本論文是利用X光吸收光譜研究Pr與Yb摻雜之Ca3Co4O9+δ之電子結構。在以Pr部份取代Ca的系統中，由Co K-edge 和Ca L3-edge發現Co 4p與Ca 3d空軌域在摻雜之後均減少，而由Co L3-edge和O K-edge發現Co 3d與Co 3d-O2p空軌域在摻雜之後均增加，推測電子會由O原子轉移到Ca 3d空軌域，且電子由Co 3d與O 2p混成軌域轉移到Co 4p空軌域。在以Yb部份取代Ca的系統中，由Ca L3-edge發現Ca 3d空軌域在摻雜之後均減少，由O K-edge發現Co 3d-O2p空軌域在摻雜之後均增加，而由Co K-edge和Co L3-edg發現Co 4p和Co 3d空軌域變化較不明顯，推測電子會由O原子轉移到Ca 3d空軌域，且電子由Co 3d與O 2p混成軌域轉移到Co 4p空軌域的趨勢較不明顯。由Co L3-edge發現Co 3d空軌域與電阻率是相關的。Co的平均價數為+3.37價。

We have performed x-ray absorption spectroscopy (XAS) study on the electronic structure of Pr and Yb doped Ca3Co4O9+δ. In Pr-doped samples, the variation of the intensities of Co K-edge and Ca L3-edge spectra indicate that the Co 4p and Ca 3d unoccupied state decreased by Pr doping. From Co L3-edge and O K-edge spectra we observe that the Co 3d and Co 3d-O2p unoccupied state were increased by Pr doping. The electronic transferred from O 2p to Ca 3d state and electronic transferred from Co 3d-O2p hybridization state to Co 4p state are possible. In Yb-doped samples, the variation of the intensities of Ca L3-edge spectra indicate that the Ca 3d unoccupied state decreased by Yb doping. The variation of the intensities of O K-edge spectra indicate that the Co 3d-O2p unoccupied state increased by Yb doping. From Co K-edge and Co L3-edge spectra we observe that the variation of Co 4p and Co 3d unoccupied state were unapparent by Yb doping. The electronic transferred from O 2p to Ca 3d state and electronic transferred from Co 3d-O2p hybridization state to Co 4p state are possible. From Co L3-edge, the results indicate that Co 3d unoccupied state is related to resistivity of Ca3-xMxCo4O9+δ(M=Pr, Yb). The average valence of Co in the compounds  Ca3-xMxCo4O9+δ(M=Pr, Yb) are about 3.37+.

目　錄
第一章 序論 …………………………………………………………  1 
第二章 樣品簡介 ……………………………………………………  3
2.1 Ca3Co4O9+δ的特性……………………………………………   3
2.2熱電性質相關理論簡介………………………………………   7
2.3樣品製程………………………………………………………   8
第三章 X光吸收光譜簡介 …………………………………………  9
3.1 X光吸收光譜近邊緣結構(XANES) ………………………  13
3.2延伸X光吸收光譜精細結構（EXAFS） …………………  14
3.3數據分析 ……………………………………………………   16
第四章 實驗設備與量測方法 ……………………………………   22
4.1 X光光源 ……………………………………………………   22
4.2單色儀 ………………………………………………………   24
4.3光譜測量方式 ………………………………………………   24
4.4測量樣品的處理與準備 ……………………………………… 28
第五章  結果與討論 ………………………………………………  29
第六章  結論 ………………………………………………………  64
參考文獻 ……………………………………………………………  66


