本實驗利用Nd-YAG雷射，在波長1064nm、脈衝時間16 ns、脈衝能量400, 600, 800 mJ/pulse的條件下，於真空中剝熔蝕具有岩鹽結構的δ-TiC計量碳化鈦多晶靶材，並且利用X光繞射、光學/電子顯微鏡與振動/吸收光譜，觀察靶材微觀結構變化，以及鑑定濺射堆積而成的凝聚物種類、成份、粒徑、形狀及振動光譜。結果顯示隨脈衝雷射功率之昇高，多晶碳化鈦塊材靶材之剝熔蝕由沿晶/穿晶破裂與液化主導機制，漸漸轉為塑性變形、再結晶與塊材局部融熔的機制。至於堆積物除了原來的母相多晶δ-TiC碎塊，還有: (1)新生依岩鹽結構晶癖面呈現的非計量δ-TiCx (x <1) 奈米顆粒，可依{111}面聚簇並且順著<113>方向生長、(2)新生三角板狀δ"/δ´-Ti2C奈米顆粒，其中δ"-Ti2C有發達的(0001){1-102}{1-10-4}表面傾向順著基底面聚簇、以及(3)新生準晶質亂層石墨烯物質(turbostratic graphene-based material)，此含少量鈦的液晶碳物質或巧妙形成洋蔥狀，或分解成石墨烯(graphene)，或集合成具有光學異向性的幾十微米長緞帶碳，以假磊晶的方式纏繞δ-TiCx與δ"/δ´-Ti2C奈米顆粒，整體強化改變了原有計量δ-TiC該有的拉曼光譜。本實驗結果有助於瞭解Ti-C二元成份系的動態相選擇，以及碳化鈦介穩相之成核生長與碳空缺調控機制，這些知識可當碳化鈦濺鍍工業應用的參考，以及天然動態環境(例如星系之間)含鈦碳物質形成機制的借鏡。

Pulsed laser ablation of polycrystalline δ-TiC was conducted in vacuum at 400, 600 and 800 mJ pulse energy to fabricate nonstoichiometric δ-TiC and δ´/δ"-Ti2C nanocondensates as well as graphene-based material for x-ray diffraction, electron microscopic and optical spectroscopic characterizations. The δ-TiC in the form of nanocondensates and target fragments tended to be produced by 400 mJ pulses which also caused significant inter- and intra-granular fractures of the target. By contrast, nonstoichiometric δ-TiC and δ´/δ"-Ti2C nanocondensates with well-developed habit planes (such as (0001), {1-102}and {1-10-4}of δ"-Ti2C) more or less encapsulated by 2-D turbostratic graphene lamellae were formed by 600 mJ pulses. Whereas faceted δ-TiC nanocondensates and graphene-based rolls/flakes were formed by 800 mJ pulses which caused also significant plastic deformation and melting of the target. In general the δ-TiC nanocondensates tended to coalesce over well-developed {100} or {111} surfaces, whereas δ"-Ti2C preferred to adjoin by its basal surface, as unity rather than twinned bicrystal. Graphene-lamellae encapsulation however limited coalescence of the titanium carbide nanocondensates. The nanocomposite of nonstoichiometric titanium carbides and graphene-based lamellae showed characteristic Raman modes and bimodal UV-visible absorbances for potential photocatalytic besides abrasive/lubricant applications.

論文審定書 i
致謝 ii
摘要 iv
Abstract v
目錄 vii
表目錄 ix
圖目錄 ix
附錄目錄 xvi

壹、前言 1
貳、實驗流程 4
參、實驗步驟與方法 5
一、脈衝雷射剝蝕(PLA) 5
二、 X光繞射分析 5
三、穿透式電子顯微鏡分析 5
四、偏光顯微鏡（OM）分析 6
五、UV-Visible吸收光譜分析 6
六、拉曼（Raman）光譜分析 6
七、掃描式電子顯微鏡分析 6
肆、實驗結果 7
一、XRD 7
二、TEM 7
三、RAMAN 10
四、UV-Visible 10
五、OM 11
六、凝聚物與靶材的SEM觀察 11
伍、討論 13
一、PLA製程的相成因 13
二、奈米TiCx與Ti2C顆粒的形狀與內應力 14
三、不同脈衝能量對於TiC多晶靶材的破壞效應 16
四、非計量TiCx與亂層石墨烯動態凝聚物的潛在應用 17
陸、結論 19
柒、參考文獻 20

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