal due to its high dissociation level, other acid chlorides, including but not limited to chloroacetic acid, chloropropionic acid, and chlorobenzoic acid, can also be used. The use of such acids at elevated temperatures, i.e. above 85 ° C (although such warming is not required), will result in improved surface purity. Of course, the invention is not intended to be limited to chlorinated or halogenated acids. The paper size of this correction applies to China National Standard (CNS) 8-4 (210X297 mm) (Please read the precautions on the back before filling out this page) Binding and printing Printed by the Employees ’Cooperative of the 1st Bureau of Intellectual Property, Ministry of Economic Affairs-8- 471053 Printed by the Consumer Cooperatives of the Intellectual Property Office of the Ministry of Economic Affairs ^ A7 _____B7_V. Description of the Invention (6) Indeed, the present invention seeks to use almost any acid capable of removing pollutants from the substrate surface. Although not a necessary condition, the fact that such acids are used at elevated temperatures is believed to be responsible for the improved surface purity. In another embodiment, the liquid acid treatment may be replaced by a gas phase scavenger. For example, the surface to be cleaned may be treated with a halogen gas or a gas of a halogenated compound before the C 0 2 cleaning step. In this way, the chemical cleaning step can be achieved by exposing the surface to a gaseous compound, such as si C 1 4. Gas-phase halogenated compounds can also be used. These compounds include, but are not limited to, 1,1,1 trichloroethane (TCA) and 1,2-trans-dichloroethylene (DCE). In another embodiment, the use of supercritical fluid as a chemical scavenger is also sought by us. A supercritical fluid is a dense gas that remains intact when it exceeds a critical temperature (the above-mentioned critical temperature means that when a certain temperature is exceeded, the gas cannot be liquefied due to pressure). Because supercritical fluids are less viscous than liquids and easier to diffuse, they are expected to provide superior results in chemical elimination applications. 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. The workpieces subject to cleaning using the method of the present invention have been found to have a particle size on the surface of particles having a particle size greater than about 0.3 # m of not more than about 0.4 particles, and preferably not more than about 0.2 particles per square centimeter, etc. The workpiece has been found to have a surface metal contaminant concentration of not more than about 600 PP m (by SIMS method, a depth of about 10 nm ^ paper size is applicable ^ National National Standard (CNS) M specifications (2Ϊ〇 × 297 (Mm) (Please read the precautions on the back before filling out this page) -Packing * 1T Line-9-471053 Printed by A7 B7, 8 Industrial Cooperative Cooperative of Intellectual Property Bureau of the Ministry of Economy ___ V. Description of Invention (7) Measurement ) _. After applying the cleaning method of the present invention to a typical workpiece, it was found that in the surface metal contamination, not more than about 4 OO PP rn metal pollutants (except alkali metals and alkaline earth metals) and not more than Approximately 2 2 5 p P m (both measured according to SIMS method at a depth of about 10 nm) remained. One method of the present invention is based on the recognition that after the chemical elimination, the debris particles causing the problem will still exist. The C 0 2 cleaning step will certainly remove particulate pollutants, but it cannot remove non-particle surface metals. Pollutants. So far, there is no suggestion related to the present invention in the related art, that is, to remove the surface metal by chemical elimination, and then to remove any remaining debris particles by a C 0 2 cleaning step. The C 0 2 cleaning step is a chemical removal step. The specificity of the combination of the two is that traditionally, the C 0 2 cleaning step is used only after a used workpiece has been mechanically removed which will generate debris particles. . In another embodiment of the invention, methods other than the C 0 2 cleaning step can be used to remove particulate debris from the surface of the workpiece. For example, 淸 Jie can be achieved by using sonic energy instead of (: 〇 2 淸 步骤 step, or by using sonic energy plus C 0 2 淸 步骤 step. Sonic energy can be ultrasonic or megahertz The megahertz cleaning step is related to the ultrasonic cleaning step in that the former uses sound waves in the cleaning operation, however, it is different from the frequency (approximately 50- 2 500 k Η z), the megahertz sonic cleaning step uses a frequency between about 10000 k Η ζ. The present