以化學氣相沈積法控制單層與雙層石墨於圖紋化矽基板之成長

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研究生：	呂俊頡 Lu, Chun-Chieh
論文名稱：	以化學氣相沈積法控制單層與雙層石墨於圖紋化矽基板之成長 Controlled Growth of Single-Layer and Double-Layer Graphene Sheets on Patterned Silicon Wafers
指導教授：	邱博文 Chiu, Po-Wen
口試委員:
學位類別：	碩士 Master
系所名稱：	電機資訊學院 - 電子工程研究所 Institute of Electronics Engineering
論文出版年：	2009
畢業學年度：	97
語文別：	中文
論文頁數：	205
中文關鍵詞：	單層石墨
相關次數：	點閱：2 下載：0
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目前製備單層石墨的方式最主要是利用機械剝離 (mechanical exfoliation) 的方式，但是這種方法不僅耗時，需要大量人力之外，也無法與半導體製程相容，因此本論文嘗試利用最常見的化學氣相沈積法 (Chemical vapor deposition, CVD)，來發展出簡單快速的單層石墨成長技術，並且逐漸改善問題，使得這套成長技術不僅能夠與半導體製程相容，且可以穩定地控制成長大量的高品質單層或雙層石墨，進而延展到單層石墨元件的製備。另外，我們也藉由一系列拉曼光譜的統計，分析各種拉曼光譜的結果，進而瞭解石墨與基板間的交互作用情況，也瞭解石墨的成長機制，對於實現日後在生產線上的運作會更有幫助。

此外，由於機械剝離方式製備的單層石墨面積不大，在試片上定義其位置不易，不利於之後的製程。而本實驗所成長出的單層石墨不僅面積頗大，有利於微影技術，加上其顏色對比鮮明，利用光學影像即可非常容易地定義其位置，在實際製程上節省不少時間。只要將催化劑移除後，便可以快速製備單層石墨元件。而本實驗的特色就是在鎳薄膜上輕易定義出單層石墨的位置，之後的製程也可完全針對同一片單層石墨上，不用轉換到其他的試片，也就是說，此種製程比較能夠符合業界生產線上的作業，我們只需要將鎳薄膜移除即可完成元件的製備。

論文大綱           1
致謝           3
目錄           5
緒論           11
1 動機           11
1.1 以矽材料為主的半導體科技           11
1.2 目前半導體技術的發展侷限           14
2 奈米碳管           16
2.1 奈米碳管的合成方法           18
2.2 奈米碳管在電子元件上的應用           19
2.3 奈米碳管的發展侷限           23
3 論文結構           25
單層石墨           27
1 石墨晶體結構           28
1.1 單層石墨           28
1.2 雙層與多層石墨           30
2 單層石墨的電子能帶           32
3 單層石墨的聲子能帶           33
4 單層石墨的製備方法           36
4.1 機械剝離           36
4.2 熱裂解磊晶成長於碳化矽上           36
4.3 氧化還原法           37
4.4 化學氣相沈積法           39
5 定單層石墨的工具           49
5.1 拉曼光譜           49
5.2 原子力顯微鏡           49
5.3 穿遂式電子顯微鏡           50
6 目前單層石墨的發展難題           50
化學氣相沈積           53
1 化學氣相沈積基本原理           53
1.1 薄膜成長           53
1.2  CVD反應機制           54
2 化學氣相沈積的分類           54
3 輸送現象討論           56
3.1 質傳控制以及表面反應控制           56
3.2 邊界層的改變以及表面消耗           59
3.3 低壓化學氣相沈積           62
4 建構實驗設備           63
拉曼光譜分析           69
1 拉曼效應           70
1.1 拉曼散射基本原理           70
1.2 拉曼散射的物理意義           73
1.3 共振拉曼散射           74
1.4 拉曼光譜之數學描述           75
2 拉曼光譜在石墨檢測上之應用           77
3 單層石墨之拉曼光譜           89
化學氣相沈積成長單層石墨           93
1 催化劑的製備           93
1.1 催化劑的選擇           93
1.2 拋光           95
1.3 蝕刻           96
2 塊材催化劑之實驗結果           97
2.1初步成長參數之測試           97
2.2成長溫度之測試           100
2.3反應氣體流量之測試           102
3薄膜催化劑之實驗結果           103
3.1 60 nm膜厚之測試           104
3.2 1µm膜厚之測試           104
3.3 拉曼光譜分析結果           104
4 快速生溫、快速降溫成長製程           106
5 在圖紋化之鎳薄膜上成長           112
5.1 碳源氣體流量           113
5.2 拉曼光譜統計分析           114
6 掃瞄式電子顯微鏡之影像           117
6.1 在鎳薄膜基板上之影像           117
6.2 在氧化矽基板上之影像           120
7 原子力顯微鏡之影像           123
單層石墨控制成長之機制探討           127
1 石墨成長機制概述           127
2 二次離子質譜儀           128
2.1 二次離子質譜術簡介           130
2.2 二次離子產生原理           131
2.3 表面效應           131
3 氫氣的使用           133
4 降溫速率之影響           135
4.1 緩慢降溫以及快速降溫           136
4.2 淬火降溫           136
5 控制成長之機制探討           141
6 表面氧化程度對析出成長之影響           144
CVD石墨之拉曼光譜統計分析           151
1 基板摻雜效應           151
2 應力與應變效應           155
3 HOPG與 CVD單層石墨之比較           159
3.1 G peak之峰值           159
3.2 2D peak之峰值           160
3.3 2D peak之強度           160
3.4 2D peak之對稱性           165
4 電子背向繞射系統           168
4.1電子背向繞射系統原理簡介           168
4.2 電子背向繞射系統裝置           169
4.3 結晶取向分析           171
5 鎳薄膜晶粒晶向對CVD單層石墨之影響           171
6  CVD雙層石墨之討論           175
6.1 Turbostratic stacking           176
6.2 Bernal stacking           178
7 總結           182
元件製程以及初步結果           185
1 移除催化劑           185
2 元件製程           189
結論與展望           193
1 實驗結果總結           193
2 未來展望           194
參考文獻           197

                                

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