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研究生： 楊雅筑
Yang, Ya-Chu
論文名稱： Ti變量對TixFeCoNi合金氧化物薄膜的微結構、電阻及磁性的影響
Ti-content effects on the microstructures, resistivity and magnetism of TixFeCoNi alloy oxide thin films
指導教授： 葉均蔚
Yeh, Jien-Wei
曹春暉
Tsau, Chun-Huei
口試委員: 洪健龍
Hong, Jian-Long
李勝隆
Lee, Sheng-Long
李英杰
Lee, Ying-Chieh
蔡哲瑋
Tsai, Che-Wei
學位類別： 博士
Doctor
系所名稱： 工學院 - 材料科學工程學系
Materials Science and Engineering
論文出版年： 2017
畢業學年度： 105
語文別： 中文
論文頁數： 170
中文關鍵詞： 導電特性 、軟磁 、氧化 、退火 、薄膜
外文關鍵詞： Electrical property, Soft magnetic, Oxidation, Annealing, Thin Films
相關次數： 點閱：2  下載：0 
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    • 本論文是以Ti做變量，接著與Fe、Co、Ni三種等莫耳比例之元素製成TixFeCoNi (x = 0, 0.5, 1.0)合金靶材。其次，藉由真空直流磁控濺鍍機來製備薄膜，並依不同熱處理條件及氧氣氛以探討其對於薄膜微結構及其電性與磁性質的影響。由於TiFeCoNi氧化物薄膜具有非常低的電阻，其為35 μΩ-cm，為了解電阻與微結構的關聯，本研究分為兩部分，第一部分在探討TixFeCoNi薄膜在高溫1000°C退火後的微結構分層變化，並從熱力學探討此分層現象與電性及磁性的關聯；第二部分為透過通以不同流率的氧氣氛下，期望透過改變製程能在低溫狀態下鍍製具低電阻的缺氧氧化物，並探討其退火前後的微結構、電性及磁性的變化。
    本論文共分為六章：第一章為簡介研究背景與動機，包含TiFeCoNi薄膜的基本結構、電性優點及挑戰等；第二章則為文獻回故與理論基礎，例如高熵合金薄膜的研究與發展、薄膜的導電及磁性理論；第三章為實驗步驟及分析方法，詳細地描述薄膜微結構及性質分析，其中微結構分析包括以X光繞射、掃瞄式電子顯微鏡與穿透式電子顯微鏡作微結構觀察，電性分析包括以四點探針法及Hall effect量測，而磁性分析是利用振動樣品磁力計量測；第四及第五章中將分別針對不同實驗製程並討論其分析結果與理論的論證，而第四章的製程是以薄膜在無通任何反應氣氛、偏壓及溫度下，探討薄膜在1000°C-30 min高溫真空退火製程的微結構及性質變化，而在第五章的製程是以薄膜在無偏壓及無升溫下，通以不同氧氣氛流率，接著探討薄膜在低溫400°C- 1 h的高真空快速升溫退火爐製程中的微結構及性質變化。最後，第六章總結了這本研究的發現及主要貢獻，首先闡明了高溫退火對加速薄膜內原子的擴散並造成分層的現象。由於金屬+氧化物的複合結構正是形成低電阻的主要因素，因此，當薄膜通以不同氧流率時，薄膜形成均勻的氧化層，由於氧含量過高，因此其電阻不如預期的低，但卻發現退火後，薄膜具有約1100 ~ 2200 emu/cm3的飽和磁化量(相當於1.4 ~ 2.8 Tesla)，而此發現亦是本研究最大的貢獻。

    In this paper, TixFeCoNi (x = 0, 0.5, 1.0) alloy targets were prepared by an arc melter, and Ti element was designed as a variable. The alloy films were prepared by a vacuum DC magnetron sputtering. The influence of the microstructures on the electrical properties and magnetic properties were investigated under different heat treatment conditions and oxygen atmosphere. The microstructures of the TixFeCoNi films after annealing at high temperature of 1000°C was studied to understand the relationship between the resistance and the microstructure of TiFeCoNi oxide film which had a very low resistance of 35 μΩ-cm, also the thermodynamics of this stratification phenomenon and electrical and magnetic correlation were discussed. Second, the TixFeCoNi oxide films were made in situ though an oxygen atmosphere under different oxygen flow rate, also the microstructure, electrical and magnetic properties of the anoxic oxide were investigated. This method could improve the application of these thin films and reduce the cost of production.
    This paper is divided into six chapters: Chapter 1 is introduction which describes the research background and motivation, including the basic structure of TiFeCoNi film, electrical advantages and challenges. Chapter 2 is literature and theoretical basis, such as high entropy alloy film research and development, film conductivity and magnetic theory. Chapter 3 is experimental steps and analytical methods, detailed describes the analysis methods of the microstructures and properties of the thin films, such as X-ray diffraction, scanning electron microscope and transmission electron microscope, electrical analysis, including four-point probe method and Hall effect measurement, and magnetic analysis is the use of vibration sample magnetic measurement. Chapter 4 discusses the annealing effects on the microstructures and properties on the TixFeCoNi alloy films. Chapter 5 studies the method to directly produce Ti0.5FeCoNi oxide films though an oxygen atmosphere, and also their properties. The films were deposited under different oxygen flow rates, without bias and no temperature-controlled, followed by annealing at a high vacuum and rapid annealing furnace at low temperature of 400 °C-1 h. Finally, Chapter 6 summarizes the findings and main contributions of this study. First, the mixed structures of a metal and oxide were the main factor to form a low resistivity. When the films were annealed at high temperature, the diffusion rate of atoms caused the stratification in films. Second, when the films were deposited with a different oxygen flow rates, the films were formed a uniform oxide layer. The resistivity of the films was not as low as expected due to the high oxygen contents. But the film had a saturation magnetization of about 1100 to 2200 emu / cm3 (Equivalent to 1.4 ~ 2.8 Tesla) was observed, and this discovery is also the biggest contribution of this study.