invention also relates to workpieces, such as ceramic boats used in semiconductor processing, It has been cleaned by using the method of the present invention. This paper is produced in accordance with the Chinese National Standard (CNS) A4 specification (2 丨 0X297 mm 1 ^--10- (Please read the precautions on the back first) (Fill in this page again) • Binding-Stitching Thread 471053 A7 B7 V. Description of the invention (8) (Please read the precautions on the back before filling this page) The specificity of the rhyme of the workpiece lies in its metallic and particulate surface contamination. Much lower than Surface contamination levels of previously available workpieces by methods known to those skilled in the art. DETAILED DESCRIPTION OF THE INVENTION The present invention provides a method for supplying ceramic workpieces, such as ceramic wafer boats used in semiconductor manufacturing, the metal of which The level of contamination and particle surface contamination is lower than previously available. In detail, although the use of acid cleaning is known to the artisan, and the comprehensive use of bead blasting and C 0 2 cleaning technology is also known to the art However, so far, there is no suggestion in the art: a chemical elimination step and a c 0 2 cleaning step are combined to clean unused or used coated ceramic workpieces. The chemical cleaning step can be used with The recognition of the combination of C 0 2 cleaning steps is to produce a cleaning method suitable for cleaning unused or used coated workpieces. As mentioned previously, the results of using the method of the present invention provide the following properties: Workpiece: | The particle size on the surface of this workpiece is greater than approximately 0.3 β m. The density of pollutants printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs does not exceed about 0.4 particles per square centimeter, and the surface Concentration of metallic pollutants does not exceed about 6 0 p pm (measured at a depth of about 10 nm according to the SI MS method). Traditionally, when a user receives an unused ceramic wafer boat from the manufacturer, it will cause The workpiece undergoes acid 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 subjected to chemical cleaning steps, Use a strong acid to clean it. As for washing unused workpieces, the acid cleaning step is to apply the Chinese standard (CNS) A4 specifications (210X 297 mm 1 " 11-471053 A7 B7) Printed by the Intellectual Property Bureau of the Ministry of Economic Affairs on the consumption and cooperation of employees. V. Invention Description (9) Provide a satisfactory method for removing metallic contaminants from the surface of the workpiece. Although the surface provided by the chemical elimination step has reduced its metallic contamination to a satisfactory level, this step has failed to provide a sufficiently low level of particulate contamination to the surface. In fact, there is some evidence that the chemical elimination step actually contributed to particulate contamination. Although we don't want to suffer from any special theory, we still have a high level of cleaned workpieces in cleaned workpieces, such as used ceramic boats, by using chemical removal operators to remove coatings. 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 accumulate on unused components, so that such components are exposed to an unclean house environment. 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 accumulation mechanism. As mentioned previously, the C 0 2 cleaning step has traditionally been used in combination with preliminary cleaning steps, such as bead blasting. The combination of bead blasting and CO2 cleaning steps is usually applied to unused workpieces, but has been applied to used workpieces. The workpieces are coated with CVD during semiconductor processing. On its surface, although this method has been found to remove particulate pollutants (please read the precautions on the back before filling out this page) • Binding and ordering • The paper scale is suitable for Chinese national standards (CNS> M Specifications (210X297 mm) -12- 471053 A7 B7_ 5. The description of the invention (10) is satisfactory, but it lacks the ability to remove metallic contamination that occurs on unused and used workpieces. (Please read the precautions on the back before filling this page) The present invention recognizes that before a workpiece that is an unused component or a chemically removed component is subjected to the final C 0 2 cleaning step, The problematic sub-micron particles that are removed from the surface of the component still exist. The need to remove such particulate pollutants and the way to achieve such removal are neither known nor implemented in traditional methods. , When