本研究以 (100-x)(Bi0.5Na0.5)TiO3-xBaTiO3，x = 0~12% (簡稱 BNT-xBT) 陶瓷系統，進行巨觀電性 (介電、鐵電、壓電) 之量測，並搭配穿透式電子顯微鏡 (Transmission Electron Microscopy, TEM) 與壓電響應力顯微鏡 (Piezoresponse Force Microscopy, PFM) 分析結果來探討 BNT-xBT 陶瓷在不同 Ba2+ 含量下之材料電性、晶體結構、微觀電域形貌與電域受施加電場的響應行為之一系列演化情形探討。
　　由巨觀電性來看 BNT-xBT (x = 0~5%) 陶瓷系統具有鐵電特性，其鐵電與應變遲滯曲線展現出典型的 “矩形” 狀 P-E 與 “蝴蝶” 狀 S-E 曲線，具高矯頑電場 ( Ec ≒ 38~56 kV/cm ) 與低應變量 (Strain% ≒ 0.12~0.17%)。而微觀電域形貌與結構方面，在 Pure BNT 晶粒內發現了具有 R3c 對稱結構之長程片狀電域。隨 Ba2+ 含量增加至 3% 時，具 P4bm 對稱結構之正方晶相 (Tetragonal) 開始出現於 R3c 對稱結構之菱方晶相 (Rhombohedral) 晶格中，並發現 R3c 長程片狀電域與 P4bm 和 R3c 混和之雜草狀 (Tweed-liked) 短程電域具有共存之現象。
　　當 Ba2+ 含量增加至 6~8% 時矯頑電場驟降 (Ec ≒ 12~13 kV/cm)，鐵電與應變遲滯曲線具有很大之驟變，由原本典型鐵電材料之 ”矩形” 狀 P-E 與 “蝴蝶” 狀 S-E 曲線轉變成類似反鐵電材料之 “船槳” 狀 P-E 與 “ V “ 狀之 S-E 曲線，其應變量 (Strain% ≒ 0.21~0.30%) 與壓電特性 (d33 ≒ 175~208pC/N) 都有大幅的提升，在 BNT-7BT 陶瓷中其應變量更高達 0.3 %，這代表材料在此成分區間之電性行為與低 Ba2+ 含量之成分點不同。在微觀結構方面，所有電域形貌皆轉變成無明顯對比的奈米電域，在電子繞射圖譜分析發現此成分區間除了 R3c 與 P4bm 兩相共存外，更在 Zone [100]p 中發現具 Pnma 對稱結構之反鐵電相，因此我們認為此區間的成分系統會有這樣優異之壓電特性以及 P-E 曲線變成 ”船槳” 狀可能是因為具鐵電行為之 R3c、P4bm 與反鐵電 Pnma 相共存的結果。
　　接著繼續添加 Ba2+ 含量至 9~12% 發現，P-E 與 S-E 曲線又變回鐵電之 “矩形” 與 “蝴蝶“ 狀曲線，壓電係數 (d33 ≒ 141~164pC/N) 與應變 (Strain% ≒ 0.14~0.17%) 特性也隨著 Ba2+ 含量的增加而下降，此時 R3c 與 Pnma 相消失並且取而代之是長程層狀 (Lamellar) 的 P4mm 電域產生，此時材料逐漸變成穩定的正方晶 (Tetragonal) 結構。
　　在 PFM 的分析結果發現，Pure BNT 陶瓷中存在著無特定排列方向的 PNRs (Polar nano-regions)，隨著 Ba2+ 含量的添加，這些 PNRs 會自我組織 (Self-organization) 而且尺寸會變得越小。在 Ba2+ 含量為 6~8% 的陶瓷系統中，我們發現這些奈米尺寸的 PNRs 除了有自我組織的行為外，還著沿特定晶格方向排列。經由微區壓電響應曲線量測，其結果發現壓電響應 (Piezoresponse) 與振幅 (Amplitude) 曲線與巨觀量測的 P-E、S-E 曲線相似，具有鐵電與反鐵電共存之現象，此現象正好呼應巨觀電性與 TEM 之分析結果。而在 9~10% Ba2+ 含量的陶瓷中，長程 Lamellar 電域則開始出現，與 TEM 的結果相同。
　　最後，我們藉由寫入正負電場的方式來探討 BNT-7BT 與 BNT-12BT 陶瓷的電域翻轉行為發現，BNT-7BT 陶瓷的 PNRs 會隨電場的方向翻轉並成核成長成長程電域結構而造成表面應變，而 BNT-12BT 陶瓷則如一般 Tetragonal 結構之鐵電材料，具有 90° 與 180° 之電域翻轉行為，因此我們可以說明 Ba2+ 含量在 x = 6~8% 的區間內，有這樣優異之壓電特性、大應變量以及 S-E 曲線變成 ” V ” 狀是因為具鐵電行為之 R3c、P4bm 與反鐵電 Pnma 的電域翻轉與相變所造成的結果。

In this work, (100-x) (Bi0.5Na0.5) TiO3-x BaTiO3 (abbreviated as BNT-xBT with x = 0 ~12%) piezoceramics had been successfully fabricated by oxide mixing route. The electrical properties measurement revealed that the optimum properties is achieved in BNT-6BT~BNT-8BT ceramics. The giant strain was occurred during the piezoelectric measurement of BNT-7BT specimen in which achieved 0.30%.
Microstructured features demonstrated that pure BNT ceramic reveals long-range sheet domain with R3c symmetrical structure. Then, microstructures of BNT-3BT ceramic reveal that partical P4bm symmetry appear in R3c matrix, and TEM image shows the large (R3c) domain and Tweed-liked (R3c+P4bm) domain co-existence in one grain. In BNT-6BT~BNT-8BT ceramics, the ferroelectric (FE) characterization of R3c and P4bm symmetrics and the anti-ferroelectric (AFE) of Pnma symmetry co-exist in one grain, demonstrating that the P-E curve pinched-off behaviors are attributed to the coexistance of FE and AFE symmetrics in the grains at room temperature. In BNT-9BT~BNT-12BT ceramics, TEM diffraction patterns reveal that disapperance of R3c symmetry and appearance of P4mm symmetry with long range lamellar domain, indicating that the structure transfer from Rhombohedral to Tetragonal and the electric properties change to a ferroelectric behaviors.
Furethremore, PFM microstructural features reveal random polar nano-regions (PNRs) in pure BNT ceramics, and then the PNRs will become smaller and self-organize with increase of BaTiO3 addition. In BNT-6BT~BNT-8BT ceramics reveal that the PNRs showing smaller and array along the specific crystal direction. In micro piezoresponse measurements, we found the FE and AFE phase co-exist in one grain. This results show good agreement with pervius electric properties and TEM results. In BNT-9BT~BNT-12BT ceramics, PFM features showed the lamellar domain as well as TEM images.
In summary, the mechanisms of giant strain in BNT-6BT~BNT-8BT ceramics are due to the coexistence of FE (R3c+P4bm) and AFE (Pnma) symmetrics.

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