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系統識別號 U0026-0309201815324200
論文名稱(中文) 錳摻雜之鈣鈦酸鋇陶瓷體的交流阻抗分析
論文名稱(英文) Impedance Spectroscopy Analysis of Mn-Doped Barium Calcium Titanate Ceramics
校院名稱 成功大學
系所名稱(中) 資源工程學系
系所名稱(英) Department of Resources Engineering
學年度 106
學期 2
出版年 107
研究生(中文) 陳思敏
研究生(英文) Szu-Min Chen
學號 N46051148
學位類別 碩士
語文別 中文
論文頁數 76頁
口試委員 指導教授-黃啟原
口試委員-黃正亮
口試委員-許志雄
中文關鍵字 鈦酸鋇  富鈦  鈣摻雜  受體摻雜  晶體結構  阻抗分析 
英文關鍵字 barium titanate  Ca doped  accepter doped  impedance spectroscopy 
學科別分類
中文摘要 本研究以鈣摻雜到鈦酸鋇(BCT)陶瓷體中為主體,研究不同濃度之受體摻雜對BCT陶瓷體微結構、晶體結構和其電性分析之影響。但 Ca2+ 會同時取代鈣鈦礦結構中的A-site以及B-site;為確保Ca2+ 取代A-site,故額外添加 0.5 mol% 的 TiO2,以促使 Ca2+ 取代 B-site進行等價取代,進而提升陶瓷體的可靠度。
實驗結果顯示,將 (Ba0.92Ca0.08)Ti1.005O3 單一相粉末,以 Rietveld 方法模擬精算結構因子,可以發現,添加鈣後會導致晶格體積縮小,且正方性無顯著變化,此行為符合Ca2+ 取代 Ba2+ 位置之行為,證實了本實驗中 Ca2+ 的確是進入 A-site 而非 B-site 。為了模擬積層陶瓷電容器之燒結條件,故以Base Metal Electrode (BME) 爐於還原氣氛 (1% H2/N2) 下燒結,故本實驗添加了不同濃度的MnCO3 作為受體(acceptor) 改善陶瓷體半導化的情況;經燒結後可得到平均粒徑為 0.36 μm 之均勻微結構。阻抗圖譜以兩組等效RC電路擬合,再藉由Curie-Weiss law 行為進行驗證等效電路之合理性。從阻抗分析的結果顯示,晶粒和晶界的導電率分別由氧空缺及電子所主導;隨著受體摻雜的濃度增加,導電度隨之增加,也為維持電中性,晶粒與晶界的導電度會呈現相似的趨勢。而其空乏層厚度及晶界能障高度;隨著受體離子濃度的增加,都有相對減小的情況。綜合結論可知,添加不同濃度之受體MnCO3,對於利用交流阻抗分析所計算出之電性分析具有一定的影響。
英文摘要 In this study, calcium-doped barium titanate (BCT) powders were used as the raw materials to study different amounts of acceptor doping effects on the microstructure, crystal structure, and electrical properties of BCT. The A/B ratio of (Ba0.92Ca0.08)Ti1.005O3 was set for Ti-excess to prevent Ca doping onto the B-site. Powder of (Ba0.92Ca0.08)Ti1.005O3 was calcined at 1100°C which temperature can make the powder no second phase. Based on the Rietveld analysis results, Ca in the BCT mainly entered A-site to replace Ba. To simulating the MLCC sintering condition, the BCT ceramics should be sintered in reduction atmosphere to prevent the Ni electrode oxidation, and we also add different amounts of MnCO3 as acceptor to prevent the ceramic samples from semiconduction. The grain sizes after sintering are approximately 0.36 μm which fits the MLCC condition. In this study, We use two RQ equivalent circuit model to fit the impedance spectroscopy data, and the results meet the Curie-Weiss behavior. According to the impedance spectroscopy data, the grain and grain boundary conductivity of acceptor-doped BCT ceramics is determined by Vo ̈ and e' respectively. With the increase of the amount of addition, the grain and the grain boundary conductivity tends to increase. The similar grain and grain boundary conductivity of BCT ceramics are due to maintain the electric neutrality. While the depletion layer and grain boundary barrier height are tend to decrease as the amounts of acceptor increase. The comprehensive conclusions show that the amounts of acceptor (MnCO3) has a certain influence on the electrical analysis calculated by the impedance spectroscopy analysis.
論文目次 摘要 I
Abstract II
致謝 XIV
目錄 XVI
表目錄 XIX
圖目錄 XX


第一章 緒論 1
1-1 前言 1
1-2 研究目的 2
第二章 文獻回顧與理論基礎 3
2-1 鈦酸鋇之晶體結構及性質 3
2-2 鋇鈦比對於鈦酸鋇之影響 7
2-3 添加物對鈦酸鋇性質的影響 11
2-3-1等價離子添加對居禮溫度(Tc)的偏移及介電性質之影響 11
2-3-2施體 (donor) 添加對鈦酸鋇性質之影響 14
2-3-3受體 (acceptor) 添加對鈦酸鋇性質之影響 14
2-3-4補償性體 (compensator) 添加對鈦酸鋇性質之影響 16
2-4 Ca2+添加對鈦酸鋇的影響 18
2-5交流阻抗分析 22
2-6 Electric Modulus分析 33
2-7 等效電路的設計 35
2-8 陶瓷體導電率分析 35
第三章 實驗方法及步驟 37
3-1 粉末製備及分析 37
3-1-1 起始原料 37
3-1-2 鈣摻雜鈦酸鋇粉末製備 38
3-1-3 粉末之熱差/熱重分析 38
3-1-4 X光繞射儀 39
3-2 陶瓷體製備及分析 40
3-2-1 陶瓷體製備 40
3-2-2燒結收縮分析 40
3-2-3 陶瓷體密度量測 40
3-2-4 掃描式電子顯微鏡與微結構觀察及分析 41
3-3 電性量測 42
3-3-1 陶瓷體電性量測樣品準備 42
3-3-2 交流阻抗分析樣品準備及量測 42
第四章 結果與討論 43
4-1 起始混合粉末之DTA/TG分析 43
4-2 煅燒粉末分析 45
4-2-1 結晶相鑑定分析 45
4-2-2晶體結構分析 47
4-3 燒結體分析 51
4-3-1燒結體密度量測 51
4-3-2燒結收縮曲線量測 52
4-3-3顯微結構分析 54
4-4 交流阻抗分析 57
4-4-1 設計等效電路 57
4-4-2 Curie-Weiss行為分析 62
4-4-3導電率行為分析 65
4-4-4空乏層(空間電荷層)分析 68
4-4-5晶界能障高度分析 70
第五章 結論 72
參考文獻 73
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