本研究使用聚合多質子酸先驅物法於不同溫度800 ~ 1400 oC下製備(Gd2-yMy)Ti2O7-y/2 (M = Ca, Sr; y = 0.050, 0.100)樣品，當燒結溫度為800 ~ 1400 oC時皆為焦綠石的結構，其空間群為Fd3m。樣品粒徑大小根據SEM圖中顯示大約為400 ~ 800 nm，緻密度為50 ~ 65%。隨燒結溫度的上升，單位晶胞a-軸的長度逐漸變大，長度為10.192(1) < a < 10.209(1) &Aring;。Gd-O(1)和Ti-O(3)鍵長相同約為2.21(1) &Aring;；Gd-O(2)鍵長較長約為2.52(1) &Aring;；而Ti-O(2)鍵長相對較短約為1.97(1) &Aring;。O(3)位置之佔有率也隨溫度升高而增加，使O(2)位置的x座標(fractional coordinate)受到O(3)位置的擠壓而有變大的趨勢。本系列樣品中Ti的價數經由XANES光譜的測量，推測沒有混價情形發生，為四價金屬離子。

Four samples with nominal compositions of (Gd2-yMy)Ti2O7-y/2    (M = Ca, Sr; y = 0.050, 0.100) were prepared with different temperatures from 700 - 1400 oC by a polymeric citrate precursor method. Pyrochlore phase with a space group of Fd3m was observed for all the samples except for those prepared at 700 oC. Particle size of (Gd2-yMy)Ti2O7-y/2 compounds are about 400 - 800 nm observed under SEM. Relative density of these samples are in the range of 50 - 65%. Unit cell a-axis (ea. 10.192(1) - 10.209(1) Å) and occupancy of the O(3) site (ea. 1 - 8%) increase with increasing the preparation temperature. Gd−O(1) and Ti−O(3) have the same bond length. They are about 2.21(1) Å. Gd−O(2) has a longer bond length, that is 2.52(1) Å. On the other hand, Ti−O(2) has a shorter bond length, that is about 1.97(1) Å. Increasing occupation factor of the O(3) site would increase the x fractional coordinate of the O(2) site. Ti L-edge XANES spectra show that all the samples have Ti(IV) valence state.

摘要 ---------------------------------------------------------------------------------------------- I
總目錄 -------------------------------------------------------------------------------------------III
表目錄 ------------------------------------------------------------------------------------------ -V
圖目錄------------------------------------------------------------------------------------------ VII

第一章、緒論 ----------------------------------------------------------------------------------- 1
1-1 固態電解質 ----------------------------------------------------------------------------- 1
1-2 氧離子導體 ----------------------------------------------------------------------------- 1
    1-2-1 螢石結構(fluorite) ---------------------------------------------------------------- 2
    1-2-2 鈦酸鈣礦結構(perovskite) ------------------------------------------------------ 5
    1-2-3 焦綠石結構(pyrochlore) --------------------------------------------------------- 6
  1-3 焦綠石結構之氧離子遷移 ----------------------------------------------------------- 8
  1-4 A2B2O7中A、B陽離子半徑與結構之關係 ---------------------------------------- 9
  1-5 R2Ti2O7系列與其相變化 ------------------------------------------------------------ 10
  1-6 X-光吸收近邊緣結構光譜 ---------------------------------------------------------- 10
  1-7 研究動機與目的 --------------------------------------------------------------------- 11

第二章、實驗方法 --------------------------------------------------------------------------- 13
  2-1 實驗藥品 ------------------------------------------------------------------------------ 13
  2-2 實驗步驟 ------------------------------------------------------------------------------ 14
  2-3 樣品鑑定與儀器 --------------------------------------------------------------------- 16
    2-3-1 X-光繞射 ------------------------------------------------------------------------- 16
    2-3-2 Rietveld精算法 ------------------------------------------------------------------ 18
    2-3-3 X-光吸收近邊緣結構光譜 ---------------------------------------------------- 19
    2-3-4 掃描式電子顯微術 ------------------------------------------------------------- 23

