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研究生： 林欽山
ching-shan Lin
論文名稱： 大型高純度氧化鋁物件製程與其在NF3/Ar電漿蝕刻行為
Processing of Large Alumina Components of High Purity and the their Etching Behavior in a NF3/Ar Plasma Environment
指導教授： 林舜天
Shun-Tian Lin
洪儒生
Lu-Sheng Hong
口試委員: 金重勳
Tsung-Shune Chin
王錫福
Sea-Fue Wang
朱瑾
Jinn P. Chu
學位類別： 博士
Doctor
系所名稱： 工程學院 - 材料科學與工程系
Department of Materials Science and Engineering
論文出版年： 2008
畢業學年度： 97
語文別： 中文
論文頁數： 310
中文關鍵詞： 電漿 、蝕刻 、氧化鋁
外文關鍵詞： plasma, etching, alumina
相關次數： 點閱：379  下載：3 
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    • 12吋半導體製程中之化學氣相沉積設備反應室內，所需之精密氧化鋁陶瓷，必須具備有高純度、能抵抗電漿環境中的侵蝕性氣體與300mm以上大尺寸物件的特性。所以，胚體成型的技術是一項重要課題，更需要鑽石工具以CNC工具機加以研磨加工，方能達到精度之要求。在半導體製程中，薄膜不僅會沉積於矽晶圓上，也會附著於反應室內部的氧化鋁表面上，形成不需要的殘渣，必須以電漿清洗反應室的內壁，以維護一定的穩定性。而高純度氧化鋁仍然含有微量的氧化矽雜質，此雜質並且傾向偏析於晶界上，在具蝕刻性的電漿環境下，顯然晶界較易受到侵蝕。因此探討氧化鋁材質與蝕刻性氣體之間的關係是有必要的。本研究在製程方面，藉由冷均壓成型方法，利用六種不同分佈的粉末顆粒，經由不同的冷均壓成型壓力設計。得知分佈比較寬廣的高純度氧化鋁粉末顆粒，經由壓力提升與持壓時間加長，可以有效抑制雙分佈晶粒結構的產生，而得到均勻的微結構。並且利用熱機力學分析（Thermo-mechanical Analysis, TMA）觀察到冷均壓成型壓力、粉末粒度分佈與胚體熱物理性質關係，也完成了大型的高純氧化鋁工件的製作。而本研究在研磨加工方面，使用三種不同成分之銅基合金，包括Cu合金、Cu-15Sn合金及Cu-15Sn-10Ti合金。從穿透電子顯微鏡繞射圖與X光繞射兩個分析方法，都證實Cu-15Sn-10Ti基材之鑽石工具中，鑽石與合金基材的中間介面層之材料為碳化鈦。pin-on-disk型式磨耗試驗與震動頻譜觀察研磨加工時，Cu-15Sn-10Ti基材之鑽石工具，有很好的效能研磨於高純度氧化鋁工件與自銳性。本研究在應用方面，利用純度99.90%與99.14%的氧化鋁試片，於PECVD設備內，使用NF3/Ar為蝕刻電漿環境，並且利用了光放射光譜（Optical Emission Spectroscopy, OES）分別觀察在270℃、300℃與350℃時的氟原子於685.75nm與氬離子750nm特定波長的強度比值。此比值轉換為Arrhenius經驗式求得蝕刻能，得知高純度氧化鋁擁有比較高的蝕刻能與比較不易與蝕刻性電漿反應的結果。

    Large alumina components, as large as 300 mm, of high purity are used in the chemical vapor deposition reactor chamber in 12-inch semiconductor processes, which can effectively resist plasma erosion. Hence, the shaping technology of green body is an important issue, in addition to an efficient and secure sintered body CNC machining procedure. In semiconductor processing, thin film is deposited not only on silicon wafers, but also on the alumina components inside the reactor chamber. In order to stably fabricate integrated circuits on silicon wafers, a plasma cleaning process must be applied to clean the interior wall of the reactor chamber. Accordingly, it is also necessary to study the relation between alumina and the plasma etching gas. In this study, alumina components were shaped by cold isostatic pressing, using spray-dried alumina granules of six different granule size distributions pressed under different pressuring profiles. The results indicated a high density could be achieved using an alumina granule with a wider distribution, and applying a larger pressure for a longer pressing time, which could substantially suppress the formation of a bimodal microstructure subsequent to sintering. A thermo-mechanical analysis could reveal the differences in sintering arising from the variations in granule size of the spray-dried powder and green body shaping pressure on the sintering behavior, which is crucial to the success of making large alumina components. In the CNC machining of the sintered components, three different diamond tools using different bonding matrices were compared, including Cu, Cu-15Sn, and Cu-15Sn-10Ti (wt%). Using Cu-15Sn-10Ti as the bonding matrix, a TiC layer was formed between the diamond grits and the bonding matrix, which effectively improved the retention of diamond grits during grinding. A self-dreesing effect was achieved in the diamond tool using Cu-15Sn-10Ti as the bonding matrix, which was evidenced in the vibration measurement during CNC machining and the frictional force measurement in pin on disk test. Alumina components of two different purity levels, including 99.90% and 99.14% respectively, were then etched in a NF3/Ar plasma environment, and wave length intensity ratio of fluorine ion (685.75 nm) to argon ion (750 nm) at 270℃, 300℃ and 350℃, respectively, were then recorded using an optical emission spectroscope. The intensity ratio was then transferred into Arrhenius plot and the activation energy for the etching of alumina could be resolved. Alumina of higher purity possesses a higher activation energy of etching and was more difficult to etch in a NF3/Ar plasma environment.

