TW200934743A - Method of making ceramic reactor components and ceramic reactor component made therefrom - Google Patents

Method of making ceramic reactor components and ceramic reactor component made therefrom

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Publication number
TW200934743A
TW200934743A TW097126675A TW97126675A TW200934743A TW 200934743 A TW200934743 A TW 200934743A TW 097126675 A TW097126675 A TW 097126675A TW 97126675 A TW97126675 A TW 97126675A TW 200934743 A TW200934743 A TW 200934743A
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Taiwan
Prior art keywords
ceramic
component
texturing
textured
unsintered
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Application number
TW097126675A
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English (en)
Inventor
Timothy Dyer
Ho Ouk
Louis Everett Jensen
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Morgan Technical Ceramics Auburn Inc
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Publication date
Application filed by Morgan Technical Ceramics Auburn Inc filed Critical Morgan Technical Ceramics Auburn Inc
Publication of TW200934743A publication Critical patent/TW200934743A/zh

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    • C04B41/53After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone involving the removal of at least part of the materials of the treated article, e.g. etching, drying of hardened concrete
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B28WORKING CEMENT, CLAY, OR STONE
    • B28BSHAPING CLAY OR OTHER CERAMIC COMPOSITIONS; SHAPING SLAG; SHAPING MIXTURES CONTAINING CEMENTITIOUS MATERIAL, e.g. PLASTER
    • B28B11/00Apparatus or processes for treating or working the shaped or preshaped articles
