氧化鈰、氧化鉍、氧化鐵三種晶種層對鐵酸鉍鐵電薄膜之影響

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研究生：	林宗儒
論文名稱：	氧化鈰、氧化鉍、氧化鐵三種晶種層對鐵酸鉍鐵電薄膜之影響
指導教授：	胡塵滌 Hu, Chen-Ti 呂正傑 Leu, Ching-Chich
口試委員:	胡塵滌簡昭欣呂正傑
學位類別：	碩士 Master
系所名稱：	工學院 - 材料科學工程學系 Materials Science and Engineering
論文出版年：	2012
畢業學年度：	100
語文別：	中文
論文頁數：	212
中文關鍵詞：	鐵酸鉍、鐵電薄膜、晶種層
相關次數：	點閱：4 下載：0
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本實驗使用溶膠凝膠法(Sol-gel method)，製備複鐵式鐵酸鉍(BiFeO3)薄膜。鐵酸鉍薄膜的鐵電與鐵磁性質耦合形成磁電效應，使材料在電能與磁能間轉換，為新興熱門研究，但鐵酸鉍薄膜磁性質較差，當前文獻指出，鐵酸鉍薄膜在室溫下具有較低的漏電流阻抗，使磁電耦合效應遭受限制無法突破。針對於此本論文以植入氧化鈰、氧化鉍、氧化鐵三種不同晶種層，並分別在鐵酸鉍薄膜的下表面、上表面與上下表面均植入晶種層，探討晶種層對於鐵酸鉍複合薄膜結晶性、鐵電性、介電性、漏電流及磁性質之影響。
實驗結果得知，植入適當晶種層可改善鐵酸鉍薄膜在鉑金底電極上不易結晶的問題，可降低鐵酸鉍薄膜結晶溫度；二次離子質譜儀(SIMS)，分析發現植入氧化鈰晶種層於B*FO薄膜及鉑金底電極之間，可避免單獨B*FO薄膜中鉍元素擴散進入底電極。植入氧化鈰晶種層於底層、上表面、三明治結構的複合薄膜皆可將單獨鐵酸鉍薄膜的漏電流降低至少一個次方約為10-8至10-7 A/cm2；電場-電流密度分析，鐵酸鉍及其複合薄膜皆呈現空間電荷限制傳導機制(SCLC mechanism)，植入各晶種層後皆降低單獨B*FO薄膜的轉換電場(Etr，Ohmic conduction→SCLC)及Trap-filled limited電場(ETFL)，應與薄膜中載子濃度及晶粒尺寸有關。複合薄膜電滯曲線中的殘留極化量(2Pr)印證X光繞射推導之結晶優選方向，並將主導各複合薄膜鐵電性質，亦使鐵電性質表現相雷同；複合薄膜的矯頑電場(2Ec)會因鐵電域壁移動受到晶粒尺寸、空間電荷、帶電缺陷限制而改變。低電場量測時，BiOx-B*FO複合薄膜有較高的鐵電極化量2Pr (4.96μC/cm2 at 250kV/cm)，應與BiOx晶種層幫助BFO(110)面成長有關；三明治結構CeO2-B*FO-CeOx複合薄膜由於漏電流相當低，外加電場至700kV/cm，依然有飽和的電滯曲線，使鐵酸鉍複合薄膜鐵電性質明顯展現(15.44μC/cm2)。從介電常數與頻率分析，底層植入氧化鈰、氧化鉍晶種層可使BFO薄膜介電常數增大約兩倍；同時該薄膜具有較低的ETFL電場，推測是空間電荷所造成介電發散特性。植入晶種層後可改善鐵酸鉍薄膜磁性質，CeOx-BFO薄膜平行膜面所量測磁滯曲線中(2kOe)的飽和磁化量(2Ms)高達15.43emu/cm3、殘留磁化量(2Mr)為1.44emu/cm3，推測是Fe2+比例增加及螺旋排列的磁矩間夾角改變，造成淨磁化量增加。Fe2O3-BFO-FeOx薄膜平行膜面量測(2kOe)的飽和磁化量(2Ms)高達103.2emu/cm3、殘留磁化量(2Mr)為5.88emu/cm3，推測因具有α-Fe2O3及氧空缺(Vo..)。