    論文摘要 I ABSTRACT III 誌 謝 V 目 錄 VI 圖表索引 X 第一章 緒論 1 1.1 研究動機與目的 1 1.2 論文組織與結構 6 第二章 文獻回顧與理論探討 7 2.1 陶瓷粒子的分散 7 2.2 電雙層理論[49-52] 9 2.3 懸浮液的穩定性與立體空間穩定作用[51] 11 2.4 研磨分散機構 13 2.5 冷等均壓成型機構[58] 14 2.6 粉末顆粒大小與其分布在冷等均壓成型與燒結的影響 18 2.7 固態燒結理論與晶粒成長 19 2.7.1 燒結理論糢型 19 2.7.2 緻密化與晶粒成長[34, 46, 76, 78] 32 2.8 鑽石工具特性 34 2.8.1 鑽石工具成份與製程之分類 35 2.8.2 金屬基材結合鑽石相關之研究 37 2.9 震動頻譜應用於評估鑽石工具研磨加工氧化鋁的效能分析 41 2.10 半導體製程上的電漿（PLASMA）的基本原理[30, 92-94] 46 2.10.1. 電漿的成份 46 2.10.2. 電漿的產生 47 2.10.3. 電漿中的碰撞 48 2.10.4. 電漿的參數 52 2.10.5. 離子轟擊 58 2.10.6. 直流偏壓 59 2.11 半導體製程上的電漿（PLASMA）薄膜的沉積與蝕刻製程[30, 92-94] 63 2.11.1. 化學氣相沉積（Chemical Vapor Deposition，CVD） 63 2.11.2. 電漿蝕刻 68 2.12 電漿輔助化學氣相沉積法（PECVD）及電漿蝕刻反應器[23, 30, 92, 93] 76 2.12.1 製程的差異性 76 2.12.2. CVD反應室設計 76 2.12.3. 蝕刻反應室的設計 77 2.13 遙控電漿製程（REMOTE PLASMA PROCESSES）[92, 93] 79 2.13.1. 光阻剝落 79 2.13.2. 遙控電漿蝕刻（Remote Plasma Etch） 80 2.13.3. 遙控電漿清潔法（Remote Plasma Clean） 80 2.13.4. 遙控電漿CVD（RPCVD） 81 2.14. 高密度電漿[92, 93] 82 2.14.1. 感應耦合型電漿（ICP） 82 2.14.2. 電子迴旋共振（ECR） 84 2.15 介電質CVD反應室的清潔[92, 93] 86 2.15.1. RF電漿清潔 86 2.15.2. 遙控電漿清潔 88 2.15.3. 蝕刻製程終點 91 2.16 電漿薄膜沉積與氧化鋁表面之關係 95 2.17 放射光譜（OPTICAL EMISSION SPECTROSCOPY, OES）原理[23, 123] 104 2.18. 光放射光譜分析應用於具有環保的NF3/AR電漿與其功能 107 2.18.1. 環保議題與NF3/Ar電漿的使用的關係與其特性 107 2.18.2. 以光放射光譜分析應用於NF3/Ar電漿的功能 113 第三章 實驗與研究方法 121 3.1 粉末粒徑與其分佈於冷等均壓成型中對氧化鋁之影響 121 3.1.1. 粉末粒度與冷等均壓成型之關係與大型高純度氧化鋁物件的製作 121 3.1.2. 粉末顆粒與成型之重要儀器與設備 123 3.2 自銳性鑽石工具組成研磨加工於高純度氧化鋁效能分析 127 3.2.1. 震動頻譜之應用於研磨加工之效能評估 127 3.2.2. 自銳性鑽石工具基材組成與研磨加工之測試條件 129 3.3. 不同粗糙度的氧化鋁表面長SIO2膜機構設計 132 3.4 NF3/AR電漿蝕刻於氧化鋁機構設計 134 第四章 研究結果與討論 138 4.1 粉末顆粒大小與其分布在冷等均壓成型的影響 138 4.2 自銳性鑽石工具加工於氧化鋁研磨效能分析 183 4.2.1. 鑽石結合基材合金的分析 183 4.2.2. 研磨加工於氧化鋁之效能評估 185 4.3 PECVD電漿沉積SIO2膜於不同粗糙度的氧化鋁表面結果 206 4.4 NF3/AR電漿蝕刻於氧化鋁結果 214 第五章 結論 225 5.1 粉末顆粒大小與其分布在冷等均壓成型影響 225 5.2. 自銳性鑽石工具研磨加工於氧化鋁研磨效能分析 226 5.3. PECVD電漿沉積SIO2膜於不同粗糙度的氧化鋁表面 227 5.4. NF3/AR電漿蝕刻於氧化鋁 228 5.5. 總結 229 參考文獻 231 附錄 243 作者簡介 304

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