and by the clean method (the party It is Co2 to clean the used coated workpiece) and compare the processed two modified products. The product obtained by the method of the present invention shows a superior metal purity level. As mentioned before The traditional method is to mechanically use a used component, such as a crystal boat, to spray the beads, remove the coating, and then use C 0 2 cleaning to complete the cleaning step. Any special theory, but in the case of used crystal boats, the traditional understanding is that metal pollution on the surface is not a problem. On the contrary, even if metal pollution on the surface causes problems, it is assumed that such problems can be borrowed. It is a mistake to apply technology known in the prior art to adequately eliminate it. Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economics, although evidence suggests that the bead blasting step does add metal to the surface of the workpiece The effect of the concentration of sexual impurities. This undesired effect may be the result of the use of impure spraying media. The method of the present invention is superior to traditional bead spraying / C 0 2 cleaning operations It is because it does not cause metallic contamination on the surface of the workpiece to be eliminated. In fact, the method of the present invention has the effect of reducing the metal concentration at the surface. Similarly, for unused workpieces, such as unused SLC crystals The paper size of the paper is applicable to the Chinese National Standard (CNS) A4 (210X297 mm) -13- 471053 Printed by the Consumers' Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs A7 B7__ 5. In the description of the invention (M), the surface metal impurities The general perception is this: HF or thermal HC i cleaning operations can only provide critical practicality, and Geyser's function can only gradually reduce the metal concentration at the surface of the component to slightly lower than the surface of the main material forming the workpiece. Metal concentration level (1-1 Ο ρ ρ πί) for si C, and the relative purity advantage of the host material will disappear over time, due to the high temperature environment, and subsequent use will promote The bulk metal diffuses into the surface area of the component. Therefore, this technique does not require chemical elimination in all cases. The material representing the unused s 1 C component, the surface of which has been subjected to a traditional method (X-ray photoelectron spectroscopy, XPS) and another method (secondary ion mass spectrometry, s IMS) Be analyzed. The traditional XPS analysis provides data at a depth of about 3 n m, and has a sensitivity of about 0.1 to 1.0%. The sensitivity range depends on the related elements. In contrast, the SI M S analysis provides data at a depth of about 10 nm, and has a sensitivity of about 0.2 to 3.0 ppm. 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 situations where XPS fails to detect any metal (and therefore does not provide a characterization of the rising surface metal concentration), the .SIMS test reports the presence of approximately 2000 ppm metal at a depth of 10 nm. In the field of high temperature semiconductor processing, these surface concentration levels are clearly not ideal. Medical 1 The results of SIMS analysis confirm the surface requirements of unused ceramic components and should be cleaned with a chemical removal step to reduce the high surface level of metallic contaminants present on the surface of semi-'conductor-treated components . This paper size must be in accordance with Chinese National Standard (CNS) A4 specification (210X297 mm) (Please read the precautions on the back before filling this page)-Packing. Order I · line-14-471053 Employee Consumer Cooperatives, Intellectual Property Bureau, Ministry of Economic Affairs Seal ¾ A7 ____B7_____ V. Description of the invention (12) It is understood that in one embodiment of the present invention, the surface is a c VD surface, which has been subjected to mechanical manufacturing or other post-processing steps at will. As briefly described previously, a variety of chemical scavengers can be used in the chemical removal step. In particular, it may be an acid having at least 1 V / 0 of an acid selected from the group consisting of: H F, having a P Ka less than about; the acid of [, and mixtures thereof. In a convenient embodiment, the chemical scavengers are selected from chlorinated acids. In particular, a chlorinated acid such as H C 1 may be used. Although H C 1 is ideal due to its high dissociation level, other acid chlorides, including but not limited to chloroacetic acid, chloropropionic acid, and chlorobenzoic acid can also be used. In a convenient embodiment, the chemical