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研究生： 張凱勛
Chung, Kai-Hung
論文名稱： 鋯鈦酸鉛(Pb(ZrTi)O3)鐵電材料之奈米電域極化及反轉研究
Study of Nanoscale Polarization and Switching in PZT Ferroelectrics
指導教授： 陳宜君
Chen, Yi-Chun
學位類別： 碩士
Master
系所名稱： 理學院 - 物理學系
Department of Physics
論文出版年： 2006
畢業學年度： 94
語文別： 中文
論文頁數： 82
中文關鍵詞： 鋯鈦酸鉛 、掃描探針顯微鏡 、奈米電性
外文關鍵詞： nano-electricity, SPM, PZT
相關次數： 點閱：87  下載：3 
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    • 在本研究中，以掃描式探針顯微鏡技術來探討奈米鐵電性質，包含電極化與電域翻轉等。樣品為有機金屬鹽裂解法製備之鋯鈦酸鉛 (Pb(ZrTi)O3, PZT) 鐵電性薄膜與模板合成法(template-based)製備之一維鋯鈦酸鉛奈米鐵電管。薄膜於高退火溫度(600℃以上)顯示具有擇優特性與良好的結晶特性。在掃描探針顯微鏡直接的觀察下顯示，結晶結構影響了奈米區域的鐵電性質。具(001)擇優的晶粒於垂直膜面的電壓施加下，可產生高的飽和極化值。結晶特性較差的薄膜，則易產生電滯偏移。本實驗中亦成功合成空心奈米鐵電管，管徑約150 nm， 管壁約厚10 nm。鐵電奈米管為多晶結構，而由於管壁厚度侷限鐵電晶粒與電域大小，其飽和極化與薄膜相較起來微弱許多，且亦有電滯偏移現象。

    In this study, nano-scale ferroelectric properties, including polarization and domain switching, were investigated by scanning probe microscopy (SPM). PZT (Pb(ZrTi)O3) thin films, which were synthesized by metal-organic decomposition, and 1-D PZT nanotubes, which were prepared by template-based method, were tested samples. Thin films annealed at higher　temperature (>600℃) will possess preferred orientation and better crystalline phases. The SPM results show that nano- ferroelectricity is strongly related to the crystal structures. While a dc voltage was applied between the film and SPM tip, higher saturation polarization was induced on the grains with (001) preferred orientation. Moreover, the ferroelectric hysteresis of the films with worse crystaline phase shows bias shift. Ferroelectric hollow tubes of diameters about 150 nm and wall thickness about 10 nm were successfully synthesized and also investigated in this study. The tubes are mainly poly crystallization. Due to the narrow constriction of the tube-wall on the grain size and domains, ferroelectric tubes have weak ferroelectric polarization and serious hysteresis shift.

