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研究生： 蔡毓書
論文名稱： 摻雜釤之鈦酸鉍鐵電薄膜電性研究
指導教授： 甘炯耀
J. Y. Gan
口試委員:
學位類別： 碩士
Master
系所名稱： 工學院 - 材料科學工程學系
Materials Science and Engineering
論文出版年： 2003
畢業學年度： 91
語文別： 中文
中文關鍵詞： 摻雜釤 、薄膜 、溶凝膠法 、鈦酸鉍 、鐵電電容
相關次數： 點閱：202  下載：0 
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    • Bi4Ti3O12-簡稱為BIT為主的材料，在鐵電的特性方面，因為有優越的抗疲勞特性，所以近來廣泛被大家所研究。這是因為鐵電記憶體在實際的運用上，若無法克服經多次讀寫所產生的劣化，將會大大的減低實用性，因而BIT為主的材料在逐漸被大家所研究。
    本論文以溶凝膠法旋鍍製作Bi4-xSmxTi3O12的BSmT薄膜，期望在Sm的摻雜後會有比Bi4Ti3O12更好的表現，因此選用了Sm摻雜量在x=0、0.25、0.5、0.75、1，在這幾成分下的變化情形。由於在BIT中有強烈的非等向性，隨著指向的不同所表現的電性也有所不同，應此我們選用Bi4-xSmxTi3O12 在x=0.75下研究其在不同混合指向時的變化。最後我們在Bi4-xSmxTi3O12 在x=0.75下探討在不同膜厚時所發生的電性表現。

    在不同的Sm摻雜研究上，我們發現在化學計量比為Bi3.25Sm0.75Ti3O12時，在殘留極化量和抗疲勞性質方面有一最好的表現。且在這成分下所表現的非等向性和BIT與BLT類似，指向上隨C軸指向的增加時，殘留極化量和抗疲勞特性會有下降的發生。在Bi3.25Sm0.75Ti3O12成分下，膜厚在約130nm以上時漏電流以電子熱發散為主，隨膜厚的增加會有漏電流減少的發生。在我們製程下，膜厚約為50nm以下會有電極之間直接導通以歐姆電流型式發生。在膜厚到達約180nm以上時，電製曲線不但有較好的表現，抗疲勞的特性也會有些微的改善。

    Bi4-xSmxTi3O12 在x=0.75時，膜厚約180nm以上會有殘留極化量高達13μC/cm2，且經過4×1010極化反轉後，仍然會有很好的抗疲勞表現。在膜厚約為130nm時，有較小的殘留極化量約11μC/cm2，在抗疲勞的性質上也有不錯表現。

    第一章 緒論 5 1-1 簡介 5 1-2 研究動機 6 第二章 文獻回顧 8 2-1 晶體結構與極化機制[11,12,13,14] 8 2-2 鈦酸鉍(Bi4Ti3O12)鐵電材料 11 2-3 鐵電材料之製作 12 2-3-1磁控濺鍍法(Magnetron Sputtering) 13 2-3-2 雷射剝鍍法(Laser Ablation) 13 2-3-3 溶凝膠旋鍍法(Sol-Gel Spin-Coating) 14 2-3-4 金屬有機化學氣相沉積法(Metalorganic chemical vapor deposition，MOCVD) 14 2-3-5 有機金屬鹽裂解法(MOD) 15 2-4 鐵電材料的特性分析 15 2-4-1 介電性質[21-23] 15 2-4-2 漏電流機制[24,25,26,27] 17 2-4-3 崩潰機制(Breakdown) 19 2-4-4 疲勞特性(Fatigue) 21 第三章 實驗程序 23 3-1 電極的鍍製 23 3-2 鐵電膜的製作 25 3-2-1溶凝膠(Sol-Gel)的製備 25 3-2-2薄膜鍍製與熱處理 27 3-3 上電極製作 28 3-4 薄膜分析與量測 29 3-4-1晶相結構 29 3-4-2表面形態與薄膜厚度 29 3-4-3電性量測 30 第四章 結果與討論 32 4-1 不同結晶指向之間的比較 32 4-1-1 晶相結構(XRD分析) 32 4-1-2 表面形態與薄膜厚度 34 4-1-3 電滯曲線(P-E curve) 36 4-1-4漏電流關係和介電常數與散逸因子 37 4-1-5 疲勞特性 38 4-2 不同Sm量摻雜入BIT 40 4-2-1 晶相結構(XRD分析) 40 4-2-2 表面形態與薄膜厚度 41 4-2-3 電滯曲線(P-E curve) 42 4-2-4 疲勞性質和漏電流關係 43 4-2-5 介電常數與散逸因子 45 4-3 Bi3.25Sm0.75Ti3O12薄膜厚度變化 46 4-3-1 晶相結構(XRD分析)和表面形態 46 4-3-2 電滯曲線(P-E curve) 疲勞性質 46 4-3-3 漏電流關係和電容值與散逸因子 48 4-4 不同V量摻雜入BIT 50 第五章 結論 51 參考文獻 54 圖2-1 電滯曲線（P-E 關係圖）..............................................................................60 圖2-2 Sawyer Tower電路........................................................................................60 圖2-3 鈣鈦礦 Perovskite結構................................................................................61 圖2-4 Aurivillius 結構.............................................................................................61 圖 2-5 Bi4-xSmxTi3O12晶體結構圖..........................................................................62 圖 2-6 內層和外層的TiO6投影在(a)(001)和(b)(100)方向上.............................62 圖2-7絕緣體中四種極化機構.................................................................................63 