第三章、結果與討論 ------------------------------------------------------------------------ 24
    3-1 樣品製備與單相鑑定 ------------------------------------------------------------ 24
 3-2 結構分析 --------------------------------------------------------------------------- 29
    3-3 X-光吸收近邊緣光譜-------------------------------------------------------------- 67
    3-4 掃描式電子顯微術----------------------------------------------------------------- 71
    3-5 樣品緻密度 ------------------------------------------------------------------------ 76

第四章、結論與未來計畫 ------------------------------------------------------------------ 78
  4-1 結論 ------------------------------------------------------------------------------------ 78
  4-2 未來計畫 ------------------------------------------------------------------------------ 79

第五章、參考文獻 --------------------------------------------------------------------------- 80
表目錄
表1-1 Bi2O3各結晶相在不同溫度下的導電度 ------------------------------------------- 4
表2-1 聚合多質子酸先驅物法所用到之樣品純度與來源 --------------------------- 13
表3-1 (Gd2-yMy)Ti2O7-y/2樣品之鑑定 ------------------------------------------------------ 25 
表3-2 (Gd1.95Ca0.05)Ti2O6.975-800oC樣品之XRD精算結果 ---------------------------- 31
表3-3 (Gd1.95Ca0.05)Ti2O6.975-900oC樣品之XRD精算結果 ---------------------------- 32
表3-4 (Gd1.95Ca0.05)Ti2O6.975-1000oC樣品之XRD精算結果 -------------------------- 33
表3-5 (Gd1.95Ca0.05)Ti2O6.975-1100oC樣品之XRD精算結果 -------------------------- 34
表3-6 (Gd1.95Ca0.05)Ti2O6.975-1300oC樣品之XRD精算結果 -------------------------- 35
表3-7 (Gd1.95Ca0.05)Ti2O6.975-1400oC樣品之XRD精算結果 -------------------------- 36
表3-8 (Gd1.9Ca0.1)Ti2O6.95-800oC樣品之XRD精算結果 ------------------------------- 37
表3-9 (Gd1.9Ca0.1)Ti2O6.95-900oC樣品之XRD精算結果 ------------------------------- 38
表3-10 (Gd1.9Ca0.1)Ti2O6.95-1000oC樣品之XRD精算結果 ---------------------------- 39
表3-11 (Gd1.9Ca0.1)Ti2O6.95-1100oC樣品之XRD精算結果 ---------------------------- 40
表3-12 (Gd1.9Ca0.1)Ti2O6.95-1200oC樣品之XRD精算結果 ---------------------------- 41
表3-13 (Gd1.9Ca0.1)Ti2O6.95-1300oC樣品之XRD精算結果 ---------------------------- 42
表3-14 (Gd1.9Ca0.1)Ti2O6.95-1400oC樣品之XRD精算結果 ---------------------------- 43
表3-15 (Gd1.95Sr0.05)Ti2O6.975-800oC樣品之XRD精算結果 --------------------------- 44
表3-16 (Gd1.95Sr0.05)Ti2O6.975-900oC樣品之XRD精算結果 --------------------------- 45
表3-17 (Gd1.95Sr0.05)Ti2O6.975-1000oC樣品之XRD精算結果 -------------------------- 46
表3-18 (Gd1.95Sr0.05)Ti2O6.975-1100oC樣品之XRD精算結果 -------------------------- 47
表3-19 (Gd1.95Sr0.05)Ti2O6.975-1200oC樣品之XRD精算結果 -------------------------- 48
表3-20 (Gd1.95Sr0.05)Ti2O6.975-1300oC樣品之XRD精算結果 -------------------------- 49
表3-21 (Gd1.95Sr0.05)Ti2O6.975-1400oC樣品之XRD精算結果 -------------------------- 50
表3-22 (Gd1.9Sr0.1)Ti2O6.95-800oC樣品之XRD精算結果 ------------------------------ 51
表3-23 (Gd1.9Sr0.1)Ti2O6.95-900oC樣品之XRD精算結果 ------------------------------ 52
表3-24 (Gd1.9Sr0.1)Ti2O6.95-1000oC樣品之XRD精算結果 ---------------------------- 53
表3-25 (Gd1.9Sr0.1)Ti2O6.95-1100oC樣品之XRD精算結果 ----------------------------- 54
表3-26 (Gd1.9Sr0.1)Ti2O6.95-1200oC樣品之XRD精算結果 ---------------------------- 55
表3-27 (Gd1.9Sr0.1)Ti2O6.95-1300oC樣品之XRD精算結果 ---------------------------- 56
表3-28 (Gd1.9Sr0.1)Ti2O6.95-1400oC樣品之XRD精算結果 ---------------------------- 57
表3-29 Ti L-edge XANES吸收光譜b2峰能量(eV) ------------------------------------- 70
表3-30 (Gd2-yCay)Ti2O7-y/2(y = 0.050, 0.100)緻密度(%) -------------------------------- 76
表3-31 (Gd2-ySry)Ti2O7-y/2(y = 0.050, 0.100)緻密度(%) --------------------------------- 77








