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研究生: 張益豪
I-Hao Chang
論文名稱: xSr(Mg1/3Ta2/3)O3-(1-x)Ba(Mg1/3Ta2/3)O3微波介電材料的光譜研究
Spectroscopic Study of xSr(Mg1/3Ta2/3)O3-(1-x)Ba(Mg1/3Ta2/3)O3 Microwave Materials
指導教授: 賈至達
Chia, Chih-Ta
學位類別: 碩士
Master
系所名稱: 物理學系
Department of Physics
論文出版年: 2009
畢業學年度: 97
語文別: 中文
論文頁數: 104
中文關鍵詞: X光繞射延伸X光吸收精細結構拉曼散射紅外反射光譜相變
英文關鍵詞: X-ray diffraction, extend X-ray absorption fine structure, Raman scattering, infrared reflection spectrum, phase transition
論文種類: 學術論文
相關次數: 點閱:257下載:1
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我們研究摻入不同Sr濃度的Ba(Mg1/3Ta2/3)O3 (xSr(Mg1/3Ta2/3)O3- (1-x)Ba(Mg1/3Ta2/3)O3,縮寫為xSMT-(1-x)BMT,x = 0.0~1.0) 的光譜特性,包含X光繞射(XRD)、延伸X光吸收精細結構(EXAFS)、拉曼散射及紅外反射光譜,並從光譜特性中找出與微波介電特性之關聯。在X光繞射實驗中,我們發現在x = 0.25之後(範圍在2θ = 42°~44.5°)會出現單斜結構 (-2 6 0) 的繞射峰,因此從X光繞射並不容易觀察出xSMT-(1-x)BMT的相變行為。在延伸X光吸收光譜中,不論是在以Ta為中心還是以Sr為中心的χ(R)光譜中,皆可看出光譜大致上有三階段的變化,證實xSMT-(1-x)BMT的晶格結構隨Sr摻入濃度x的增加產生改變。拉曼散射從單斜結構所主導之拉曼散射峰的出現,預測在x = 0.625時可能已經產生相變。紅外反射光譜的波形不容易看出相變,但從聲子的頻移分析可以得到相變發生的事實。
我們發現B位置 (Mg和Ta) 的有序程度與微波品質因子有很高的關聯性,而兩個A1g(O)聲子的寬度亦與微波品質因子有密切關係。相變之後(x ≥ 0.65),BO6才是決定微波介電常數趨勢的重要因素,因此我們推論x ≤ 0.5時A位置對微波介電常數的影響是顯著的。異常紅外聲子和微波介電特性是有關聯的,但是需要更多來自第一原理的資訊才能有清晰的解釋。

X-ray diffraction (XRD), extend x-ray absorption fine structure (EXAFS), Raman scattering, and infrared reflection spectroscopy were adopted to analyze the correlation of microwave properties with the microstructural parameters of xSr(Mg1/3Ta2/3)O3-(1-x)Ba(Mg1/3Ta2/3)O3 perovskite ceramics (xSMT-(1-x)BMT) with x = 0.0 to 1.0. We found the XRD peak (-2 6 0) of monoclinic phase near 2θ = 42°~44.5° appeared when x = 0.25, so the phase transition does occure, but it does not clearly find when it happens by XRD pattern. By EXAFS results, we found a three-stage variation in the χ(R) spectra for the Ta core or the Sr core, and this confirms the minor change of crystal symmetry through the slight displacement of atomic rearrangement as x increases. In Raman scattering experiments, the dominant scattering peaks of monoclinic phase appeared when x ≥ 0.625, and we think it transfers from trigonal symmetry to monoclinic phase for x ≥ 0.625. The shape of peak is not easy to recognize the phase transformation in infrared reflection spectrum, but we can find the at x ≥ 0.625 phase transformation from analyzing shift of phonon peaks.
The strong correlation of ordering parameter of B site (Mg and Ta) is obtained by XRD and microwave quality factor such correlation also exists between widths of two Raman A1g(O) phonons and microwave quality factor. After the phase transformation (x ≥ 0.65), the BO6 oxygen octahedra dominate the trend of microwave dielectric constant, so we predict that A site effect on the microwave dielectric properties is remarkable when x ≤ 0.5. The anomaly of the infrared active phonon modes may be connected with microwave dielectric properties, but we need more information from first-principles calculations to get the precise picture of the phase transition by the IR measurements.

致謝 I 中文摘要 V Abstract VI 總目錄 VII 圖目錄 IX 表目錄 XI Chapter 1 緒論 1 1.1 陶瓷材料簡介 1 1.2 樣品來源介紹 2 1.3 研究動機與目的 3 1.4 參考資料 4 Chapter 2 實驗設置及原理 6 2.1 X光繞射簡介 6 2.2 X光吸收光譜簡介 6 2.3 拉曼散射簡介 11 2.4 紅外反射光譜簡介 13 2.5 參考資料 14 Chapter 3 X光繞射圖譜分析 16 3.1 樣品的晶體結構 16 3.1.1 鈣鈦礦 (perovskite) 結構 16 3.1.2 B位置1:2的鈣鈦礦結構 (Pm3m與P3-m1) 17 3.1.3 近似xSMT-(1-x)BMT組成的結構比較 18 3.2 X光繞射圖譜數據處理 22 3.2.1 多峰比較的晶格常數計算法 23 3.2.2 結構精算法 23 3.3 X光繞射圖譜研究 24 3.3.1 晶格常數分析結果 24 3.3.2 有序程度的分析 26 3.3.3 繞射峰的分裂 27 3.3.4 有序性與微波品質因子的關聯 30 3.4 結論 31 3.5 參考資料 31 Chapter 4 X光吸收光譜分析 34 4.1 X光吸收光譜數據處理 34 4.1.1 建立理論模型 35 4.1.2 實驗數據轉換 35 4.1.3 光譜擬合 36 4.2 延伸X光吸收精細結構光譜研究 36 4.2.1 EXAFS理論模型 36 4.2.2 以鉭原子為吸收中心的分析 39 4.2.3 以鍶原子為吸收中心的徑向光譜定性分析 41 4.2.4 X光吸收光譜與微波介電特性之關聯 42 4.3 結論 42 4.4 參考資料 43 Chapter 5 拉曼散射光譜分析 44 5.1 複合性鈣鈦礦結構xSMT-(1-x)BMT的群論分析 44 5.2 拉曼散射光譜數據處理 46 5.3 拉曼散射光譜研究 46 5.3.1 BMT拉曼聲子與第一原理的對照 46 5.3.2 分區段拉曼光譜分析 48 5.3.3 拉曼散射光譜與微波介電特性之關聯 55 5.4 結論 57 5.5 參考資料 57 Chapter 6 紅外反射光譜分析 59 6.1 紅外反射光譜數據處理方法 59 6.1.1 克拉馬-克隆尼(Kramers-Kronig)轉換的積分近似方法 59 6.1.2 紅外反射光譜擬合 60 6.2 紅外反射光譜研究 60 6.2.1 BMT紅外聲子與第一原理的對照 60 6.2.2 紅外反射光譜分析 63 6.2.3 紅外反射光譜與微波介電特性之關聯 70 6.3 結論 71 6.4 參考資料 71 Chapter 7 全文總結 73 Appendix 74

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