本文第一部分將鈷靶材放在四乙基正矽酸鹽溶液(tetraethyl orthosilicate, TEOS)中，進行脈衝雷射剝熔蝕(pulsed laser ablation, PLA)，結果產生C-Si-H摻雜具有岩鹽結構的Co1-xO，以及少量亂層石墨烯、平面狀石墨和管/帶狀Co(OH)2，而且C-Si-H摻雜的Co1-xO，在後續常溫TEOS中，可以長期保存良好，有別於在大氣氧分壓情況下，在大約900oC 溫度以下，會自發氧化形成Co3-δO4的行為。C-Si-H摻雜Co1-xO凝固顆粒，傾向以球狀呈現，而且有~(100)和{111}小平面，聚簇形成的低角度傾轉界面。而C-Si-H摻雜的Co1-xO奈米凝聚物，則有發達的{100}和{110}晶面，而且有點缺陷集合形成的順晶排列，其間距約為2.5倍晶格常數，還有大量面缺陷的存在，即1-D 3x和5x{111}超晶格伴隨著Co緊密堆積交替混合排列。此外，根據膠體溶液的吸收光譜分析，發現這些顆粒於紫外-可見光範圍內有多組吸收值，對應於最小能隙值約為3.1-3.7eV，可望有光觸媒催化方面的用途。
第二部分利用脈衝雷射剝熔蝕法在0.25M 氨水中打擊鈷靶材，合成摻雜了氮氫元素的Co3-δO4尖晶石奈米凝聚物與凝固顆粒，使其具有點缺陷聚集造成的順晶結構，以及比純Co3-δO4塊材較大的晶格常數，顯示氮原子佔據了尖晶石結構中的間隙位置。當顆粒快速凝固時，在包含Co3-δO4沉澱物的Co1-xO基體上會因Co3+、N和H+的雜質摻入而衍生出3x3x3尖晶石態的超晶格結構。至於共存的含鈷雙層狀氫氧化物奈米凝聚物在電子束照射下，容易非晶質化。此外，在氨水中脈衝雷射剝熔蝕鈷靶並沒有形成六方晶Co2O3和三斜晶硝酸鈷。氮氫摻雜的氧化鈷顆粒有組成元素鍵結的電子能譜特徵，以及吸收紫色光的特性，其對應最小能隙值約為2.9eV，有潛在光催化應用價值。

In the first part, predominant C-Si-H doped Co1-xO particulates/nanocondensates and minor turbostratic graphene, faceted graphite and Co(OH)2 tubes/belts, were formed by pulsed laser ablation (PLA) of Co plate in TEOS without appreciable transformation into Co3O4 which would otherwise be stable below ca. 900oC under open air condition. The C-Si-H doped Co1-xO particles are ~(100) and {111} faceted for (hkl)-specific coalescence and contain paracrystalline distribution of defect clusters with interspacing ca. 2.5 times that of the host lattice parameter as well as abundant planar defects, i.e. 1-D 3x and 5x{111} commensurate superstructures occasionally mixed with alternating Co close packed interlayer. UV-visible absorbance spectrum of the resultant colloidal suspension indicates the particles and nanocondensates have multiple absorptions in UV-visible range corresponding to a minimum band gap of 3.1 to 3.7 eV.

In the second part, PLA of Co plate in aqueous solution of ammonium hydroxide (0.25 M NH4OH) caused the predominant formation of N-H-doped Co3-δO4 particulates and nanocondensates with paracrystalline distribution of defect clusters and larger lattice parameter than the ambient value of undoped bulk Co3-δO4, indicating that N enters the interstitial site in the spinel-type structure. The 3x3x3 spinel-type derived superstructure, due to tramp Co3+, N and H+ doping, along with Co3-δO4 and Co1-xO domains were also found in the rapidly solidified particulates. The co-existing Co layer-double hydroxide ribbons are optically birefringent and vulnerable to electron irradiation; whereas the hexagonal Co2O3 and triclinic cobalt nitrate were not favored by the present PLA process in aqueous ammonia. The N-H doped cobalt oxide particulates/nanocondensates showed characteristic bonding states of the constituent elements in the XPS as well as a significant violet absorbance corresponding to a minimum band gap of 2.9 eV for potential optocatalytic applications.

目錄
論文審定書 i
誌謝 ii
摘要 iii
Abstract iv
目錄 v
圖目錄 viii
表目錄 xiii
附錄目錄 xiii
第一部分 …………………………………………………………………………1
壹、 前言 .1
貳、 實驗流程 5
參、 實驗步驟及方法 6
一、靶材切割 6
二、雷射剝蝕 6
三、X-ray繞射 6
四、UV-Visible吸收光譜 6
五、偏光顯微鏡(POM) 6
六、掃描式電子顯微鏡(SEM) 7
七、穿透式電子顯微鏡(TEM) 7
八、拉曼光譜(Raman) 7
九、光致螢光光譜(Photoluminescence, PL) 7
十、霍氏轉換紅外光譜儀(FR-IR) 7
十一、X光-光電子能譜分析(XPS) 7
肆、 實驗結果 9
一、XRD分析 9
二、UV-Vis吸收光譜分析 9
三、偏光顯微影像分析 9
四、掃描式電子顯微鏡 10
五、穿透式電子顯微鏡觀察 10
六、拉曼、光致螢光光譜及霍氏轉換紅外光譜分析 12
七、X光-光電子能譜分析 12
伍、 討論 14
陸、 結論 17
柒、 參考文獻 18
第二部分 …………………………………………………………………………54
壹、 前言 54
貳、 實驗流程 56
參、 實驗步驟及方法 57
一、靶材切割 57
二、雷射剝蝕 57
三、X-ray繞射 57
四、UV-Visible吸收光譜 57
五、偏光顯微鏡(POM) 57
六、掃描式電子顯微鏡(SEM) 58
七、穿透式電子顯微鏡(TEM) 58
八、X光-光電子能譜分析(XPS) 58
肆、 實驗結果 59
一、XRD分析 59
二、UV-Vis吸收光譜分析 59
三、偏光顯微影像分析 59
四、掃描式電子顯微鏡觀察 60
五、穿透式電子顯微鏡觀察 60
六、X光-光電子能譜分析 63
伍、 討論 64
陸、 結論 68
柒、 參考文獻 69

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