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研究生(外文):Hua-Chiang Wen
論文名稱(外文):Effects of the Growth Parameters on the Synthesis of Carbon Nanotubes
指導教授(外文):Koho Yang
外文關鍵詞:MPCVDgrowth parameterscobalt silicidesphase transformation
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本研究以物理氣相沉積(PVD)得到鈷(Co)為觸媒,並利用微波電漿化學氣相沉積(MP-CVD)法,再加入甲烷等碳氫化合物為碳源,來製備奈米碳管。運用片電阻值量測(Sheet resistance)證實鈷與矽原子間的相轉變,成長奈米碳管後,應用原子力顯微鏡(AFM)、掃描式電子顯微鏡(SEM)、X光繞射儀(XRD)、傅利葉轉換紅外線光譜儀(FT-IR)、應力量測儀(Stress)X光光電子能譜儀(X-ray photoelectron spectroscopy,XPS)、拉曼光譜儀(Raman spectroscopy)分析其特性,鈷與矽原子等由高解析穿透式電子顯微鏡(HR-TEM)、能量散佈光譜儀 (EDS)作微結構分析。
在前處理製程下形成奈米觸媒,因為鈷與矽原子間受到熱能,產生互融現象,由於鈷與矽原子間已發生結合,產生的高溫相變化的互擴散效應(Kirkendall Effect),鈷與矽原子間發生空孔對於體積轉變扮演重要的角色。但高於4000C到5000C溫度下鈷的消耗持續使電阻降低,原子間化合成鈷矽化合物(Co/Si),持續進行相變化,使鈷矽相發生持續的相轉換(CoSi2)現象,以確實了解到相轉換的現象。
奈米碳管運用在氣體感測,在常溫下施與不同的氣體氣氛下(H2、NH3) 並以X光光電子能譜儀量(XPS)量測奈米碳管於不同的氣體氣氛下對於碳管表面產生的氣體鍵結能之變化,來印證奈米碳管對於氣體感測之靈敏性質。
Cobalt catalytic-layers were deposited on silicon substrates by sputtering. Nanostructured carbon nanotubes were prepared by the MPCVD method using the methane and hydrogen as source gases. Furthermore, to realize the phase transformation of cobalt silicides, resistivity variations were detected by four-point probe system. After the carbon nanotubes were deposited, samples were characterized using AFM, SEM, XRD, FTIR, XPS ,and Raman spectroscopy. Microstructures and chemical compositions of cobalt silicides were analyzed by TEM and EDS.
It has been observed that nanoscaled CoSi2 films of the top part of the film and then the lower part separates into islands. Thinner films are more susceptible to this phenomenon due to their dependence on the ratio of silicide grain size and layer thickness. Voids due to the phase formation and Kirkendall effect induced volume changes played an important role in this phenomena. Formation of low resistivity CoSi2 phase from the reaction between a cobalt layer and a Si substrate proceeds sequentially by Co/Si phase transformation at 400, 500 ℃ and higher temperatures, respectively. The voids have been observed at the phase boundaries of cobalt silicides, which help determine the exact reaction route and the dominant diffusing species for each phase formation.
It is believed that the catalytic-layer phase transformation through plasma and surface diagnostics will affect the growth mechanism of CNTs. Since a metal particle is consumed partly by silicide formation and partly by inclusions into the tubes during the growth. For long time in CNT growth, the liquid Co, particularly of small particles, is totally consumed and the growth stops. While CNTs keep on larger particles, they lift up the growth-stopped thin tubes casing a sparse tube density at the bottom. This induces a poor adhesion of the tubes to the Co/Si stacks. CNTs grown with a base growth mode were proved by TEM. In addition, the interface of CNTs and cobalt silicides formed by Co/Si was also observed by XTEM.
Carbon nanotube can be used to detect the presence of a number of gases(such as H2,NH3 etc. )with high sensitivity at ppm level. XPS is applied to the research of the characteristics of the gaseous molecular.sensitivity by measuring the binding energy of transformation at the surface of carbon nanotube.
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