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研究生: 高嘉沁
Kao, Chia-Chin
論文名稱: 摻雜P型ZnBi2O4對變阻器之微觀結構和變阻性質之研究
Effect of ZnBi2O4 and Bi2O3 addition on the microstructure and electrical properties of the ZnO-based varistor ceramics
指導教授: 向性一
Hsiang, Hsing-I
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: 57
中文關鍵詞: ZnO變阻器降溫速率ZnBi2O4
外文關鍵詞: ZnO varistor, cooling rate, ZnBi2O4
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  • 本研究於ZnO變阻器中加入Bi2O3(B)、ZnBi2O4(BZ)及複合型(Bi2O3與ZnBi2O4依不同比例混合),觀察晶界添加劑對其變阻性質及微觀結構之影響。研究顯示,當晶界添加劑從1wt% Bi2O3改成1wt%ZnBi2O4,因晶粒尺寸縮小以及緻密程度提升使α值從42.37提升至54.47、崩潰電壓從775V/mm提升至1011V/mm及漏電流從0.59μA降至0.11μA。當晶界添加劑從1B2BZ增加為1B4BZ時,過多的晶界添加劑使晶粒成長及緻密化程度下降,導致α值從47.76降至25.98、崩潰電壓從1232V/mm降至718V/mm及漏電流從0.10μA上升至1.52μA。接著從上述研究中挑選變阻性質較佳的三個樣品:1B、1BZ及1B2BZ進行後續研究。分別以不同降溫速率之爐冷(0C)、2˚C/min(2C)及5˚C/min(5C),觀察其變阻性質。實驗發現當以2˚C/min降溫至室溫時各樣品之非線性指數皆有所提升,尤其以1BZ2C效果最為顯著,α值提升至65.43、崩潰電壓提升至1361V/mm及漏電流為0.11μA。因在緩慢的降溫過程中,有充足的時間使Co2+氧化成Co3+並丟掉電子,而電子會與進入材料內部的氧在晶界處形成吸附氧。此外部分的吸附氧會與材料內部的氧空缺反應生成晶格氧,最終受體濃度(Nt)上升、施體濃度(Nd)下降使蕭特基能障提升。

    In the study, 1wt% Bi2O3(1B), 1wt% ZnBi2O4(1BZ), and composite type (mixture of 1wt% Bi2O3 and 2wt% ZnBi2O4, 1B2BZ) were added to ZnO varistor to investigate the influence of grain boundary additives on the microstructure and varistor properties. It has shown that when the additive changed from 1wt% Bi2O3 to 1wt% ZnBi2O4, the value of α increased from 42.37 to 54.47, the breakdown voltage increased from 775V/mm to 1011V/mm, and the leakage current decreased to 0.11μA because of the decrease in grain size and the increase in density. Then the different cooling rates of furnace cooling (0C), 2˚C/min (2C) effects on the varistor properties were also investigated. Experiments have found that when the cooling rate was 2˚C/min, the non-linear index of each sample was improved., For the sample 1BZ2C, the α value of 65.43, the breakdown voltage of 1361V/mm, and the leakage current of 0.11 μA were obtained. In the slow cooling rate, O2 easily diffused from the grain boundary to the interior, leading to the oxidation of Co2+ to Co3+ and accompanying releasing an electron. The released electron combined with O2 to form the adsorbed oxygen, which can improve the varistor properties. In addition, part of the adsorbed oxygen reacted with the oxygen vacancies to form lattice oxygen. Eventually, the trap concentration (Nt) was increased, the donor concentration (Nd) was decreased, increasing the Schottky barrier.

    摘要 i 誌謝 vii 目錄 viii 圖目錄 x 表目錄 xi 第一章 緒論 1 1.1 前言 1 1.2 研究目的 1 第二章 文獻回顧 2 2.1 變阻器 2 2.1.1 變阻器之介紹[1] 2 2.1.2 鉍系-氧化鋅變阻器 3 2.2 蕭特基能障(Double Schottky barrier) 4 2.2.1 晶界缺陷模型 5 2.2.2 晶界參數(Mott-Schottky) 6 2.3 摻雜劑(Dopant) 8 2.4 ZnBi2O4之簡介 9 2.5 非線性電流-電壓特性 11 2.6 變阻特性參數 12 2.7 交流阻抗(Cole-Cole plot) 13 2.8 介電譜之研究 16 2.9 降溫速率對變阻器之影響 18 第三章 實驗方法 19 3.1 實驗原料 19 3.2 實驗流程 20 3.3 實驗分析方法 22 3.3.1 X光繞射儀分析 22 3.3.2 燒結收縮曲線分析 22 3.3.3 變阻性質分析 22 3.3.4 微結構分析 23 3.3.5 密度量測 23 3.3.6 交流阻抗分析 23 3.3.7 XPS分析 23 3.3.8 Mott-Schottky 分析 23 3.3.9 介電譜分析 24 3.3.10 熱重熱差分析 24 3.4 代號名稱 25 第四章 結果與討論 26 4.1 不同晶界添加劑對變阻器緻密化、微結構及變阻性質之影響 26 4.1.1 結晶相分析 26 4.1.2 熱收縮行為分析 28 4.1.3 變阻性質 30 4.1.4 微結構及阿基米德密度分析 32 4.1.5 Cole Cole plot 分析 35 4.1.6 X光電子光譜儀分析 37 4.1.7 Mott-Schottky 分析 39 4.2 不同降溫速率對各性質之影響 41 4.2.1 變阻性質 41 4.2.2 熱重熱差分析 44 4.2.3 Cole Cole plot 分析 46 4.2.4 X光電子光譜儀分析 47 4.2.5 Mott-Schottky 分析 48 第五章 結論 51 參考文獻 52 附錄 56

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