臺灣博碩士論文加值系統

為提高單位體積電容值，積層陶瓷電容器（multilayer ceramic capacitors, MLCCs）須使用次微米或奈米晶粒大小之鈦酸鋇粉體，在燒結時控制晶粒之尺寸，使其能降低有效介電質層（active dielectric layer，AD）之厚度，提高堆積介電質層數，而提升其單位體積之電容值。積層陶瓷電容器中之X7R配方有平整之電容值對溫度之變化率，在-55℃∼125℃間，電容值變化率在±15﹪內、而具3000∼4000介電常數，適用於薄介電層高層數之積層陶瓷電容器之製作。本研究以0.3∼0.5μm次微米鈦酸鋇為介電質材料，以添加不同稀土元素及鎂（Mg）、鎳（Ni）等，以沉澱塗佈法，開發X7R配方粉體，且具施體受體之複合體結構，得以能在還原氣氛中燒結用以製作卑金屬電極之積層陶瓷電容器（Base Metal Electrode Multilayer Ceramic Capacitor，BME MLCC）
研究結果顯示，當鉺（Er）、鎂（Mg）摻雜量分別為2.0mol.﹪時，在1350℃空氣中燒結持溫3小時，其電容溫度係數接近EIA之X7R規格，介電常數約為4000，晶粒具core-shell結構。添加不同稀土元素配方粉體，居理溫度（Curie temperature，Tc）會隨添加量增加而往低溫方向移動。添加鑭（La）、釤（Sm）元素其散逸因子（Dissipation factor）低於添加鉺（Er）、鏑（Dy）元素，而絕緣電阻（Insulation resistance）高於添加鉺（Er）、鏑（Dy）元素之配方成分。
粉體配方於還原氣氛中燒結，其電容溫度係數曲線在低氧分壓有介電峰（dielectric peak）出現而有異於在空氣中燒結之配方粉體，且因還原氣氛燒結，使燒結緻密、孔隙率低，散逸因子高於空氣中燒結之配方粉體。
積層陶瓷電容器採用鎳（Ni）為主之內電極材料，在燒結時鎳（Ni）會擴散至有效介電層內而影響其電性。故添加鎳（Ni）元素於配方成分中探討其在燒結時、晶粒成長及其絕緣電阻之關係。
將介電性質接近EIA之X7R規格之配方粉體製作卑金屬積層陶瓷電容器元件，觀察其顯微結構、介電性質及電極與有效介電層間之作用。

In order to increase the capacitance per unit volume, the multilayer ceramic capacitors (MLCCs) have to adopt the using of sub-micron or nano-sized barium titanate powders to control the grain size during sintering to decrease the thickness of the active layer increase the number of the dielectric layers, and the packing density of capacitance per unit volume the capacitance is increasing. X7R is dielectric formulation the temperature coefficient of capacitor are within ±15﹪between the temperature range -55℃∼125℃ and the dielectric constant 3000∼4000, is suitable to be used to thin AD high number of layers MLCC fabrication. In this study, 0.3∼0.5μm sub-micron barium titanate powders was adopted to synthesize the dielectric formulation of X7R to form the complex structure of donor and acceptor using the coprecipitation coating method and manufacture the base metal electrode multilayer ceramic capacitors from the dielectric powder that are suitable to sinter in reducing atmosphere.
It is observe that the concentration of dopant equals to 2mol.﹪of Er、Mg , the temperature coefficient of capacitor is close to the EIA requirement of X7R, dielectric constant 4000, and the grain exhibits core-shell structure, the Curie temperature is toward to the direction of lower temperature. The dissipation factor of sample added La、Sm is lower than the sample added Er、Dy and the insulation resistance is higher than the sample added Er、Dy.
There is a dielectric peak of the temperature coefficient of capacitor at low oxygen partial pressure when sample sintering in reducing atmosphere that is different when the sample sintering in air. The densification of the sample sintering in reducing atmosphere is the best than the sample sintering in air.
It is the influence factor of the electrical property that the nickel diffuses into the active dielectric layers in MLCCs, so that, we add the nickel element to the dielectric powder to investigate the relation between the sintering, grain growth, and insulation resistance.
We use the dielectric powders that the electrical properties close to the EIA requirement of X7R, to manufacture the devices of base metal electrode multilayer ceramic capacitors, and investigate the microstructure, dielectric properties and the relation between the electrodes and the active dielectric layers.