elimination step is performed at a temperature, i.e., above 85 ° C, which has been found to lead to improved surface purity. It is also mentioned that the chemical elimination step can be performed by using a gas-phase chemical scavenger. Exemplary gas-phase chemical scavengers include halogen gases and gases containing halogenated compounds. Thus, the chemical elimination step can be performed by using a gas-phase chlorine, fluorine, bromine, iodine, or the like, or a gas-phase chlorinated compound such as S 1 C 1 4. Gas-phase halogenated organic compounds can also be used. As mentioned previously, such compounds include, but are not limited to, 1, 1, 1-trichloroethene (TCA) and 1, 2-trans-dichloroethene (DCE). Specifically, you must understand The reason is that the method of the present invention is intended to be applied to a variety of inorganic surfaces, which 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 surface papers that are sized for the Chinese National Standard (CNS) M (210X297 mm) (Please First read the precautions on the back and then fill out this page.)-Binding Line-15- 471053 A7 B7 V. Description of the invention (13) (Please read the precautions on the back before filling out this page) Surface, such as silicon and diamond. In this way, the focus of the discussion is of course on semiconductor processing components, such as ceramic 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, sand (S i), silicon carbide (si C), nitridation (Sia N 4), diamond, yttrium oxide, zirconia (ZrO2), aluminum nitride (A 1 N), alumina (A 1 2 03), graphite and polycrystalline form fused quartz.
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Μ積而形成。此類表面包括，但不限於多 晶形或其他 c V D S i，C V D S i C.，c V D S i Ο 2 , C V D 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。 經濟部智慧財產局員工消費合作社印製 •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，簡早由S i C形成之工件乃被使用。在另 —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 1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^ - 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 1 逃出，非常純淨之/3 — S i C層乃藉由使c V D方法而被 澱積在組件之表面上。該/3 - S 1 C層係企求封合表面， 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） "" - 16- 471053 A7 B7 五、發明説明（14) 並抑制接近工件表面之s !的損失。 必須瞭解的是：澱積在工件上以防止s i逃出之点-S 1 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 被澱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， 於應用時，未用過之被塗層的工件會獲得一額外，非所欲 之塗層，而該塗層之移除乃形成本發明之一體現。 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（：〇2淸潔之本發明方法不僅 對垂璋:式框架提供意想不到之（淸潔）裨益，而且對於任 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，篩板，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。 本紙张尺度適用中國國家標率（CNS ) A4規格（21〇X297公釐） —---’--丨·--裝-- (請先閱讀背面之注意事項再填寫本頁) 訂 __線 經濟部智慧財產局S工消骨合作社印製 -17- 471053 A7 B7 經濟部智葸財凌局3(工消費合作钍印製 五、發明説明（15) 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得係因爲此類組件藉 由表面處理而帶有最低可能量之表面金屬及粒子。 詳言之，在本發明之一方法中，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〇2淸潔步驟 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〇_2淸潔後，直接被包裝，即，被放入一可封合 之容器，例如袋子內，並加以封合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。 在某些場合中，使用本發明之淸潔過之組件的人員可 能於將工件安裝於半導體處理組件前，需要額外之表面塗 層於工件上，舉例來說，於使用工件於半導體製造作業前· ，可能合意的是使一多晶砂層，一氧化砂層，一氮化砂層 (請先閱讀背面之注意事項再填寫本頁) •裝· 訂 線 本紙張尺度適用中國國家標準（CNS ) A4規格（21〇X297公釐〉 -18- 471053 經濟部智慧財產局M3C工消費合作社印製 A7 B7 五、發明説明（16) ，一金-屬層，一光阻層或某些其他層澱積在該工件上。典 型上，一旦工件已由任何包裝體取出時，半導體製造業者 必須使上述之層澱積或沈澱在工件。然而，該作業具有將 污染物引入工件表面上之潛在性。本發明.然而藉由下列 方式消除該問題：於淸潔作業完成後，以及立即於包裝二 件以供裝運或貯存前，容許工件在其表面上帶有一以上之 所需層。因此，本發明乃預期一種方法，其中，於淸潔步 驟完全後，一個以上之塗層乃被設置在工件表面上，或者 ，一旦所指之一種以上額外之塗層被設置於工件之表面上 時，任意地於包裝前，可將採用化學淸除步驟及C 0 2步驟 之第二次淸潔作業施加於受塗覆之工件上。 在某例情況中，例如當使用未曾用過之工件時，粒子 狀污染物並不需予以移除。如此，在本發明之進一步體現 中，工件先以前述方式予以化學淸除，再提供額外之表面 塗層，例如多晶形矽層，氧化矽層，氮化矽層，金屬層， 光阻層或其他層，然後予以包裝或直接予以放置在半導體 處理裝置，以供立即使用。該體現所供應之益處是：它提 供已被淸潔，塗覆之現成工件，此工件一旦由其包裝體取 出後即能立即加以使用，而不需在半導體處理裝置內進行 額外之淸潔或塗覆步驟。 純度可藉於一淸潔室環境內執行任何或所有之處理步 驟而得以進一步增強。因此來自最初化學淸潔步驟之工件 可在一淸潔室環境內予以全部整理，或於C〇2步驟，隨意 之塗覆步驟，隨意之最終化學，或隨意之c 0 2步驟前，將 本紙張尺度適用中國國家標準（CNS ) A4規格（210X2?7公釐） (请先閱讀背面之注意事項再填寫本買) -裝- 訂 -19- 471053 經濟部智慧財產局員工消资合作社印製 A7 B7 _五、發明説明（17 ) 工件移至此類淸潔室環境內。 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之酸的溶液內進行簡單淸洗的結果乃提供 一種具有不令人滿意之粒子污染物水平的表面。或者，於 一弱酸溶液內進行簡單淸洗，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（進行化學 淸除後，緊接著進行C 0 2淸潔步驟）問世以前，人們從未 能獲致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 與一改良型高純度珠子噴擊步驟偶合。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 種酸的溶劑接觸，該酸係選自下列之群體：H F，具有 p K a小於約1之酸，及其混合體。繼之，使用C 0 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 1 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 1 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 〇 〇 〇 - 2 0 0 0份/每百萬水 本紙張尺度適用中國國家揉準(CNS ) A4胁（210X297公釐） -- -20 - (請先閱讀背面之注意事項再填寫本頁) •裝· 訂 I·線 471053 A7 B7 五、發明説明（18) 平之雜質（即，0 · 1 — 0 ♦ 2 %雜質水平）。 (請先閱讀背面之注意事項再填寫本頁) 在本發明之另一體現中，化學淸潔步驟可予以消除而 代之以前述使用綠色s 1 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，化學淸除步驟之 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 一 S i C之工件可予裝設以CVD澱積之Α - 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 〇微 米之厚CVD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。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騾，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 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） -21 - 471053 經濟部智慧財產局5S工消費合作社印製 Α7 Β7 五、發明説明（19 ) 無化學谓潔步驟之方法，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 1 c之各體現中， 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欽述於U.S.Patent Application Serial Number 08 /890,116 內，發明名稱 '、 Carbon Dioxide Cleaning Process 〃者，其教示乃藉由參考 方式予以列入本文中。 進一步之改良包括於C 0 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。 貫施例 就使用於本發明方法之步驟之幾個試驗而言，所得之 結果乃予列示於後。於表1內，業已受機械製造（例如濕 式或乾式砂噴擊）之受CVD 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 砂噴擊弱酸處理後，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。 本紙張尺度適用中國國家揉準（CNS ) Α4規格（2丨0><297公釐1 -----* -22- (請先閲讀背面之注意事項再填寫本頁)The surface may be formed by vapor-deposition, and as previously discussed, it may be formed by CVD technology. Such surfaces include, but are not limited to, polycrystalline or other c V D S i, C V D S i C., c V D S i Ο 2, C V D 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. Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs • When it comes to S i C artifacts, several artifacts are used in this field. In one embodiment, the artifacts formed by S i C are used. In another embodiment, the workpiece contains S i C with reduced porosity, which is formed by loading the pores of the Si C structure with si. Since s 1 is easy to escape 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 ^ -S i C body with the α-S i C body filled with pores. In order to prevent s 1 from escaping, a very pure / 3-S i C layer is deposited on the surface of the module by using the c V D method. The / 3-S 1 C layer is designed to seal the surface. The paper size is applicable to the Chinese National Standard (CNS) A4 specification (210X297 mm). &Quot; "-16- 471053 A7 B7 V. Description of the invention (14) Loss near the surface of the workpiece! It must be understood that the point where the S 1 C material is 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 a 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, _ unused coated workpiece refers to a workpiece that is novelly manufactured with a desired coating formed on the surface, and has been used and coated workpiece refers to an undesired coating. Layer of the workpiece, the unwanted coating is deposited during semiconductor processing. Of course, during application, an unused uncoated workpiece will get an additional, undesired coating, and the removal of this coating forms an embodiment of the present invention. Although it can be used for (淸 洁) vertical frame, it must be understood that: using a strong acid, and then applying (: 〇2 淸 洁 's method of the present invention not only provides unexpected (对): Benefits), 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, focus rings, Image ring, chamber, base, lifting rod, dome, end manipulator, lining, bracket, nozzle channel, pressure channel, wafer insertion channel, sieve plate, heater, and vacuum chuck. Can be used by Examples of semiconductor processing components in the batch process applied in the present invention include, but are not limited to, stirring rods, working tubes, wafer boats, linings, cradles, wafer boats; and simulated wafers, which can be applied by the present invention. Examples of semiconductor processing components in chemical mechanical polishing include, but are not limited to, conditioning pads and wafer holders. This paper size applies to China National Standard (CNS) A4 specifications (21〇297 Li) —---'-- 丨 · --install-- (Please read the notes on the back before filling out this page) Order __ Printed by S Industrial Bone Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs-17- 471053 A7 B7 Intellectual Property Finance Bureau of the Ministry of Economic Affairs 3 (Printed by the Industrial and Consumer Cooperation V. Invention Description (15) Finally, I am convinced that this invention is the first product to be provided ready-made, that is, it can be used in the user's factory A product that can be safely and protectively removed from the bag and directly installed in a semiconductor furnace without further cleaning by the user. This product is available because such components are brought through surface treatment. There is the lowest possible amount of surface metal and particles. In particular, in one method of the present invention, the cleaned workpiece is immediately mounted to a semiconductor wafer for processing semiconductor wafers immediately after the complete cleaning step. In the