將BaO-excess鈦酸鋇粉末添加3 mol.% CaTiO3和5.0 mol.% MgO，並在低氧分壓氣氛下燒結成試片1,2。將試片以電子順磁共振（electron paramagnetic resonance, EPR）分析，以研究其中的外來缺陷行為。而試片的組成成份類似EIA-X7R鎳卑金屬電極多層陶瓷電容(base-metal-electrode multilayer ceramic capacitors, BME-MLCC)。在g = 1.974 and g = 2.004所出現的兩條EPR光譜特徵線，代表分別表示鈦空缺與氧空缺形成的缺陷、鋇空缺與氧空缺形成的缺陷。
而g = 1.974 EPR譜線也出現在SrO-exess SrTiO3試片當中，這意謂EPR譜線所對應到的缺陷與鈦空缺有關。另外以陰極光射線系統( cathodoluminiscence, CL )分別在77 K和室溫所測得的CL譜線，由這兩組譜線更能佐證EPR譜線所對應的的缺陷種類。BaO-excess鈦酸鋇可藉由低氧氣氛燒結和添加施體以產生氧空缺，這是因為鈦空缺所造成的電荷補償所產生的。

A commercial BaO-excess BaTiO3 powder added with 3.0 mol.% CaTiO3 and 5.0 mol% MgO and sintered under low pO2 is studied for the extrinsic defect behavior through electron paramagnetic resonance (EPR). The composition resembles a formulation for making EIA-X7R base-metal-electrode multilayer ceramic capacitors (BME-MLCC). Two characteristic EPR lines at g = 1.974 and g = 2.004 are assigned to Ti-vacancy and Ba-vacancy forming complex defects with O-vacancy, respectively. The EPR line at g = 1.974 also appears in SrO-exess SrTiO3 reinforces the claim that the corresponding paramagnetic sensitive defect is associated with Ti-vacancy. Both room-temperature and low-temperature (77 K) cathodoluminiscence (CL) spectra are obtained to support the defect species assigned to EPR lines. Extrinsic oxygen vacancies generated by low-pO2 and by the acceptor-doping level in the BaO-excess BaTiO3 composition when sintered at 1200oC and 1000oC are charge-compensated by cation vacancies, principally by Ti-vacancies.

論文摘要......................................................................................................................................................I
Abstract......................................................................................................................................................II
目錄............................................................................................................................................................III
表目錄........................................................................................................................................................V
圖目錄.......................................................................................................................................................VI
第一章 前言...............................................................................................................................................1
第二章 原理及文獻回顧........................................................................................................................3
2-1鈦酸鋇的基本性質.....................................................................................................................................3
2-2平衡相圖.................................................................................................................................................7
2-3鈦酸鋇相圖以及顯微結構...........................................................................................................12
2-4半導體陶瓷....................................................................................................................................12
2-5鈦酸鋇的缺陷化學................................................................................................13
2-5-1本質缺陷(Intrinsic Defects)
2-5-2 外來缺陷 (Extrinsic Defects)
2-6施體/受體元素對鈦酸鋇性質的影響.......................................................................................14
2-7添加物對鈦酸鋇的影響......................................................................................................................14
2-8燒結驅動力......................................................................................................................................................15
2-9關於鈦酸鋇的模型.....................................................................................................................................................................................................16
2-10電子順磁共振...............................................................................................................17
2-11MLCC...........................................................................................................................................................20
2-12MLCC劣化...............................................................................................................................................23

第三章 實驗步驟...................................................................................................................................25
3-1鈦酸鋇起始粉末.....................................................................................................................25
3-2試片製程.................................................................................................................................26
3-3導電度量測..............................................................................................................................29
3-4EPR量測...................................................................................................................................29
3-5CL試片前處理.......................................................................................................................30
第四章 實驗結果..................................................................................................................................32
4-1起始粉末.................................................................................................................................32
4-2未添加的試片........................................................................................................................34
4-3 CL光譜...................................................................................................................................35
4-4添加CaTiO3的試片...............................................................................................................37
4-5添加MgO的試片....................................................................................................................38
4-6共同添加CaTiO3、MgO的試片...........................................................................................39
第五章 討論...........................................................................................................................................40
5-1譜線意義.................................................................................................................................40
5-2因低氧分壓與非計量組成所造成的缺陷.......................................................................41
5-3 CaTiO3 and MgO共同添加................................................................................................43
5-4氧空位和缺陷中心的譜線..................................................................................................43
第六章 結論...........................................................................................................................................44
第七章 未來工作...................................................................................................................................45
參考文獻..................................................................................................................................................46

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