    • B28B11/08Apparatus or processes for treating or working the shaped or preshaped articles for reshaping the surface, e.g. smoothing, roughening, corrugating, making screw-threads
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    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01JELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
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Description

200934743 九、發明說明: 【發明所屬之技術領域】 本發明係關於半導體反應器中所用組件之製造及恢復, 且尤其係關於在此一組件上提供粗糙化表面以提供金屬化 或其他殘餘物層的經改善黏著力之方法。 【先前技術】 雙金屬絲電弧喷塗(TWAS)鋁(A1)及電漿喷塗陶瓷膜通常 係用於塗佈半導體反應器組件表面。該等膜藉由提高表面 0 粗糙度以提高組件壽命。在T WAS製程中,純A1經由兩個 金屬絲連接產生的電弧霧化並藉由空氣噴射輸送至基板。 金屬絲係鋁沈積之來源。'藉由電漿喷塗方法使用粉末化原 料並使用空氣或氮氣作為推進劑來沈積A卜氧化鋁、氧化 鈦、氧化釔及氧化锆膜。圖1顯示PVD膜/TWAS/粗糙化氧 化鋁堆疊佈置10之實例《堆疊10形成於由金屬、石英或陶 瓷材料製成之基板12上。將陶瓷層14施加至基板12之上。 TWAS層16形成於陶瓷層14之上且PVD臈18沈積於TWAS層 〇 之上。一般而言’彼等膜提供粗糙的、通常表面粗糙度為 約 300-1200 μίη Ra之表面。 ,研磨介質噴射亦已用於粗糙化經陶瓷塗佈之室組件表 面。由於氧化鋁陶瓷之硬度,當使用研磨介質噴射時,通 常將所用表面粗糙度限制於1 00 μίη Ra以下。該低粗糙度 限制TWAS及電漿喷塗膜對陶瓷表面之黏著力。對於藉由 CVD或HDPCVD沈積的二氧化矽膜、藉由PVD、SiP、及 IMP PVD沈積的金屬膜(例如Al、Cu、Ta、TaN、Ti、 133097.doc 200934743
TiN、Ni、W)、及自晶圓電漿清潔及乾触刻產生之钱刻副 產物(例如A1、矽石、金屬氧化物)、及多晶矽蝕刻方法而 言,粗糙化表面係用於捕獲沈積物及處理副產物及殘餘 物。
Schutze, "Failure of Oxide Scales on Advanced Materials Due to the Presence of Stresses", High Temperature
Corrosion of Advanced Materials and Protective Coatings,
Elsevier Science Pub (1992)教示理想表面係具有峰至谷高 〇 波幅之正弦表面。高峰至谷表面波形(粗縫度)使得壓縮應 力可自拉伸脫層力轉化為剪切力。易碎固體(例如反應器 殘餘物或電漿喷塗膜)在剪切力下比在張力下更堅固。因 此,高波幅粗糙波形膜可為該等壓縮膜提供最佳錨。另 外’ CVD、PVD及蝕刻膜殘餘物在陶瓷組件表面上非均相 成核。其亦以相同方式在TWAS塗佈或電漿喷塗膜表面成 核。非均相成核依賴於尖端表面(凹凸體)以自氣相開始膜 生長。較尖端可促進成核且大型規則性敏密凹凸體陣列將 冒 促進膜在基板上均勻生長。因此,殘餘物生長及黏著之理 想表面係具有整體一致粗糙度之高波幅高頻波形表面。殘 .餘物黏著之理想表面紋理特性係粗糙度大於4〇〇 U英吋Ra 且峰至谷粗糙度介於2000-5000 u_in之間之均勻表面。 