furnace, or in a bag for transportation and storage of cleaned semiconductor processing components. In the former operation, the workpiece is directly transferred from the CO2 cleaning step to the furnace without further cleaning steps. In the latter operation, the workpiece is subject to C〇_2 淸 洁, Directly packed, that is, put into a sealable container, such as a bag, and sealed without further cleaning steps. In the latter case, after the workpiece is taken out of the package, The workpiece is directly installed in one of the furnaces for processing semiconductor wafers without further cleaning steps. Different from the methods known in the art (this method requires the workpiece to be removed from the package and the workpiece to be installed in the furnace). In addition, an additional cleaning step is provided): The components cleaned using the method of the present invention can be installed in the furnace immediately after being removed from its packaging. The advantage of this operation is that this operation saves additional processing steps This step may cause pollution, especially an increase in the level of particulate pollution. In some cases, personnel using the cleaned components of the present invention may require an additional surface coating before mounting the workpiece on a semiconductor processing component On workpieces, for example, before using workpieces in semiconductor manufacturing operations, it may be desirable to make a polycrystalline sand layer, an oxide sand layer, a nitrided sand layer (please Read the notes on the reverse side and fill in this page) • Binding and binding The paper size applies the Chinese National Standard (CNS) A4 specification (21 × 297 mm) -18- 471053 Printed by A3, M3C Industrial and Consumer Cooperative, Intellectual Property Bureau, Ministry of Economic Affairs B7 V. Description of the invention (16), a gold-metal layer, a photoresist layer or some other layer is deposited on the workpiece. Typically, once the workpiece has been removed from any package, the semiconductor manufacturer must deposit or deposit the above layers on the workpiece. However, this operation has the potential to introduce contaminants onto the surface of the workpiece. The present invention, however, eliminates this problem by allowing the workpiece to carry more than one desired layer on its surface after the cleaning operation is completed, and immediately before the two pieces are packaged for shipment or storage. Therefore, the present invention contemplates a method in which more than one coating is provided on the surface of the workpiece after the cleaning step is completed, or once more than one additional coating is provided on the surface of the workpiece At any time, before the packaging, a second cleaning operation using the chemical removal step and the C 02 step can be applied to the coated workpiece. In some cases, such as when using unused parts, particulate contamination does not need to be removed. Thus, in a further embodiment of the present invention, the workpiece is first chemically eliminated in the aforementioned manner, and then an additional surface coating is provided, such as a polycrystalline silicon layer, a silicon oxide layer, a silicon nitride layer, a metal layer, a photoresist layer or The other layers are then packaged or placed directly on the semiconductor processing device for immediate use. The benefit provided by this embodiment is that it provides ready-to-clean, coated workpieces that can be used immediately after being removed from their packaging without the need for additional cleaning or cleaning in the semiconductor processing equipment. Coating step. Purity can be further enhanced by performing any or all processing steps in a clean room environment. Therefore, the workpieces from the initial chemical cleaning step can be completely arranged in a clean room environment, or before the C02 step, the optional coating step, the random final chemistry, or the random c 0 2 step. The paper size applies the Chinese National Standard (CNS) A4 specification (210X2 ~ 7mm) (Please read the notes on the back before filling in this purchase) A7 B7 _V. Description of the invention (17) The workpiece is moved to this clean room environment. Although there are several previous cleansing laws, advantages and disadvantages of which have been described previously, those skilled in the art have not been able to provide the following surface: this surface has a low level that can be obtained by the inventive method described herein Metal and particle pollution levels. The result of a simple rinsing in a strong acid solution, such as a solution containing HF or other acids having a pKa of less than about 1, provides a surface with unsatisfactory levels of