臺灣博碩士論文加值系統

以卑金屬（Base metal）為內電極之積層陶瓷電容器（MLCC），逐漸取代其他電容器成為市場上的主流，為防止鎳（Nickel）電極在燒結時之氧化，電容元件必須在還原氣氛下燒結。以鈦酸鋇（Barium Titanate）為主體之配方粉體在還原氣氛下會產生的氧空缺（Oxygen Vacancy），在有電場之狀況下移動，而使介電層的鈦酸鋇粉體產生半導化現象。因此之故，同時在配方中加入施體（donor）與受體（acceptor）元素可形成複合體（Complex），解決導電及可靠度問題。
採用傳統的固態反應法製作鈦酸鋇為主的Y5V配方粉體[(Ba0.996Ca0.004)O]1.004[(Ti0.82Zr0.18)O2]，此配方具有高介電常數及其在產業上實際應用之特性，在配方粉體中加入鐿離子與鎂離子，比較不同添加量彼此間差異，並在空氣及不同氧分壓下燒結，探討不同氣氛對於電性與顯微組織的影響，引用穿透式電子顯微鏡（TEM）和電子微探儀（EPMA）分析元素分佈狀況。
實驗結果顯示添加1.0at%鐿離子及添加0.1at%鐿離子與0.3at%鎂離子之配方粉體，在還原氣氛下燒結時，具有較佳介電常數及絕緣電阻之電性，並且符合EIA之Y5V規格，此乃是形成施體與受體之複合體之故。
利用掃描式電子顯微鏡（SEM）觀察積層陶瓷電容器顯微結構，並探討鎳電極對與有效介電層間（active dielectric layer, AD）擴散的情形。使用穿透式電子顯微鏡（TEM）或電子微探儀（EPMA）來做進一步地分析。

It is trends that multilayer ceramic capacitors (MLCC) with base metal inner electrode will substitute for other capacitors in market gradually. These capacitors must be fired in reducing atmosphere to protect nickel electrode from oxidation. The main powder formulation with barium titanate creates oxygen vacancy in reducing atmosphere. That vacancy could be moved by electric field to make barium titanate powders in dielectric layers resulting in semiconducting. For this reason, the additions of donor and acceptor simultaneously will form complex to solve conducting and reliability problems.
Use traditional solid state methods to prepare barium titanate based Y5V powder formulation in the system of [(Ba0.996Ca0.004)O] 1.004[(Ti0.82Zr0.18)O2]. The formulation has high dielectric constant and very popular in the market. We can compare difference by varying atmosphere and different ratio of ytterbium cation and magnesium cation in the powder. The effect could be studied in electric properties and microstructure. Elements distribution could be investigated by TEM and EPMA.
The results indicated that 1.0at% ytterbium cation formulation has better dielectric constant and insulation resistance in reducing sintering, and 0.1 at% ytterbium cation and 0.3 at% magnesium cation simultaneously formulation also has same result. These compositions meet Y5Vspecification in EIA, owing to complex composed of donor and acceptor.
We can further study microstructure in multilayer ceramic capacitors by SEM and diffusion of nickel from electrode into the active dielectric layers by use of TEM and EPMA.

總 目 錄
中文摘要……………………………………………………………………..…I
英文摘要………………………………………………………………………IIII
誌謝………………………………………………………………………………..V
總目錄…………………………………………………………………………. VI
圖目錄……………………………………………………………………….. IX
表目錄…………………………………………………………………………XI
