臺灣博碩士論文加值系統

未摻雜之鈦酸鍶陶瓷微結構分析做了完整之解析。研究中發現在 Sr/Ti 大於1時的鈦酸鍶粉末燒結過後，有第二相 (Ruddlesden-Popper phase) 產生。在 X 光繞射分析、掃描式電子顯微鏡 (SEM)與穿透式電子顯微鏡 (TEM) 的配合觀察，其中選區繞射 (selected area diffraction patterns, SADP) 之結果可得知母相鈦酸鍶與第二相 (Ruddlesden-Popper phase) 間的結晶向關係，計算後可列出兩相間的 matrix 關係列表。兩相介面的微結構觀察部分，發現鈦酸鍶 (001)ST 平面與第二相之 (001)RP2 共用，並且此平面維持彈性應變。此外，對於第二相 (Ruddlesden-Popper phase) 爭論已久的疊差 (stacking fault)，於 TEM 下觀察得到其為 α fringe，並且其位移向量 R = 1/2 <111> ST。
鈣離子添加劑對於鈦酸鍶之研究部分，實驗中利用 LCR 4294a 進行電性量測，並使用 X 光繞射分析、拉曼光譜分析、掃描式電子顯微鏡 (SEM)、穿透式電子顯微鏡 (TEM) 觀察微結構發展。吾人發現其因化學成分中鈣含量分布不均勻，所直接影響到的是不同鈣含量的晶粒擁有不同的相結構。在光集束電子繞射圖 (CBED) 之實驗結果顯示，當鈣含量為 26 at.% 時，晶體結構為正方相 (I4/mcm) ，當鈣含量為 31 at.% 時則為斜方相 (Pbnm)。 利用 Diffracplus-TOPAS® 系統進行凝合計算，結果顯示其試片為正方相 (I4/mcm) 與斜方相 (Pbnm) 以 4:1 之比例存在之兩相混合結構。此外，從相變化產生的微結構變化，吾人從中推論相變化途徑由高溫至低溫過程中應為 C-Pm3m → T-I4/mcm → O-Pbnm。

The crystalline phase mixture and microstructure of SrO-excess SrTiO3 powder sintered at 1350oC/4 h is analyzed using X-ray diffractometry (XRD), scanning and transmission electron microscopy (SEM and TEM). Second phases represented by Ruddlesden-Popper Sr3Ti2O7 (RP2) and Sr4Ti3O10 (RP3) coexist with SrTiO3 (ST), consistent with the SrO-TiO2 phase equilibrium diagram. Some ST grains contain inter-grown RP2 lamellae which permits analysis of the ST-RP2 interface. The ST-RP2 boundary shared by (001)ST and (001)RP2, although containing a lattice mismatch, is accommodated by long range elastic strain. The crystallographic orientation relationships of ST and RP2 at the interface are determined by selected area diffraction patterns (SADP) and described by transformation matrices. The crystallographic shear structure across the ST-RP boundary exhibiting the characteristic α-fringe pattern can be represented by a fault vector R = 1/2<111>ST.
X-ray diffractometry (XRD) and Rietveld refinement combined with transmission electron microscopy (TEM), energy-dispersive spectrometry (EDS) and convergent beam electron diffraction (CBED) techniques are used to analyze crystalline phases and their symmetry in Sr0.65Ca0.35TiO3 (SCT35 with x = 0.35) sintered ceramic. The tetragonal (T)- and orthorhombic (O)-phase crystalline mixture at a ratio of approximately 4:1 is found in sintered Sr0.65Ca0.35O3.
Adopting the Buxton-Tanaka-Champness CBED procedures and examining the Gjǿnnes and Moodie (GM) lines enable determining the crystal symmetry to 4/mmm point group and I4/mcm space group for a grain with x = 0.26, and mmm point group and Pbnm space group for a grain with x = 0.31. The paraelectric C-Pm3m → antiferrodistortive T-I4/mcm → antiferroelectric O-Pbnm transition sequence for SCT upon cooling is confirmed, only that for x = 0.26 it stops at the T-phase at room temperature. The discrepancy in Ca-content is accounted for by chemical inhomogeneity in the initial powder prepared via mixed oxides route. The PE C-Pm3m → AFD T-I4/mcm → AFE O-Pbnm transition sequence for SCT upon cooling holds true, but with leaner Ca-content, e.g., x = 0.26, it only arrives at AFD T-I4/mcm.

