隨著積層陶瓷電容器邁向小型化發展已經是未來的趨勢，由於元件尺寸小型化，介電層厚度及電極厚度也必須跟著降低，以介電層為1μm為例，其電極厚度約在0.8μm左右，由於過薄的內電極厚度在燒結過程中易容易因為camber效應導致有不連續情況產生，因此快速升溫方法將被引用，利用快速通過不同材料之起始收縮溫度點，降低陶瓷與電極間的收縮不匹配性，進而提高內電極收縮率。雖然快速升溫可以有效改善電極連續性，但對於將電極薄層化尚未得到改善，我們期望搭配抑制燒結方式，一方面利用抑制層與被抑制層間產生的摩擦力，抑制積層陶瓷電容器之X-Y方向平面的收縮，另一方面由於抑制燒結方式，整體元件大部分收縮率將被集中在Z軸方向上，如此便可在x-y方向不收縮下提高電極連續性，又進一步將電極薄層化。此外，根據前人研究指出，抑制燒結可有效改善元件內部晶粒尺寸變化，但其缺點為造成凹型的外觀。因此本研究中，一種新穎式的燒結方式將被提出，結合快速升溫與抑制燒結方式對於(Ba,Ca)(Ti,Zr)O3之積層陶瓷電容器之研究，在此對於採用升溫速率和抑制燒結條件下，無凹型的外觀積層陶瓷電容器可被成功製作出，且內部的電極連續性和微結構變化將被詳細討論。根據結果顯示，透過快速升溫搭配抑制燒結的方式(Ba,Ca)(Ti,Zr)O3-based之積層式陶瓷電容器的內電極連續性可高達98%且平均厚度小於1μm，在微結構方面除了其內部晶粒均勻分佈外，平均晶粒大小可控制在1.5±0.1μm。
銅電極有較低的電阻係數且在高頻訊號傳輸上具有低等校串聯電阻和優越的高頻率特性，但由於銅電極溶點遠低於鎳，故其材料相對燒結溫度也必須大幅降低。此外，降低材料燒結溫度對於陶瓷體內部殘留應力有極大幫助，因此我們進一步將(Ba,Ca)(Ti,Zr)O3 添加Li2CO3和SiO2當燒結助劑，並成功在1050度與銅電極共燒，其低溫系統材料介電常數可達9500以上、介電損失為23×10-4、絕緣電阻可到達1.2×1012Ω，然而過量的Li2CO3含量添加將會導致 Ba1.55Ca0.45SiO4的二次相生成，進而影響整體(Ba,Ca)(Ti,Zr)O3材料之介電特性，造成介電常數和絕緣電阻的下降並增加材料的介電損失。此外，文中也提及在銅電極與陶瓷體間在燒結過程中之介面反應，我們利用背相電子顯微鏡和線掃瞄偵測銅電極擴散情況。此外，進一步將可低溫燒結的(Ba,Ca)(Ti,Zr)O3材料製作成與銅內電極共燒並搭配快速升溫與抑制燒結條件，在低溫燒結下達到高的電極連續性與均勻的晶粒分佈情況，經過實驗結果，在搭配抑制燒結和快速升溫下，具有銅內電極之積層陶瓷電容器元件，其內電極連續性可高達98%，均勻晶粒分佈情況可被實現，平均晶粒大小被控制在0.75±0.1μm。
在追求高介電常數下，具備高穩定的電容溫度係數特性也同樣重要，在介電薄層化趨勢下，存在於介電層間的晶粒尺寸不但要下降且晶粒數量也必須跟著減少，因此兩種問題將被呈現出。一方面為晶粒尺寸下降導致材料介電常數也大幅被減少，導致要製作出高電容量的積層陶瓷電容器方向相互矛盾。另一方面為在減少的晶粒數量存在於介電層中，此結果最終將導致積層陶瓷電容器元件的可靠度壽命降低。一般來說，以殼核結構之具有高穩定性的溫度介電曲線情況下，存在於介電層中的晶粒至少約5-6顆才能有效抵擋直流偏壓能力。基於此，本研究提出利用新穎式燒結方式製作出非殼核結構之晶粒，其一在利用抑制層和介電層間的不匹配性可以有效抑制晶粒成長，進而將(Ba,Ca)(Ti,Zr)O3之電容溫度係數從Y5V抑制到X5R。其二在薄層化的介電層中，因核部分是由高介電常數且低電阻特性的純BaTiO3材料所構成，殼部分則是由高電阻特性之BaTiO3材料與其它微量添加化合物所構成，故只有殼部分可承受較高的直流偏壓，而本研究利用新穎式燒結製作出非殼核結構之晶粒，在可靠度的實驗測試下，證明只需2-3顆晶粒下便可以有效抵擋直流偏壓能力。

The multilayer ceramic capacitors (MLCCs) have been progressively miniaturized in recent years. In order to achieve high capacitance for a small size MLCC, the thickness of electrode and dielectric layer must be simultaneously decreased. However, the miniaturization of Ni–BaTiO3 multilayer ceramic capacitors (MLCCs) offers a variety of challenges to the capacitor industry in the areas of particulate materials, dielectric compositions, and manufacturing technology. Currently, one of the main problems arising in the processing of ultrathin, base-metal electrode MLCCs with dielectric and electrode layer thicknesses around 1 mm or less is the microstructural evolution of the electrode layers during co-sintering, which leads to electrode discontinuities. Therefore, the rapid heating rate was adopted to fire the BaTiO3-based MLCCs in order to reduce the shrinkage mismatch by quick passage through the different onset temperature between the dielectric material and the inner electrode. Though rapid heating can effectively improve the inner electrode continuity, the thinning inner electrode has not yet been solved.