第一章 緒論……………………………………………………………………1
1-1 前言………………………………………………………………….1
1-2 研究目的…………………………………………………………….2
第二章 文章回顧與理論基礎…………………………………………………3
2-1 積層陶瓷電容器之歷史發展………………………………………..3
2-1-1 積層陶瓷電容器原理與構造…………………………………...3
2-1-2 積層陶瓷電容器粉體的製備…………………………………...4
2-1-3 積層陶瓷電容器製程…………………………………………...6
2-2 卑金屬電極積層陶瓷電容器之發展………………………………..7
2-2-1 鎳與氧化鎳之關係…………….………………………………..7
2-2-1 施體與受體對介電性質之影響………………………………...8
2-3 積層陶瓷電容器的分類……………………………………………..9
2-3-1 高介電常數Y5V之積層陶瓷電容器………………………….9
2-3-2 中介電常數X7R之積層陶瓷電容器………………………….9
2-3-3 溫度補償型NPO之積層陶瓷電容器………………………...10
2-4 鎳電極與還原氣氛之關係…………………………………………10
2-5 純鈦酸鋇的基本性質………………………………………………10
2-5-1 鈦酸鋇單晶的基本結構及介電性質………………………….10
2-5-2 孔隙存在對介電常數的影響………………………………….11
2-6 稀土元素對介電性質的影響……………………………………….11
2-6-1 稀土元素對電阻率的影響……………………………………..12
2-6-2 稀土元素之離子半徑大小對鈦酸鋇取代的關係……………..12
第三章 實驗方法……………………………………………………………...21
3-1 實驗流程…………………………………………………………….21
3-1-1 鈦酸鋇粉體配製………………………………………………..21
3-1-2 薄片(disk)之製程……………………………………………….21
3-1-3 積層陶瓷電容器(MLCC)之製程……………………………….22
3-2 氣體流量控制………………………………………………………..22
3-3 氧分壓量測…………………………………………………………..22
3-4 X-ray繞射分析………………………………………………………23
3-5 掃描式電子顯微鏡顯微(SEM)結構觀察…………………………...23
3-6 介電常數(dielectric constant)量測…………………………………..23
3-7 介電損失(dissipation factor)量測……………………………………24
3-8 絕緣電阻(insulation resistance)量測………………………………...24
3-9 電子微探儀(EPMA)量測分析……………………………………….24
3-10 穿透式電子顯微鏡(TEM)分析…………………………………….25
第四章 結果與討論…………………………………………………………….29
4-1 添加鐿在空氣中燒結………………………………………………..29
4-1-1 添加鐿對絕緣電阻的影響……………………………………...30
4-1-2 添加鐿對電容溫度係數與介電損失的影響…………………...30
4-2 添加鐿在還原氣氛中燒結…………………………………………..31
4-2-1 添加鐿對絕緣電阻的影響……………………………………...31
4-2-2 添加鐿對電容溫度係數與介電損失的影響…………………...32
4-3 添加鐿與鎂在空氣中燒結…………………………………………..33
4-3-1 添加鐿與鎂對絕緣電阻的影響………………………………...34
4-3-2 添加鐿與鎂對電容溫度係數與介電損失的影響……………...34
4-4 添加鐿與鎂在還原氣氛中燒結……………………………………..35
4-4-1 添加鐿與鎂對絕緣電阻的影響………………………………...35
4-4-2 添加鐿與鎂對電容溫度係數與介電損失的影響……………...36
4-5 電子微探儀(EPMA)量測分析………………………………………37
4-6 穿透式電子顯微鏡(TEM)分析……………………………………...38
4-7 積層陶瓷電容器分析………………………………………………...38
4-7-1 積層陶瓷電容器之顯微結構分析………………………………38
4-7-2 積層陶瓷電容器之絕緣電阻分析………………………………39
4-7-3 積層陶瓷電容器之電容溫度係數與介電損失分析……………39
第五章 結論……………………………………………………………………73
第六章 參考文獻………………………………………………………………75
圖 目 錄
圖2-1　電容器的基本構造與迴路…………………………………………………...15
圖2-2　七層電極積層陶瓷電容器與六個並聯狀陶瓷電容器……………………...15
圖2-3　鈦酸鋇結晶構造與溫度的關係……………………………………….16
圖2-4　X7R添加Ho2O3不同氣氛之冷卻階段（a）還原氣氛（b）輕微氧氣氛………………………………………………………………….…17
圖2-5　300℃時(Ba1-2xR2x)(Ti1-xMgx)O3之晶格常數與x關係圖（R＝La, Sm, Dy, Ho, Er, Yb）……………………………………………………….18
圖2-6　還原氣氛1380 ℃(Ba1-2xR2x)(Ti1-xMgx)O3之電阻率與x關係圖（R＝La, Sm, Dy, Ho, Er, Yb）……………………………………………19