圖2-8 極化機構在頻率變化中對介電常數及散逸因子之影響圖........................64 圖2-9實際電容器的I-V相圖..................................................................................64 圖2-10 Barrier limited 傳導機構(a)Schottky emission (b)tunneling..................65 圖2-11 Bulk limited 傳導機構(a)空間電荷限制傳導(b)陽離子傳(c)Poole-Frenkel................................................................................................65 圖 2-12 以高能的電子打入ABO3結構所形成的數狀結構.................................66 圖2-13 在鈣鈦礦(0k0)方向的投影，圖為單一氧空缺在(101)方向成長為鍊狀..66 圖3-1 流程圖︰實驗主流程圖................................................................................67 圖3-2 元件示意圖....................................................................................................68 圖3-4 RT66A鐵電測試系統之量測元件等效電路圖............................................68 圖3-5 RT66A量測P-E電滯曲線所使用電壓波形圖……...........................……69 圖3-6 RT66A疲勞量測所使用脈衝模式(pulse mode)之脈波序列圖………..…69 圖4-1 在Bi不過量時BIT不同溫度15min熱處理的XRD………...............…70 圖4-2 在Bi不過量下以680oC做15min熱處理後的SEM….................………70 圖4-1-1 在不同溫度下BSmT的XRD……......................................................... 71 圖4-1-2 在不同溫度下BSmT中的peak(117)相對強度關係圖..........................72 圖4-1-3十層BSmT在680℃熱處理後的膜厚......................................................73 圖4-1-4十層BSmT在各溫度下熱處理後的SEM...............................................74 圖4-1-5在不同溫度下BSmT的SPM...................................................................76 圖4-1-6在不同溫度下BSmT對RMS關係圖......................................................77 圖4-1-7在不同溫度下BSmT的電滯曲線圖........................................................78 圖4-1-8在不同溫度下BSmT所能施加最大電場的電滯曲線圖.........................79 圖4-1-9在不同溫度下BSmT的殘留極化量和矯頑電場對量測電壓關係圖........................................................................................................................80 圖4-1-10在不同溫度下BSmT的漏電流圖..........................................................81 圖4-1-11在不同溫度下BSmT的散逸因子和介電常數對頻率關係圖..............82 圖4-1-12 BSmT在650℃退火後的疲勞性質........................................................83 圖4-1-13 BSmT在680℃退火後的疲勞性質........................................................83 圖4-1-14 BSmT在700℃退火後的疲勞性質........................................................84 圖4-1-15 BSmT在720℃退火後的疲勞性質........................................................84 圖4-1-16在不同溫度下BSmT的散逸因子和介電常數對頻率關係圖..............85 圖4-2-1 BIT在不同溫度熱處理時XRD圖..........................................................86 圖 4-2-2 在Sm摻雜為x=0、0.25、0.5、0.75、0.1下的XRD.............................87 圖 4-2-3 空試片載具的XRD..................................................................................88 圖 4-2-4 在鍍製6層後的膜後................................................................................88 圖 4-2-5 