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研究生:張矩嘉
研究生(外文):Chu-Chia Chang
論文名稱:鈥(Ho2O3)對鈦酸鋇電性以及介電的影響
論文名稱(外文):The effect of Ho dopant on the electrical and dielectric properties of BaTiO3
指導教授:方滄澤
指導教授(外文):T. T. Fang
學位類別:碩士
校院名稱:國立成功大學
系所名稱:材料科學及工程學系碩博士班
學門:工程學門
學類:材料工程學類
論文種類:學術論文
論文出版年:2003
畢業學年度:91
語文別:中文
論文頁數:76
中文關鍵詞:正溫度係數氧化鈥鈦酸鋇積層陶瓷電容
外文關鍵詞:Positive temperature coefficientHo2O3BaTiO3Mulitilayer ceramic capacitors
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本研究主要討論氧化鈥(Ho2O3)對鈦酸鋇電性以及介電的影響。共分成兩部分:第一部分主要添加微量x%的氧化鈥(x=0.05, 0.1, 0.2,0.3, 0.4,0.6,0.8,1.0)於鈦酸鋇中,探討在空氣與氧氣兩種不同氧分壓的氣氛下,室溫的電阻值變化以及利用SEM觀察其微結構,得到晶粒大小變化與氧化鈥添加量及電阻變化的關係。可以發現隨著添加量的增加,電阻的變化可以分成兩個階段。在第一個階段中(x<0.2),電阻隨著添加量的增加而降低,直到x=0.2時為最低。而第二個階段中(x>0.2),電阻隨著添加量的增加而增加,因此,可以得到一個在x=0.2時的轉折點。
在本研究的第二個部分中,主要探討在不同氣氛下燒結的結構與電性性質之變化。以鈦酸鋇粉末為主,均添加1% Ho2O3與y %BaCO3(y=0, 0.5, 1, 1.5, 2)。並分別在空氣中與還原氣氛(5%H2-95%N2)下燒結。從電阻的變化,可以得知隨著添加Ba2+離子的增加去改變鈦酸鋇的Ba/Ti 比,影響H03+離子所佔據的位置,使得H03+離子從起初
的Ba位置上,開始部份轉移佔據到Ti位置上,其電性也從半導化變成絕緣。並以X光繞射分析來觀察其結構,由原來的正方晶(tetragonal)轉變為立方晶(cubic)以及晶格常數的變化;其介電常數也隨著Ba2+離子添加量的增加而降低,居禮溫度(Tc)也隨之往低溫偏移。
The research work on barium titanate mainly discussed the effect of doped with Ho2O3 on its electricity and dielectric. It will be divided into
two parts: first, probing into the change of resistance at room temperature, the SEM analysis, grain size, and the amount of dopant by doping with a trace of x% Ho2O3 (x=0.05, 0.1, 0.2, 0.3, 0.4,0.6,0.8,1.0)fired under different oxygen partial pressures. From increasing of dopant the
variation of resistance can be separated into two steps. The resistance decreased with adding the dopant until x=0.2 in the first step(x<0.2). On
the other hand, it increased when x>0.2 for the second step. There is a turning point on x=0.2 hence. Second, structural changes and electricity
of barium titanate(BT)ceramics doped with 1﹪Ho2O3 and y﹪BaCO3(y=0, 0.5, 1, 1.5, 2)are discussed in this investigation. Sintering of BT
is proceeded both in air and reducing atmosphere. Variations in resistance indicates that, with the increasing the amount of Ba2+ ions, Ho3+ ions are
removed from A sites and then occupy the B sites, which result in a switch from semiconducting into insulating behavior. And the original tetragonal structure transforms into cubic structure, which in turn lowers the dielectric constant.
