臺灣博碩士論文加值系統

陶瓷材料雖具有熱化學及結構的穩定性，然而由於其韌性不佳易碎裂而大大地降低了其應用性。理論上欲增加陶瓷在常溫下的韌性，可以降低結晶粒徑至奈米級來達成。本論文中提案以對陶瓷微結構控制可行的化學氣相沈積法(CVD)，以共沈積複合物方式來合成具有穩定的奈米結構陶瓷材料，期能增加其韌性。研究的重點乃先對複合CVD系統作反應動力的探討以獲致合成奈米微結構材料的方針，並進而對複合材性質作分析。實驗上，採用矽甲烷/乙炔/氨的複合CVD系統來共沈積碳化矽/氮化矽複合陶瓷。採用macrocavity法來分析CVD反應系統內複合物生成的機構，包括探討複合反應動力以及其與合成出的複合材在組成、結構及韌性上的相關性。實驗結果顯示，在1323 K下固定總壓7 torr及SiH4分壓0.756 torr時，於SiH4/C2H2-SiC中添加少量NH3（[C2H2]/[SiH4]=2, [NH3]/[SiH4]=0.25~0.75）即可形成碳化矽微晶（約6奈米）分散於主要組成為氮化矽非晶質相的複合材料。此一結構材料可使韌性提高為碳化矽塊材的3~4倍。另外對於複合CVD長膜時的異質球狀結構成長提出解釋為在基材表面的成核點上長膜速率不一所致。即在氮化物表面上含碳量多的成核點具有以一弧面放射方式的較大成長速率而形成突起的異長生長形態，此一現象可藉由改變基材表面為碳化物而有效抑止。

An attempt to synthesize ductile ceramic materials by chemical vapor deposition technique has been made. Theoretically, ductile ceramic can be achieved even in normal temperature by decreasing the crystalline size into a few nanometers. Here in this study, we proposed chemical vapor deposition (CVD) as a process for this purpose, by co-depositing multi-component nanoparticles to form nanocrystalline ceramic materials. Emphasis was laid upon reaction kinetics study to get the policy to design the properties of complex nanostructure materials in a multi-component CVD reaction system. In this experiment, the SiH4/C2H2/NH3-CVD reaction system was selected to synthesize SiC/Si3N4 nanostructured composite. An experimental method named the macrocavity method was apply to understand the relation between the reaction kinetic and the properties of the deposited composite material, including composition, structure and toughness. A composite material composed by nanocrystalline silicon carbide dispersed in amorphous silicon nitride was obtained by adding a few NH3 ([C2H2]/[SiH4]=2, [NH3]/[SiH4]=0.25~0.75) into SiH4/C2H2 reaction system under the conditions of temperature 1323K, total pressure 7 torr, and SiH4 partial pressure 0.76 torr. This material showed a fracture toughness value three to four times of the bulk value of silicon carbide. On the other hand, a reasonable explanation about the abnormal cone structure growth on substrate surface has also been made.It is found that the high growth rate on carbon-rich nuclei positioned on the nitride surface resulted in the formation of abnormal cone structure which can inhibited by using carbide substrate surface.

中文摘要I
英文摘要II
誌謝III
目錄IV
圖表索引V
第一章 緒論1
第二章 實驗相關部份14
2.1. 實驗氣體與藥品14
2.2實驗設備和分析儀器16
2.2-1 實驗裝置及方法16
2.2-2 分析儀器19
2.3 反應系統之分析模型21
2.4 維氏硬度及破壞韌性量測27
2.4-1 維氏硬度的量測27
2.4-2 破壞韌性的量測29
第三章 結果與討論32
3.1 多元CVD複合物系統反應動力的分析32
3.2 陶瓷複合材物性的探討48
3.2-1 在SiH4/C2H2-SiC反應系統中添加NH3對薄膜的成長效應48
3.2-2 NH3添加至SiH4/C2H2反應系複合物對化學鍵結及組成的變化51
3.2-3 添加NH3進入SiH4/C2H2反應系中對薄膜結晶性的影響60
3.2-4 不同NH3添加至SiH4/C2H2反應系對複合物硬度及韌性的影響63
3.3 複合材表面異常的球狀結構成長的抑止72
3.3-1 異常成長現象的發生72
3.3-2 不同基材表面對球狀結構的影響74
3.3-3 異常成長模式的分析80
第四章 結論85
第五章 參考文獻87
作者簡介91

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