臺灣博碩士論文加值系統

本實驗以射頻濺鍍法生長鉍釹鈦(Bi,Nd)4Ti3O12 (BNT)薄膜，探討O2/Ar流量比、氧化鉍緩衝層、鎢摻雜及佈植磷(P+)和硼(BF2+)離子對其鐵電性質及微結構的影響。當O2/Ar流量比在1:9~1:1.5之間，殘餘極化量隨著O2/Ar流量比增加而增加，直至O2/Ar流量1.5:1以上，由於晶粒尺寸變小則2Pr有隨之遞減的趨勢。對於摻雜鎢的BNT（BNTWx）薄膜而言，隨著W含量增加至x=0.005-0.1其2Pr有稍微增加，而超過x=0.03則2Pr明顯下降。這代表摻雜鎢將對BNT薄膜的2Pr值造成兩種相反的效應（1）減少氧缺陷的數量（2）晶粒尺寸變小。有Bi2O3緩衝層的BNT薄膜，會由於Bi2O3模板效應和（001）BNT/Pt低界面能因素而促進c軸優選方向生長，造成小的2Pr。佈植P+和 BF2+的BNT薄膜在佈植劑量1x1015~5x1015/cm2範圍內，由於晶粒變小其2Pr普遍下降。然而，佈植BF2+離子劑量為1x1015/cm2的BNT薄膜，其2Pr有稍微增加，可能是晶界或晶域壁（domain wall）中的缺陷被摻雜物BF2+離子消除，緩和了由電荷捕獲（charge trapping）所造成的釘札（pinning）效應。

Effect of O2/Ar ratio, buffered Bi2O3 layers, W doping, and P+ and BF2+ implantation on the ferroelectricity and microstructures of radio-frequency sputtered (Bi,Nd)4Ti3O12 (BNT) films were studied. The remanent polarization (2Pr) increased with the O2/Ar ratio in the range of 1:9-1:1.5 and then decreased with the ratio larger than 1.5:1 because of the reduction of grain size. For W-doped BNT (BNTWx) films the 2Pr slightly increased with the W concentration in the range of x=0.005-0.01, and then remarkably decreased with the W concentration larger than x=0.03. W doping induces two contrary effects on 2Pr, i.e., reducing the amount of oxygen vacancies and decreasing the grain size. The buffered Bi2O3 layers enhanced the c-axis-oriented growth of BNT films due to the template effect and the lower interfacial energy of (001)BNT/Pt, resulting in the smaller 2Pr. For the P+- and BF2+- implanted BNT films the 2Pr generally decreased with the doses in the range of 1x1015-5x1015 /cm2 due to the reduction of the grain size. However, for the BF2+-implanted BNT films the 2Pr slightly increased at the does of 1x1015/cm2. It is suggested that the defects present in the grain boundaries or the domain walls can be annihilated by the BF2+ dopants alleviating the effect of domain walls pinning due to charge trapping.

本 文 目 錄
中文摘要……………………………………………………………Ⅰ
英文摘要……………………………………………………………Ⅱ
誌謝感言……………………………………………………………Ⅲ
本文目錄……………………………………………………………Ⅳ
表目錄………………………………………………………………Ⅵ
圖目錄………………………………………………………………Ⅵ
本 文
第一章 簡介……………………………………………………………………1
1. 前言……………………………………………………………………………1
1-1. 電子記憶體……………………………………………………………………1
1-2. 鐵電材料………………………………………………………………………3
1-3. 鐵電材料之基本結構…………………………………………………………5
2. 基本理論………………………………………………………………………...…7
2-1. 極化原理………………………………………………………………………7
2-2. 脈衝極化（pulse polarization）及疲勞（fatigue）量測原理…………………10
2-3. 鐵電記憶體…………………………………………………………………..11
3. 儀器操作原理………………………………………………….…………………12
3-1. 射頻（RF）濺鍍法（Radio-frequency sputtering）…………………………12
3-2. 電子槍蒸鍍系統……………………………………………………..………13
3-3. RT66A電滯曲線量測原理………………………………………….……..14
4. 研究理論基礎與動機……………………………………………………………15
4-1. PZT鐵電薄膜………………………………………………………………...16
4-2. SBT鐵電薄膜………………………………………………………….……17
4-3. BTO與BLT鐵電薄膜………………………………………………………18
4-4. BNT鐵電薄膜………………………………………………………………20
4-5. 以高價陽離子摻雜之鐵電薄膜……………………………………………..20
4-6. 有Bi2O3緩衝層對鐵電薄膜的影響………………………………………22
4-7. 磷和硼對鐵電薄膜的影響……………………………………………23
4-8. 本實驗研究動機─BNT鐵電薄膜………………………………………..24
第二章 實驗步驟與方法…………………………………………………………25
1. 實驗流程圖……………………………………….………………………………25
2. 粉末配置與靶材燒結……………………………………………….……………26
3. 基板（底電極）Pt/Ta/SiO2/Si製備─電子槍蒸鍍系統…………….……………26
4. BNT鐵電薄膜製備─射頻濺鍍系統…………………………………………….27
4-1. 離子佈植（ion implantation）………………………………………………27
4-2. 製備Bi2O3緩衝層…………………………………………………….……..28
5. 上電極製作─電子槍蒸鍍系統………………………………………….………29
6. 退火─管形爐…………………………………………………………….………29
7. 鐵電性質量測與分析………………………………………………….…………29
7-1. 結晶相鑑定─XRD……………………………………………….…………29
7-2. 成分分析─RBS…………………………………………………….…….…30
7-3. 薄膜厚度測定─α-step…………………………………………….………..31
7-4. 電滯曲線（P-E curve）及疲勞（fatigue）曲線量測─RT66A ……….……32
7-5. SEM及TEM觀察…………………………………………………….…..…32
第三章 結果與討論………………………………………………………………33
1、以不同氧流量鍍製BNT薄膜……………………………………………..……33
2、摻雜鎢（W）對BNT薄膜鐵電性質之影響……………………………….……35
3、Bi2O3緩衝層對BNT薄膜的影響………………………………………….……39
4、離子佈植硼或磷對BNT薄膜鐵電性質之影響………………………..….……44
5、不同Nd含量之BNT薄膜鐵電性質之影響…………………………………..…46
5-1. RBS成分分析………………………………………………………………...46
5-2. 分析BNT薄膜鐵電性質……………………………………………………47
5-3. 摻雜釩（V）對BNT薄膜鐵電性質之影響…………………………….…50
第四章 結論………………………………………………………………………..51
參考文獻……………………………………………………………………………..53

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