第一部分
摻雜鉻(Cr3+)之矽酸鋅(Zn2SiO4)釉藥塗佈於氧化鋁(Al2O3)多晶基材上，經1270 ℃熔釉與1080 ℃過冷失透(devitrification)之二階段熱處理後，以偏光與掃瞄式電子顯微鏡觀察，發現在釉層表面會產生針狀的矽酸鋅結晶與非晶態之玻璃液相，鉻則大部分分佈於非晶質玻璃相中，且矽酸鋅會隨著鉻含量增加而抑制針狀結晶的生長。用解析穿透式電子顯微鏡觀察釉層與氧化鋁基板的界面，發現氧化鋁多晶燒結體之晶界為熱處理時擴散之捷徑，使得鋁元素沿之向外擴散至釉層，造成鋅鋁氧三元素反應，導致界面處化學反應並且異質成核，所以出現緊密堆疊且厚度達微米級之鋅鋁尖晶石的反應層，因而阻擋釉層元素向內擴散至氧化鋁基材中，此點顯示含鉻矽酸鋅釉藥是氧化鋁多晶材料理想的接合劑。此外，鋅鋁尖晶石結晶的成核與生長能力會受到含鉻量額外的影響，鉻含量愈多，結晶性會降低。造成矽酸鋅與鋅鋁尖晶石結晶性的改變，主要是因Cr3+增加使矽酸鋅釉層液相中，SiO4和ZnO4單體的接合更為順暢，因此降低過冷液相自由能使之不易結晶，與成核位置的減少較無關係。根據陰極光導致螢光(CL)光譜對矽酸鋅表面之分析，摻雜0.1%鉻的結晶釉於極低溫時(6 K)會在455 nm附近發光；摻雜1%的鉻的結晶釉則於同樣溫度發生約470 nm波長的光，發光光譜的紅偏移是由於鉻離子佔據格隙四面體或八面體，使晶格產生扭曲，減少晶格內部應力。

第二部分
在水溶液中利用Nd-YAG雷射剝蝕合成具懸浮奈米氧化鋯粉體(ZrO2)之水溶液，經減壓濃縮與離心機把氧化鋯之奈米顆粒萃取出來去分析其結構、相變化與不同配位原子振動模式。我們發現當雷射能量為700 mJ/pulse時，奈米顆粒以單斜晶系(monoclinic)為主，另含有微量之正方(tetragonal)及立方(cubic)晶系的氧化鋯；雷射能量增加至800 mJ/pulse時，正方(t-ZrO2)及立方(c-ZrO2)晶系的氧化鋯會增多。其是因雷射能量的提升使單位面積能量密度增加，在更高溫高壓的環境下合成，然後遇水急冷，t-或c-ZrO2沒時間由介穩相(metastable phase)相變至m-ZrO2。另外，奈米顆粒的氧化鋯在以PLAL的方法合成後，因為H+、OH-和氧空缺的存在，形同異質原子摻雜於其中，使得能隙相較於理論計算的氧化鋯塊材而言會降低。在穿透式電子顯微鏡下觀察氧化鋯表面以及奈米顆粒內所含有的缺陷及微結構情形，發現大部分t-m的相變化僅在合成的瞬間發生，且氧化鋯奈米顆粒內不易有雙晶或疊差(twins/faults)。造成此結果的原因與OH基有很大的關係，因PLAL是在水中進行，所以合成瞬間會有OH基附著於顆粒的表面並進而與氧空缺反應，使得氧空缺減少，而無法穩定介穩相t-, c-ZrO2的存在，因此大部分都是m-ZrO2。而因奈米顆粒很小(大部分小於50 nm)，所以其可被視為單晶域(single domain)，在顆粒內的成核位置鮮少使其可能在瞬間就已達到飽和，沒機會讓twins/faults產生。但是OH基卻讓顆粒的表面出現了許多階檻(ledges)，反而藉由此來讓顆粒內部應力紓緩。此外，因氧化鋯是在動態的雷射剝蝕下合成，會使其受到非靜水狀態(non-hydrostatic)的壓力，t-m之間的相變化臨界顆粒大小也會隨之由30 nm降到20 nm以下。