第一章 緒論    1
1-1前言    1
1-2研究動機與方向    2
第二章 文獻回顧    3
2-1鐵電薄膜簡介    3
2-1-1鐵電薄膜演進    3
2-1-2鐵電材料結構    3
2-1-3鐵電特性    4
2-2極化原理簡介    6
2-2-1極化現象與介電常數    6
2-2-2極化機制    6
2-3漏電流機制    7
2-3-1能障限制(Barrier limited)    7
2-3-1-1蕭基特發射(Schottky emission)    7
2-3-1-2穿遂效應(Tunneling effect)    7
2-3-2本體限制(Bulk limited)    8
2-3-2-1空間電荷限制傳導(Space charge limited conduction)，SCLC    8
2-3-2-2離子傳導(Ionic condution)    10
2-3-2-3普爾-夫倫克爾放射(Pool-Frenkel emission)    10
2-3-2-4本質傳導(Intrinsic condution)    11
2-4磁性原理簡介    11
2-4-1磁性的來源    11
2-4-2磁性物質的分類    12
2-4-3磁性特徵溫度    14
2-4-3-1居禮溫度    14
2-4-3-2尼爾溫度    14
2-4-4磁滯曲線    15
2-5鐵酸鉍系統(BiFeO3)    15
2-5-1鐵酸鉍的結構與性質    15
2-5-2鐵酸鉍研究文獻回顧    17
2-5-2-1鐵酸鉍植入晶種層(緩衝層)的研究文獻    19
第三章 實驗步驟    35
3-1基板的製備    35
3-1-1製備擴散阻絕層及黏著層    35
3-1-2製備鉑金下電極    35
3-2鐵酸鉍及晶種層薄膜的製備    36
3-2-1實驗藥品    36
3-2-2製備鐵酸鉍BFO溶膠    36
3-2-3製備晶種層溶膠    37
3-2-4鐵酸鉍與晶種層薄膜的鍍製    38
3-2-5鐵酸鉍、複合薄膜、晶種層薄膜的熱處理    39
3-3鐵電薄膜特性分析    39
3-3-1物性分析    39
3-3-2電性分析    40
3-3-3 VSM磁性分析(Vibrating Sample Magnetometer)    41
第四章 結果與討論    45
4-1化學成份分析EDS    45
4-2 SIMS成份縱深分析    45
4-3 XRD晶體結構分析    46
4-3-1晶種層薄膜之XRD分析    47
4-3-2 BFO、B*FO薄膜之XRD分析    47
4-3-3底層植入不同晶種層的BFO、B*FO複合薄膜之XRD分析    48
4-3-3-1氧化鈰晶種層複合薄膜之XRD分析    48
4-3-3-2氧化鉍晶種層複合薄膜之XRD分析    49
4-3-3-3氧化鐵晶種層複合薄膜之XRD分析    50
4-3-4上表面植入不同晶種層的BFO、B*FO複合薄膜之XRD分析    50
4-3-5各種三明治結構的BFO、B*FO複合薄膜之XRD分析    51
4-3-6薄膜X光繞射結晶優選方向與鐵電特性間之關係分析    51
4-4表面微觀結構及橫截面分析(SEM)    52
4-4-1晶種層薄膜表面形貌分析    52
4-4-2 BFO、B*FO薄膜表面及橫截面形貌分析    53
4-4-3底層植入不同晶種層的BFO、B*FO複合薄膜表面及橫截面形貌    53
4-4-3-1氧化鈰晶種層複合薄膜之形貌分析    53
4-4-3-2氧化鉍晶種層複合薄膜之形貌分析    54
4-4-3-3氧化鐵晶種層複合薄膜之形貌分析    55
4-4-4上表面植入不同晶種層的BFO、B*FO複合薄膜表面及橫截面形貌56
4-4-5各種三明治結構的BFO、B*FO複合薄膜表面及橫截面形貌分析    57
4-4-5-1 氧化鈰三明治結構之形貌分析    57
4-4-5-2 氧化鉍三明治結構之形貌分析    58
4-4-5-3 氧化鐵三明治結構之形貌分析    59
4-5電流密度量測    59
4-5-1晶種層薄膜之電流密度分析    60
4-5-2 BFO、B*FO薄膜之電流密度分析    60
4-5-3底層植入不同晶種層的BFO、B*FO複合薄膜之電流密度分析    61
4-5-3-1氧化鈰晶種層複合薄膜之電流密度分析    61
4-5-3-2氧化鉍晶種層複合薄膜之電流密度分析    63
4-5-3-3氧化鐵晶種層複合薄膜之電流密度分析    64
4-5-4上表面植入不同晶種層的BFO、B*FO複合薄膜之電流密度分析    65
4-5-5各種三明治結構的BFO、B*FO複合薄膜之電流密度分析    66
4-5-5-1 氧化鈰三明治結構之電流密度分析    66
4-5-5-2 氧化鉍三明治結構之電流密度分析    67
4-5-5-3 氧化鐵三明治結構之電流密度分析    67
4-6鐵電特性量測    68
4-6-1 BFO、B*FO薄膜之鐵電特性    68
4-6-2底層植入不同晶種層的BFO、B*FO複合薄膜之鐵電特性    69
4-6-2-1氧化鈰晶種層複合薄膜之鐵電特性    69
4-6-2-2氧化鉍晶種層複合薄膜之鐵電特性    70
4-6-2-3氧化鐵晶種層複合薄膜之鐵電特性    71
4-6-3上表面植入不同晶種層的BFO、B*FO複合薄膜之鐵電特性    72
4-6-4各種三明治結構的BFO、B*FO複合薄膜之鐵電特性    73
4-6-4-1三明治結構的BFO複合薄膜之鐵電特性    73
4-6-4-2三明治結構的B*FO複合薄膜之鐵電特性    74
4-7介電特性量測    74
4-7-1 BFO、B*FO薄膜之介電特性    75
4-7-2底層植入不同晶種層的BFO、B*FO複合薄膜之介電特性    75
4-7-2-1氧化鈰晶種層複合薄膜之介電特性    75
4-7-2-2氧化鉍晶種層複合薄膜之介電特性    76
4-7-2-3氧化鐵晶種層複合薄膜之介電特性    77
4-7-3上表面植入不同晶種層的BFO、B*FO複合薄膜之介電特性    77
4-7-4各種三明治結構的BFO、B*FO複合薄膜之介電特性    78
4-7-4-1氧化鈰三明治結構之介電特性    78
4-7-4-2氧化鉍三明治結構之介電特性    79
4-7-4-3氧化鐵三明治結構之介電特性    79
4-8磁性分析    80
4-8-1 BFO、B*FO薄膜的磁性分析    80
4-8-2底層植入不同晶種層的BFO、B*FO複合薄膜之磁性分析    80
4-8-2-1氧化鈰晶種層複合薄膜之磁性    80
4-8-2-2氧化鉍晶種層複合薄膜之磁性    81
4-8-2-3氧化鐵晶種層複合薄膜之磁性    81
4-8-3上表面植入不同晶種層的BFO、B*FO複合薄膜之磁性分析    82
4-8-4各種三明治結構的BFO、B*FO複合薄膜之磁性分析    82
第五章 結論    203
參考文獻    206
                                

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