使用角度擴散Ｘ光繞射 (angle-dispersive Ｘ-Ray diffraction, ADXRD) 及拉曼光譜 (Raman spectroscopy) 探討磷化銦摻雜鐵(InP:Fe) 及磷化銦摻雜鋅 (InP:Zn) 高壓下物理特性。摻雜機制的不同造成壓力對InP:Fe 及InP:Zn有不同程度的影響。另外，透過Ｘ光吸收近邊緣結構(Ｘ-Ray absorption near-edge structure, XANES)，確認InP:Fe中鐵的氧化價數為三價。
結果顯示，InP:Fe及InP:Zn在高壓下皆由閃鋅礦結構 (zinc-blende) 轉變為氯化鈉 (rock-salt) 結構並金屬化。由ADXRD數據發現InP:Fe與InP:Zn 相轉變開始壓力分別為8.2(2)和8.6(1) GPa，InP:Fe閃鋅礦結構與氯化鈉結構重量百分率交換壓力與相變結束之壓力分別為10.4(1)及16.0(2) GPa皆較InP:Zn的9.2(1)及14.1(2) GPa高。InP:Fe及InP:Zn拉曼光譜所觀察相變壓力同為8.8(1) GPa，但InP:Fe金屬化壓力為11.6(2) GPa較InP:Zn之14.5(2) GPa低，此因摻雜機制與摻雜元素不同所造成。InP:Fe為鐵三價鐵取代銦的位置與磷鍵結。InP:Zn之摻雜機制為鋅不取代磷的位置而與磷化銦中磷位置的空缺(vacancy)形成鍵結。

Using ADXRD (angle-dispersive Ｘ-Ray diffraction) and Raman spectroscopy, discussed physical properties of Iron doped indium phosphide (InP:Fe) and Zinc doped indium phosphide (InP:Zn) under high pressure. Because different doping mechanism, cause the pressure have different degrees of impact on InP:Fe and InP:Zn. In addition, Using XANES(Ｘ-Ray absorption near-edge structure) to confirm the valence of Iron is trivalent ions forming ionic bonds with phosphorous in InP:Fe. The results showed that both the InP:Fe and InP:Zn are transform from zincblende structure to rock-salt structure and metallic under high pressure. Through the ADXRD data can found the begin phase transition pressure is almost the same with InP:Fe and InP:Zn, at 8.2(2) GPa and 8.6(1) GPa, respectively. The Weight Fraction change pressure and phase transition finish pressure of InP:Fe is at 10.4(1) and 16.0(2) GPa which is higher than InP:Zn at9.2(1) and 14.1(2) GPa. In Raman spectroscopy can observed the begin phase transition pressure of InP:Fe and InP:Zn is the same at 8.8(1) GPa, but the transition to metallic phase pressure of InP:Fe is at 11.6(2) GPa which is lower than InP:Zn at 14.5(2) GPa, the result is because of the different doping mechanism and dopping element. The doping mechanism of InP:Fe is that the iron forming trivalent ions and replace the indium to form ionic bonds with phosphorous. The doping mechanism of InP:Zn is that the zinc forming ionic bonds with vacancy of phosphorous.

目錄
摘要 I
Abstract II
目錄 III
圖目錄 V
表目錄 VI
第一章 緒論 1
1.1 前言 1
1.2 半導體的摻雜 2
1.3 磷化銦及摻雜 3
1.4 Ｘ光吸收近邊緣結構 6
1.5 角度擴散Ｘ光繞射 6
1.6 拉曼散射 7
1.7 研究動機 7
第二章 文獻回顧 9
2.1 磷化銦的摻雜 9
2.2 Ｘ光吸收近邊緣結構 10
2.3 高壓實驗之發展與應用 11
2.4 磷化銦高壓下結構相變 12
2.5 磷化銦拉曼光譜 15
第三章 儀器與實驗方法 17
3.1 樣品來源 17
3.2 實驗器材 17
一. 鑽石高壓砧 17
二. 樣品腔 18
三. 傳壓介質 18
四. 紅寶石螢光壓力計 19
3.3 實驗儀器 19
一. 同步輻射光源 19
(1) Ｘ光吸收近邊緣結構 20
(2) Ｘ光吸收光譜實驗架設 21
(3) 高壓角度擴散Ｘ光繞射 22
二. 拉曼光譜 24
(1) 拉曼散射 24
(2) 拉曼光譜儀 26
3.4 實驗步驟 27
一. Ｘ光吸收光譜實驗 27
二. 高壓實驗 28
3.5 數據分析 29
一. Ｘ光吸收近邊緣結構 29
二. 高壓角度擴散Ｘ光繞射 30
三. 高壓拉曼光譜 30
4.1 磷化銦摻雜鐵 31
一. Ｘ光吸收近邊緣結構 31
二. 高壓Ｘ光粉末繞射圖譜 31
三. 高壓拉曼光譜 40
四. 討論 43
4.2 磷化銦摻雜鋅 43
一. 高壓Ｘ光粉末繞射圖譜 43
二. 高壓拉曼光譜 51
三. 討論 54
第五章 結論 55
第六章 未來工作 57
參考資料 58
 