particulate contaminants. Alternatively, a simple rinsing in a weak acid solution followed by bead blasting results in less desirable levels of metallic contaminants. Prior to the advent of the present invention, which was followed by a chemical elimination step followed by a C 0 2 cleaning step, people had 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 coupled with an improved high-purity bead spraying step. In detail, in this embodiment, the present invention includes the step of applying a bead blast to the surface of the workpiece using green s i C particles. The surface is then contacted with a solvent with at least 1 v / 0 of 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. The surface was then treated with a C 0 2 cleaning job. In bead blasting, the specificity of using Si C is that so far, only black S 1 C has been used for bead blasting. In the present invention, it has been found that the result of spraying with green S1C beads is to provide a surface with significantly lower levels of contaminants. This is believed to be the result of the composition of black Si C beads to green Si C beads. The former contains fine sand with about 98% SiC (and impurity level of about 2%) +, while the latter contains between about 1000-2000 parts per million water-based paper. China National Standards (CNS) A4 (210X297 mm)--20-(Please read the precautions on the back before filling out this page) • Binding and ordering I · Thread 471053 A7 B7 V. Description of the invention (18) Flat Impurities (ie, 0 · 1 — 0 ♦ 2% impurity level). (Please read the notes on the back before filling this page.) In another embodiment of the present invention, the chemical cleaning step can be eliminated and replaced with the aforementioned bead spraying step using green s 1 C beads. Therefore, this method adopts the step of bead spraying with green SiC, followed by C02 cleaning. Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs. In another embodiment, the use of chemical elimination steps can be omitted when cleaning certain components. In particular, as mentioned earlier, some workpieces can be coated. 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 an A-s i C coating deposited by CVD to form a very pure surface. Similarly, SiC deposited by CVD with a thickness of up to 500 micrometers usually does not require additional mechanical manufacturing steps and therefore avoids an important source of metallic contamination. Alternatively, workpieces made of other ceramic materials can be such that these workpieces do not require certain processing steps, such as sand blasting that directs metallic impurities to the ceramic surface. 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 aforementioned surfaces will include certain low levels of unavoidable impurities. However, the level of such impurities is significantly lower than the level of impurities introduced by mechanical manufacturing steps such as sand blasting. These parts can be cleaned directly by using only CO2 or installed directly in a furnace and can be immediately packed without additional cleaning steps. Similarly, this type of packaged workpiece can be taken out of the packaged body and immediately installed in a furnace without additional cleaning steps. In this way, although the previous technique includes the use of C 0 2 operations, this paper size applies the Chinese National Standard (CNS) A4 specification (210X297 mm) -21-471053 printed by the 5S Industrial and Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs A7 B7 V. Description of the invention (19) There are no methods of chemical cleaning steps, but none of these methods are used by users of the aforementioned types of unused workpieces. By eliminating the cleaning steps required for some unused parts, cleaning time and complexity can be minimized. It must be mentioned that in the embodiments of the aforementioned green s 1 c, the C0 2 cleaning step can adopt technologies and devices well known in the art. An example of a satisfactory CO2 method and conveying system is the one described in US Patent Application Serial Number 08 / 890,116, the invention name ', Carbon Dioxide Cleaning Process, and its teachings are included by reference. In this article. Further improvements include the use of high-purity CO 2 in the C 0 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, in the cleaning During or after, any action to reduce impurities will eventually lead to a cleaner workpiece. Examples For several tests used in the steps of the method of the present invention, the results obtained are shown below. In Table 1, CVD S i C-coated components that have been mechanically manufactured (such as wet or dry sandblasted) are analyzed for impurities. These samples were measured directly after being subjected to sandblasting, after being treated with weak acid after sandblasting, or after the samples have been subjected to the method of the present invention (HF / C02). The improved metal (especially iron) removal ability provided by the method of the present invention can be seen in the table. This paper size applies to China National Standard (CNS) Α4 specification (2 丨 0 > < 297 mm 1 ----- * -22- (Please read the precautions on the back before filling this page)
