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研究生： 陳弘銘
Chen, Hung-Ming
論文名稱： 鋯摻雜之鈦酸鋇的製備、分析與介電性質
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： 2021
畢業學年度： 109
語文別： 中文
論文頁數： 127
中文關鍵詞： 鈦酸鋇 、介電常數 、鋯摻雜 、晶體結構
外文關鍵詞： Barium titanate, dielectric constant, zirconium doping, crystal structure
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    • 近年來的積層陶瓷電容堆疊技術的進步，且由於積層陶瓷電容內部介電層厚度大幅下降，使得電極間電場強度增加，進而產生可靠度的問題。再加上製作積層陶瓷電容時，為了降低成本，因此選用卑金屬作為內電極 (Base metal Electrode, BME)；而為了防止卑金屬氧化，因此會使用還原氣氛下進行燒結，但也因此出現半導化的現象。根據過去的研究發現，添加鋯之鈦酸鋇由於可以使還原焓上升，而使得可靠度變得更好；學者[1]認為選擇具有較高能階差的化合物可以適用於高工作電壓的環境，尤其以鋯酸鹽為主之化合物就是具有較高之能階差。綜合以上，本研究將透過不同摻雜比列的Zr4+取代Ti4+的位置，並去觀察添加Zr4+對晶體結構、拉曼光譜、比表面積、微觀結構的變化，最後再探討添加Zr4+對介電常數與絕緣電阻率的影響。
    本研究利用固相反應法進行鋯添加於鈦酸鋇之合成，形成Ba(Ti1-xZrx)O3 (x = 0、0.03、0.05、0.1、0.2) 之固溶體，透過X光繞射圖譜與GSAS分析可以觀察到x = 0、0.03較趨向正方晶系；x = 0.05較趨向斜方晶系；x = 0.1較趨向菱方晶系；x = 0.2較趨向立方晶系；配合拉曼光譜的分析的結果發現隨著鋯添加量的增加，拉曼特徵峰會漸漸地寬化且強度變得越來越低；除了添加量x = 0以外，添加量x = 0.03~ 0.2在大約800 cm-1皆有因Zr4+取代Ti4+而產生的峰。為了模仿積層陶瓷電容之燒結條件，將添加量x = 0與x = 0.1的樣品在還原氣氛下燒結，此兩種粉末皆在燒結條件1340℃與1380℃下，相對密度達90%達以上。在電性分析方面，從介電常數與溫度曲線來看，BaTiO3¬在35℃的介電峰值為與shell有關之介電峰值，而在大約130℃為與core有關之介電峰值；而在Ba(Ti0.9Zr0.1)O3，由於PS dopant與添加鋯的關係會出現擴散式相轉換的峰。在室溫下之電阻率方面，在燒結溫度1380℃下，Ba(Ti0.9Zr0.1)O3電阻率小於BaTiO3電阻率，推測其原因與晶粒大小與core-shell structure有關。在介電損耗方面，由於晶粒大小與相對密度的影響，使Ba(Ti0.9Zr0.1)O3在燒結溫度1340℃較1380℃還要大；而BaTiO3在燒結溫度1340℃與1380℃時幾乎相同。

    According to past research, the Zr-doped barium titanate can increase the reduction enthalpy, and the compounds mainly composed of zirconate have a higher energy gap. In this study, the solid-phase reaction method was used to synthesize Zr-doped barium titanate to form a solid solution of Ba(Ti1-xZrx)O3 (x = 0, 0.03, 0.05, 0.1, 0.2). Through X-ray diffraction pattern and GSAS analysis, it can be observed that x = 0, 0.03 tends to the tetragonal ; x = 0.05 tends to the orthorhombic; x = 0.1 tends to the rhombohedral; x = 0.2 tends to the cubic. With the analysis of Raman spectroscopy, it is found that as the amount of Zr doping increases, the peak gradually broadens and the intensity becomes lower and lower; in addition to x = 0, x = 0.03~ 0.2 have a peak at about 800 cm-1 due to the substitution of Zr4+ for Ti4+. Both of these two powders (x =0、 0.1¬) have a relative density of more than 90% under sintering conditions of 1340°C and 1380°C. In terms of electrical analysis, from the dielectric constant vs. temperature , the dielectric peak of BaTiO3 at 35°C is the dielectric peak related to the shell, and at about 130°C it is the dielectric peak related to the core; Ba(Ti0.9Zr0.1)O3, due to the PS dopant and Zr doping, there will be a diffusion phase transition peak. In terms of resistivity, Zr doping has no tendency to increase resistivity.

    中文摘要 I 目錄 XIII 表目錄 XVI 圖目錄 XVII 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 3 2-1鈦酸鋇陶瓷之性質 3 2-1-1介電性質 3 2-1-2鈦酸鋇之晶體結構及介電性質 6 2-1-2鋇鈦比對於鈦酸鋇之影響 9 2-1-3鈦酸鋇之粉末顆粒大小之影響 17 2-1-4 鈦酸鋇陶瓷體晶粒大小之影響 23 2-2 置換作用 26 2-2-1置換原理 26 2-2-3 容忍因子 28 2-3添加物對鈦酸鋇之影響 31 2-3-1 加入添加物於鈦酸鋇中之目的 31 2-3-2 Zr4+的添加對鈦酸鋇之影響 32 2-4鈦酸鋇之半導化現象與改善 39 2-5 拉曼光譜分析 40 2-5-1 拉曼原理 40 2-5-2拉曼對鈦酸鋇之應用 41 第三章 實驗方法與步驟 45 3-1粉末製備及分析 47 3-1-1起始原料 47 3-1-2 鋯摻雜之鈦酸鋇粉末製備 47 3-1-3粉末熱重/熱重分析 49 3-1-4 X光繞射分析 49 3-1-5粉末拉曼光譜分析 52 3-1-6 粉末之微觀結構分析 52 3-1-7 粉末比表面積分析 52 3-2陶瓷體的製備及分析 53 3-2-1鈦酸鋇陶瓷體製備 53 3-2-2 燒結收縮分析 55 3-2-3陶瓷體密度測量與分析 55 3-2-4掃描式電子顯微鏡與微觀結構分析 56 3-3電性測量 56 3-3-1介電常數與電容變化率 57 3-3-2 陶瓷體電阻率之量測 57 第四章 結果與討論 58 4-1起始粉末之分析 58 4-1-1 起始粉末燒失量測試 58 4-1-2 起始粉末相鑑定分析 58 4-1-3起始粉末比表面積與微結構觀察 61 4-1-4起始粉末之DTA/TG分析 63 4-2煅燒粉末分析 65 4-2-1結晶相分析 65 4-2-2 Rietveld refinement 72 4-2-3 拉曼分析 92 4-2-4 煅燒粉末微結構觀察 96 4-2-5粉末比表面積分析 102 4-3陶瓷體分析 105 4-3-1燒結收縮量測與分析 105 4-3-2陶瓷體密度測量 107 4-3-3顯微結構分析 110 4-4電性分析 116 4-4-1介電常數-溫度曲線分析 116 4-4-2 室溫下介電性質與電阻率分析 120 第五章 結果與討論 123 參考文獻 124

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