粗糙表面藉由改變表面應力進而降低施加在表面上的分 離/彎曲力而增強沈積(製程產物或副產物)殘餘物在以電漿 為主的反應器組件上之黏著力。容納更多膜殘餘物導致室 内組件之使用壽命延長。粗糙表面藉由將易拉出膜殘餘物 133097.doc 200934743 之張應力轉變成剪切力來降低變曲力。由於該等殘餘物實 質上係易碎的,故其在剪切力下比在張力下堅固。可在 CVD、PVD或#刻室組件上發現壓縮沈積產物及副產物。 該等組件可為室屏蔽、陰極(其中Si晶圓經塗佈)附近的環 及/或製程鐘形罩。晶圓附近所用環形組件包括沈積環、 • 壓緊環及蓋環。圖2A至2D顯示陶£組件實例。更具體而 言,圖2A顯示氧化⑪製圓頂,圖2B顯示聚焦環,圖^顯 不邊緣環’及圖2D顯示侧屏㉟。當沈積變得過厚時,定期 〇 蝕刻組件以去除沈積殘餘物(經清潔)。由於反應器殘餘物 具有壓縮應力特性,TWAS或電聚喷塗材料與沈積(或組 件)表面間之介面應力最終可變得高至足以剝離陶究組件 之TWAS或電漿喷塗膜。由此產生殘餘物及粗糙黏合層之 剝離或壓縮應力驅動之膜脫層。因此,粗糖表面膜及/或 製程殘餘物層對反應器組件之黏著力限制反應器組件之使 用哥命。 使沈積或㈣組件具有長❹壽命的重要需求係多次清 «良好的对酸腐勒性及使製程殘餘物黏著力豸大化之高 粗链度。本發明方法提供耐酸性粗縫化氧化紹或氧化結反 應器組件,其具有能提高TWAS及製程殘餘物二者黏著力 之紋理化表面。 TWAS及電漿嘴塗膜對氧化銘組件之點著力在性質上一 般係化學性較弱且機械性較強。氧化錐提供較佳twas黏 著力乃因其藉由喷珠較易粗糙化其表面。氧化錯亦因其對 鋁具有化學親和性而較為有利。對TWAS主要關注之一係 133097.doc 200934743 其對氧化鋁之黏著力。通常實踐係對硬化氧化鋁及氧化錘 實施喷珠以提供紋理《然而,由於彼等材料之高硬度不 可能以研磨方式將該等基板粗糙化5〇 μίη Ra以上而不產生 顯著表面下損傷。甚至在50 μίη Ra的粗梭度下,氧化鋁中 亦可產生某些表面下損傷。在喷珠過程中,氧化鋁中亦引 入表面缺陷。該等缺陷在晶圓處理中導致顆粒污染且當膜 處理殘餘物積累時促進TWAS/氧化鋁表面之内聚失效。對 該問題之一個嘗試性解決方法係喷珠後對氧化鋁實施退 ❹ 火。然而,退火不能修復大型表面下缺陷。 【發明内容】 藉由本發明提供之方法及物件可顯著解決上述已知方法 及物件之缺點。根據本發明之第一態樣,其提供改善處理 材料在陶竟組件上之黏著力之方法。方法包括形成未燒結 陶瓷組件及紋理化未燒結陶瓷組件表面之步驟。然後燒製 已紋理化之組件以硬化陶瓷材料。 _ 根據本發明之第二態樣,其提供改善處理材料在陶瓷組 件上之黏著力之另一方法。方法包括形成未燒結陶瓷反應 器組件及紋理化未燒結陶瓷組件表面之步驟。然後燒製已 紋理化之組件以緻密化及硬化陶瓷材料。然後將塗層施加 至已燒製之陶瓷組件表面以提供第二黏著層。 根據本發明之第三態樣,其提供用於蝕刻或沈積反應器 至中之組件。本發明此態樣之組件包括由陶瓷材料形成之 基板。基板具有形成於其上之紋理化表面,其令該紋理化 表面之粗糙度約為100_1000 μίη Ra。 133097.doc 200934743 【實施方式】 本發明方法允許製造氧化鋁及氧化锆組件(圓頂、環、 屏蔽等),其對TWAS、電漿喷塗及/或其他反應器製程殘 餘物具有經改善之黏著力。改善該黏著力可延長組件使用 壽命。當陶瓷處於未燒結狀態時(即燒製之前),藉由紋理 化陶瓷組件表面可改善TWAS/殘餘物黏著力。當組件表面 實質上係軟及聚合物本質時,可以最小表面下損傷完成該 製程。然後將紋理燒製於組件内,且由於陶瓷材料提供極 © 佳耐酸腐蝕性,故可在多個組件循環中保持該紋理。已燒 製基板上形成有紋理化表面,其中紋理化表面之粗糙度約為 100-1000 μήι Ra。較佳地,紋理化表面之粗糙度為至少約 150μίη. Ra,且更佳地,粗糙度為至少約2〇〇μίη Ra。 參見圖3,其顯示根據本發明在陶瓷組件上提供粗糙化 陶瓷表面之方法之實施例的基本步驟。