不同的Sm摻雜量經退火660℃-30min.................................................89 圖 4-2-6 不同的Sm摻雜量經退火660℃-30min之SPM...................................90 圖 4-2-7 在不同Sm含量下的RMS比較.............................................................92 圖 4-2-8 在不同Sm含量下的P-E曲線圖............................................................93 圖 4-2-9 在不同Sm含量下，殘留極化量和矯頑電場對不同電場下的關係圖........................................................................................................................94 圖 4-2-10 最大殘留極化量和矯頑電場對不同Sm含量關係圖........................ 94 圖 4-2-11 Bi4Ti3O12 之疲勞性質.............................................................................95 圖 4-2-12 Bi3.75Sm0.25Ti3O12 之疲勞性質................................................................96 圖 4-2-13 Bi3.5Sm0.5Ti3O12 之疲勞性質..................................................................97 圖 4-2-14 Bi3.25Sm0.75Ti3O12 之疲勞性質................................................................98 圖 4-2-15 Bi3Sm1Ti3O12 之疲勞性質......................................................................99 圖 4-2-16 Bi4-xSmxTi3O12 之x=0、x=0.25、x=0.5、x=0.75、x=1 normalize疲勞性質比較..........................................................................................................100 圖 4-2-17 Bi4-xSmxTi3O12 之x=0、x=0.25、x=0.5、x=0.75、x=1 漏電流曲線......................................................................................................................101 圖 4-2-18 Bi4-xSmxTi3O12 之x=0、x=0.25、x=0.5、x=0.75、x=1 在不同頻率下之介電常數與散射因子..................................................................................102 圖4-3-1 BSmT在不同層數下以660℃熱處理30min的XRD圖.....................103 圖4-3-2 BSmT在不同層數下以660℃熱處理30min的橫截面SEM..............104 圖4-3-3 BSmT在不同層數下以660℃熱處理30min的SEM..........................106 圖4-3-4 BSmT在不同層數下以660℃熱處理30min的SPM..........................108 圖4-3-5 BSmT在不同層數下電滯曲線對不同電壓圖.......................................110 圖4-3-6 BSmT在不同層數下所能施加最大電場的殘留極化量與電滯曲線.......................................................................................................................111 圖4-3-7 BSmT在不同層數下(a)殘留化量對電場(b)矯頑電場對電場關係圖......................................................................................................................112 圖4-3-8 BSmT在不同層數下±2Pr Normalize後的疲勞表現............................113 圖4-3-9 BSmT在不同層數下(a)散逸因子(b)電容值Cp對頻率關係圖...........114 圖4-3-10 BSmT在不同層數下漏電流和電場關係圖......................................... 115 圖4-3-11 BSmT在不同層數下漏電流..................................................................116 圖4-4-1在不同溫度下Bi3.25Sm0.75Ti2.95V0.05所得的XRD................................. 118 圖4-4-2在不同溫度下Bi3.25Sm0.75Ti2.9V0.1所得的XRD....................................119 圖4-4-3在不同溫度下Bi3.25Sm0.75Ti2.5V0.5所得的XRD....................................120

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