本論文第一部分是利用固態核磁共振光譜觀察層狀結構的含水金屬鈷氧化合物水和鈷氧層之間的作用力。將含水鉀鈷氧樣品（KxCoO2．yH2O）置換成含重水的樣品（KxCoO2．yD2O），在經過25℃、80℃、150℃三種不同溫度處理後進行2H-MAS NMR實驗。光譜裡可以看到，在不同的處理溫度下，2H原子都有三種不同的環境存在，並且由模擬光譜得知，當溫度越高鈷氧層之間的距離越近，2H原子所受到的作用力越大；第二部分為利用固態核磁共振光譜觀察層狀結構的含水金屬鈷氧化合物中金屬陽離子所受到的作用力。含水銫鈷氧樣品（CsxCoO2．yH2O）則是在170~390K逐漸升溫的條件下進行133Cs -MAS NMR實驗。結果顯示銫原子在層狀結構裡應該不是被侷限在特定的位置上，當溫度升高銫原子會離開結構，在200K附近可以看到化學位移由三個變成一個，原因有兩個，可能是因為溫度降低了電子跳躍的速度，導致鈷原子顯現出不同價態，銫原子感受到周圍環境價太不同所導致光譜有不同位置；另一個則是銫原子在結構中是可以互相交換的，當溫度低時銫原子的交換速度低，造成銫原子停留在結構中的不同位置，導致不同位移的光譜，溫度升高光譜則又回復成一個訊號。

Solid state nuclear magnetic resonance spectroscopy is applied to probe the local electronic structure of hydrous alkali-metal cobaltates. In the first part of the thesis, deutered hydrous potassium cobaltates are synthesized and characterized by XRD and TGA along with annealing process. 2H-NMR experiments are applied to probe the dynamics of water intercalating the layered cobaltates. The results correlate the space between the layers and the quadrupole interaction between the deuterium and the layers of the cobaltates. In the second part of the thesis, hydrous cesium cobaltates are synthesized and characterized by XRD and TGA. Varied temperature 133Cs-NMR experiments are performed to probe the local environment of the cesium ions in the hydrous and anhydrous cobaltates from 170 K to 390 K. Our data suggest either a dramatic change in the Co 3d-electron spin dynamics below 200 K interpreted as the evidence for a tendency to electron localization, or a slow exchange among different cesium sites in the layered structure.

中文摘要 i
Abstract ii
目錄 iii
圖目錄 v
表目錄 viii
壹、序論 1
ㄧ、超導體簡介 1
1-1 超導性 2
1-1.1 零電阻 2
1-1.2 完全抗磁性 3
1-2 超導體的種類 4
1-2.1 高溫超導體 4
1-2.2 超導體 YBa2Cu3O7 的結構 7
1-2.3超導體 Na0.35CoO2‧1.3H2O 的結構 8
二、核磁共振光譜之發展 10
2-1 核磁共振之原理 11
2-1.1 核磁現象 11
2-1.2 固態核磁共振 12
2-1.2a Zeeman 作用力 12
2-1.2b 非均向化學位移作用力( Chemical Shift Anisotropy) 13
2-1.2c 偶極－偶極作用力（Dipole-Dipole interactions） 15
2-1.2d 四極作用力 （Quadrupolar Interaction） 16
2-2 魔角旋轉（Magic Angle Spinning） 18
2-3 化學位移與磁化率 19
貳、實驗 24
ㄧ、藥品 24
二、儀器 24
三、實驗步驟 25
3-1 含水鉀鈷氧樣品合成與分析 25
3-2 銫鈷氧樣品合成及分析 26
參、結果與討論 27
3-1 鉀鈷氧樣品分析 27
3-1.1a 粉末X光繞射 27
3-1.1b核磁共振光譜 29
3-1.2a 粉末X光繞射 44
3-1.2b核磁共振光譜 45
3-2.2 銫鈷氧樣品分析 52
3-2.1 XRD與133Cs-NMR光譜 52
3-2.2 變溫133Cs-NMR光譜 53
肆、結論 63
伍、參考資料 64

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