圖目錄
圖1-1 螢石單位晶胞 -------------------------------------------------------------------------- 3
圖1-2 Bi2O3不同溫度下的結晶相變化情形 ----------------------------------------------- 4
圖1-3 鈦酸鈣礦單位晶胞 -------------------------------------------------------------------- 5
圖1-4 1/8單位晶胞焦綠石的晶體結構 ----------------------------------------------------- 6
圖1-5 焦綠石的單位晶胞 -------------------------------------------------------------------- 7
圖1-6 Ln2Zr2O7 (Ln = rare earth)之離子導電度-------------------------------------------- 8
圖1-7 Ln2Zr2O7 (Ln = rare earth)陽離子半徑比與結構關係 ---------------------------- 9
圖1-8 Ti L-edge XANES吸收光譜 --------------------------------------------------------- 11
圖2-1 布拉格繞射示意圖 ------------------------------------------------------------------ 17
圖2-2 GSAS精算之流程圖 ----------------------------------------------------------------- 20
圖2-3 XANES與EXAFS區分圖 ----------------------------------------------------------- 21
圖3-1 (Gd2-yMy)Ti2O7-y/2 (T = 700 oC) X-光粉末繞射圖譜 ---------------------------- 26
圖3-2 (Gd1.95Sr0.05)Ti2O6.975 (T = 800~1000oC) X-光粉末繞射圖譜 ------------------ 26
圖3-3 (Gd1.95Ca0.05)Ti2O6.975 (T = 800~1400 oC) X-光粉末繞射圖譜 ----------------- 27
圖3-4 (Gd1.9Ca0.1)Ti2O6.95 (T = 800~1400 oC) X-光粉末繞射圖譜 -------------------- 27
圖3-5 (Gd1.95Sr0.05)Ti2O6.975 (T = 1100~1400 oC) X-光粉末繞射圖譜 ---------------- 28
圖3-6 (Gd1.9Sr0.1)Ti2O6.95 (T = 800~1400 oC) X-光粉末繞射圖譜 -------------------- 28
圖3-7 (Gd1.95Ca0.05)Ti2O6.975-800oC樣品之XRD精算結果 ----------------------------- 31
圖3-8 (Gd1.95Ca0.05)Ti2O6.975-900oC樣品之XRD精算結果 ----------------------------- 32
圖3-9 (Gd1.95Ca0.05)Ti2O6.975-100oC樣品之XRD精算結果 ----------------------------- 33
圖3-10 (Gd1.95Ca0.05)Ti2O6.975-110oC樣品之XRD精算結果 ---------------------------- 34
圖3-11 (Gd1.95Ca0.05)Ti2O6.975-1300oC樣品之XRD精算結果 -------------------------- 35
圖3-12 (Gd1.95Ca0.05)Ti2O6.975-1400oC樣品之XRD精算結果 -------------------------- 36
圖3-13 (Gd1.9Ca0.1)Ti2O6.95-800oC樣品之XRD精算結果 ------------------------------- 37
圖3-14 (Gd1.9Ca0.1)Ti2O6.95-900oC樣品之XRD精算結果 ------------------------------- 38
圖3-15 (Gd1.9Ca0.1)Ti2O6.95-1000oC樣品之XRD精算結果 ----------------------------- 39
圖3-16 (Gd1.9Ca0.1)Ti2O6.95-1100oC樣品之XRD精算結果 ----------------------------- 40
圖3-17 (Gd1.9Ca0.1)Ti2O6.95-1200oC樣品之XRD精算結果 ----------------------------- 41