目 錄
中文摘要………………………………………………………………………….Ⅰ
英文摘要…………………………………………………………….……………Ⅲ
致謝………………………………………………………………………………..V
目錄………………………………………………………………………………VI
圖目錄……………………………………………………………………………IX
表目錄…………………………………………………………………………...XV
第一章 緒 論……………………………………………………………………..1
1-1 前 言…………………………………………………………………...1
1-2 本研究的重點及目的………………………………………………….2
第二章 理論基礎及文獻回顧……………………………………………….…...3
2-1 積層陶瓷電容器的沿革與發展…………………………………….…...3
2-2 卑金屬電極與積層陶瓷電容器的發展…………………………….…...6
2-3 添加稀土元素對以BaTiO3為基之配方粉體之介電性質的影響……...9
2-3-1 介電性質與顯微結構的影響………………………………….……9
2-3-2晶粒核（grain core）-晶粒殼（grain shell）形成之行為……………..10
2-3-3 位置取代（site occupancy）之探討………………………………...12
2-4 積層陶瓷電容器的分類………………………………………………..14
2-4-1 高介電常數Y5V之積層陶瓷電容器………………………..……14
2-4-2 中介電常數X7R之積層陶瓷電容器……………………………..14
2-4-3 溫度補償型NPO之積層陶瓷電容器……………………………..15
第三章 實驗方法及步驟………………………………………………….…….24
3-1 實驗流程及樣品準備…………………………………………….…...24
3-2 性質測試………………………………………………………….…...25
3-2-1 粉末顯微結構……………………………………………….……25
3-2-2 X光繞射分析…………………………………………………….25
3-2-3 密度量測…………………………………………………….……26
3-2-4 介電性質量測…………………………………………………….26
3-2-5 晶粒大小之計算………………………………………………….26
3-2-6 氣體流量器（Mass Flow Meter）控制……………………….……27
3-2-7 氧分壓控制……………………………………………………….27
3-2-8 SEM顯微結構分析………………………………………….…...28
3-2-9 TEM顯微結構分析………………………………………….…...28
3-2-10 EPMA 分析……………………………………………………..29
第四章 結果與討論……………………………………………………………..36
4-1 Er和Mg添加入BT在空氣中燒結性質……………………………..36
4-1-1 結晶結構分析……………………………………………….…...36
4-1-2 不同燒結條件對介電性質的影響………………………….…...36
4-1-3 散逸因子分析……………………………………………….…...37
4-1-4 絕緣電阻分析……………………………………………….…...38
4-1-5 顯微結構分析……………………………………………….…...39
4-2 不同稀土元素和Mg添加入BT在空氣中燒結性質………………...40
4-2-1 結晶結構分析……………………………………………….…...40
4-2-2 不同稀土元素添加對介電性質的影響…………………….…...40
4-2-3 散逸因子分析……………………………………………….…...43
4-2-4 絕緣電阻分析……………………………………………….…...43
4-2-5 顯微結構分析……………………………………………….…...44
4-3 添加Ni對介電穩定的影響…………………………………………..45
4-4 還原氣氛燒結性質……………………………………………..…….46
4-4-1 還原氣氛燒結對介電性質的影響………………………….…...46
4-4-2 散逸因子分析……………………………………………….…...48
4-4-3 絕緣電阻分析……………………………………………….…...48
4-4-4 顯微結構分析……………………………………………….…...49
4-4-5 討論在空氣中燒結及在還原氣氛中燒結之異同………….…...50
4-4-6 添加Ni對介電穩定的影響……………………………………...51
4-5 積層陶瓷電容器（MLCC）元件之測試………………………………53
4-5-1 還原氣氛燒結對積層陶瓷電容器元件之介電性質的影響……53
4-5-2 散逸因子分析……………………………………………………54
4-5-3 絕緣電阻分析……………………………………………………54
4-4-4 顯微結構分析……………………………………………………54
4-5-5 討論積層陶瓷電容器元件與Disk的異同……………………...55
第五章 結論……………………………………………………………………103
第六章 參考文獻………………………………………………………………106

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