    摘要 I Abstract II 誌謝 III 目錄 IV 圖目錄 VII 第一章　緒論....................1 第二章　文獻回顧................3 2.1　鐵電性.....................3 2.2　PZT鐵電材料................4 2.2.1　鈣鈦礦結構...............4 2.2.2　鋯鈦酸鉛（PZT）之相圖....7 2.2.3　變形相界（MPB）..........8 2.2.4　遲滯曲線.................9 2.3　鐵電性記憶體...............10 2.4　鐵電材料之發展及製作.......12 2.4.1　鐵電薄膜製作方法.........13 2.4.2　有機金屬鹽裂解法.........16 2.4.3　旋鍍法的原理.............17 2.4.4　鐵電奈米管製作方法.......19 2.5　掃描探針顯微術相關研究.....20 2.5.1　原子力顯微鏡.............22 2.5.2　靜電力顯微鏡.............26 2.5.3　壓電力顯微鏡.............28 第三章　實驗方法................31 3.1　鐵電薄膜的製作.............32 3.1.1　鍍膜基材準備.............32 3.1.2　基板之清洗...............32 3.1.3　薄膜的披覆...............32 3.2　鐵電性奈米管狀物的製作.....34 3.3　薄膜原子力顯微鏡量測.......37 3.3.1　樣品表面形貌量測.........37 3.3.2　靜電力顯微鏡的電性量測...38 3.3.3　壓電力顯微鏡的電性量測...38 3.3.4　極化強度-電場的量測......39 3.4　樣品基本特性檢測...........39 3.4.1　薄膜厚度量測.............39 3.4.2　X光繞射分析儀............40 3.4.3　掃瞄式電子顯微鏡.........40 第四章　結果與討論..............42 4.1　鋯鈦酸鉛(PZT)鐵電性薄膜的合成.42 4.1.1　退火溫度對晶相的影響.....43 4.1.2　退火溫度對表面結構的影響.46 4.1.3　膜厚量測.................52 4.2　膜厚量測...................55 4.2.1　填充製程對鐵電管的影響...55 4.2.2　奈米鐵電管微結構分析.58 4.2.3　奈米鐵電管X-ray晶相分析..61 4.3　奈米區域電性的研究.........61 4.3.1　靜電力顯微鏡(EFM)量測....62 4.3.2　壓電力顯微鏡(PFM)量測 ...66 4.3.3　電滯曲線的測量與分析.....70 第五章　結論....................76 參考文獻........................77 圖目錄 圖 2 1 鐵電域極化情形示意圖..............4 圖 2-2 鈣鈦礦結構示意圖..................5 圖 2-3 Pb(Zr0.2Ti0.8)O3 結構晶胞受極化圖.6 圖 2-4 PbZrO3-PbTiO3相圖.................7 圖 2-5 室溫下PbZrO3-PbTiO3系統的吉布斯自由能 　　　圖.....8 圖 2-6 MPB成份材料性質表現圖.............9 圖 2-7 鐵電體的電滯曲線圖................10 圖 2-8 記憶體元件圖......................11 圖 2-9 旋鍍法示意圖......................18 圖 2-10 陽極氧化鋁模板....................20 圖 2-11 空心和實心之奈米管狀物圖..........20 圖 2-12 掃描探針顯微鏡裝置圖..............21 圖 2-13 一般探針與CNT探針所測得的表面形貌與電荷 　　　分佈圖.....22 圖 2-14 凡得瓦力與距離關係圖..............23 圖 2-15 AFM探針運作模式圖.................24 圖 2-16 探針振盪振幅A與振盪頻率ω間的頻率響應關係 　　　圖.....25 圖 2-17 靜電力顯微鏡裝置圖................26 圖 2-18 AFM表面形貌和EFM相位圖............27 圖 2-19 PZT薄膜的PFM影像圖................29 圖 2-20 鐵電樣品out-plane與in-plane的壓電回應訊 　　　號圖.....30 圖 3-1 實驗流程圖........................31 圖 3-2 薄膜二階段退火升溫過程圖..........34 圖 3-3 管狀物製程流程圖..................35 圖 3-4 陽極氧化鋁實驗裝置圖..............35 圖 3-5 多孔性模版之填充與去除示意圖......36 圖 3-6 di-CP II 原子力顯微鏡.............37 圖 3-7 膜厚測量示意圖....................40 圖 4-1 不同退火溫度之鐵電薄膜X-Ray繞射圖.44 圖 4-2 晶相(100)與晶相(101)的峰值強度比值與溫度 　　　關係圖......44 圖 4-3 PZT(100)與PZT(101)繞射角度與退火溫度關係 　　　圖.....45 圖 4-4 不同退火溫度之鐵電薄膜表面一萬倍SEM圖.47 圖 4-5 不同退火溫度之鐵電薄膜表面五萬倍SEM圖.48 圖 4-6 不同退火溫度的鐵電薄膜之原子力顯微鏡表面 　　　形貌圖......51 圖 4-7 退火溫度對薄膜表面結晶顆粒大小之趨勢圖52 圖 4-8 薄膜膜面與白金基板之間的AFM表面形貌圖.53 圖 4-9 不同退火溫度之薄膜的膜厚表示圖....54 圖 4-10 覆蓋前置溶液之氧化鋁模板圖........56 圖 4-11 第一種製程之氧化鋁模板截面圖......57 圖 4-12 第二種製程之氧化鋁模板截面圖......57 圖 4-13 第三種製程之氧化鋁模板截面圖......58 圖 4-14 模板溶解過程中顯露出來的奈米鐵電管圖..59 圖 4-15 單根與群聚的奈米鐵電管............60 圖 4-16 奈米鐵電管X-ray晶相分析圖.........61 圖 4-17 於550℃退火之PZT鐵電薄膜之EFM圖...63 圖 4-18 不同退火溫度之PZT鐵電薄膜之EFM圖..64 圖 4-19 奈米鐵電管EFM圖...................65 圖 4-20 於650℃退火之PZT 鐵電薄膜之正向壓電力顯 　　　微鏡圖.67 圖 4-21 於600℃退火之PZT 鐵電薄膜之正向壓電力顯 　　　微鏡圖.67 圖 4-22 於550℃退火之PZT 鐵電薄膜之正向壓電力顯 　　　微鏡圖.68 圖 4-23 於500℃退火之PZT 鐵電薄膜之正向壓電力顯 　　　微鏡圖.68 圖 4-24 側向壓電力顯微鏡10V飽和極化圖....69 圖 4-25 奈米鐵電管PFM圖..................69 圖 4-26 不同退火溫度之PZT薄膜於(100)晶粒上之正向 　　　壓電力顯微鏡電滯曲線圖...........71 圖 4-27 不同退火溫度之PZT薄膜於(100)晶粒上之正向 　　　壓電力顯微鏡電訊相位圖...........71 圖 4-28 退火溫度與翻轉電壓關係圖.........72 圖 4-29 退火溫度與偏移電壓關係圖.........72 圖 4-30 奈米鐵電管之電滯曲線圖...........73 圖 4-31 於600℃退火之PZT 鐵電薄膜於定點之壓電力 　　　顯微鏡隨電壓改變之曲線圖.........74 圖 4-32 退火溫度與PFM極化強度關係圖......75

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