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研究生:賴吉泰
研究生(外文):Chi-tai Lai
論文名稱:錳離子摻雜對BiFeO3薄膜之材料性質及顯微結構的影響
論文名稱(外文):Effects of Mn doping on the materials properties and microstructure of BiFeO3 thin films
指導教授:齊孝定
指導教授(外文):Xiao-ding Qi
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:76
中文關鍵詞:鐵酸鉍複鐵式材料
外文關鍵詞:multiferroicBiFeO3
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本研究是利用Sol-gel法配製BiFe1-xMnxO3 (X=0.0 to x=0.15)薄膜分別成長在Si (100)和Pt/TiO2/SiO2/Si基板上。添加Mn至BiFeO3的動機為能夠找出具有高轉變溫度的鐵電性與鐵磁性之複鐵式材料。
本研究使用低掠角x光繞射儀、x光光電子能譜儀、掃描式電子顯微鏡、震動樣品量測儀、等儀器來進行量測與分析。
當Mn摻雜至BiFeO3 的主要影響,其包括下列:
(1)Mn 是以Mn3+價態存在
(2)當未添加Mn(X=0.0)時,Fe的價態以Fe2+ -Fe3+共存;當添加Mn至BiFeO3時,Fe幾乎是以Fe 3+存在
(3)當Mn摻雜至BiFeO3時,隨著Mn添加量上升,晶粒大小隨之下降。
(4)在BiFe1-xMnxO3 (X=0.0 5 to X=0.15)薄膜,觀察有一些磁矩,此磁矩隨著Mn添加量增加而上升。然而,平均每個Mn離子所具有的磁矩卻隨著Mn添加量增加而下降,這意謂著此磁矩可能不是來自任何含Mn 之雜相的貢獻。
In this study, mixed BiFe1-xMnxO3 films with x=0 to 0.15 have been grown on the Si(100) and Pt/Ti/SiO2/Si substrates by the sol-gel method. The motive of adding Mn into BiFeO3 was to develop new ferroelectric ferromagnetic (multiferroic) materials with high transition temperatures.
The grown films were characterized by the x-ray diffraction, X-ray photoelectron spectroscopy, scanning electron spectroscopy, vsm, etc. The main findings about the effects of the Mn incorporation into BiFeO3 are summarized as follow:
(1) Mn dopant had 3+ valence.
(2) While pure BiFeO3 (i.e. x=0.0) films might include certain amount of Fe2+, in the Mn doped films Fe existed mostly in 3+.
(3) The grain size of BiFe1-xMnxO3 films decreased as the increase of the Mn amount.
(4) BiFe1-xMnxO3 films showed some magnetic moment, which was increasing as the Mn content increased. However, the magnetic moment per Mn ion reduced as the Mn doping level increased, implying that the magnetic moment did not come from any possible Mn-containing impurity phase.
中文摘要........................................................................................................I
Abstract....................................................................................................... II
總目錄.........................................................................................................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....................................................................................................3
第二章 文獻回顧.................................................................................................5
2-1 材料的極化 [9-11]...........................................................................................5
2-2鐵電性質.....................................................................................................11
2-2-1自發性極化(spontaneous polarization)[11]...................................................................11
2-2-2 鐵電滯曲線[11]............................................................................................13
2-3 磁性的產生..................................................................................................15
2-4 磁性的種類[12]..............................................................................................16
2-5 磁滯曲線[11]...............................................................................................20
2-6 Perovskite 結構............................................................................................23
2-7 BiFeO3的晶體結構...........................................................................................25
2-8 BiFeO3鐵電性質.............................................................................................27
2-9 BiFeO3磁性質...............................................................................................29
第三章 實驗方法與步驟...........................................................................................32
3-1 實驗材料與配製.............................................................................................32
3-3 薄膜的鍍製.................................................................................................35
3-4 薄膜退火熱處理.............................................................................................36
3-5 分析儀器...................................................................................................37
3-5-1 膜厚量測 (α-step).........................................................................................37
3-5-2 表面粗糙度量測 (AFM)......................................................................................39
3-5-3 晶體結構(低掠角X光薄膜繞射儀).............................................................................41
3-5-4高解析電子能譜儀(ESCA-XPS).................................................................................43
3-5-5場放射型掃描式電子顯微鏡(FESEM)............................................................................45
3-5-6 振動樣品磁力儀 Vibrating Sample Magnetometer(VSM).........................................................46
第四章 實驗結果與討論...........................................................................................49
4-1 晶體結構....................................................................................................49
