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研究生:李健銘
研究生(外文):Chien-ming Lee
論文名稱:以溶膠-凝膠法製備鈮摻雜鈦酸鉍鐵電薄膜之特性研究
論文名稱(外文):The Properties of Nb-dope Bismuth Titanate Ferroelectric Thin films prepared by the Sol-Gel Processes
指導教授:陳宏仁陳宏仁引用關係
指導教授(外文):Hone-Zern Chen
口試委員:高銘政黃俊達陳宏仁
口試日期:2009-07-08
學位類別:碩士
校院名稱:修平技術學院
系所名稱:電機工程研究所
學門:工程學門
學類:電資工程學類
論文種類:學術論文
論文出版年:2009
畢業學年度:97
語文別:中文
論文頁數:72
中文關鍵詞:鐵電薄膜快速熱處理溶膠-凝膠法
外文關鍵詞:rapid thermal annealingsol-gel methodferroelectric
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本研究以溶膠-凝膠法及快速熱處理技術製備鈮(Nb)摻雜鈦酸鉍[Bi4Ti3-yNbyO12鐵電薄膜,簡稱BTNO] 鐵電薄膜,以旋轉塗佈法將薄膜沈積於Pt/Ti/SiO2/Si(100)基板上,改變鈮(Nb)元素的摻雜濃度(y= 0、0.02、0.04、0.06、0.08、0.1)及熱處理溫度(500~800 oC),探討不同製程參數對BTNO鐵電薄膜之晶體結構、晶粒大小、漏電流特性、介電特性及鐵電特性之影響。
實驗結果顯示,薄膜中鈮(Nb)含量濃度會直接影響到BTNO薄膜的晶體結構及鐵電特性。在結晶特性方面,BTNO薄膜之(117)軸優選排向強度比例值y=0.04時會有最大值為0.91,且鈮(Nb)摻雜濃度y=0.04時,在外加電場E=100 kV/cm下,具有最小之漏電流密度為J=6.14×10-9 A/cm2,同時在鐵電特性方面,在y=0.04時具有最佳之鐵電特性,其殘留極化量Pr及矯頑電場Ec分別2Pr=33 μC/cm2、2Ec= 160 kV/cm。這是因為BTNO薄膜中4價之Ti4+ 離子被5價之Nb5+ 離子所取代,使薄膜產生多餘電子補償氧空缺濃度,且(117)軸排向是最靠近極化軸之排向,故Bi4Ti2.96Nb0.04O12薄膜具有最佳之鐵電特性,最適合於非揮發性鐵電記憶體之應用。
In this study, the Bi4Ti3-yNbyO12 (BTNO) ferroelectric thin films with various Nb-dope contents were prepared by sol-gel method and heated by rapid thermal annealing (RTA).The BTNO thin films were deposited on Pt/Ti/SiO2/Si(100) substrate by spin coating. The concentrations of Nb(y=0, 0.02, 0.04, 0.06, 0.08, 0.1)and heattreatments temperature (500 ℃, 600 ℃, 700 ℃ and 800 ℃), studied the BTNO ferroelectric thin films that effected to crystal structure, dielectric, leakage current and ferroelectric properties in different conditions.
The experimental results, the Nb concentrations effected to BTNO thin films crystal structure and ferroelectric properties. In crystal structure aspect, (117) orientation of BTNO thin films to intensitying proportion value when y=0.04 have the maximum value for ?=0.91. In elevated cycling field E=100 kV/cm that had the leakage current J=6.14×10-9 A/cm2. The ferroelectric properties had better property at the concentration of y=0.04. The remanent polarization (2Pr) of 33 μC/cm2 and coercive field (2Ec) of 160 kV/cm respectively. Because the valence of BTNO thin films Nb5+ substituted for Ti4+ ions , the extra electrons atone for oxygen vacant concentration. The (117) orientation of crystal structure approach the polarized orientation furthermore. Therefore Bi4Ti2.96Nb0.04O12 had better ferroelectric properties, to agree application to the non-volatile ferroelectric memory.