在步驟31〇中,等 靜壓壓縮陶瓷粉末以形成呈期望組件之一般形狀之生壓 @。等靜壓壓縮可使用濕式布袋或乾式布錄術來實施。 在步驟320中,藉由未燒結機械加工技術(例如)使用具 有超硬刀具之數值控制機械將生壓坯機械加工成近終形。 • 在步驟330中,使用下述任一技術對經機械加工之生壓坯 表面實施紋理化《可將硬或軟掩膜應用於不需要紋理化表 面之生壓坯區域。 在步驟340中,將紋理化陶竟層燒結成終形或近終形。 如步驟350所述,燒製後,可對組件實施進一步機械加工 及/或整平以滿足特定處理套組應用之精確幾何要求。如 133097.doc -10- 200934743 步驟360所述,可原樣使用經陶瓷塗佈之組件或可例如藉 由TWAS或電漿喷塗施加金屬層。在TWAS或電漿喷塗塗 佈之刖’紋理化組件表面不需經研磨劑喷砂處理。燒製成 的紋理化表面即使未經塗佈亦可用於反應器室内累積製程 殘餘物。 在實際試驗中,已可生產粗糙度超過9〇〇 μίη &且經針 筆輪廓測量儀所量得之範圍(峰至谷)超過4〇〇〇 μίη之氧化 鋁環及屏蔽表面。 〇 本發明紋理化步驟330可按多種不同方式來實施。在第 一實施例中,用高純度氧化鋁或氧化錯之喷霧乾燥球體來 噴射陶瓷生壓坯。彼技術提供上凸及下凹紋理化表面之組 合’乃因其在表面上提供極小壓痕(下凹紋理)及某些附著 於表面之陶瓷球體(上凸紋理)。在另一實施例中,藉由將 同純度氧化鋁或氧化錯粉末與丙烯酸或聚乙稀醇(pVA)黏 結劑混合之濃釉漿或漿液喷塗於未燒結陶瓷表面上來紋理 化該未燒結陶瓷塗層。較佳地,釉漿中包括分散劑以幫助 ® 喷塗。 喷塗搶通常具有30度風扇。在某些情形下,喷塗風扇可 更大。當漿液喷塗及喷霧乾燥微粒技術用於本發明未燒結 紋理化方法時,如圖4所示氧化鋁表面所形成之粗糙部分 可具有分支《吾人已在紋理化氧化锆表面上觀察到粗糙度 大於600 Uin Ra之分支結構。基於吾人已獲得之拉力試驗 數據,吾人已推論出分支型粗糙度不利於殘餘物黏著並實 際上可降低殘餘物之黏著強度。因此,較佳將嘴塗顆粒或 133097.doc ,, 200934743 漿液液滴基本垂直地引導至未燒結陶瓷表面,而非以與陶 瓷表面成斜角之方式引導。 現在參見圖5,其中顯示物理準直器5〇〇,其係用於過濾 來自噴嘴520且以基本不垂直於待紋理化部分之表面53〇行 進之液滴510。準直器500係用作過濾器以阻止由喷嘴以斜 角行進之液滴。準直器500之較佳實施例為其内具有孔之 板。準直器係位於喷嘴520與基板表面530之間。準直器較 佳具有&截面為六角形之孔,如圖6A所示;但亦可使用具 ❹ 有其他幾何形狀之孔(例如圓形孔),如圖6B中所示。該板 較佳係約1-3英吋厚。 或者’藉由將氧化鋁/氧化锆與丙烯酸/PVA混合物之稀 釉漿刷塗至生壓坯表面來實施紋理化。紋理化未燒結陶竟 之另一技術係用由99%純的氧化鋁、氧化鍅或氧化釔組成 之膜電漿喷塗生壓坯。紋理化生壓坯之另一技術包括用精 細介質對該壓坯實施喷射以在生壓坯表面上形成複數個極 小壓痕。用於此技術之較佳介質係高純度氧化鋁球體、高 ® 純度氧化锆球體、塑料球體、玻璃珠、核桃殼、糖及玉米 穗。作為另一選擇,未燒結陶瓷材料可經壓花紋裝置或經 硬毛刷紋理化。 當實施任一前述紋理化技術時,可將掩膜應用於未燒結 陶瓷材料中以使僅紋理化表面所選區域,如圖2E所示般。 掩膜可為諸如膠帶或另一撓性織物等應用於生壓坯表面之 軟掩膜。或者,可將硬掩膜(例如由金屬或其他硬材料製 成之板或帶)定位於所選區域上。較佳地,若掩蔽不足, 133097.doc 12 200934743 可藉由鑽石研磨移除紋理化表面β TWAS或反應器殘餘物之目標黏著強度係等於或大於經 退火Α1之拉伸強度,通常為約1〇〇〇〇13〇〇〇 psi。當前, 使用環氧樹脂拉力試驗所量得TWAS對氧化鋁之黏著力通 常為3,000-5,000 psi。由於氧化锆對μ之化學親和力,據 k TWAS對氧化锆之黏著力係大約5 〇〇〇 7 〇〇〇 psi。在實際 5式驗中,吾人使用藉由本發明之燒製紋理化方法製備之試 樣來量測TWAS剝離強度,其超過1〇 〇〇〇 psi。