臺灣博碩士論文加值系統

在 本 論 文 中 ， 我 們 利 用 溶 膠 - 凝膠法與固態反應法製備
(Bi0.9Sr0.1)(Fe1-xCox)O3 (x=0, 0.025, 0.05, 0.075, 0.1) 磁電複材，並觀察其
熱膨脹係數、微結構、及介電性質的變化。我們發現當添加第三元素Sr
後對於純BFO的性質有顯著的影響。
BSFCO複材在空氣環境下經650~900 °C的溫度燒結，在相同燒結時
間下，其相對密度皆能達到88%以上。熱膨脹係數溫度量測範圍為20~180
°C，溶膠-凝膠法製備之磁電塊材中，以純BFO有最小之熱膨脹係數，其
值為8.09 ppm/°C﹔最大值為添加Co 10 mol%之磁電塊材，其值為11.65
ppm/°C。在相同組成比例下，其值皆略大於固態反應法製備之複材。
以阻抗分析儀量測介電性質，掃描頻率為100 Hz ~ 40 MHz，在頻率
為40 MHz時，BSFO的介電常數為81.15，其值大於純BFO之53.69，再隨
著Co的添加量增加，值略微下降。在相同頻率下，BSFO磁電塊材的介
電損失為0.16，其值小於純BFO之0.35。在相同組成比例下，其值皆略小
於固態反應法製備之複材。
利用網路分析儀作高頻量測，掃描頻率為6 ~ 13 GHz，溶膠-凝膠法
及固態反應法製備之複材添加Co 2.5 mol%時，在掃描頻率7 GHz下，分
別有最大介電常數值5.36及5.49。

In this study, we reported on the thermal expansion coefficients,
microstructural and dielectric properties of (Bi0.9Sr0.1)(Fe1-xCox)O3 (x=0,
0.025, 0.05, 0.075, 0.1) magnetoelectric composites prepared by sol-gel
method and solid state method. Doping Sr has a strong influence on the
properties of BSFCO composites.
The thermal expansion coefficients were measured under an air
atmosphere from 20 to 180 °C. The thermal expansion coefficient of pure
BFO prepared by sol-gel method has a minimum value of 8.09 ppm/°C.
Nevertheless, the BSFCO composites doping 10 mol% Co has a maximum
value of 11.65 ppm/°C.
The dielectric properties were measured by impedance analyzer in the
frequency range from 100 Hz to 40 MHz. The dielectric constant of BSFO
ceramic is 81.15, which is higher than that of pure BFO of 53.69 at 40 MHz.
However, dielectric constant of BSFCO decreases with increasing Co%. The
dielectric loss of BSFO ceramic is 0.16, which is lower then that of pure
BFO of 0.35 at 40 MHz. The dielectric loss of BSFCO decreases with
increasing Co%.
The permittivities were measured by network analyzer in the frequency
range from 6 to 13 GHz.
The BSFCO composites of doping 2.5 mol% Co have maximum values
of 5.36 and 5.49 at 7 GHz which were prepared by sol-gel and solid state
methods, respectively.

