本研究以鈣鈦礦結構（ABO3）之鑭系氧化物LaCoO3為基材，添加KNbO3，以固態反應法(Solid State Reaction)備製La1-xKxCo1-xNbxO3(x=0~1)陶瓷粉末，以期在鑭位置以鹼金族的鉀取代，在鈷位置則以過渡金屬元素的鈮取代，探討鉀及鈮對LaCoO3鈣鈦礦結構、微結構及電性之影響，藉由不同添加量x及不同燒結條件的控制，探討陶瓷體之介電性質。
本實驗結果顯示，成功的以兩階段固態反應法合成La1-xKxCo1-xNbxO3之複合型鐵電陶瓷系統。在1400 ℃燒結2小時後所有試片皆形成單一之鈣鈦礦結構；在添加量為0.1 ＜ x時，其結構為菱方晶體（rhombohedral）；當添加量在0.1 ≦ x ≦ 0.7的範圍裡，則轉變為立方晶體（cubic）；最後當添加量為0.7 ＜ x，則轉變為斜方晶體（orthorhombic）。在熱差-熱重分析發現x = 0.1與0.3的結晶活化能分別為121.75、116.82 kJ/mol，而x = 0.5和0.7的結晶活化能分別為111.89、106.96 kJ/mol。利用Rietveld法精算x = 0.1之XRD所得之結果顯示，精算wRp、Rp、X2值分別為0.0345、0.0277、1.28，為相當良好的精算結果，其化學方程式為：La0.91K0.09Co0.89Nb0.11O3.12，此成份的比例與我們所設定的化學方程式La1-xKxCo1-xNbxO3非常一致，這代表了絕大部分的K、Nb、La與Co離子，分別以一價、五價和三價的狀態存在於本系統內，本實驗所合成之La1-xKxCo1-xNbxO3陶瓷結構屬於立方晶系（cubic），空間群為 ，其中a = 3.88 Å α = 90°。由TEM觀察分析得到，當添加量x = 0.1時，晶格常數a = 3.89 Å，同時在沿著[001]方位的擇區繞射圖中也鑑定出了，(100)平面的超晶格結構(superlattice structure)，另外在沿著[011]和[ ] 方位的擇區繞射中，也分別發現了( ) 和 ( )平面的超晶格結構。
La1-xKxCo1-xNbxO3弛緩體鐵電陶瓷是由半導化的晶粒與高電阻晶界所組成的晶界層電容，在室溫下，x = 0.1之樣品經過1400 oC燒結2小時，可獲得約58000之介電常數( )而介電損失(tanδ)約0.8。根據Arrhenius方程式所得之La1-xKxCo1-xNbxO3弛緩體鐵電陶瓷在介電弛緩過程所需的活化能約為5.88 kJ/mol，而偶極弛緩時間約10-3s。由XPS分析結果可以發現，在La1-xKxCo1-xNbxO3的系統裡，La離子是以三價的狀態來存在；當添加量x = 0.1時，Co是以三價陽離子狀態存在；為了形成ABO3結構，一價的K離子僅取代A位置的三價La離子；Nb離子在此系統裡只以五價陽離子狀態存在。

In this study, lanthanide oxides LaCoO3 with perovskite structure (ABO3) is used as the substrate and KNbO3 is added to prepare La1-xKxCo1-xNbxO3 (x = 0 to 1) ceramic powder by solid state reaction with a view to replace La with K and Co with Nb to study the effect of K and Nb on microstructure and electrical properties of LaCoO3 perovskite structure. Meanwhile, through different content of x and sintering conditions, ceramic dielectric properties are studied as well.
The results show the success of synthesizing ferroelectric ceramic composite system La1-xKxCo1-xNbxO3 with two-stage solid-state reaction. All the specimens form a single perovskite structure after two hours of sintering at 1400 °C. When adding amount is less than 0.1 (0.1 < x), the crystal structure is rhombohedral. When adding amount is between 0.1 and 0.7 (0.1 ≦ x ≦ 0.7 ) the crystal structure transforms into cubic. When adding amount is greater than 0.7 (0.7 < x), the crystal structure transforms into the orthorhombic. By DSC analysis, the activation energy of crystallization of the powders with x = 0.1 and 0.3 are 121.75 and 116.82 kJ/mol respectively, x = 0.5 and 0.7 are 111.89 and 106.96 kJ/mol respectively. The calculation result of XRD when x = 1 using Rietveld method shows the values of wRp, Rp and X2 are 0.0345, 0.0277, and 1.28 respectively, and its chemical formula: La0.91K0.09Co0.89Nb0.11O3.12 is consistent to the formula La1-xKxCo1-xNbxO3 that we have set, which represents most of the K, Nb, La and Co ions exist in the state of monovalent, quinquevalent, and trivalent respectively in this system. The space group of La1-xKxCo1-xNbxO3 synthesized in this experiment whose ceramic structure is cubic is , in which a = 3.88 Å α = 90°. Observed in TEM analysis, when adding amount x = 0.1, the lattice constant a = 3.89 Å. Meanwhile, in the selected-area-diffraction (SAD) patterns along [001] direction, the super-lattice structure of (100) plane is identified, and in SAD patterns along the [011] and [ ] direction, super-lattice structures of ( ) and ( ) plane are also discovered.
La1-xKxCo1-xNbxO3 flaccid ferroelectric ceramics is the grain boundary layer capacitance composed of semi-conductive process gains and high-resistance grain boundaries , at room temperature, x = 0.1 sample sintered at 1400°C for two hours will have the dielectric constant (E) of approximately 58,000 and dielectric loss (tan δ) of approximately 0.8. Based on the Arrhenius equation, The activation energy of the dielectric relaxation is estimated to be 5.88 kJ/mol and the lattice vibrational phonon frequency τ0 is 1.881 × 10-3 s. From XPS analysis results, La exists in the state of trivalent ions in La1-xKxCo1-xNbxO3 system. When the adding amount x = 0.1, Co exists in the state of trivalent cation. In order to form an ABO3 structure, K+ only replaces the La3+ in A position; Nb exists only in the state of quinquevalent in the system.

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