使用上述技 ® 術製成之試樣表面通常提供至少7,500 psi之剝離強度。該 鬲鍵結強度應藉由降低週期性清潔頻率來使反應器組件之 使用壽命延長高達3〇〇〇/0。 經氧化鋁-及經氧化鍅塗佈之反應器組件(例如圓頂、屏 蔽及蓋環)之特徵在於已在未燒結狀態下紋理化之經燒製 表面可比表面僅經TWAS或電漿喷塗膜塗佈之組件潛在具 f較厚製程殘餘物。該等中間膜之黏著強度將不再係組件 公 奇命之影響因素,由此消除"鏈中弱連接"。CVD、PVD及 餘刻室殘餘物緊密附著於陶£上,且在優化表面上之黏著 強度可能超過12,000 ps卜另外,可對未燒結陶瓷表面本 身實施掩蔽及沈積或喷珠,因此產生微觀黏著圖案及可見 黏著圖案。形狀或圖案可成像至組件表面内,由此改善對 以製程副產物形式產生之壓縮膜之管控。紋理化圖案可由 柵格或尺寸範圍為0.U mm直徑之點、星形 '橢圓形或正 方形之隨機圖案所組成。 實例 133097.doc -13- 200934743 下述係本發明方法之預見性實例。等靜壓壓縮包含丙烯 酸或PVA基黏合劑之喷霧乾燥氧化㈣聽末以形成呈環 /弋之生壓趣。开》成之環具有3英对外徑、0.75英叶内徑 英t厚度。在12000-6000 psi、較佳15 000 PSI壓力 _ 下,藉由濕式布袋等靜壓壓縮形成生壓坯,但亦可使用乾 式布袋方法。 垄縮後使用數值控制機械(例如Hass CNC車床)及傳統 超硬刀具將生壓场機械加工至近終形。機械加工後,可掩 G ㈣分環’之後實施紋理化。在良好通風之卫業喷漆室内 使用市售自動化设備來完成紋理化製程。在此實例中,將 環置於26直徑之工業轉臺上之12"半徑處。紋理化藉由在 40-80 PSI範圍内、較佳6〇 psi之壓力下作業之工業粗砂喷 射搶實施。將與生壓坯(PVA或丙烯酸黏合劑)具有相同無 機組成之噴霧乾燥氧化鋁球體(其尺寸係-1〇〇至+325目、 較佳+230目)置於供至粗砂喷射搶中之材料中。裝載搶之 後,將其直接置於轉臺上組件路徑上方約2·6英吋、較佳 約4英吋處。使用振蕩支架使喷射槍在多達4英吋範圍内左 右掃掠。振蕩速率可介於約1〇次振蕩/分鐘與約6〇次振蕩/ 分鐘之間。較佳地,振蕩速率係約2〇次振蕩/分鐘。以ι〇· 40轉/分鐘、較佳約5_10轉/分鐘啓動轉臺,及啓動電磁閥 以為喷射槍提供空氣^然後使喷霧乾燥氧化鋁顆粒揸擊至 未燒結組件表面中,其中某些顆粒黏附於其上且其他顆粒 彈開,由此產生粗糙表面。實施紋理化約304 2〇秒、較佳 約60秒。完成紋理化後,停止通氣並小心自轉台移除部 133097.doc 14 200934743 分。 爾後,使用工業氣體乾燥爐於15〇〇_17〇〇〇c溫度下燒結 紋理化陶究層至近終形。燒製後,組件之表面粗輪度特徵 可使用光學面形測定器(例如由Wyco of Tucson、Ariz〇na 所售者)或針筆輪廓測量儀(例如由曰本Mitut〇y〇所售者)來 測疋。可原樣使用紋理化組件或將其進一步機械加工以提 供更精確尺寸。燒製後表面粗糙度係介於1〇〇_6〇〇 pin Ra 之間並與紋理化時間成正比。圖7顯示由本發明方法製成 β 之陶瓷組件之已燒製表面。組件表面具有峰及谷之均句分 佈及至少約100 μίη 1之表面粗糙度。 如步驟360所述,藉由(例如)TWAS或電漿喷塗可將第二 金屬層施加至紋理化陶瓷基板上。TWAS或電漿喷塗塗佈 之前,紋理化組件表面不需經研磨劑喷砂處理。已燒製成 的紋理化表面即使未經塗佈亦可用於在反應器室内累積製 程殘餘物。圖8顯示根據本發明製成之陶瓷反應器組件之 複合層結構。陶瓷基板810具有紋理化表面區域812。藉由 ® TWAS技術,鋁層814沈積於陶瓷基板810之上。藉由 PVD ’组外層816形成於鋁層814之上。 - 【圖式簡單說明】 參照附圖閱讀可更好地理解前述說明及下述實施方式, 其中: 圖1係已知類型層狀組件之局部剖面; 圖2A至2D係用於半導體電路處理室中之已知陶究組件 之照片; 133097.doc •15· 200934743 圖2E係根據本發明處理之陶瓷組件之照片. 圖3係根據本發明方法實施例之流程圖;
