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研究生:蔡柏舟
研究生(外文):Tsai-po Chou
論文名稱:利用sol-gel法製備鐵酸鉍薄膜及不同燒結條件對鐵酸鉍薄膜性質之影響
論文名稱(外文):Preparation of BiFeO3 thin films by sol-gel method and the effects of different sintering conditions
指導教授:齊孝定
指導教授(外文):Qi-xiao ding
學位類別:碩士
校院名稱:國立成功大學
系所名稱:材料科學及工程學系碩博士班
學門:工程學門
學類:材料工程學類
論文種類:學術論文
畢業學年度:96
語文別:中文
論文頁數:125
中文關鍵詞:鐵酸鉍溶膠-凝膠法
外文關鍵詞:sol-gelmultiferroics
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本實驗是利用sol-gel法製備複鐵式薄膜BiFeO3和氧化物電極材料LaNiOx,由於BiFeO3 目前最大的問題就是在室溫下漏電流太大,而限制其應用的價值。因此本論文欲藉由改變BiFeO3的製程參數,希望降低BiFeO3的漏電流,所以分別探討在不同的退火溫度、不同的退火持溫時間、不同的退火氣氛下,對BiFeO3薄膜所造成的影響。
實驗結果發現,在空氣中700 oC 持溫一小時,會得到最佳的LaNiOx電極薄膜。 而純相BiFeO3可在較低的溫度450 oC,於Ar氣中退火合成。BFO若在550oC,Ar氣中退火5min,發現會有雜相Bi2Fe4O9形成,但在較長的燒結時間(20min),此雜相即會消失。而由於Bi2Fe4O9在650 oC較長持溫時間下(20min)退火仍會存在,因此推測Bi2Fe4O9 有可能是一個高溫相。此外,雜相Bi2Fe4O9似乎在高氧分壓下更穩定,因為薄膜在O2及空氣中,550 oC退火20min,仍可發現Bi2Fe4O9的存在。
測量電壓-電流(I-V)曲線,發現在450 oC、500oC、550oC退火的薄膜其I-V曲線符合冪指數的關係,由此推測導電機制可能屬於Space charge limited conduction。
XPS測量發現,在550oC不同氣氛下退火的BiFeO3,薄膜中的Bi原子與Fe原子之比皆略小於一,這很有可能就是造成薄膜漏電流過大導致無法獲得飽和電滯曲線的主要原因。
In this study, we used sol-gel method to prepare multiferroic material BiFeO3 and the bottom electrode material LaNiOx. Currently, leakage current is one of the main problems preventing BiFeO3 from practical application. Therefore, the aim of the study was to identify how the preparation parameters, such as sintering temperature, time and atmosphere, change the leakage currents of the grown films.
The experimental results showed that the LaNiOx films of highest conductivity were prepared at 700oC in air for 1hr, while pure BiFeO3 could be obtained at the temperature as low as 450 oC in flowing Ar. An impurity phase Bi2Fe4O9 (PDF card﹟72-1832) started to occur at 550 oC for a short sintering time (5 min) in Ar, but disappeared after prolonged sintering (20 min). This compound seemed to be a high temperature phase, because it persisted for a much longer sintering time(20 min) at 650 oC. This compound was more stable in higher PO2, as it still existed at 550 oC in flowing oxygen and air after sintering for 20 min.
The I-V curve measurements showed that all the films annealed in flowing Ar at 450 oC、500oC、550oC had the power law behavior, indicating the conduction mechanism might be space charge limited.
XPS analysis showed that there was a small deficiency of Bi for all the films sintered at 550 C in air, Ar and O2. This might be the main reason for the large leakage currents observed in these films, which prevented them to obtain a saturated ferroelectric hysteresis loop.
目 錄
摘要...................................I
Abstract...............................II
誌謝...................................IV
目錄...................................V
表目...................................VIII
圖目錄.................................IX

第一章 緒論
1-1 前言..................................1
1-2 研究動機及方向........................3

第二章 理論基礎及前人研究
2-1 溶膠-凝膠法...........................4
2-1-1 溶膠-凝膠法的簡介...................4
2-1-2 溶膠-凝膠法製備原理.................5
2-1-3 溶膠-凝膠法的優缺點.................6
2-1-4 溶膠-凝膠法鍍膜.....................7
2-1-5 低溫乾燥及退火熱處理................9

2-2 鈣鈦礦型鐵電材料.....................10
2-3 鐵電滯迴曲線及壓電性.................13
2-4 極化機制與極化頻率...................19
2-5 磁性物質分類.........................22
2-6 漏電流機制與漏電流密度...............25
2-7 LaNiO3下電極.........................29

2-8 複鐵式材料BiFeO3特性介紹.............32
2-8-1 BiFeO3的晶體結構...................33
2-8-2 BiFeO3的鐵電性質...................36
2-8-3 BiFeO3製程方法文獻回顧.............38

第三章 實驗方法與步驟
3-1 實驗材料.............................42
3-1-1 實驗藥品...........................42
3-1-2 實驗設備...........................42
3-1-3 基板(Substrate)..................43
3-2 實驗流程圖...........................44
3-2-1 LaNiO3 製作、測試流程圖............44
3-2-2 BiFeO3 製作、測試流程圖............45

3-3 溶液調配.............................46
3-3-1下電極LaNiO3溶液配製................46
3-3-2 BiFeO3溶液配製.....................47

3-4 旋轉塗佈法成膜.......................49
3-5 薄膜退火熱處理.......................50
3-6 分析儀器.............................51
3-6-1 X光粉末繞射儀......................51
3-6-2 低掠角薄膜繞射儀...................54
3-6-3 場發式掃瞄電子顯微鏡(Fe-SEM).....57
3-6-4 原子力顯微鏡(Atomic Force Microscopy,AFM). .....57
3-6-5 光電子能譜分析儀(XPS) ……………….59
3-6-6 電性測量...........................60


第四章 結果與討論
4-1 LaNiOx下電極性質研究................61
4-1-1 XRD結構分析....................... 61
4-1-2 顯微結構SEM分析....................70
4-1-3 LaNiOx 電阻率測量..................74

4-2 不同退火溫度對BiFeO3薄膜性質的影響........75
4-2-1 XRD結構分析..............................75
4-2-2 SEM顯微結構分析..........................80
4-2-3 表面形貌AFM分析..........................85
4-2-4 薄膜電性分析.............................88
4-2-5 漏電流分析...............................91

4-3 不同退火持溫時間對BiFeO3薄膜性質的影響....94
4-3-1 XRD結構分析..............................94
4-3-2 SEM顯微結構分析..........................96
4-3-3 薄膜電性分析.............................100
4-3-4 漏電流分析...............................103

4-4 不同退火氣氛對BiFeO3薄膜性質的影響.......105
4-4-1 XRD結構分析..............................105
4-4-2 SEM顯微結構析............................107
4-4-3 XPS 分析.................................110
4-4-4 薄膜電性分析.............................111
4-4-5 漏電流分析...............................112
第五章 結論....................................114
文獻參考.......................................115
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