本研究利用穿透式電子顯微鏡鑑別技術 (影像電子繞射、化學元素分析、高解析原子影像、集束電子繞射)、X光繞射與Rietveld refinement分析、Raman散射光譜及介電特性量測去分析EIA-Y5V陶瓷的微觀結構與介電特性。

根據實驗結果，獲得以下結論：
1. 從介電量測的結果顯示，EIA-Y5V積層陶瓷電容器具有散佈式相變化，以及頻率分佈行為，因此可視其為弛緩型強電陶瓷 (Relaxor ferroelectrics)。其頻率與Tm之關係符合Vögel-Fulcher關係式，說明EIA-Y5V陶瓷可以用「偶極玻璃模型」 (Dipolar glass model) 來加以描述。
2. 經由穿透式電子顯微鏡的鑑定下，EIA-Y5V陶瓷呈現「無特徵」晶粒 (featureless grains)。經由能量分散光譜分析，溶質原子 (鋯及鈣) 呈現巨觀地均勻分佈。無特徵晶粒的擇區電子繞射圖皆顯示{100}* 漫散射強度 (diffuse scattering intensity)，與早期Comés、Lambert及Guinier (1969) 在鈦酸鋇單晶中觀察到的DS相同。
3. X光繞射分析結果顯示EIA-Y5V陶瓷為具有單一 {200}PC 寬繞射峰之假立方相 (pseudo-cubic phase)。然而，從Rietveld refinement分析獲得C+T+R 多重結晶相，並且結晶相的含量從室溫到200oC都維持不變。
4. 根據高解析原子影像，觀察到鈦原子偏離八面體中心而朝向[001]及[111] 位移，分別為T-PNR及R-PNRs (極性奈米區域)存在於Y5V陶瓷的直接證據。
5. 室溫下的Raman光譜顯示EIA-Y5V陶瓷具有C-BaTiO3、T-BaTiO3及R-BaTiO3的特徵峰，這些特徵峰維持到至少200oC，意味著沒有發生巨觀的C→T相變化。
6. EIA-Y5V陶瓷經過長時間高溫退火後，在無特徵晶粒的晶界附近出現強相900 a-a T-晶域 (經由擇區電子繞射分析及X光繞射分析)。同時，介電常數從退火前的13,300下降至退火24小時後的9,000。強相900 a-a T-晶域的出現是肇因於於T- 或R-PNRs在高溫退火時的成長。晶界附近的局部隨機應變場 (local random strain field) 較小，以致於晶界附近的應變場在退火期間優先被解除而發生PNR→強電T-晶域之變化。

從上述的實驗結果，EIA-Y5V多層陶瓷電容器的高介電常數肇因於T-PNR及R-PNRs共存於C-matrix裡。一旦PNRs經由退火而被誘導成長為強電T-晶域時，PNRs的濃度下降以致介電常數隨之下降。我們還在未摻雜的鈦酸鋇陶瓷裡發現存在relaxors特性以及{100}* DS，可以證實鈦酸鋇中存在沒有發生C→T相變化的intrinsic PNRs。然而，經由ZrO2摻雜的EIA-Y5V陶瓷，其所衍生的extrinsic PNRs因為沒有發生C→T相變化而被以介穩態保留下來至室溫，因此PNRs濃度遠高於純鈦酸鋇陶瓷。

Both the microstructure of EIA-Y5V MLCCs are examined and crystalline phases determined through TEM using diffraction-contrast imaging, selected-area diffraction pattern, chemical elemental analysis, high-resolution atomic imaging, X-ray diffraction combined with Rietveld refinement analysis, and Raman scattering spectra. The corresponding dielectric measurements were also conducted at room temperature using LCR spectrometry.

The experimental results are summarized as follows:
1. From the dielectric measurement, EIA-Y5V MLCCs can be regarded as a relaxor ferroelectric, exhibiting the representative features of diffuse phase transition (DPT) and both the dielectric constant and loss tangent follow the characteristic frequency-dispersion of a relaxor. The relationship between frequency and Tm (temperature at dielectric constant maximum) obeys the Vögel-Fulcher relation, suggesting that the dielectric behavior of Y5V ceramic is consistent with the dipolar glass model proposed by Viehland and Cross (1990).
2. Under TEM analysis, featureless grains containing homogeneously distributed solute content. Further, all featureless grains show {100}* diffuse scattering (DS) intensity that is a characteristic of PNRs initially observed and a model of 1D PNRs proposed by Comés, Lambert and Guinier (1968) from X-ray diffuse scattering.
3. XRD analysis shows pseudocubic phase characterized by a singe and broadened diffraction peak of {200}PC. However, Rietveld refinement analysis suggests that it is a phase mixture consisting of C-, T- and R-phase.
4. HRTEM images suggest that Ti4+ displacing off-center toward both [001] and [111] is observed simultaneously, which is consistent with the phase mixture concluded by Rietveld refinement.
5. From Raman spectra , characteristic phonon modes from T-BaTiO3 and R-BaTiO3 are observed in EIA-Y5V MLCCs. These Raman scattering bands persist until at least 200oC, indicating the lack of macroscopic phase transitions that is in accordance with temperature-dependent XRD results.
6. After long-term annealing, Y5V grains show ferroelectric 900 a-a T-domain in the vicinity of grain boundary, confirmed by both SADP and XRD. Meanwhile, dielectric permittivity decreases from 13,300 to 9,000 with increasing annealing time. The formation of ferroelectric T-domains is attributed to the growth of T- and R-PNRs triggered by annealing. Local random strain field caused by chemical disorder (the size difference between Zr and Ti ion) is preferentially released in the vicinity of grain boundary to encourage the growth of PNRs to form the ferroelectric T-domain.