圖目錄
圖2.1 Ca3Co4O9+δ之結構圖….……………………...………… 3
圖2.2 Ca3-xPrxCo4O9+δ，與溫度相關的電阻圖……………………..…..4
圖2.3 Ca3-xPrxCo4O9+δ，與溫度相關的熱電功率圖……………………5  
圖2.4 Ca3-xYbxCo4O9+δ，與溫度相關的電阻率圖….…….……………5  
圖2.5 Ca3-xYbxCo4O9+δ，與溫度相關的熱電功率圖……………………6  
圖3.1 物質吸收截面與能量之關係圖………………………………...11
圖3.2 XANES與EXAFS分界圖…………………………………... ...12
圖3.3 光電子平均自由路徑與能量關係圖…………………………...13
圖3.4 單一散射與多重散射之圖示…………………………...............14  
圖3.5 出射電子受鄰近原子的背向散射，而產生干涉現象…….........15  
圖3.6 X光吸收光譜之數據分析流程…………………………............16
圖3.7 選擇能量底限E0值的不同方法……………………..................18
圖4.1 X光吸收光譜實驗示意圖………………………………………23
圖4.2 穿透式………………………………………………..…….........25   
圖4.3 X光通過物質之強度衰減……………………………................25 
圖4.4 螢光式………………………..…………………………….........27
圖4.5 電子逸出式…………………………………………………….27
圖 4.6 光子吸收過程………………...………………………………..27
圖5.1 Ca3-xPrxCo4O9+δ，Ca L2,3-edge吸收光譜..............................33
圖5.2 Ca3-xPrxCo4O9+δ，扣除背景後Ca L3-edge吸收光譜............34
圖5.3  Ca3-xPrxCo4O9+δ， Ca L3-edge積分值.............................................35
圖5.4  Ca3-xPrxCo4O9+δ，Co K-edge近邊吸收光譜.............................36
圖5.5  Ca3-xPrxCo4O9+δ，譜線相疊之Co K-edge近邊吸收光譜圖.....37
圖5.6  外插法所得Co平均價數........................................................38
圖5.7  Ca3-xPrxCo4O9+δ，Co L2,3-edge吸收光譜..................................39
圖5.8  Ca3-xPrxCo4O9+δ，扣除背景後Co L3-edge吸收光譜...............40
圖5.9  Ca3-xPrxCo4O9+δ， Co L3-edge積分值...............................................41
圖5.10 Ca3-xPrxCo4O9+δ，O K-edge近邊吸收光譜圖...........................42
圖5.11 Ca3-xPrxCo4O9+δ，扣除背景後a峰吸收光譜圖.....................43
圖5.12 Ca3-xPrxCo4O9+δ， a峰積分值..................................................44
圖5.13 Ca3-xPrxCo4O9+δ，簡化平面示意圖.....................................45
圖5.14 Ca3-xPrxCo4O9+δ，與溫度相關的電阻率圖...........................46
圖5.15 Ca3-xYbxCo4O9+δ，Ca L2,3-edge吸收光譜..................................51
圖5.16 Ca3-xYbxCo4O9+δ，扣除背景後Ca L3-edge吸收光譜................52
圖5.17 Ca3-xYbxCo4O9+δ， Ca L3-edge積分值.................................53
圖5.18 Ca3-xYbxCo4O9+δ，Co K-edge近邊吸收光譜...........................54
圖5.19 Ca3-xYbxCo4O9+δ，譜線相疊之Co K-edge近邊吸收光譜圖.....55
圖5.20 Ca3-xYbxCo4O9+δ，Co L2,3-edge吸收光譜..................................56
圖5.21 Ca3-xYbxCo4O9+δ，扣除背景後Co L3-edge吸收光譜...............57
圖5.22 Ca3-xYbxCo4O9+δ， Co L3-edge積分值.............................58
圖5.23 Ca3-xYbxCo4O9+δ，O K-edge近邊吸收光譜圖...........................59
圖5.24 Ca3-xYbxCo4O9+δ，扣除背景後a峰吸收光譜圖..................... ..60
圖5.25 Ca3-xYbxCo4O9+δ， a峰積分值..................................................61
圖5.26 Ca3-xYbxCo4O9+δ，簡化平面示意圖......................................62
圖5.27 Ca3-xYbxCo4O9+δ，與溫度相關的電阻率圖...............................63

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