本研究根據過去以鈦酸鋇為基礎之高容介電陶瓷材料所做的深入研究及資料蒐集整合後發現，欲使鈦酸鋇達到高容且同時具備穩定的溫度-電容變化曲線，主要可以藉由改變其組成 (composition) 及其顯微結構 (microstructure) 兩大方向去達成。因此，本研究選擇以Ca2+、Zr4+、Mg2+、Y3+及(Bi0.5Na0.5)TiO3做為添加於鈦酸鋇中的參雜物 (dopants)，探討組成改變對於鈦酸鋇結構及介電特性的影響，同時藉由控制製程參數及燒結方法改變顯微結構藉此瞭解顯微結構對於鈦酸鋇介電特性的影響。
研究結果顯示，額外添加Ba2+於(Ba, Ca)(Ti, Zr)O3可以藉此使Ca2+同時取代鋇位置及鈦位置，藉此調整鈦酸鋇的居里溫度及提升鈦酸鋇於室溫下之介電常數。顯微結構的控制上，透過二階段燒結的燒結方式可以有效的控制(Ba, Ca)(Ti, Zr)O3燒結體的晶粒大小，製備出具高緻密性小晶粒(0.5 μm)之燒結體，且粒徑的縮減對於電容率的平坦化具有正面的幫助。選擇低容忍因子之化合物(Bi0.5Na0.5)TiO3作為參雜物，可以有效地提升鈦酸鋇的居里溫度，並同時具有降低燒結溫度的效果，此外，於BaTiO3-(Bi0.5Na0.5)TiO3系統中加入氧化鎂，亦可以達到電容率平坦化之效果。氧化鎂及氧化釔的添加可以調整鈦酸鋇的居里溫度及電容率，使其可以符合高溫介電陶瓷材料之規範(X8R)，且綜合氧化鎂及氧化釔共添加之系統其顯微結構的變化、晶體結構的變化、溫度-電容曲線的變化及擴散實驗的結果，發現Mg2+在形成殼核結構上扮演了相當重要且主導整個顯微結構及介電特性變化的角色。

The effects of Ca2+, Zr4+, Mg2+, Y3+ and (Bi0.5Na0.5)TiO3 doping on the microstructure, crystal structure and dielectric properties in BaTiO3 were investigated. The XRD and Raman results confirm the crystalline phase of BCTZ and BCTZ with excess Ba2+ powders are both tetragonal phases and without any other second phases. The results also show that Ca2+ ions can be pushed from Ba-site to Ti-site via the addition of excess Ba2+. SEM micrographs indicate that a fine-grain microstructure of both BCTZ and BCTZ with excess Ba2+ can be obtained using a two-step sintering method. The average grain size of BCTZ was around 0.25 μm, and the average grain sizes of two BCTZ samples with extra addition of Ba2+ were 0.5 μm and 0.3 μm, respectively. The fine-grain samples were obtained by two-step sintering and had a higher Curie temperature and flatter temperature coefficient of capacitance (TCC) curves.
The single phase of BaTiO3-(Bi0.5Na0.5)TiO3 powders can be synthesized at 800 oC for 3 h. The tetragonality and dielectric constant decreased as the BNT concentration increased. The Curie temperature increased with the BNT concentration increased.The sintering temperature of BaTiO3-(Bi0.5Na0.5)TiO3 decreased when MgO concentration increased.The flattened TCC curve of BaTiO3-(Bi0.5Na0.5)TiO3 can be obtained when the MgO concentration increased.
The TEM micrographs show that, core-shell structure can be obtained in the BaTiO3 ceramics co-doped with MgO and Y2O3. In addition, the addition of MgO enhances sintering shrinkage and inhibits the grain growth of BaTiO3 ceramics. Moreover, the addition of 1.0 mol% Y2O3 can promote sintering shrinkage and suppress the grain growth of BaTiO3 ceramics. However, the sintering shrinkage is suppressed when the amount of Y2O3 is increased to 3.0 mol%. The diffusion depths of Mg2+ and Y3+ are obtained by high-resolution transmission electron microscopy. The results indicated that Y3+ dissolved in BaTiO3 lattice with 5~10 nm depths inside the grain whereas Mg2+ tended to stay at the grain surface rather than being incorporated into BaTiO3. It is considered that Mg2+ plays an important role as a shell maker in the formation of core-shell structure.

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