ZrN具有立方晶體結構，為導電氮化物，具有高熔點、高硬度等優越之性質，可適合做為鑽石成長於矽晶片之緩衝層。本研究第一部分使用脈衝雷射沉積系統於Si(100)基板上成長出具磊晶關係之ZrO2薄膜，並以此薄膜進行氮化製程，利用氮氫氣體之微波電漿成功將ZrO2薄膜氮化成與基板具磊晶關係之ZrN薄膜。第二部分則利用雙金剛烷(diamantane)與二乙二醇之混合溶液塗佈於Si基板上進行輔助鑽石成核之實驗，觀察其成核過程，紀錄塗佈後試片表面於微波電漿系統中以甲烷和氫氣混合氣體沉積時間之變化所造成之成核情況，以Raman光譜與掃描式電子顯微鏡(SEM) 影像紀錄，並利用不同方法使雙金剛烷能大幅提升鑽石成核之密度，如增加塗佈次數、基板表面改質及ZrN緩衝層之利用等。
從穿透式電子顯微鏡(TEM)與X光繞射(XRD)研究結果顯示，以磊晶之ZrO2薄膜進行氮化較易形成磊晶之ZrN薄膜，而微波氮化製程之壓力以低壓20 torr之條件較佳，於50 torr時電漿密度過高，會導致蝕刻速率大於氮化速率，使薄膜呈現非連續狀。由XRD與TEM觀察在未完全氮化之試片，發現影像分為三層，分別為ZrN/ZrO2/Si，互相之間具有磊晶關係: (100)ZrN // (020)ZrO2 // (001)Si與[011] ZrN // [101] ZrO2 //[011]Si；從而可知氮化之過程為從ZrO2表面往界面進行，而氮化速率~ 3-4 nm/min。
雙金剛烷輔助鑽石成核之部分，由Raman光譜分析與SEM影像觀察可得知雙金剛烷鍵結之消減與鑽石生成之變化；於電漿沉積10分鐘後，在矽晶片上並無偵測到鑽石之訊號，或觀察到具鑽石特徵之顆粒；而於30分鐘後則有鑽石之Raman訊號，代表鑽石已產生，SEM影像顯示鑽石之尺寸為250 nm。利用不同之方法鍍附雙金剛烷，可有效增加密度達最高密度值 2.9 x 107 cm-2，適用於Si基板與具ZrN緩衝層之試片。

ZrN has cubic crystal structure and is a conducting nitride with many excellent properties such as high melting point and high hardness, such that it can be a appropriate buffer layer for diamond growth on Si wafer. This thesis focuses on the study of growth of epitaxial ZrN film on Si and diamantine-assisted diamond nucleation on ZrN. In the first part of this study, an epitaxial ZrO2 film on Si (100) substrate was grown by pulsed laser deposition, followed by nitriding the ZrO2 film to form epitaxial ZrN by microwave plasma with gas mixture of nitrogen and hydrogen. In the second part, coating on Si and ZrN/Si with a mixed solution of diamantane and diethylene glycol was performed to assist diamond nucleation in microwave plasma chemical vapor deposition (CVD) with gas mixture of CH4 and H2. The evolution of nucleation and growth for diamond formation was observed with micro-Raman spectroscopy and scanning electron microscopy (SEM). Various methods were also explored to enhance the diamond nucleation density, such as increasing diamatane coating times, surface treatments of the Si substrate, and using ZrN buffer layer on Si.
In the nitriding process for ZrN film formation, it is observed from transmission electron microscopy (TEM) and x-ray diffraction (XRD) that epitaxial ZrO2 can be much easier to form epitaxial ZrN than polycrystalline ZrO2. The favorable nitriding conditions determined by varying the processing parameters of power, pressure, and time were found to be under low pressure (below 20 torr). In contrast, at high pressure (> 50 torr), ZrN might be discontinuous with many holes appeared on the surface probably due to etching under a high plasma density. TEM observations on ZrO2 with incomplete nitridation show that epitaxial ZrN is on top of ZrO2, indicating that the nitriding process starts from the ZrO2 surface and gradually moves toward the interface between ZrO2 and Si. Furthermore, XRD and TEM results show that the epitaxial relationship between ZrN, ZrO2 and Si is (100)ZrN // (020)ZrO2 // (001)Si and [011]ZrN // [101]ZrO2 //[011]Si.
For diamond deposition by microwave plasma CVD, diamantane coating was applied onto Si and ZrN/Si substrates for seeding without any other surface pretreatment. The bonding change of diamantane under short period of plasma was observed from Raman spectroscopy and SEM. After first 10 min of microwave plasma CVD, the Raman and SEM showed no diamond evidence. After 30 min, the diamond crystallites appeared, and the size was 250 nm. It is found that diamantane coating can effectively enhance the diamond nucleation density to 2.9 × 107 cm-2.