英文摘要為none

目錄
摘要…………………………………………………………………………………...I
目錄..............................................................................................................................III
圖目錄………………………………………………………………………………..VI

Part I
一、研究動機……………………………………………………………………1
二、文獻回顧……………………………………………………………………2
2-1. 矽酸鋅結晶的溶解行為與微結構……………………………………2
2-2. 矽酸鋅結晶的光譜……………………………………………………3
2-3. 寄主開裂癒合機制……………………………………………………4
三、研究方法及步驟…………………………………………………………….5
3-1. X-ray繞射分析(XRD)…………………………………………………5
3-2. 拉曼光譜分析(Raman)………………………………………………..5
3-3. 陰極光偵測系統(CL)…………………………………………………6
3-4. 場發式掃瞄式電子顯微鏡(SEM)…………………………………….6
3-5. 雙束型聚焦離子束(FIB)……………………………………………...6
3-6. 解析型穿透式電子顯微鏡(AEM)……………………………………6
四、實驗結果…………………………………………………………………....7
(一)釉層俯視面之觀察…………………………………………………….7
4-1. 偏光顯微鏡(OM)..………………………………………………7
4-2. X-ray繞射儀分析(XRD)………………………………………...7
4-3. 拉曼光譜(Raman)………………………………………………..7
4-4. 陰極射線光譜(CL)………………………………………………8
4-5. 掃瞄式電子顯微鏡(SEI)………………………………………...8
(二)釉層與氧化鋁界面處之橫截面觀察………………………………….9
4-6. 橫截面之偏光顯微鏡觀察(OM)………………………………..9
4-7. 掃瞄式電子顯微鏡(BEI)……………………………………....10
4-8. 穿透式電子顯微鏡(AEM)……………………………………..10
五、討論…………………………………………………………………………12
5-1. 鉻對結晶性的影響…………………………………………………..12
5-2. 鉻對發光光譜的影響………………………………………………..13
5-3. 釉層與氧化鋁層界面之擴散、成核與生長………………………...14
六、結論…………………………………………………………………………16
七、參考文獻……………………………………………………………………17

Part II
一、研究動機……………………………………………………………………39
二、文獻回顧……………………………………………………………………40
2-1. 在水中進行雷射剝蝕(PLAL)……………………………………….40
2-2. 氧化鋯的基本性質…………………………………………………..40
2-3. 氧化鋯的奈米顆粒相變與聚簇行為………………………………..42
三、研究方法與步驟…………………………………………………………...44
3-1. X-ray繞射分析(XRD)………………………………………………..44
3-2. 拉曼光譜分析(Raman)………………………………………………44
3-3. 霍式轉換紅外光譜儀(FTIR)………………………………………..44
3-4. 場發式掃瞄式電子顯微鏡(SEM)……………….…………………..45
3-5. X光光電子能譜儀(XPS)………………………….…………………45
3-6. UV-Vis吸收光譜…………………………….……………………….45
3-7. 解析型穿透式電子顯微鏡(AEM)…………………………………..45
四、實驗結果…………………………………………………………………..47
4-1. X-ray繞射儀分析(XRD)……………………………………………..47
4-2. 拉曼光譜分析(Raman)………………………………………………47
4-3. 霍式轉換紅外光譜儀分析(FTIR)…………………………………..49
4-4. UV-Vis吸收光譜…………………………………………………….49
4-5. X-ray光電子能譜儀(XPS)…………………………………………..50
4-6. 掃瞄式電子顯微鏡(SEM)…………………………………………..51
4-7. 穿透式電子顯微鏡之觀察(AEM)…………………………………..51
五、討論………………………………………………………………………..54
5-1. OH基的影響…………………………………………………………54
5-2. 相變化之臨界顆粒粒徑……………………………………………..55
5-3. 相變化與缺陷分析…………………………………………………..56
5-4. 能隙改變……………………………………………………………..57
六、結論………………………………………………………………………...59
七、參考文獻…………………………………………………………………...60

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