圖3-18 (Gd1.9Ca0.1)Ti2O6.95-1300oC樣品之XRD精算結果 ----------------------------- 42
圖3-19 (Gd1.9Ca0.1)Ti2O6.95-1400oC樣品之XRD精算結果 ----------------------------- 43
圖3-20 (Gd1.95Sr0.05)Ti2O6.975-800oC樣品之XRD精算結果 ----------------------------- 44
圖3-21 (Gd1.95Sr0.05)Ti2O6.975-900oC樣品之XRD精算結果 ----------------------------- 45
圖3-22 (Gd1.95Sr0.05)Ti2O6.975-1000oC樣品之XRD精算結果 --------------------------- 46
圖3-23 (Gd1.95Sr0.05)Ti2O6.975-1100oC樣品之XRD精算結果 --------------------------- 47
圖3-24 (Gd1.95Sr0.05)Ti2O6.975-1200oC樣品之XRD精算結果 --------------------------- 48
圖3-25 (Gd1.95Sr0.05)Ti2O6.975-1300oC樣品之XRD精算結果 --------------------------- 49
圖3-26 (Gd1.95Sr0.05)Ti2O6.975-1400oC樣品之XRD精算結果 --------------------------- 50
圖3-27 (Gd1.9Sr0.1)Ti2O6.95-800oC樣品之XRD精算結果 ------------------------------- 51
圖3-28 (Gd1.9Sr0.1)Ti2O6.95-900oC樣品之XRD精算結果 ------------------------------- 52
圖3-29 (Gd1.9Sr0.1)Ti2O6.95-1000oC樣品之XRD精算結果 ------------------------------ 53
圖3-30 (Gd1.9Sr0.1)Ti2O6.95-1100oC樣品之XRD精算結果 ------------------------------ 54
圖3-31 (Gd1.9Sr0.1)Ti2O6.95-1200oC樣品之XRD精算結果 ------------------------------ 55
圖3-32 (Gd1.9Sr0.1)Ti2O6.95-1300oC樣品之XRD精算結果 ------------------------------ 56
圖3-33 (Gd1.9Sr0.1)Ti2O6.95-1400oC樣品之XRD精算結果 ------------------------------ 57
圖3-34 燒結溫度與晶胞長度的關係 ----------------------------------------------------- 60
圖3-35 燒結溫度與相對晶胞長度的關係 ----------------------------------------------- 61
圖3-36 離子半徑比與晶胞長度的關係 -------------------------------------------------- 61
圖3-37 燒結溫度與O(2) x位置的關係 --------------------------------------------------- 62
圖3-38 燒結溫度與相對O(2) x位置的關係 --------------------------------------------- 62
圖3-39 燒結溫度與O(3)佔有率的關係 -------------------------------------------------- 63
圖3-40 燒結溫度與相對O(3)佔有率的關係 -------------------------------------------- 63
圖3-41 燒結溫度與Gd-O(1)和Ti-O(3)長度的關係 ------------------------------------ 64
圖3-42 燒結溫度與Gd-O(2)和Ti-O(2)長度的關係 ------------------------------------ 64
圖3-43 燒結溫度與O(1)-Gd-O(2)和O(2)-Gd-O(2)角度的關係 ---------------------- 65
圖3-44 燒結溫度與O(2)-Ti-O(2)和O(2)-Ti-O(3)角度的關係 ------------------------ 65
圖3-45 燒結溫度與A,B位置互換的關係 ------------------------------------------------ 66
圖3-46 Ti L-edge XANES吸收光譜 ------------------------------------------------------- 68