圖目錄
圖1-1 磷化銦閃鋅礦結構 4
圖1-2 Edward-Yi Chang團隊所發表之快速元件多層膜結構圖 6
圖2-1 磷化銦摻雜鋅結構示意圖 9
圖2-2 磷化銦氯化鈉結構 14
圖2-3 (1)塊材(bulk)磷化銦拉曼光譜(2)鑲嵌在二氧化矽薄膜上磷化銦奈米顆粒拉曼光譜 16
圖3-1 鑽石高壓砧結構裝製圖 18
圖3-2 Ｘ光吸收光譜實驗架設示意圖 22
圖3-3 布拉格繞射定律 23
圖3-4 SPring-8,BL12B1,高壓Ｘ光粉末繞射實驗架設示意圖 24
圖3-5 雷利散射與拉曼散射 26
圖3-6 拉曼光譜儀實驗架設示意圖 27
圖3-7 XANES實驗流程 28
圖3-8 高壓實驗流程 29
圖4-1 InP:Fe之鐵Ｘ光近邊緣結構 33
圖4-2 InP:Fe從常壓加壓到19.0(2) GPa繞射圖譜疊圖 36
圖4-3 InP:Fe(a)晶格常數a隨著壓力變化(b)晶格體積歸一化後隨著壓力變化(c)閃鋅礦結構及氯化鈉結構佔全部重量百分率隨著壓力變化，黑色點代表閃鋅礦結構，紅色點代表氯化鈉結構，虛線為以波茲曼方程式 (Boltzmann equation) 所擬合趨勢線 41
圖4-4 InP:Zn加壓至14.5(2) GPa，拉曼光譜疊圖 44
圖4-5 InP:Fe振動模拉曼位移(Raman shift)隨壓力變化圖 45
圖4-6 InP:Fe振動模強度隨壓力變化圖 46
圖4-7 InP:Zn從常壓加壓到17.3(2) GPa繞射圖譜疊圖 49
圖4-8 InP:Zn(a)晶格常數a隨著壓力變化(b)晶格體積歸一化隨著壓力變化(c)閃鋅礦結構及氯化鈉結構佔全部重量百分率隨著壓力變化，黑色點代表閃鋅礦結構，紅色點代表氯化鈉結構，虛線為以波茲曼方程式 (Boltzmann equation) 擬合之趨勢線。 54
圖4-9 InP:Zn加壓至14.5(2) GPa，拉曼光譜疊圖 57
圖4-10 InP:Zn振動模拉曼位移(Raman shift)隨壓力變化圖 58
圖4-11 InP:Zn振動模強度隨壓力變化圖 59
InP:Zn晶格常數a=5.944(1)Å，晶格體積V=210.038 Å3皆較標準檔的5.861Å及201.3Å3大。為摻雜鋅所導致。相變化開始壓力在XRD光譜中為8.6(1) GPa，拉曼光譜中為8.8(1) GPa，皆較前人文獻中相變壓力低。閃鋅礦結構與氯化鈉結構所佔重量百分率於9.2(1) GPa交叉並於14.1(2)相變化結束，結構由閃鋅礦結構完全轉變為氯化鈉結構。拉曼光譜觀察得知在14.5(2) GPa時金屬化。 59
 
表目錄
表1-1 磷化銦閃鋅礦結構 4
表2-1 Ｘ光吸收近邊緣結構:不同鐵錯合物之兩價鐵及三架鐵pre-edge peak、absorption edge及white line整理 11
表2-2 Ｘ光吸收邊緣結構：不同鐵化合物兩價鐵及三價鐵absorption edge 11
表2-3 磷化銦氯化鈉結構 14
表2-4 磷化銦高壓相變文獻統整 15
表2-5 磷化銦拉曼光譜文獻統整 16
表4-1 InP:Fe常壓下繞射平面(hkl)對應之2θ及d-spacing 34
表4-2 InP:Fe在8.2(2) GPa時各繞射峰對應之2θ及d-spacing 37
表4-3 InP:Fe在14.6(2) GPa時各繞射峰對應之2θ及d-spacing 38
表4-4 InP:Fe在16.0(2) GPa時各繞射峰對應之2θ及d-spacing 38
表4-5 InP:Fe之氯化鈉結構各個繞射峰出現之壓力與出現時之2θ及d-spacing 39
表4-6 InP:Fe晶格常數與晶格體積隨壓力變化 40
表4-7 InP:Fe晶格常數及晶格體積線性壓縮率 41
表4-8 InP:Zn常壓下繞射平面(hkl)對應之2θ及d-spacing 48
表4-9 InP:Zn在8.6(1) GPa時各繞射峰對應之2θ及d-spacing 50
表4-10 InP:Zn在12.5(2) GPa時各繞射峰對應之2θ及d-spacing 51
表4-11 InP:Zn在14.1(2) GPa時各繞射峰對應之2θ及d-spacing 51
表4-12 InP:Zn之氯化鈉結構各個繞射峰出現之壓力與出現時之2θ及d-spacing 52
表4-13 InP:Zn晶格常數與晶格體積隨壓力變化 53
表4-14 InP:Zn晶格常數及晶格體積線性壓縮率 55

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