Using the constraining layer laminated on the MLCCs, the friction force between constraining layer and constrained layer are generated, which can reduce the shrinkage rate in X-Y direction and then the overall shrinkage will be concentrated on the Z direction. Both the residual stress can be minimized and the homogeneity of grain size can be obtained. Therefore, we expect a novel sintering approach by combination of constrained sintering with rapid heating rate can obtain both high electrode continuity and thinner electrode layer thickness of MLCCs
. In this studies, the thin inner electrode (<1μm) with high continuity (>98%) and the fine grain size (1.5μm) with narrow distribution (±0.1μm) of (Ba,Ca)(Ti,Zr)O3-based MLCCs with a concave-free morphology can be attained by using a rapid constrained sintering technique.
In comparison with Ni electrode, the Cu electrode has better conductivity. As expected, the electrical performance of Cu-MLCCs is superior to that of Ni-MLCCs, especially for the high Q and low ESR properties. However, the melt temperature of Cu is lower and around 1086C, the sintering temperature of (Ba,Ca)(Ti,Zr)O3 dielectric has to be reduced by using SiO2 and Li2CO3 as sintering aids. The contents of SiO2 and Li2CO3 are studied to achieve the optimum dielectric characteristics such as dielectric constant of up to 9500, low dielectric loss of 23×10-4 and high insulation resistance of up to 1.2×1012Ω. By the precise control of the thickness of constraining layer and heating rate, the Cu inner electrode with high continuity (98%) and fine grain size (0.75μm) with narrow distribution (±0.1μm) of (Ba,Ca)(Ti,Zr)O3-based MLCCs can be attained by using a rapid constrained sintering technique.
In order to pursue high dielectric constant, having stable temperature coefficient of capacitance of MLCCs is also an important issue. A (Ba,Ca)(Ti,Zr) O3-based MLCC with X5R temperature characteristic (C/C  15% within –55 to 85C) was attained by using a novel sintering technique. It has been demonstrated that the grain size of (Ba,Ca)(Ti,Zr)O3-based MLCCs is inhibited by the novel sintering approach so that a non-core-shell microstructure of (Ba,Ca)(Ti,Zr)O3-based MLCCs to meet X5R temperature characteristic can be obtained. In comparison with conventional X5R BaTiO3-base dielectric with core-shell, the novel X5R (Ba,Ca)(Ti,Zr)O3 base dielectric with non-core-shell shows very promising performance especially for high dielectric constant and long lifetime, which are very important characteristics for a dielectric materials to further pursuit a super high capacitance of MLCC.

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