圖3-47 (Gd1.95Ca0.05)Ti2O6.975 (T = 700, 900, 1100 and 1400oC)系列樣品之Ti L-edge XANES吸收光譜 ----------------------------------------------------------------------------- 68
圖3-48 (Gd1.9Ca0.1)Ti2O6.95 (T = 700, 900, 1100 and 1400oC)系列樣品之Ti L-edge XANES吸收光譜 ----------------------------------------------------------------------------- 69
圖3-49 (Gd1.95Sr0.05)Ti2O6.975 (T = 700, 900, 1100 and 1400oC)系列樣品之Ti L-edge XANES吸收光譜 ----------------------------------------------------------------------------- 69
圖3-50 (Gd1.9Sr0.1)Ti2O6.95 (T = 700, 900, 1100 and 1400oC)系列樣品之Ti L-edge XANES吸收光譜 ----------------------------------------------------------------------------- 70
圖3-51 (a) (Gd1.95Ca0.05)Ti2O6.975-1100oC樣品影像(10 kX) ----------------------------- 72
      (b) (Gd1.95Ca0.05)Ti2O6.975-1100oC樣品影像(30 kX) ----------------------------- 72
圖3-52 (a) (Gd1.95Ca0.05)Ti2O6.975-1400oC樣品影像(10 kX) ----------------------------- 72
      (b) (Gd1.95Ca0.05)Ti2O6.975-1400oC樣品影像(30 kX) ----------------------------- 72
圖3-53 (a) (Gd1.9Ca0.1)Ti2O6.95-1100oC樣品影像(10 kX) -------------------------------- 73
      (b) (Gd1.9Ca0.1)Ti2O6.95-1100oC樣品影像(30 kX) -------------------------------- 73
圖3-54 (a) (Gd1.9Ca0.1)Ti2O6.95-1400oC樣品影像(10 kX) -------------------------------- 73
      (b) (Gd1.9Ca0.1)Ti2O6.95-1400oC樣品影像(30 kX) -------------------------------- 73
圖3-55 (a) (Gd1.95Sr0.05)Ti2O6.975-1100oC樣品影像(10 kX) ------------------------------ 74
      (b) (Gd1.95Sr0.05)Ti2O6.975-1100oC樣品影像(30 kX) ------------------------------ 74
圖3-56 (a) (Gd1.95Sr0.05)Ti2O6.975-1400oC樣品影像(10 kX) ------------------------------ 74
      (b) (Gd1.95Sr0.05)Ti2O6.975-1400oC樣品影像(30 kX) ------------------------------ 74
圖3-57 (a) (Gd1.9Sr0.1)Ti2O6.95-1100oC樣品影像(10 kX) --------------------------------- 75
      (b) (Gd1.9Sr0.1)Ti2O6.95-1100oC樣品影像(30 kX) --------------------------------- 75
圖3-58 (a) (Gd1.9Sr0.1)Ti2O6.95-1400oC樣品影像(10 kX) --------------------------------- 75
      (b) (Gd1.9Sr0.1)Ti2O6.95-1400oC樣品影像(30 kX) --------------------------------- 75
圖3-59 溫度與緻密度的關係 -------------------------------------------------------------- 77

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