摘要 I
英文摘要 III
目錄 V
圖目錄 X
表目錄 XXXI
第一章 前言 1
第二章 文獻回顧 3
2.1 鈣鈦礦結構與特性 3
2.2 鈦酸鍶的相變化 6
2.3 Ruddlesden-Popper Phase 9
2.3.2 Ruddlesden-Popper Phase 的面缺陷 13
2.3.3 Ruddlesden-Popper Phase 與鈦酸鍶 (SrTiO3) 之結晶向關係 17
2.4 量子順電性陶瓷 21
2.4.1 古典強電性理論 21
2.4.2 極化與介電常數特性 24
2.4.3 介穩態與量子力學效應 27
2.5 摻雜添加劑之效應 33
2.5.1 殼核結構 (core-shell structure) 33
2.5.2擴散型相變化 (diffuse phase transion, D.P.T.) 40
2.5.3 極化的奈米晶域 (polar nano-region) 44
2.6 同價陽離子添加劑於鈦酸鍶之效應 52
2.6.1 鈦酸鈣摻雜鈦酸鍶之影響 54
2.6.2 相變化引起之晶域結構 73
2.7 斜方晶系的空間群 (space group) 變化 85
2.8 光集束電子繞射圖 (convergent beam electron diffraction) 91
2.8.1 光集束電子繞射圖之原理 91
2.8.2光集束電子繞射圖之種類 96
2.8.3 Gjǿnnes and Moodie (GM) lines 101
第三章 實驗步驟 108
3.1 試片製作 108
3.1.1 原始粉末 108
3.1.2 試片製程 111
3.2 介電性質與溫度變化關係量測 114
3.2.1 整體儀器系統組裝 114
3.2.2 電性量測試片製作 120
3.3 密度量測 122
3.4 X-光繞射分析 (XRD) 123
3.4.1 結晶相分析 123
3.4.2 晶格常數量測 124
3.4.3 Rietveld Refinement 之 Diffracplus-TOPAS 系統 126
3.5 拉曼光譜儀 129
3.6 光學顯微鏡 (Optical Microscope) 130
3.7 掃描式電子顯微鏡 (Scanning Electron Microscopy) 131
3.8 穿透式電子顯微鏡之試片備製 133
3.9 穿透式電子顯微鏡 (Transmission Electron Microscopy) 135
3.9.1 光集束電子繞射圖於點群 (point group) 之解析 136
3.9.2 光集束電子繞射圖於空間群 (space group) 之解析 149
第四章 實驗結果 153
4.1 鈦酸鍶 (SrTiO3) 與 Ruddlesden-Popper結晶向關係 153
4.1.1 X-ray 繞射分析 153
4.1.2 掃描式電子顯微鏡 (SEM) 觀察 160
4.1.2.1 TEM下晶粒形貌觀察 160
4.1.2.2 EDS 定性、定量分析 163
4.1.3 穿透式電子顯微鏡 (TEM) 觀察 165
4.1.3.1 TEM下晶粒形貌觀察 165
4.1.3.2 HR 觀察 166
4.1.3.3 沿 SrTiO3 (001) Kikuchi line tilting 之選區繞射 (SADP) 分析 169
4.1.3.4 Sr3Ti2O7 (116)、(211) 與SrTiO3 之結晶向關係判斷 173
4.2 Ruddlesden-Popper phase的疊差 182
4.3 SrTiO3 與 Ruddlesden-Popper phase界面差排 186
4.4 Sr0.65Ca0.35TiO3 之介電性質 190
4.5 Sr0.65Ca0.35TiO3 之 X-ray 繞射分析 192
4.6 X-ray 繞射光譜於 Rietveld Refinement 結果 195
4.7 Sr0.65Ca0.35TiO3 之拉曼光譜分析 200
4.8 Sr0.65Ca0.35TiO3 之掃描式電子顯微鏡觀察 202
4.9 Sr0.65Ca0.35TiO3 之穿透式電子顯微鏡觀察 206
4.10 Sr0.65Ca0.35TiO3 於穿透式電子顯微鏡之晶粒觀察與化學分析 206
4.10.1 Sr1-xCaxTiO3 (x = 0.26) 之 grain I 觀察 206
4.10.2 Sr1-xCaxTiO3 (x = 0.31) 之 grain II 觀察 210
4.11 光集束電子繞射圖之點群分析 212
4.11.1 Sr0.74Ca0.26TiO3 (grain I) 之點群分析 212
4.11.2 Sr0.69Ca0.31TiO3 (grain II) 之點群分析 232
4.12 光集束電子繞射圖之空間群分析 251
4.12.1 Sr0.74Ca0.26TiO3 之空間群分析 251
4.12.2 Sr0.69Ca0.31TiO3 之空間群分析 255
4.13 Sr0.74Ca0.26TiO3 之相變化衍生微結構變化觀察 259
4.14 Sr0.69Ca0.31TiO3 之相變化衍生微結構變化觀察 266
第五章 結果討論 272
5.1 鈦酸鍶 (SrTiO3) 與 Ruddlesden-Popper結晶向關係 272
5.2 Ruddlesden-Popper phase的疊差 277
5.3 鈣摻雜之鈦酸鍶電性與相結構關係 280
5.4 鈣摻雜之鈦酸鍶試片中產生的不均勻現象 281
5.5 光集束電子繞射圖之模擬對照 282
5.6 鈣摻雜之鈦酸鍶試片中之混合相討論 288
5.7 鈣摻雜之鈦酸鍶試片之相變化討論 297
第六章 結論 303
第七章 未來研究方向 304
參考文獻 306
附錄 319

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