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研究生： 黃莉雯
Huang, Li-Wen
論文名稱： 鋯摻雜鈦酸鋇介電材料 (Ba0.997(Ti1-xZrx)O3, x = 0 - 0.5)之製備、分析、與電性
Preparation, Characterization, and Dielectric Property of Zirconium-Doped Barium Titanates
指導教授： 黃啓原
Huang, Chi-Yuen
學位類別： 碩士
Master
系所名稱： 工學院 - 資源工程學系
Department of Resources Engineering
論文出版年： 2023
畢業學年度： 111
語文別： 中文
論文頁數： 98
中文關鍵詞： 鈦酸鋇 、鋯摻雜 、介電性質 、絕緣電阻率 、核殼結構
外文關鍵詞： Barium titanate, zirconium doped barium titanate, dielectric constant, insulation resistivity, core-shell structure
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    • 本研究利用固態反應法進行鈦酸鋇 (BT) 與鋯摻雜鈦酸鋇 (BTZ) 合成 Ba0.997(Ti1-xZrx)O3 (x=0, 0.1, 0.2, 0.3, 0.4, 0.5) 之固溶體，在固定鋇鈦比的條件下，添加多量的鋯於鈦酸鋇中進行陶瓷體的製備及電性量測，為了驗證添加多量的鋯會使能階上升，進而絕緣電阻率亦會隨之上升的表現，因此在這項研究中，根據dopant的混合與否將實驗分為兩個部分。第一部分以不加任何dopant為主作為前置評估，藉此觀察大範圍添加Zr4+對結晶相、顯微結構、介電性質、晶體結構及絕緣電阻率的影響，以絕緣電阻率提升為純鈦酸鋇的兩倍為目標；第二部分則是選擇第一部分最佳的成分點範圍 Ba0.997(Ti1-xZrx)O3 (x=0, 0.3, 0.4, 0.5) 進行後續混合dopant (PS/ BZ01/ BZ02)的實驗。本研究透過二階段煅燒的實驗設計，合成出純相的鋯摻雜之鈦酸鋇粉末，且藉由調整第二階段的溫度及持溫時間能有效控制粉末粒徑大小。在無混合dopant之介電性質，發現隨著鋯添加量增加，其立方相結晶量提高，使極化量降低導致室溫下之介電常數呈現下降趨勢，居禮溫度也會同時往低溫偏移，而在室溫下之絕緣電阻率，Ba(Ti0.7Zr0.3)O3具有最好之表現，樣品絕緣電阻率值達到36 GΩ∙m約為BaTiO3的三倍；在混合dopant的實驗中，介電常數一樣會隨著鋯含量增加而下降，不過三種dopant對溫度與電容變化率曲線 (TCC curve) 影響不大，趨勢皆為相同，而在電阻率方面，發現混合Gd3+量較多的BZ02 dopant，Ba(Ti0.6Zr0.4)O3 之電阻率有相對較好的表現，經由TEM分析觀察其核殼結構 (Core-Shell structure)，發現此成分點之shell較厚，因此本研究判斷含有 Gd3+ 之dopant相對較適合摻鋯的BTZ系統，能有效提升其絕緣電阻率之表現。

    This study used the solid-solution reaction method to synthesize Zr-doped barium titanate Ba0.997(Ti1-xZrx)O3 (x=0, 0.1, 0.2, 0.3, 0.4, 0.5). In the conditions of the same barium-titanate ratio, a large amount of zirconium was added to barium titanate for preparation of the ceramic body and electrical measurement. In this study, we discussed the effects of adding different dopants (PS/ BZ01/ BZ02) to the synthesis process. The results of the research show that the zirconium-doped barium titanate powder can be successfully synthesized by controlling the particle size through two-stage calcination to meet the industrial specification of 500nm. Through X-ray diffraction pattern and Rietveld refinement actuarial calculation, it can be observed x = 0 tends to the tetragonal; x = 0.1 - 0.5 tends to the cubic. In terms of electrical analysis without adding dopant, the dielectric constant of Ba(Ti1-xZrx)O3 ceramics decrease with the increase of Zr content at room temperature. At room temperature, the insulation resistivity of Ba(Ti0.7Zr0.3)O3 is higher than that of BaTiO3. The insulation resistivity of the sample reaches 36 GΩ·m, which is three times that of BaTiO3. In terms of electrical analysis with adding dopant, it is found that the resistivity of Ba(Ti0.6Zr0.4)O3 performs better than that of BaTiO3, so this study judges that the dopant containing Gd3+ is relatively suitable for the BTZ system doped with zirconium, which can effectively improve its performance of insulation resistivity.

