類鑽碳(Diamond-like carbon，DLC)薄膜具有高硬度、低摩擦係數、抗化學腐蝕性、高熱傳導性、高電阻性等可在業界上做應用。在本研究主題中，主要是以電沉積的方式，以不同特性的溶液在不同粗糙度的矽基板上沉積類鑽碳薄膜，在此使用氫氧化鉀(KOH)對矽基板做蝕刻蝕刻以得到不同粗糙度之基板，並且使用掃描式電子顯微鏡(SEM)以及原子力顯微鏡(AFM)來觀察其表面形貌以及粗糙度，拉曼光譜(Raman spectroscopy)與X光光電子能譜分析儀(XPS)來觀察薄膜之中的化學鍵結結構，n&k薄膜分析儀( n&k analyze )對薄膜的光學特性做分析。
由AFM可以觀察到使用氫氧化鉀對矽基板做蝕刻，時間為20、40和60分鐘，其粗糙度會由未蝕刻的2.64上升到14.07，且使用SEM觀察沉積之後的表面形態，可以看出隨著基板粗糙度的增加，是有利於類鑽碳薄膜在矽基板上的沉積的，並且在改變沉積溶液的實驗下發現使用鹼性溶液來沉積類鑽碳薄膜是比酸性溶液下沉積更好的選擇。而且隨著基板粗糙度的增加，使用Raman量測出之ID/IG比值以及XPS量測出之sp2/sp3比值也會漸漸增加，是因為石墨結構的增加，使得薄膜呈現石墨化的現象，而且發現在醋酸+醋酸氨+氨水此一溶液條件中可以得到較低的ID/IG比值。而後再針對此條件下去做微調，發現醋酸氨摻雜的量增加時，ID/IG比值也會隨之下降，可能是由於甲基團增加的關係，再使用n&k量測其消光係數並帶入Tauc方程式中求光能隙，發現光能隙也因為薄膜偏向石墨化的影響而造成能隙值的下降。

Diamond-like Carbon (DLC) film exhibits an extreme hardness, low friction coefficient, chemical stability, heat conductivity, and high resistance. Their properties lead to remarkable applications on industry. In the experiment, we use electrondeposition to deposit the DLC film on Si substrate. Different concentrations of electrolyte were used to deposit on the of silicon substrates with different roughness surface. KOH solution was used to etch and to get the different roughness on the surface of silicon substrates. the morphology of surface were observed by SEM and AFM. Composition and microstructure of the DLC film were characterized by the Raman spectroscopy and XPS, repectively. The optical properties of DLC film were investigated by the N&K analyzer.
From the AFM results, the surface morphology observed by KOH etching on the surface of silicon substrates during etching time as 0、20、40、60 min, the surface roughness increased from 2.64 to 14.07 nm. Based on thevariation of surface roughness, the growth rate was observed more quicker than the non etch surface. Moreover, to deposit the DLC film on the alkalinity solution was better then acid solution. However, the ID/IG ratio and the sp2/sp3 ratio obtained from Raman and XPS increase with the roughness surface from 1.09 to 1.82 and 0.985 to 2.15, respectively. It is because that the microstructure of DLC film varies and exchange to graphitization.
The mixed the ammonia water and ammonium acetate into acetic acid solution was used to deposit DLC film on Si surface, and film shows with lower ID/IG ratio. Additionally, as the amount of ammonium acetate was varied in the solution, the ID/IG ratio of the films observed as decrease from 1.2 to 0.93 with increasing amount of ammonium acetate 10g to 40g. It was due to the methyl radicals increase in the solution. Besides, we can find the optical band gap decreased with DLC films changing to graphitization.

國立中山大學研究生學位論文審定書 i
致　　謝 ii
摘　　要 iii
表目錄 xi
第一章　緒論 1
1-1前言 1
1-2 研究目的 1
1-3 論文架構 2
2-1 碳的簡介 3
2-2 類鑽碳薄膜 4
2-3 類鑽碳的結構 7
2-4 類鑽碳的特性與應用 8
2-5 類鑽碳改質膜 8
2-6 類鑽碳的成長機制 9
2-6-1 電沉積的起源 9
2-6-2 薄膜沉積現象 10
2-6-3 長晶 10
2-6-4 晶粒成長 11
2-6-5 晶粒聚結 11
2-6-6 縫道填補與薄膜的成長 12
3-1 實驗材料與儀器設備 13
3-1-1 實驗材料 13
3-1-2 儀器設備 13
3-2 類鑽碳成膜實驗操作步驟 13
3-2-1 基板的前置處理 13
3-2-2 電沉積之操作步驟 14
3-3 量測儀器與其原理 15
3-3-1 掃瞄式電子顯微鏡 15
3-3-2 X光光電子能譜儀 17
3-3-3-1拉曼光譜原理 19
3-3-3-2類鑽碳膜之拉曼光譜量測 20
3-3-5 原子力顯微鏡(AFM) 26
3-4 矽基板蝕刻機制 29
3-4-1 廣義蝕刻機制 29
第四章 結果與討論 31
4-1 基板表面形貌分析 31
4-1-1 使用掃描式電子顯微鏡(SEM)觀察基板表面形貌 31
4-1-2 使用原子力顯微鏡(AFM)觀察基板表面形貌 31
4-2 使用各種水溶液沉積類鑽碳薄膜(DLC) 32
4-2-1 使用醋酸水溶液沉積類鑽碳薄膜 32
4-2-2 使用鹼性電解液沉積類鑽碳薄膜 33
4-2-3 使用氨水製作電解液沉積類鑽碳薄膜 34
4-2-4 使用醋酸氨加氨水製作沉積類鑽碳薄膜 35
4-2-5 使用醋酸加醋酸氨加氨水製作沉積類鑽碳薄膜 36
4-3 使用拉曼光譜(Raman spectroscopy)分析類鑽碳薄膜 37
4-4 使用X光光電子能譜分析儀(XPS)分析類鑽碳薄膜 38
4-5 改變摻雜之醋酸氨的量來製備類鑽碳薄膜 39
4-5-1 使用掃描式電子顯微鏡(SEM)觀察類鑽碳薄膜表面形態 40
4-5-2 使用拉曼光譜(Raman spectroscopy)觀察類鑽碳薄膜表面形態 40
4-5-3光學特性分析 41
4-6-4 化學反應機制 43
第五章　　總結 44
參考文獻 86

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