471053 A7 B7 五、發明説明（20 ) 表1 -金屬性雜質，以P P m計 作業 N a A 1 Τι V C r F e N i W S 6 54 3 0.5 14 1 15 2 W S 弱酸 6 33 1 0.1 8 38 0.8 W S 本發明 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 —--^---^---β-裝-- (請先閱讀背面之注意事項再填寫本頁) 訂 經濟部智慈財產局8工消費合作社印製 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 〇 n m處測得之結果。 表2乃列示不帶有C V D塗覆表面之非機械製造樣品 上的粒子狀雜質。樣品1 - 6係受傳統之工件淸潔步驟處 理，而樣品7 - 1 0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。 本紙张尺度適用中國國家標準（CNS )八4規格（210Χ 297公釐） -23- 471053471053 A7 B7 V. Description of the invention (20) Table 1-Metallic impurities, working in PP m Na A 1 T VC r F e N i WS 6 54 3 0.5 14 1 15 2 WS Weak acid 6 33 1 0.1 8 38 0.8 WS The present 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 The present invention 7 107 20 3 4 211 4 --- ^ --- ^ --- β -Install-(Please read the precautions on the back before filling this page) Order printed by the 8th Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs WS = Wet Sand Blasting DS = Dry Sand Blasting is based on the SIMS method. Results measured at about 10 nm on the surface. Table 2 lists particulate impurities on non-machined samples without CV D coated surfaces. Samples 1-6 were processed by the conventional workpiece cleaning step, while samples 7-10 were cleaned by the method of the present invention. The number of particulate impurities is listed on the two sides of each sample. This paper size is applicable to China National Standard (CNS) 8-4 specifications (210 × 297 mm) -23- 471053
A 五、發明説明（21 ) 表2〜舫子狀菊 !質I ______ 樣品 作業 側面1 側面2 1 傳統 0.98 1.12 2 傳統 0 . 8 0.67 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 0 2 0 . 0 3 0.17 8 C 0 2 0.14 0.12 9 G 0 2 0 . 0 5 0 . 0 3 10 C〇2 0.04 0.12 ----;----裝-- (請先閲讀背面之注意事項再填寫本頁) 訂 ·線 經濟部智慧財產局員工消費合作社印製 表3乃列示於受前述C 0 2作業之處理前及後之樣品的 粒子狀雜質資料。於樣品A、B及C中，樣品係機械製造 之S i C,它不帶有一 DVD塗層在其表面上。樣品D係 一非機械製造之樣品，它帶有一CVD S 1 C表面。由 表3可見，C〇2淸潔作業之使用導致粒子狀污染物之量顯 者地減少。 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 是：由陶瓷工件移除金屬性及粒子性污染物用之新穎系統 業已被敘述。固然特別之體現已在本文中加以詳述，且上 本紙張尺度適用中國國家標準（CNS ) A4規格（210X 297公釐） -24- 471053 A7 B7 五、發明説明（22 但。及代 ，圍神取 明範精之 說利明樣 以專發各 加請本式 例申離各 施之脫作 實屬不下 之附在況 的下可情 目如明的 明制發圍 說限本範 作來期之 供用預定 僅求乃界 由企者所 藉非明圍。 已並發範飾 業例本利修 賓施，專及 事實之請變 之等言申改 述此詳如 ， (請先閱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） -25-A V. Description of the invention (21) Table 2 ~ Gardenia-like chrysanthemum! Quality I ______ Sample operation Side 1 Side 2 1 Traditional 0.98 1.12 2 Traditional 0. 8 0.67 3 Traditional 0-77 0.78 4 Traditional 0.99 0.86 5 Traditional 1.34 1.23 6 Traditional 0.79 0.86 7 C 0 2 0. 0 3 0.17 8 C 0 2 0.14 0.12 9 G 0 2 0. 0 5 0. 0 3 10 C〇2 0.04 0.12 ----; ---- install-(please Please read the precautions on the back before filling this page.) Printed in Table 3 of the Consumer Goods Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs, is a list of particulate impurities in the samples before and after the C 0 2 operation. In samples A, B, and C, the samples are mechanically manufactured Si C, which does not have a DVD coating on its surface. Sample D is a non-mechanical sample with a CVD S 1 C surface. As can be seen from Table 3, the use of CO2 cleaning operations resulted in a significant reduction in the amount of particulate pollutants. Equivalents As detailed above for the specific embodiment of the present invention, it is apparent that novel systems for removing metallic and particulate contaminants from ceramic workpieces have been described. Although the special embodiment has been detailed in this article, and the above paper size applies the Chinese National Standard (CNS) A4 specification (210X 297 mm) -24- 471053 A7 B7 V. Description of the invention (22 dan. And generation, wai God said that Ming Fanjing said that it is necessary to send this example and apply this example to apply for the separation of each application. The situation is clear and clear. The intended supply is only required to be borrowed by the enterprise but not the Mingwei. The fan industry has been concurrently benefited from the Benxi repair, and the special and factual please change the words. Please read the details. (Please read the back Please fill in this page for the matters needing attention) The paper printed by the Employees' Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs applies the Chinese National Standard (CNS) A4 specification (210X297 mm) -25-