    摘要 I 目錄 X 表目錄 XIII 圖目錄 XV 第一章 緒論 1 1-1 前言 1 1-2 研究目的 2 第二章 文獻回顧與實驗理論 3 2-1 鈦酸鋇之晶體結構與性質 3 2-2 鈦酸鋇之介電性質 6 2-3 固態反應法合成鈦酸鋇系統之粉末 9 2-4 鋇鈦比對鈦酸鋇之影響 10 2-4-1 固溶範圍 10 2-4-2 Ba-excess之影響 12 2-4-3 Ti-excess之影響 13 2-5 鈦酸鋇粉末之晶粒效應 16 2-6 鈦酸鋇中之置換作用 18 2-6-1 置換原理 18 2-6-2 容忍因子 19 2-7 添加物對鈦酸鋇之影響 22 2-7-1 同價離子添加對於鈦酸鋇之影響 22 2-7-2 異價離子添加對於鈦酸鋇之影響 23 2-7-3 鋯離子添加對於鈦酸鋇之影響 25 2-8 鈦酸鋇之半導化現象與改善 31 2-9 溫度穩定性 32 第三章 實驗方法與步驟 34 3-1 粉末製備及分析 35 3-1-1 起始原料 35 3-1-2 鋯摻雜之鈦酸鋇粉末製備 35 3-1-3 粉末之熱差/熱重分析 36 3-1-4 X光繞射分析 36 3-1-5 晶體結構之精算與分析 37 3-1-6 拉曼光譜分析 38 3-1-7 掃描式電子顯微鏡與微結構分析 38 3-1-8 比表面積與粒徑分析 39 3-2 鋯摻雜鈦酸鋇陶瓷體製備與分析 39 3-2-1 鋯摻雜鈦酸鋇陶瓷體製備 39 3-2-2 鋯摻雜鈦酸鋇陶瓷體收縮曲線分析 40 3-2-3 陶瓷體密度量測 40 3-2-4 陶瓷體顯微結構分析 40 3-3 鋯摻雜鈦酸鋇陶瓷體電性量測 41 3-3-1 陶瓷體電性樣品製備 41 3-3-2 介電常數與電容變化率 41 3-3-3 絕緣電阻率之量測 42 3-3-4 電壓電容變化率之量測 42 第四章 結果與討論 43 4-1 起始粉末之分析 43 4-1-1 起始粉末預燒處理 43 4-1-2 起始粉末相鑑定分析 43 4-1-3 起始粉末比表面積與顯微結構分析 45 4-1-4 起始粉末之熱差/熱重分析 48 4-2 煅燒粉末之分析 49 4-2-1 煅燒粉末結晶相分析 49 4-2-2 煅燒粉末結晶結構擬合分析 51 4-2-3 煅燒粉末拉曼分析 56 4-2-4 煅燒粉末顯微結構與比表面積分析 58 4-3 陶瓷體分析 63 4-3-1 陶瓷體密度分析 63 4-3-1-1 無混合dopant之陶瓷體密度分析 63 4-3-1-2 有混合dopant之陶瓷體密度分析 65 4-3-2 陶瓷體顯微結構分析 68 4-3-2-1 無混合dopant之陶瓷體顯微結構分析 68 4-3-2-2 有混合dopant之陶瓷體顯微結構分析 72 4-4 電性量測 78 4-4-1 介電性質與絕緣電阻率量測 78 4-4-1-1 無混合dopant之介電性質與絕緣電阻率量測 78 4-4-1-2 有混合dopant之介電性質與絕緣電阻率量測 82 4-5 穿透式電子顯微鏡分析與電性之探討 89 4-6 電壓電容變化率曲線 92 第五章 結論 93 參考文獻 94

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