4-2 薄膜厚度....................................................................................................53
4-3 表面粗糙度之量測............................................................................................54
4-4 化學鍵結 ESCA/XPS...........................................................................................56
4-5 FESEM顯微組織...............................................................................................62
4-6 磁滯曲線M-H 量測............................................................................................65
第五章 結論.....................................................................................................70
參考文獻........................................................................................................72



圖目錄
圖2-1 四種極化機構之示意圖[10].................................................................................8
圖2-2 電子極化與原子價數之示意圖...............................................................................9
圖2-3 頻率影響極化機構的介電常數和介電損失之示意圖[10].........................................................10
圖2-4 典型的電滯曲線[12].......................................................................................14
圖2-5 磁偶極的產生[12].........................................................................................15
圖2-6 順磁性磁偶極排列[12].................................................................................... 18
圖2-7 鐵磁性材料磁偶極排列和磁區[12]...........................................................................18
圖2-8 亞鐵磁性的磁偶極排列[12].................................................................................19
圖2-9 反鐵磁性的磁偶極排列[13].................................................................................19
圖2-10 典型的磁滯曲線...........................................................................................22
圖2-11 為一典型軟磁與硬磁材料的磁滯曲線.........................................................................22
圖2-12 ABO3鈣鈦礦(perovskite)結構.............................................................................. 24
圖2-13 於週期表上適合Perovskite 結構的元素[16]..................................................................24
圖2-14 BiFeO3 六方晶原子排列示意圖[17]..........................................................................26
圖2-15 BiFeO3菱形晶與正方晶的原子排列示意圖[18].................................................................26
圖2-16 Perovskite結構發現有七種不同的磁化結構...................................................................30
圖2-17 BiFeO3六方晶的自旋結構[26].............................................................................. 31
圖3-1 BiFe1-xMnxO3 sol-gel 配製流程圖......................................................................... 33
圖3-2 基板清洗流程圖.......................................................................................... 34
圖3-3 為退火熱處理流程圖...................................................................................... 36
圖3-4 (a) BiFe1-xMnxO3 PtTiO2SiO2Si (b) BiFe1-xMnxO3 Si 測量α-step試片膜厚準備前要先遮蔽一小角示意圖......37
圖3-5 α-step 是利用探針探測此凹陷的圓點的高度差來判斷其膜厚....................................................38
圖3-6 AFM示意圖............................................................................................... 40
圖3-7 低掠角X光薄膜繞射儀示意圖............................................................................... 42
圖3-8 化學分析電子儀之基本原理[28]............................................................................ 44
圖3-9 VSM示意圖............................................................................................... 48
圖4-1 BiFe1-xMnxO3 (x=0.0、0.05、0.1、0.15) Si的低銳角X-ray 比較圖........................................... 51
圖4-2 BiFe1-xMnxO3(x=0.0、0.05、0.1、0.15)PtTiO2SiO2Si的低掠角X-ray 比較圖................................ 52
圖4-3 (a)BiFeO3(x=0.0)/Si;(b) BiFe0.85Mn0.15O3(x=0.15)/Si;(c) BiFeO3(x=0.0)/Pt;(d)BiFe0.85Mn0.15O3(x=0.15)/
Pt之AFM表面形貌......................................................................................... 55
圖4-4 Bi 4f能譜圖:(a) x=0.0(BiFeO3);(b) x=0.15(BiFe0.85Mn0.15O3)............................................. 59
圖4-5 Fe 2p 能譜圖:(a)為x=0.0(BiFeO3);(b) x=0.15(BiFe0.85Mn0.15O3)........................................... 60
圖4-6 Mn 2p 能譜圖: x=0.15(BiFe0.85Mn0.15O3).................................................................. 61
圖4-7 BiFe1-xMnxO3/Si之SEM觀察: (a)x=0.0;(b)x=0.05;(c)x=0.1;(d)x=0.15...................................... 63
圖4-8 BiFe1-xMnxO3/Pt之SEM觀察: (a)x=0.0;(b)x=0.05;(c)x=0.1;(d)x=0.15...................................... 64
圖4-9 BiFe1-xMnxO3 (x=0.0、0.05、0.1、0.15)/Si之M-H磁滯曲線圖........................................... 67
圖4-10 BiFe1-xMnxO3 (x=0.0、0.05、0.1、0.15)/Si在室溫下之磁滯曲線圖:(a)μB/Fe與H磁滯曲線圖;(b)μB/Mn與H磁滯
曲線圖.................................................................................................. 68
圖4-11 BiFe1-xMnxO3 /Pt之M-H磁滯曲線圖: (a)x=0.0;(b)x=0.05;(c)x=0.1;(d)x=0.15............................... 69

表目錄
表3-1 BiFe1-xMnxO3配製配方.....................................................................................32
表4-1 BiFe1-xMnxO3(x=0.0、0.05、0.1、0.15)Si和PtTiO2SiO2Si膜厚.............................................53
表4-2 為BiFe1-xMnxO3(取X=0.0和X=0.15)分別鍍在Si(100)和PtTiO2SiO2Si二種基板的表面粗糙度......................54
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