    摘要 I Abstract III 誌謝 VI 目錄 VII 圖目錄 XII 表目錄 XIX 第一章 緒論 1 1.1 TiFeCoNi合金基本性質及其薄膜生長概況 1 1.1.1 TiFeCoNi薄膜相關問題 3 1.2 研究目的 4 第二章文獻回顧與理論基礎 7 2.1高熵合金及薄膜的發展與應用 7 2.2薄膜的導電特性[46, 47] 8 2.2.1導電的物理現象 8 2.2.2多晶材料中的電傳導 11 2.2.3影響薄膜導電性能的因素 12 2.3 薄膜磁性理論[46] 15 2.3.1 磁性來源 15 2.3.2磁交換作用力的種類 17 2.3.3 鐵磁性材料 23 2.3.4軟磁材料 29 2.3.4 晶粒尺寸對軟磁性質的影響 29 2.4直流濺射鍍膜系統 [47, 63] 31 2.4.1系統原理及功能 32 2.4.2濺鍍注意事項 34 2.4.3 PVD製程優、缺點 35 2.5 薄膜形成與微結構 36 2.5.1 沉積與附著機制 36 2.5.2 薄膜結構 37 第三章實驗流程與分析方法 41 3.1 實驗流程 41 3.2 薄膜之沉積 42 3.2.1 靶材製備 42 3.2.2 薄膜沉積設備與參數 43 3.2.3基板準備與前處理 44 3.4 熱處理製程及參數 45 3.5薄膜特性分析方法 47 3.5.1 微結構分析 47 3.5.1.2 低掠角X光繞射儀 47 3.5.1.3 掃瞄式電子顯微鏡 47 3.5.1.4 穿透式電子顯微鏡 47 3.5.1.5 掃描探針顯微鏡 48 3.5.1.6 電子微探儀 48 3.5.1.7 X-ray光電子能譜儀 48 3.5.2 電性分析方法 49 3.5.3 磁性分析方法 50 第四章 TixFeCoNi合金薄膜透過熱處理後其微結構與電性、磁性的影響 51 4.1 前言 51 4.2實驗步驟 52 4.3結果與討論 52 4.3.1 TixFeCoNi (x = 0, 0.5及1.0)薄膜退火前後微結構的變化 52 4.3.2熱力學 68 4.3.3電性 74 4.3.4磁性 80 4.3.5 結論 88 第五章 研究Ti0.5FeCoNiOy薄膜通以氧分壓下，其微結構在初鍍態及退火態與磁性、電性質的影響 90 5.1前言 90 5.2實驗步驟 91 5.3 Ti0.5FeCoNiOy薄膜退火前後微結構的變化 92 5.3.1 薄膜退火前後的化學組成分析 92 5.3.2薄膜退火前後的XRD結晶結構 94 5.3.3薄膜退火前後的SEM橫截面與表面形貌觀察 97 5.3.4薄膜退火前後的TEM微觀結構分析 106 5.4 Ti0.5FeCoNiOy薄膜退火前後的磁性變化 118 5.5 薄膜退火前後，薄膜表面鍵結分析 126 5.5.1 薄膜在初鍍態及退火態之表面結構內層能階(Core-level)的化學狀態 126 5.5.2 Ti0.5FeCoNiOy薄膜退火前後各元素的化學狀態 127 5.6 結論 140 第六章 總結 142 6.1 結論 142 6.1.1 TixFeCoNi薄膜1000°C-30 min高溫真空熱處理 142 6.1.2 Ti0.5FeCoNiOy薄膜400°C-1 h高真空快速升溫熱處理 143 6.2本研究的貢獻 144 6.3 建議未來研究方向 144 參考文獻 146 作者簡歷 169 研究著作 169

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