中文摘要 …………………………………………………………………………................ Ⅰ
英文摘要 …………………………………………………………………………................ Ⅱ
誌謝 …………….................................................................................................................... Ⅲ
目錄 …………….................................................................................................................... Ⅳ
表目錄 ……………................................................................................................................ Ⅵ
圖目錄 ……………................................................................................................................ Ⅶ
第一章 前言 .......................................................................................................................... 1
第二章 文獻回顧與理論分析 .............................................................................................. 4
2-1 鐵電記憶體的原理 .................................................................................................... 4
2-2 鈣鈦礦結構 ................................................................................................................ 4
2-3 鉍層鈣鈦礦結構特性 ................................................................................................ 5
2-4摻雜鉍(Bi)或鈦(Ti)對薄膜之影響 ............................................................................ 6
2-5 鐵電材料特性 ............................................................................................................ 6
2-5-1介電極化和極化理論 .......................................................................................... 6
2-5-2 鐵電性質 ............................................................................................................ 8
2-5-3漏電流理論 .......................................................................................................... 8
2-6薄膜製備方法 .............................................................................................................. 9
2-6-1-1 濺鍍原理 .......................................................................................................... 9
2-6-1-2 直流輝光放電 .................................................................................................. 9
2-6-1-3 磁控射頻濺射 .................................................................................................. 10
2-6-1-4 反應性濺射 ...................................................................................................... 10
2-6-2 雷射剝鍍法 ........................................................................................................ 11
2-6-3 有機金屬化學氣相沈積法 ................................................................................ 11
2-6-4 金屬有機分解法 ................................................................................................ 12
2-6-5溶膠-凝膠法 ........................................................................................................ 12
2-6-5-1 調製起始溶液 .................................................................................................. 13
2-6-5-2 薄膜製作方式 .................................................................................................. 13
2-7 低溫焦化處理 ............................................................................................................ 14
2-8 高溫結晶熱處理 ........................................................................................................ 14
第三章 實驗方法與步驟 ...................................................................................................... 26
3-1 Bi4Ti3-yNbyO12溶液調配 ............................................................................................ 26
3-2 Pt/Ti/SiO2/Si基板清洗 ................................................................................................ 26
3-3薄膜的製作 .................................................................................................................. 27
3-3-1 BTNO之薄膜披覆 .............................................................................................. 27
3-3-2 熱處理 ................................................................................................................ 27
3-4 MFMS結構之製作 .................................................................................................... 28
3-5鐵電薄膜特性分析 .................................................................................................... 28
3-5-1 X光繞射儀(X-Ray Diffraction, XRD ) ............................................................ 28
3-5-2 掃描式電子顯微鏡(Scanning Electron Microscopy,SEM)分析 ........................ 28
3-6 Pt/BTNO/Pt鐵電電容元件之電性量測 .................................................................... 29
3-6-1 介電特性 ............................................................................................................ 29
3-6-2 漏電流特性 ........................................................................................................ 29
3-6-3 電滯曲線P-E特性 .............................................................................................. 29
第四章 實驗結果與討論 ...................................................................................................... 34
4-1膜厚分析 …………………………………………………………………………….. 34
4-2 X光繞射儀(XRD)分析 …………………………………………………………… 34
4-3薄膜表面結構(SEM)分析 ………………………………………………………….. 35
4-4電性量測 …………………………………………………………………………….. 36
4-4-1介電常數-頻率特性分析(C-F特性曲線) ……………………………………… 36
4-4-2介電損失-頻率特性分析(Loss Tangent-F特性曲線) ………………………… 36
4-4-3電滯曲線特性分析 ..…………………………………………………………… 37
4-4-4漏電流特性分析 ……………………………………………………………...... 40
第五章 結論 ……………………………………………………………………………….. 54
參考文獻 …………………………………………………………………………………… 55
參與論文發表 …………………………………………………………………………….... 59
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