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研究生： 陳珮儀
Pei-Yi Chen
論文名稱： 無電鍍銅在Ta(N)阻隔層上成核與成長之研究
A Study on Nucleation and Growth of Electroless Copper on Ta(N) barrier
指導教授： 林樹均
Su-Jien Lin
口試委員:
學位類別： 碩士
Master
系所名稱： 工學院 - 材料科學工程學系
Materials Science and Engineering
論文出版年： 2001
畢業學年度： 89
語文別： 中文
中文關鍵詞： 無電鍍銅 、阻隔層 、濕式活化法 、金屬化
外文關鍵詞： electroless copper, barrier, wet activation, metallization
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    • 本實驗以AFM、SEM、TEM研究Ta(N)/SiO2/Si無電鍍銅的成長過程，無電鍍銅前處理採用敏化活化與置換活化兩種溼式活化法。結果顯示Ta(N) 阻隔層厚度約為100 nm，表面粗糙度為0.12 nm。Ta(N)經35 °C蝕刻、60 °C敏化活化處理後，可得細小、緻密且均勻的Pd催化顆粒，大小約20-30 nm，部分Pd顆粒聚集成團，表面粗糙度為2 nm。而經室溫蝕刻、置換活化3分處理後，其Pd催化顆粒大小可達100 nm以上，表面粗糙度為15 nm；Pd顆粒的分佈明顯較敏化活化處理來得粗大而稀疏。兩種溼式活化法之Pd顆粒成長方式都是由約5 nm 的Pd晶粒堆疊聚集而成；顯然既存之Pd可以成為優先成長位置，如同自我催化一般，尤其在置換活化處理中更明顯。
    Ta(N) 敏化活化再無電鍍成長的銅膜是以3-5 nm的銅奈米晶先在Pd上堆疊成銅顆粒，再透過自我催化於銅上繼續堆疊銅奈米晶，銅顆粒彼此也可能聚集成更大的聚團；鍍覆15秒後逐漸形成有銅顆粒界線的連續銅膜，而使片電阻急遽下降，表面粗糙度也下降；鍍覆120秒則已經成為完全連續銅膜。而Ta(N) 置換活化再無電鍍成長的銅膜，因為Pd催化顆粒過於稀疏，而使銅膜成長緩慢，銅顆粒粗大；即使鍍覆5分，仍在成膜初期階段。

    摘要.......................................................I 誌謝......................................................II 總目錄....................................................Ⅳ 圖目錄....................................................Ⅶ 表目錄...................................................XⅡ 壹、前言...................................................1 貳、文獻回顧...............................................3 2-1 積體電路金屬內連線................................3 2-1-1 積體電路金屬內連線之演進..........................3 2-1-2 積體電路銅金屬內連線之沉積技術....................6 2-1-3 積體電路銅金屬內連線之製程........................6 2-2 擴散阻隔層.............................................7 2-3 無電鍍製程之前處理....................................12 2-3-1 置換活化法.......................................12 2-3-2 敏化活化法.......................................14 2-4 無電鍍銅..............................................15 2-4-1 無電鍍銅製程發展簡介.............................15 2-4-2 無電鍍銅鍍浴之組成與特性.........................16 2-4-3 無電鍍銅之化學反應式與反應機制...................19 2-4-3-1 化學反應式........................................19 2-4-3-2 反應機制[50]......................................20 2-4-4 近年來無電鍍銅在積體電路製程應用上之發展.........21 2-5 研究目的..............................................22 參、實驗步驟..............................................24 3-1 基材.............................................24 3-2 基材之前處理.....................................24 3-2-1 敏化活化處理.....................................24 3-2-2 置換活化處理.....................................26 3-3 無電鍍處理.......................................26 3-4 TEM試片製備......................................27 3-4-1 平面視野(plane-view)試片製備.....................27 3-4-2 橫截面(cross-section)試片製備....................27 3-5 微結構觀察及性質分析.............................30 3-5-1 掃描式電子顯微鏡(SEM)分析........................30 3-5-2 片電阻(sheet resistance)量測.....................30 3-5-3 原子力顯微鏡(AFM)分析............................31 3-5-4 X光繞射分析......................................31 3-5-5 穿透式電子顯微鏡(TEM)分析........................31 肆、結果與討論............................................33 4-1 擴散阻隔層.......................................33 4-2 敏化活化處理.....................................38 4-3 置換活化處理.....................................51 4-4 無電鍍銅膜.......................................58 4-4-1 微結構觀察.......................................58 4-4-2 表面粗糙度.......................................64 4-4-3 片電阻量測.......................................71 4-4-4 X光繞射分析......................................73 4-4-5 退火處理.........................................75 4-4-6 置換活化法之無電鍍銅.............................75 伍、結論..................................................81 陸、參考文獻..............................................82

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