本論文主要以X光吸收光譜實驗研究成長於SrTiO3 (STO) (對LZMO薄膜僅具些微的壓縮應力) 以及MgO (對LZMO薄膜具拉撐應力) 基板的鑭鋯錳氧 (LZMO) 薄膜其電荷、軌道、自旋、傳輸和磁性特質的相關性。實驗包含在不同溫度下Mn K、L3,2-edge X光吸收近邊緣結構 (XANES)、線二向性 (XLD)、磁圓二向性 (XMCD) 以及 Mn K-edge延伸X光吸收精細結構 (EXAFS)。X光線二向性實驗發現在室溫時，LZMO/STO Mn 3d eg電子，傾向較多之佔據在 x2-y2 軌域；LZMO/MgO傾向較多之佔據在 3z2-r2 軌域。在80K時則呈現相反的趨勢，LZMO/STO Mn 3d eg電子，傾向較多之佔據在 3z2-r2 軌域； LZMO/MgO傾向較多之佔據在 x2-y2 軌域。由Mn K、L3,2-edge XANES得知在LZMO薄膜其多重價數由 Mn2+、 Mn3+、 Mn+4所貢獻。對LZMO/STO而言，傾向較多佔據在 3z2-r2 軌域、多重價數的雙交換機制與Mn-Mn鍵結變短，導致電荷傳輸與磁性變強。

The correlation among the charge, orbital, spin, transport and magnetic properties of strained tetravalent ion-doped La0.85Zr0.15MnO3 (LZMO) thin films epitaxially grown on two substrates, SrTiO3 (STO) and MgO, were extensively studied using the x-ray absorption near-edge structure (XANES), x-ray linear dichroism (XLD), x-ray magnetic circular dichroism (XMCD) and the extended x-ray absorption fine structure (EXAFS) at the Mn L3,2- and K-edge at various temperatures. The Mn 3d eg preferential orbital occupation of LZMO/STO changed from in-plane x2-y2 to out-of-plane 3z2-r2 as the temperature was reduced from room temperature to below the transition temperatures of 80 K, while LZMO/MgO, the eg orbital occupation changed oppositely from 3z2-r2 to x2-y2. Mn3+/Mn4+ and Mn+2 multiple valence states were involved in the double-exchange mechanism, the stabilization of a preferential orbital occupation of the out-of-plane 3z2-r2 orbital of Mn ions and the shortening of the Mn-Mn bond distance, all of which may play an important role in improving the transport and magnetic properties, owing to the distortion of the MnO6 octahedron by the strain in the LZMO/STO.

致謝	Ⅰ
中文摘要	Ⅱ
英文摘要	Ⅲ
目錄	Ⅳ
圖表目錄	Ⅵ
第一章、 緒論	1
第二章、 X光吸收光譜簡介	7
(一)、吸收邊緣與E0值	9
(二)、X光吸收近邊緣結構 (X-ray Absorption Near Edge Structure、XANES)	10
(三)、延伸X光吸收精細結構 (Extended X-ray Absorption Fine Structure、EXAFS)	11
(四)、實驗方法	16
(五)、數據分析	20
第三章、X 光磁圓偏振二向性簡介 (X-ray Magnetic Circular         Dichroism、XMCD)	24
(一)、理論模型	24
(二)、實驗方法	25
第四章、 實驗數據分析與討論	28
(一)、LZMO樣品製備與基本量測	28
(二)、X光吸收近邊緣結構 (X-ray Absorption Near Edge      Structure、XANES) 與X光吸收之線二向性能譜 (X-ray Linear Dichroism、XLD) 之析	40
(三)、X光磁圓二向性能譜 (X-ray Magnetic Circular Dichroism 、XMCD) 之分析	48
(四)、延伸X光吸收精結構 (Extended X-ray Absorption Fine Structure、EXAFS) 之分析	55
第五章、結論	59
參考文獻	60

圖1-1 LaMnO3單位晶胞鈣鈦礦結構圖	4
圖1-2 錳位於八面體中心與氧鍵結方向示意圖	4
圖1-3 八面體中心過渡金屬離子Mn 3d 能階分裂圖	6
圖1-4 錳離子Mn3+與Mn4+雙交換作用示意圖	6
圖2-1 光子能量與銅吸收截面關係圖	8
圖2-2 XANES與EXAFS分界圖		13
圖2-3 光電子平均自由路徑與能量關係圖	13
圖2-4 單一散射與多重散射之圖像(a) 為單一散射路程示意圖
      (b) 為多重散射路程示意圖	14
圖2-5 射出電子受鄰近原子的背向散射，而產生干涉現象
(a) 建設性干涉 (b) 破壞性干涉	15
圖2-6 X光吸收光譜實驗示意圖	17
圖2-7 三種光譜量測方法	19
圖2-8 X光吸收光譜之數據分析流程	20
圖3-1 Ni L3,2-edge 吸收光譜。實線和虛線分別表示Ni 對正磁場和負磁場的X光吸收光譜	27
圖3-2 Ni L3,2-edge XMCD 譜圖	27
圖4-1 LZMO塊材之X光繞射圖	32
圖4-2 (a) LZMO塊材單位晶胞之斜菱晶結構，(b) LZMO塊材單位晶胞沿(111)軸向之俯視圖，(c) LZMO薄膜受STO基板平面壓縮應力的影響，(d) LZMO薄膜受MgO基板平面拉撐應力的影響	33
圖4-3 (a) LZMO/STO於(002)附近角度之X光繞射圖 (右上角插圖為LZMO/STO 2θ-θ scan across (002) peak圖；右下角插圖為LZMO/STO AFM 薄膜表面掃描圖)	34
(b) LZMO/MgO於(002)附近角度之X光繞射圖 (右上角插圖為LZMO/MgO 2θ-θ scan across (002) peak圖；右下角插圖為                    LZMO/MgO AFM 薄膜表面掃描圖)	35
圖4-4 為LZMO、LZMO/STO與LZMO/MgO薄膜的變溫電阻率與定磁場變溫磁化率的量測結果	37
圖4-5 (a) 變溫之LZMO/STO樣品與標準樣品歸一化後的Mn L3,2-edge XANES	41
(b) 變溫之LZMO/MgO樣品與標準樣品歸一化後的Mn L3,2-edge XANES	42
圖4-6 (a) 低溫之樣品與標準樣品歸一化後的Mn K-edge XANES
	43
     (b) 室溫之樣品與標準樣品歸一化後的Mn K-edge XANES
      	44

圖4-7 (a) LZMO/STO正負磁場下變溫之Mn L3,2-edge及 XMCD 譜圖	50
(b) LZMO/MgO正負磁場下變溫之Mn L3,2-edge及 XMCD 譜圖	51 (c) LZMO正負磁場下變溫之Mn L3,2-edge及 XMCD 譜圖
	52
圖4-8 LZMO、LZMO/STO與LZMO/MgO薄膜的定磁場變溫磁化率與XMCD Mn L3-edge面積積分比較圖	53
圖4-9 LZMO/STO正負磁場下變溫之Ti L3,2-edge及 XMCD 譜圖	54
圖4-10 (a) θ= 00時變溫之Mn K-edge EXAFS傅立葉轉換圖	57
 (b) θ= 700時變溫之Mn K-edge EXAFS傅立葉轉換圖	58
表4-1 LZMO塊材之參數	32

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