摘要 I
Abstract III
第一章 緒論 1
第二章 文獻回顧 2
2.1二氧化鋯的基本性質、應用及相關成長研究 2
2.1.1二氧化鋯的基本性質 2
2.1.2 二氧化鋯的成長方法 4
2.2氮化鋯 7
2.2.1氮化鋯之基本性質 7
2.2.2氮化鋯成長方法 8
2.3鑽石 12
2.3.1鑽石之基本性質 12
2.3.2鑽石之應用 14
2.3.3人工合成鑽石成長方法 16
2.4氮化法 19
2.4.1微波電漿氮化法 19
2.4.2氮氫電漿 21
2.5輔助鑽石成核方法 22
2.5.1刮痕法(scratching) 23
2.5.2偏壓法(Bias-Enhanced Nucleation) 23
2.5.3金剛烷(adamantane) 24
2.5.4 雙金剛烷(Diamantane) 25
2.6鑽石成長於緩衝層的相關研究 27
第三章 實驗設備與流程 29
3.1薄膜成長設備與技術 29
3.1.1 脈衝雷射沉積系統 (Pulsed Laser Deposition) 29
3.1.2微波電漿化學氣相沉積系統(Microwave Plasma Chemical Vapor Deposition) 30
3.1.3.鉬基座 32
3.2實驗流程 33
3.2.1二氧化鋯沉積的製程步驟 33
3.2.2二氧化鋯氮化製程步驟 34
3.2.3鑽石成長製程步驟 35
3.3分析技術與設備 37
3.3.1 X光繞射儀 (X-ray diffractometer，XRD) 37
3.3.2掃描式電子顯微鏡 (Scanning Electron Microscope，SEM) 37
3.3.3拉曼光譜 (Raman Spectroscopy) 38
3.3.4聚焦離子束 (Focused Ion Beam，FIB) 38
3.3.5穿透式電子顯微鏡 (Transmission Electron Microscope，TEM) 39
3.3.6 X光光電子能譜儀 (X-ray photoelectron spectroscopy，XPS) 39
第四章 二氧化鋯氮化及磊晶氮化鋯之形成 40
4.1 PLD沉積二氧化鋯 40
4.1.1 XRD結構分析 40
4.1.2 TEM分析 46
4.2微波電漿氮化法製備磊晶氮化鋯 49
4.2.1二氧化鋯之方向性 49
4.2.2 氮化時間 61
4.3氮化鋯之TEM分析 65
4.4氮化鋯XPS縱深分析 75
4.5小結 83
第五章 鑽石成核 84
5.1偏壓於ZrN緩衝層輔助成核 84
5.2雙金剛烷輔助鑽石成核 87
5.2.1雙金剛烷於矽基板上輔助成核－過程 89
5.2.2雙金剛烷於矽基板上成核密度改善 99
5.2.3雙金剛烷於ZrN緩衝層上輔助鑽石成核 106
5.3小結 109
第六章 結論 111
6.1 氮化鋯薄膜製程 111
6.2 雙金剛烷輔助鑽石成核 112
6.3 未來建議與展望 112
參考文獻 114
附錄一 XRD 2θpeak位置和d-spacing 121
附錄二 TEM模擬繞射圖 122
附錄三 ZrO2試片之XRD 2θ掃描 124
附錄四 XPS Binding Energy (eV) 125
附錄五 雙金剛烷之Raman訊號[77] 126
附錄六 雙金剛烷之XRD 2θ掃描 [48] 127

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