目錄
摘要 ....................................................................... I
ABSTRACT .................................................................. II
目錄 ...................................................................... III
圖目錄 ..................................................................... VI
表目錄 ..................................................................... IX
第一章 緒論.................................................................. 1
1-1 前言 ................................................................... 1
1-2 研究目的與動機 ........................................................... 2
第二章 文獻回顧 .............................................................. 3
2-1 介電材料 ................................................................ 3
2-1-1 鈣鈦礦材料特性 ......................................................... 3
2-1-2 極化機構 (polarized mechanism) ......................................... 7
2-1-3 介電性質 .............................................................. 11
2-2 磁性材料 ................................................................ 15
2-2-1 磁性原理 .............................................................. 15
2-2-2 磁性分類 .............................................................. 19
2-2-3 磁性性質 .............................................................. 22
2-3 鉍鐵氧(BiFeO3)的基本性質 ................................................. 24
2-3-1 晶體結構 .............................................................. 25
2-3-2 鐵電性質 .............................................................. 27
2-3-3 磁性質 ................................................................ 28
2-4 溶膠-凝膠法 (sol-gel method) ............................................ 30
2-5 固態反應法 (solid state method) ......................................... 34
第三章 實驗方法及設備 ......................................................... 37
3-1 實驗藥品 ................................................................ 41
3-2 粉體之製備 ............................................................... 42
3-2-1 溶膠-凝膠法製備粉體 ..................................................... 42
3-2-2 固態反應法製備粉體 ...................................................... 42
3-3 磁電塊材之製備 ........................................................... 43
3-4 性質測量與分析 ........................................................... 45
3-4-1 塊材密度量測 ........................................................... 45
3-4-2 X 光繞射分析儀 ( XRD) .................................................. 45
3-4-3 掃描式電子顯微鏡 ( SEM) ................................................. 45
3-4-4 熱機械分析儀 ( TMA) .................................................... 46
3-4-5 介電性質量測 ............................................................ 46
3-4-6 微波性質量測 ............................................................ 46
第四章 結果與討論 .............................................................. 47
4-1 密度測量 .................................................................. 47
4-2 XRD 結構分析 .............................................................. 50
4-3 斷面微結構 ................................................................ 54
4-4 熱性質分析 ................................................................ 61
4-5 介電性質分析 .............................................................. 63
4-6 微波訊號分析 .............................................................. 75
第五章 結論.................................................................... 77
5-1 溶膠-凝膠法 ............................................................... 78
5-2 固態反應法 ................................................................ 80
第六章 參考文獻 ................................................................ 82
附錄 .......................................................................... 87
圖目錄
圖 2.1 鈣鈦礦結構 ............................................................... 5
圖2.2 鈦酸鋇於(100)方向極化時，鈦離子相對於氧離子的位移量 ........................... 5
圖2.3 隨溫度的改變，鈦酸鋇結構晶體上的變化 ......................................... 6
圖2.4 極化的四種物理機制 ......................................................... 9
圖2.5 不同頻率對不同極化機構之介電常數及介電損失的影響 .............................. 10
圖2.6 室溫下，離子遷移損失、離子震動與變形損失在tan δ 中所佔的比例.................... 14
圖2.7 電子之軌道角動量與軌道磁矩 .................................................. 17
圖2.8 電子之自旋角動量與自旋磁矩 .................................................. 17
圖2.9 磁交互作用力 .............................................................. 18
圖2.10 磁滯曲線 ................................................................. 23
圖2.11 BiFeO3 結構圖 ............................................................ 26
圖2.12 BiFeO3 溫度分布圖 ......................................................... 26
圖2.13 BiFeO3 六方晶的自旋結構 .................................................... 29
圖2.14 溶膠凝膠法變化示意圖 ........................................................ 33
圖2.15 溶膠-凝膠法的反應程序 ....................................................... 33
圖2.16 不同轉速下，磨球在罐中運動的情形 ............................................. 36
圖3.1 溶膠-凝膠法製作磁電塊材與薄膜流程圖 ........................................... 38
圖3.2 固態反應法製作磁電塊材流程圖 .................................................. 39
圖3.3 BSFCO 塊材性質量測流程圖 ..................................................... 40
圖4.1 溶膠-凝膠法和固態反應法添加不同比例Co 相對密度關係圖 ............................. 49
圖4.2 標準BiFeO3 XRD 繞射圖譜 ...................................................... 52
圖4.3 溶膠-凝膠法Co 添加比例之XRD 量測結果 ........................................... 52
圖4.4 固態反應法Co 添加比例之XRD 量測結果 ............................................ 53
圖4.5 溶膠-凝膠法添加不同mol%比例Co 之磁電塊材SEM 微結構圖 ，放大倍率為3000 倍 .......... 56
圖4.6 固態反應法添加不同mol%比例Co之磁電塊材SEM微結構圖，放大倍率為3000 倍 .............. 57
圖4.7 溶膠-凝膠法添加不同mol%比例Co 之磁電塊材SEM 微結構圖 ，放大倍率為10000 倍 ......... 58
圖4.8 固態反應法添加不同mol%比例Co之磁電塊材SEM微結構圖，放大倍率為10000 倍。 ........... 59
圖4.9 不同Co 添加比例的BSFCO 磁電塊材之熱膨脹係數變化圖 ............................... 62
圖4.10 溶膠-凝膠法添加不同比例Co 之磁電塊材之介電常數對頻率變化圖 ....................... 64
圖4.11 固態反應法添加不同比例Co 之磁電塊材之介電常數對頻率變化圖 ........................ 64
圖4.12 溶膠-凝膠法添加不同比例Co 之磁電塊材之介電損失對頻率變化圖 ....................... 66
圖4.13 固態反應法添加不同比例Co 之磁電塊材之介電損失對頻率變化圖 ........................ 66
圖4.14 磁電塊材在10 MHz 時介電常數比較圖 ............................................. 69
圖4.15 磁電塊材在40 MHz 時介電常數比較圖 ............................................. 69
圖4.16 磁電塊材在10 MHz 時介電損失比較圖 ............................................. 71
圖4.17 磁電塊材在40 MHz 時介電損失比較圖 ............................................. 71
圖4.18 溶膠-凝膠法添加不同比例Co 之磁電塊材之低損耗對頻率變化圖 ......................... 74
圖4.19 固態反應法添加不同比例Co 之磁電塊材之低損耗對頻率變化圖 .......................... 74
圖4.20 溶膠-凝膠法製備之磁電塊材在高頻下，介電常數差的變化圖............................. 76
圖4.21 固態反應法製備之磁電塊材在高頻下，介電常數差的變化圖.............................. 76
表目錄
表 2-1 磁性分類表 .................................................................. 21
表2-2 BiFeO3 摻雜之第三元素及其修飾性質 .............................................. 24
表3-1 溶膠-凝膠法BSFCO 塊材添加Co mol%比例與燒結溫度關係 ...............................44
表3-2 固態反應法BSFCO 塊材添加Co mol%比例與燒結溫度關係 ............................... 44
表4-1 溶膠-凝膠法與固態反應法磁電塊材之平均粒徑大小 .................................... 60

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