We can conclude that EIA-Y5V MLCCs high permittivity is originated from T- and R-PNRs embedded in a C-matrix. Once these PNRs grow into ferroelectric domains, the relative permittivity would drop as a result of both decreased PNRs content and probably also increased PNRs sizes. It is also found that undoped BaTiO3 at grain size ~1.0 m also exhibits DPT and frequency dispersion behavior at room temperature, it also shows {100}* DS sheets. It suggests that PNRs also exist in undoped BaTiO3 even though it undergoes the C→T phase transition. Therefore, it is suggested that a large amount of PNRs formed at the Burns temperature are retained at room temperature in EIA-Y5V MLCCs because chemical disorder creates a local random strain field to inhibit the C→T phase transition through adding ZrO2 to BaTiO3.

論文審定書 i
誌謝 ii
摘要 iii
英文摘要 v
目錄 viii
圖次 xiii
表次 xxvii
第一章 前言 1
1.1 研究背景 1
1.2 研究目的 4
第二章 文獻回顧 6
2.1 鈣鈦礦結構 6
2.2 鈦酸鋇的晶體結構 9
2.3 鈦酸鋇陶瓷的尺寸效應 13
2.4 鈦酸鋇的固溶體 16
2.5 鈣鈦礦結構的八面體傾轉 19
2.6 強電特性 22
2.7 位移型強電相變化 26
2.8 序化-無序化型強電相變化 33
2.9 Comes-Lambert-Guinier模型 36
2.10 多層陶瓷電容器 49
2.10.1 多層陶瓷電容器的構造 49
2.10.2 多層陶瓷電容器的發展趨勢 52
2.10.3 多層陶瓷電容器的製造方法 58
2.10.4 多層陶瓷電容器的類型及微結構特徵 60
2.11 弛緩型強電陶瓷 (Relaxor Ferroelectrics) 71
2.11.1 成分不均勻理論 (Chemical Inhomogeneity) 78
2.11.2 偶極玻璃理論 (Dipolar Glasses) 83
2.11.3 超順電相理論 (Superparaelectricity) 85
2.11.4 序化-無序化理論 (Order-Disorder) 86
2.11.5 隨機電場理論 (Random Filed) 89
2.11.6 巨大壓電效應之物理源起 90
2.12 極性奈米區域 (Polar Nanoregions) 93
2.13 極性奈米區域的實驗證據 98
2.14 鋯摻雜之鈦酸鋇固溶體 109
第三章 實驗部分 109
3.1 實驗材料 117
3.2 實驗儀器 118
3.3 儀器原理 123
第四章 實驗結果 143
4.1 EIA-Y5V多層陶瓷電容器的起始粉體分析 143
4.2 EIA-Y5V多層陶瓷電容器的分析 153
4.3 EIA-Y5V多層陶瓷電容器的顯微結構分析 161
4.4 EIA-Y5V多層陶瓷電容器的電子繞射分析 172
4.5 EIA-Y5V多層陶瓷電容器的高解析原子影像 188
4.6 EIA-Y5V多層陶瓷電容器退火後的微結構分析 191
4.7 EIA-Y5V多層陶瓷電容器退火後的介電特性 203
4.8 EIA-Y5V多層陶瓷電容器的Multibeam分析 206
4.9 EIA-Y5V多層陶瓷電容器的CBED分析 210
4.10 EIA-Y5V多層陶瓷電容器的超晶格反射點 212
4.11 EIA-Y5V多層陶瓷電容器的Raman散射光譜 214
4.12 Raman散射光譜之溫度相依性 222
4.13 EIA-Y5V多層陶瓷電容器施加電壓後的Raman散射光譜 239
4.14 不同退火時間對Y5V多層電容器的Raman散射光譜之影響 241
4.15 不同Zr添加量對Raman散射光譜之影響 243
4.16 EIA-Y5V多層陶瓷電容器的X光繞射分析 249
4.17 升溫X光繞射及Rietveld Refinement分析 254
第五章 結果討論 261
5.1 EIA-Y5V多層陶瓷電容器的介電特性 261
5.2 Diffuse Scattering與極性奈米區域 266
5.3 EIA-Y5V多層陶瓷電容器的100}* DS 271
5.4 退火對Y5V多層陶瓷電容器的微結構與介電特性之影響 284
5.5 EIA-Y5V多層陶瓷電容器的Raman光譜 288
5.6 CBED與HRTEM的實驗結果比較 301
5.7 R-相奈米極性區域與T-相奈米極性區域 303
5.8 R-相奈米極性區域 307
5.9 EIA-Y5V多層陶瓷電容器-散佈式相變化之物理起源 308
5.10 動態及靜態奈米極性區域 308

第六章 結論 314
第七章 未來研究建議 316
參考文獻 317
附錄 327
論文著作 328

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