圖4係根據本發明處理之陶竟組件& A 卞句部剖面之顯微照 片; 圖5係用於本發明方法中之準直裝置之佈置示音圖; 圖6A及6B係圖5準直裝置中孔室之幾何形狀之局部示意 圖; 圖7係根據本發明製成之陶瓷組件部分表面之照片(放大 ❹ 15x);且 圖8係根據本發明具有第二黏著層的陶瓷組件之局部立, 面顯微照片(放大ΙΟΟχ) 〇 ° 【主要元件符號說明】 10 PVD膜/TWAS/粗糙化氧化铭堆疊佈置 12 由金屬、石英或陶瓷材料製成之基板 14 陶瓷層 16 TWAS 層 18 PVD膜 500 物理準直器 510 液滴 520 噴嘴 530 待紋理化部分之表面 133097.doc •16-

Claims (1)

  1. 200934743 十、申請專利範圍: 1 · 一種改善處理材料在陶瓷組件上之黏著力之方法,其包 含以下步驟: 形成未燒結陶瓷反應器組件; 紋理化該未燒結陶瓷組件之表面;及然後 燒製該紋理化陶瓷組件使其緻密化及硬化。 2.如請求項1之方法,其中該紋理化步驟包含用紋理化介 質喷射該未燒結陶瓷組件表面之步驟。 ® 3·如請求項2之方法,其中該紋理化介質包含精細、高純 度陶瓷球體。 4. 如請求項3之方法,其中該等陶瓷球體係由高純度氧化 銘或高純度氧化鉛形成。 5. 如請求項2之方法’該紋理化介質係選自由下列各物組 成之群:氧化紹顆粒、氧化錯顆粒、塑料球體、玻璃 珠、核桃殼、糖 '玉米穗及其組合。 6·如請求们之方法’其中該紋理化步驟包含對該未燒結 髎 陶兗組件表面實施壓花紋之步驟。 7’如請求们之方法’其中該紋理化步驟包含刷塗該未燒 • 結陶瓷組件表面之步驟。 8.如請求項1之方法,其中該紋理化步驟包含施加包含含 有陶究粉末及黏結劑的釉漿之塗層之步驟。 如明求項8之方法,其中該施加該塗層之步驟包含用含 有該陶竞粉末及該黏結劑之稀釉激刷塗該未燒結陶竟組 件表面之步驟。 133097.doc 200934743 !〇.如請求項8之方法,其中該施加 ^ ^ 步驟包含用含 有該陶瓷粉末及該黏結劑之濃釉漿 件表面之步驟。 聚货盒該未燒結陶究組 u.=:r:’該喷塗步驟包含經由準直器或過濾 器嘴堂該塗層之步驟。 12. 如凊求項8、9或10之方法,其中今陷 丹甲该陶是粉末係高純度氧 化銘氣末或高純度氧化锆粉末。 13. 如請求項1至j j中任一項 孭之万去其包含在實施該紋理 化步驟之前將掩骐應用於該未燒結陶 -種改善處理材料在陶究組件上之黏著力之之方步法驟,其包 含以下步驟: 形成未燒結陶究反應器組件; 紋理化該未燒結陶瓷組件表面; 燒製該紋理化陶瓷組件以使其緻密化及硬化;及然後 用第二黏著層塗佈該紋理化且經燒製之陶瓷組件表 面。 ❹ 15.如請求項14之方法,其中該表面塗佈步驟包含將鋁層雙 金屬絲電弧喷塗(TWAS)至該組件表面上以形成該第二黏 著層。 16·如請求項14之方法,其中該表面塗佈步驟包含電漿噴塗 選自由下列各物組成之群之材料層之步驟:鋁、氧化 記、氧化锆、二氧化铪及其組合。 17. —種用於餘刻或沈積反應器室之組件,其包含: 由陶瓷材料形成之基板;及 133097.doc 200934743 在該基板上形成之紋理化表面,其中該紋理化表面之 粗链度為約100-1000 μίη Ra。 1 8·如印求項丨7之組件,其中該組件係選自由環圓頂及屏 蔽組成之群之部件。 19·如明求項17之組件,其包含形成於該紋理化表面上的第 二黏著層。 20.如請求項19之組件,其中該第二黏著層包含選自由下列 各物組成之群之材料:鋁、氧化纪、氧化錯、二氧化給 ❹ 及其組合。 21·如請求項17之組件,其中該紋理化表面包含形成於該陶 瓷材料中的壓痕。 22·如請求項17之組件’其中該紋理化表面包含粉末化陶究 材料層。 23.如請求項22之組件,其中該陶瓷材料包含高純度氧化鋁 粉末或高純度氧化鉛粉末。 φ 133097.doc
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