臺灣博碩士論文加值系統

低壓固態碳源合成鑽石法技術，是在1993年由美國賓州大學R.Roy教授所提出，它是在低壓下（＜1atm），將過渡金屬粉末與固態碳源熔融，形成過飽和碳的金屬熔液，並在純氫氣的催化下析出鑽石。此法結合已往高溫高壓合成鑽石法，使用過渡金屬作為”溶劑-催化劑”，及低壓氣相合成鑽石法中使用氫原子催化，以這兩種生長鑽石的特點，作為合成鑽石的新方法。
本實驗是用熱燈絲化學氣相沉積法進行實驗，研究的目的在了解下列影響鑽石成核的變數(a)二元合金(Cu、Mn、Pd、Ni)共晶成份、溫度 (b)純氫氣、甲烷+氫氣的反應氣體 (c)固態碳源(石墨)的存在，對低壓液相合成鑽石法中鑽石成核大小、數量分布及晶形的影響。
實驗樣品經掃瞄式電子顯微鏡、拉曼光譜及X-Ray繞射分析，發現以甲烷+氫氣作為反應氣體的實驗樣本，在基材表面產生的鑽石核，其大小、數目及晶形與一般的熱燈絲化學氣相法在其他固態基材生成的鑽石相似。尤以含有鈀、鎳金屬的合金效果較佳。而以純氫氣＋石墨作為碳源的實驗樣本，無鑽石核生成在基材表面，但發現有類似鑽石顆粒被合金液包覆的現象。含有鈀、鎳金屬的實驗樣本均出現此現象。
由實驗的結果可知，低壓固態碳源合成鑽石（反應氣體純氫氣）的速率，比一般熱燈絲化學氣相沉積法鑽石的速率為低。不同基材的元素及改變成份比例會影響鑽石的成核的結果。

The idea of low pressure solid state synthetic(LPSSS) diamond was first proposed by professor R.Roy in 1993. It was the technique to precipitate diamond from the saturated carbon melt mixture of the transition metal and graphite powders under pure hydrogen atmosphere. It combines the characteristics of transition metal as “catalyst-solvent” in HPHT and the catalyst effect of atomic hydrogen in CVD , and may become a potential method for diamond synthesis.
The experimental method used in this study is hot filament chemical vapor deposition. The experimental purpose in this study is to understand the following variables that are (a) the eutectic temperature and composition in binary metals, (b) two type reactive atmosphere─pure hydrogen and methane + hydrogen (c) solid state carbon source(graphite) , which influence the size, number and crystalline of diamond in the synthetic progress
Through the analysis of SEM, Raman spectra, and X-ray diffraction, specimens in the methane + hydrogen atmosphere produced diamond crystals on the surface of metal melt which size, number and crystalline were similar to those in ordinary CVD reactor. We found that the catalyst effect of Pd and Ni are better than other metals in the study. Otherwise, specimens in pure hydrogen atmosphere did not produce any diamond crystals on the surface of metal melt, but we found a phenomenon that diamond was covered with metal melt. Sample containing Pd, Ni metal powder would appear this phenomenon.
The experimental results show that the diamond nucleation rate in low pressure solid state synthetic(LPSSS) method is much less than in ordinary CVD reactor, and different element and alloy composition will influence the result of diamond nucleation

摘要 iii
Abstract iv
誌謝 vi
目次 vii
表目錄 xi
圖目錄 xii
第一章 前言 1
1.1人工合成鑽石的發展 2
1.2鑽石的特性 3
1.3研究目的 10
第二章 背景 11
2.1鑽石的回顧 11
2.1.1鑽石的合成及結構 11
2.1.1.1鑽石合成的方式 11
2.1.1.2碳的同素異形體 12
2.1.2鑽石結構 15
2.2化學氣相沉積法的介紹 15
2.2.1化學氣相沉積的原理 15
2.2.2化學氣相沉積法 17
2.2.3影響化學氣相沉積的因子 21
2.3液相合成鑽石回顧 22
2.3.1低壓液相合成鑽石的理論基礎 22
2.3.2低壓液相合成鑽石的文獻回顧 23
第三章 實驗方法 27
3.1實驗流程 27
3.2實驗材料 28
3.3實驗設備 29
3.4試片製備 30
3.5實驗參數配置 31
3.5.1矽晶片實驗參數配置 31
3.5.2液相合成鑽石實驗參數配置 31
3.6實驗步驟 33
3.7實驗分析 33
第四章 結果與討論 36
4.1矽晶片實驗結果 36
4.1.1不同甲烷濃度實驗 37
4.1.2基材至燈絲距離為4mm實驗 39
4.1.3基材至燈絲距離為3mm實驗 41
4.1.4基材至燈絲距離為2mm實驗 43
4.2低壓液相合成鑽石實驗 46
4.2.1銅錳系統實驗 48
4.2.1.1銅錳系統：100% H2+2wt%Graphite結果 49
4.2.1.2銅錳系統：1%CH4+99%H2結果 49
4.2.1.3銅錳系統：100% H2+2wt%Graphite討論 53
4.2.1.4銅錳系統：1%CH4+99% H2討論 53
4.2.2銅鎳系統實驗 54
4.2.2.1銅鎳系統100% H2+2wt%Graphite結果 55
4.2.2.2銅鎳系統：1%CH4 +99%H2結果 57
4.2.2.3銅鎳系統：100%H2+2wt%Graphite討論 59
4.2.2.4銅鎳系統：1%CH4 +99%H2討論 59
4.2.3銅鈀系統實驗 60
4.2.3.1銅鈀系統：100%H2+2wt%Graphite結果 61
4.2.3.2銅鈀系統：1%CH4+99%H2結果 63
4.2.3.4銅鈀系統：100%H2+2wt%Graphite結果 65
4.2.3.4銅鈀系統：1%CH4+99%H2討論 65
4.2.4鎳錳系統實驗 66
4.2.4.1鎳錳系統:100% H2+2wt%Graphite結果 67
4.2.4.2鎳錳系統：1%CH4+99%H2結果 69
4.2.4.3鎳錳系統:100% H2+2wt%Graphite討論 71
4.2.4.4鎳錳系統:1%CH4+99% H2討論 71
4.2.5鎳鈀系統實驗 72
4.2.5.1鈀鎳系統：100% H2+2wt%Graphite結果 73
4.2.5.2鈀鎳系統1%CH4+99%H2結果 75
4.2.5.3鈀鎳系統：100% H2+2wt%Graphite討論 77
4.2.5.4鈀鎳系統：1%CH4+99% H2討論 77
4.2.6錳鈀系統實驗 78
4.2.6.1鈀錳系統：100%H2+2wt%Graphite結果 79
4.2.6.2鈀錳系統：1%CH4+99%H2結果 81
4.2.6.3鈀錳系統：100%H2+2wt%Graphite討論 83
4.2.6.4鈀錳系統：1%CH4+99%H2討論 83
4.3綜合討論 84
第五章 結論 86
參考文獻 87

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