目錄
第一章前言……………………………………………………………..1
第二章理論基礎與文獻回顧………………………………….……….4
2-1 半導體陶瓷的簡介……………………………………….……..4
2-1-1 半導體陶瓷…………………………………………….…..4
2-1-2 半導體陶瓷的典型導電機構…………………………….4
2-1-3 施體/受體元素對鈦酸鋇性質的影響……………………6
2-2 鈦酸鋇的基本性質……………………………………………..9
2-2-1 鈦酸鋇單晶的晶體結構……………………………….....9
2-2-2 多晶鈦酸鋇的介電性質………………………………….12
2-2-3 組成對鈦酸鋇陶瓷顯微結構與介電性質的影響………15
2-2-4 孔隙率與晶粒大小對介電的影響………………………18
2-3 添加物對鈦酸鋇性質之影響………………………………...21
2-3-1 添加物的種類使Tc 點往高溫或低溫偏移………….…..21
2-3-2 添加物種類對介電性質的影響………………………...21
2-3-3 添加物對燒結行為的影響……………………………...22
2-4 PTCR……………………………………………………………24
2-4-1 PTCR 基本理論…………………………………………..24
2-4-2 PTCR 特性………………………………………………..29
2-5 Cole-Cole plots………………………………………………….30
第三章實驗步驟及方法………………………………………………36
3-1 藥品…………………………………………………………...36
3-2 實驗流程……………………………………………………...36
3-3 性質測試……………………………………………………...39
3-3-1 密度量測………………………………………………...39
3-3-2 X 光繞射分析………………………………………….39
3-3-3 介電性質量測…………………………………………...40
3-3-4 電阻之量測……………………………………………...40
3-3-5 SEM 顯微結構分析……………………………………40
3-3-6 晶粒大小之計算………………………………………...41
第四章結果與討論……………………………………………………42
4-1 製程一……………………………………………………………..42
4-1-1 添加量對電性的影響………………………………………...42
4-1-2 燒結過程對電性的影響………………………………………46
4-1-3 鈥添加對PTCR 的影響……………………………………….47
4-1-4 利用Impedance 分析電性……………………………………51
4-1-5 鈥添加對顯微結構分析……………………………………...49
4-2 製程二……………………………………………………………..64
4-2-1 密度量測……………………………………………………...64
4-2-2 晶格常數分析…………………………………………………64
4-2-3 添加量對相的影響…………………………………………...67
4-2-4 電性性質的分析………………………………………………69
第五章結論……………………………………………………………71
第六章參考文獻……………………………………...……………….72
圖目錄
圖2-1(a)本質傳到的價帶模型
(b)半導體陶瓷的能帶模型………………………………..……7
圖2-2 鈦酸鋇在不同溫度下,導電率隨氧分壓之變化曲線………......8
表一、離子半徑表………………………………………………..…..…..8
圖2-3(a) 鈦酸鋇晶體中原子的排列
(b)鈦酸鋇之晶體結構對溫度變化之關係……………..……10
圖2-4:(a) 鈦離子偏離中心位置
(b)鈦酸鋇之自發極化隨溫度之變化關係………………...….11
圖2-5:(a)鈦酸鋇之晶格常數對溫度的變化關係
(b)a-軸、c-軸介電常數對溫度的變化關係……………...……13
圖2-6 鈦酸鋇多晶結構與其晶域……………………………………..14
圖2-7 BaO-TiO2的相平衡圖…………………………………………16
圖2-8 BaTiO3-TiO2 的平衡相圖…………………………………...…17
圖2-9 鈦酸鋇晶粒大小與介電性質的關係……………………....…20
圖2-10 晶粒大小對正方性(Tetragonality)的影響…………………20
圖2-11 為等價置換對鈦酸鋇相轉換溫度之影響………………...….23
圖2-12 鈦酸鋇陶瓷半導體電阻的正溫度係數(PTCR)特性……..28
圖2-13 Heywang’s model…………………………………………….28
圖2-14 利用惠斯敦電橋量測電阻與電容……………………………32
圖2-15 多晶的固體電解質的平衡電路圖…………………………….32
圖2-16 電阻和電容串聯且各別有電壓E1 和E2 通過………………….34
圖2-17 電阻和電容的並聯……………………………………………34
圖2-18 電阻與電容串聯的阻抗圖……………………………………34
圖2-19 電阻與電容並聯的阻抗圖……………………………………35
圖3-1 製程一流程圖……………………………………………….….37
圖3-2 製程二流程圖……………………………………………….….38
圖4-1 導電率隨著不同的燒結條件與添加量的關係…………….….44
表4-2 電阻在不同的燒結過程中與添加量的關係……………….….45
圖4-3 (a)A與CA的PTCR行為…………………………………....…48
圖4-3 (b)O 與CO 的PTCR 行為………………………………….49
表三各試片的室溫電阻係數以及min max ρ ρ 值的比較………………....51
圖4-4 在A 燒結條件下,添加量與室溫impedance 的關係圖……....51
圖4-5 在A 燒結條件下,添加量與與Tc 點impedance 的關係……..52
圖4-6 在CA燒結條件下,添加量與室溫impedance 的關係圖…...…53
圖4-7 在CA燒結條件下,添加量與與Tc點impedance 的關係……...54
圖4-8 在O燒結條件下,添加量與室溫impedance 的關係圖………..55
圖4-9 在O燒結條件下,添加量與與Tc 點impedance 的關係…….…56
圖4-10 在CO燒結條件下,添加量與室溫impedance 的關係圖….....57
圖4-11 在CO 燒結條件下,添加量與與Tc 點impedance 的關係….58
圖4-12 隨著A、CA、O、CO 四種製程添加量的晶粒變化………59
圖4-13 A 製程中添量x%的SEM 圖……………………………..…60
圖4-14 CA 製程中添量x%的SEM圖…..……………………….….61
圖4-15 O 製程中添量x%的SEM 圖…………………………….….62
圖4-16 CO製程中添量x%的SEM圖……………………………….63
圖4-17 為c/a 對不同的BaTiO3 添加量的作圖…………………….…65
圖4-18 在空氣中與還原氣氛中,a、c 軸分別對不同BaCO3 添加量作
圖..……………………………………………………………...66
圖4-19、在空氣中不同的BaCO3 添加量之XRD 圖………….…….67
圖4-20、在還原氣氛中不同的BaCO3 添加量之XRD 圖………..….68
表四、在還原氣氛下,隨著BaCO3 添加量對電阻的量測………..….69
圖4-21、不同的BaCO3 添加量之介電常數對溫度作圖…………..…70
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