圖3-1　鈦酸鋇之(tetragonal)結晶結構圖……………………………………...26
圖3-2　實驗流程圖……………………………………………………………..27
圖3-3　氧分壓量測器示意圖…………………………………………………..28
圖4-1　不同Yb添加量在空氣中燒結與絕緣電阻關係圖…………………...41
圖4-2　添加(a)0.1at%Yb與(b)1.0 at%Yb在空氣中燒結與電容溫度係數……42
圖4-3　不同Yb添加量在空氣中燒結介電損失關係圖………………………..43
圖4-4　不同Yb添加量在空氣中燒結溫度為1350℃之SEM照片……………..44
圖4-5　不同Yb添加量在空氣中燒結溫度1350℃之SEM剖斷面照片………..45
圖4-6　不同Yb添加量在不同氧分壓燒結與絕緣電阻關係圖………………..46
圖4-7　不同Yb添加量在不同氧分壓下燒結與電容溫度係數關係圖(a)10-7atm (b)10-9atm (c)10-11atm…………………………………………………...47
圖4-8　不同Yb添加量在空氣中燒結電容溫度係數關係圖…………………..48
圖4-9　1.0 at% Yb在不同氣氛之SEM照片比較，左邊為表面，右邊為剖斷面…………………………………………………………...…………49
圖4-10　不同Yb添加量在不同氧分壓燒結與室溫介電常數關係圖…………50
圖4-11　0.1at%Yb與不同Mg添加量在空氣中燒結與電容溫度係數關係圖...51
圖4-12　0.1at%Yb與不同Mg添加量在空氣中燒結溫度為1350℃之SEM照片……………………………………………………………………...52
圖4-13　0.1at%Yb與不同Mg添加量在空氣中燒結溫度1350℃之SEM剖斷面照片……………………………………………………………………53
圖4-14　0.1at%Yb與不同Mg添加量在不同氧分壓燒結與絕緣電阻關係圖...54
圖4-15　0.1at%Yb與不同Mg添加量在不同氧分壓TCC圖(a)10-7atm (b)10-9atm (c)10-11atm……………………………………………………………..55
圖4-16　0.1at%Yb與不同Mg添加量在不同氧分壓燒結與室溫介電常數關係圖……………………………………………………………………...56
圖4-17　0.1at%與不同Mg添加量在不同氧分壓燒結與室溫介電損失關係圖………………………………………………………………………56
圖4-18　0.1at% Yb與0.3at% Mg在不同氣氛之SEM照片比較，左邊為表面，右邊為剖斷面…………………………………………………………..57
圖4-19　1.0at%Yb在氧分壓10-7atm燒結背向散射電子影像………………….58
圖4-20　1.0at%Yb在氧分壓10-7atm燒結，Zr、Ca、Yb分佈狀況……………58
圖4-21　0.1at%Yb與0.3at%Mg在氧分壓10-7atm燒結背向散射電子影像……59
圖4-22　0.1at%Yb與0.3at%Mg在氧分壓10-7atm燒結，Zr、Ca、Yb分佈狀況………………………………………………………………………59
圖4-23　0.1at%Yb在空氣燒結TEM之B.F.影像………………………………..60
圖4-24　添加0.1at%Yb在空氣燒結，Ca、Yb含量分布狀況………………61
圖4-25　添加0.1at%Yb在空氣燒結，Zr含量分布狀況…………………….61
圖4-26　添加0.1at%Yb與0.1at%Mg在空氣燒結TEM之B.F.影像…………….62
圖4-27　添加0.1at%Yb與0.1at%Mg在空氣燒結，Ca、Yb、Mg含量分佈狀況……………………………………………………………………63
圖4-28　添加0.1at%Yb與0.1at%Mg在空氣燒結，Zr含量分佈狀況。………63
圖4-29　以刮刀的方式所形成的薄帶胚體正反面之比較，(a)為正面，(b)為反面……………………………………………………………………64
圖4-30　MLCC之添加1.0at% Yb在不同氣氛之SEM照片比較，左邊為表面，右邊為剖斷面………………………………………………………65
圖4-31　添加1.0at%鐿離子之積層陶瓷電容器在不同氧分壓下燒結之絕緣電阻關係圖……………………………………………………………...66
圖4-32　添加1.0at%鐿離子之積層陶瓷電容器在10-11atm氧分壓下燒結之電容溫度係數與介電損失關係圖………………………………………...66
表 目 錄
表2-1　不同溫度下所需要的氧分壓………………………………………….20
表2-2　不同燒結溫度與不同氧分壓下，二氧化碳與氫氣所需要的比例。…………………………………………………………………...20
表4-1　不同鐿離子含量於空氣中燒結電性測試之總表…………………….67
表4-2　不同鐿離子含量在還原氣氛下中燒結電性測試之總表……………..68
表4-3　添加0.1at%鐿離子與不同鎂離子於空氣中燒結電性測試之總表…..69
表4-4　添加0.1at%鐿離子與不同鎂離子含量在還原氣氛下燒結電性測試之總表……………………………………………………………………….70
表4-5　積層陶瓷電容器添加1.0at%鐿離子含量在還原氣氛下中燒結電性測試之總表…………………………………………………………………...71
表4-6　1.0at%Yb添加量在氧分壓10-7燒結溫度為1350℃各化合物莫爾比...72
表4-7　0.1at%Yb與0.3at%Mg添加量在氧分壓10-7燒結溫度為1350℃各化合物莫爾比………………………………………………………………….72

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