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研究生: 陳錫釗
Hsi-Chao Chen
論文名稱: 二氧化鈦光學薄膜在熱回火過程的光學和機械特性之研究
Investigation of Thermal Annealing on the Optical and Mechanical Properties of TiO2 Thin Films
指導教授: 李正中
Cheng-Chung Lee
口試委員:
學位類別: 博士
Doctor
系所名稱: 理學院 - 光電科學與工程學系
Department of Optics and Photonics
畢業學年度: 94
語文別: 中文
論文頁數: 117
中文關鍵詞: 熱回火二氧化鈦薄膜殘留應力
外文關鍵詞: residual stress, titanium oxide thin films, thermal annealing
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  • 本論文探討熱回火處理對二氧化鈦(TiO2)光學薄膜的光學特性,殘留應力的機械性質和微觀柱狀結構等影響。光學特性是經由穿透光譜加以判讀,殘留應力的量測則是透過自己架設的相位偏移式干涉儀。在微觀結構方面, X光繞射儀判斷薄膜內部的結晶狀況,X光光電子能譜儀可以了解熱回火過程的氧化模態變化,掃描式電子顯微鏡可以觀察不同熱回火溫度的柱狀微觀結構變化,原子力顯微鏡可以觀看膜質的表面輪廓和粗糙度,顯微干涉儀可量測較大面積的表面粗糙度。
    在TiO2光學薄膜的製鍍過程中,選擇不同的基板溫度;發現基板溫度為150℃的TiO2光學薄膜,在不同溫度的熱回火中,不穩定的氧化鍵會斷裂形成次氧化鍵,隨熱回火溫度增加,會再度氧化為氧化鍵。在200℃的熱回火溫度時有最小的殘留應力,因此次氧化鈦在熱回火過程中扮演消除殘留應力的緩衝功能。在穿透光學頻譜、殘留應力、表面粗糙度變化和微觀結構觀察中,發現TiO2光學薄膜製鍍在基板溫度200℃和250℃中比150℃來的穩定。
    在製鍍的方式中,選擇離子輔助電子槍蒸鍍法,射頻離子濺鍍和直流磁控濺鍍法等三種鍍膜方式製鍍TiO2光學薄膜,可以發現濺鍍出來的TiO2光學薄膜較為穩定。對不同的基板溫度製鍍出來的TiO2光學薄膜做再回火穩定度研究,發現再回火過程中,殘留應力變化量變小,不會高低起伏變化很大,表示膜質已經達到穩定的狀態。
    綜合上述研究,對製鍍完的TiO2光學薄膜做熱回火處理,確實可以改變膜質的內部結構,也能使膜質趨向穩定。


    The effect of the thermal annealing of titanium oxide (TiO2) thin films on the optical properties, residual stress and microstructures were researched in this paper. Optical properties were analyzed by transparent spectra and residual stress was studied by phase-shift interferometer. In microstructure, crystallization was investigated by X-ray diffraction. The phase transformation during thermal annealing was studied by X-ray photo-electronic spectroscopy. Scanning electron microscopy was used to observe the status of column structure. Atomic force microscopy studied the profile of surface. Microscopy interferometer could get the roughness for large area.
    We deposited the TiO2 thin films by different substrate temperature. At the substrate temperature of 150℃, the unstable TiO2 would break and form sub-titanium oxide by increasing temperature of thermal annealing. The smallest residual stress exited at the annealing temperature of 200℃, so the sub-titanium oxide could relax the residual stress by different Young’s module. The TiO2 thin films deposited at substrate temperature of 200℃ and 250℃ were more stability than 150℃.
    Three different types deposited the TiO2 thin films—E-gun evaporation with IAD, RF ion-beam sputter, and DC magnetron sputter. The properties at both sputters were more stability than evaporation. In the reliability test, the variations of residual stress by the re-baking were small than before. These results told us that TiO2 thin films already got constant by thermal annealing.
    In a word, the thermal annealing has improved the microstructure of the TiO2 thin films result that they were more stability than before.

    中文摘要…………………..……………………………………….....………....Ι 英文摘要………………..………………………………………..…..………….Ⅱ 致謝詞………………….……..…………………………………………………Ⅲ 目錄…………………………..……………………………………..….………..Ⅳ 圖目錄………………..……………………………………………...…………..Ⅵ 表目錄……………………………..……………………………….…..………..Ⅸ 符號說明……………………………………..…………………………...……..Ⅹ 第一章 緒論 1 1-1 研究動機 1 1-2 文獻回顧 3 1-3 論文架構 5 第二章 基本理論 6 2-1 前言 6 2-2 基本材料力學觀念 7 2-2-1 應力定義 7 2-2-2 應變定義 8 2-2-3 線彈性及廣義應力應變關係式 (廣義虎克定律) 9 2-2-4 熱應力 (Thermal stress) 11 2-3 薄膜應力 13 2-3-1 薄膜應力定義 13 2-3-2 Stoney 公式推導 15 2-3-3 薄膜熱應力 18 2-4 應力成因模態 19 2-4-1 缺陷模態 (Defect Model) 19 2-4-2 表面張力模態 (Surface Tension Model) 19 2-4-3 顆粒邊界模態 (Grain Boundary Model) 20 2-4-4 敲擊模態 (Peening Model) 21 2-5 相位偏移干涉法 23 2-5-1 相位偏移干涉儀的原理 23 2-5-2 相位還原疊加雜訊的消除 26 第三章 微觀結構和表面輪廓的量測方法 31 3-1 前言 31 3-2 結晶態分析--X光繞射儀(X-ray Diffraction) 34 3-3 鍵結態分析-- X光光電子能譜儀(X-ray Photoelectron Spectroscopy) 36 3-4 剖面微觀態分析--掃描式電子顯微鏡(Scanning Electron Microscopy) 40 3-5 表面微觀分析--原子力顯微鏡和WYKO顯微干涉儀 43 3-5-1 原子力顯微鏡(Atomic force Microscopy) 43 3-5-2 WYKO 顯微干涉儀(WYKO microscopy interferometry) 45 第四章 離子助鍍之TiO2光學薄膜在熱回火中光學和機械性質的變化 47 4-1 前言 47 4-2 實驗過程 49 4-3 量測儀器 50 4-4 實驗結果和討論 53 4-4-1 殘留應力量測 53 4-4-2 光學特性量測 54 4-4-3 X光光電子能譜儀(XPS)量測 56 4-4-4 X光繞射儀(XRD)量測 58 4-5 結論 59 第五章 基板溫度對熱回火中TiO2光學薄膜應力和微觀結構影響 60 5-1 前言 60 5-2 實驗過程和量測儀器 62 5-3 實驗結果 63 5-3-1 殘留應力量測 63 5-3-2 光學特性量測 64 5-3-3 X光能譜儀分析結果 67 5-3-4 表面粗糙度量測 68 5-3-5 結晶特性 71 5-3-6 掃瞄式電子顯微鏡柱狀結構的量測 72 5-3-7 原子力顯微鏡(AFM)表面粗糙度的量測 74 5-4 結論 76 第六章 不同製鍍方式對TiO2光學薄膜在熱回火中應力和光學特性影響 78 6-1 前言 78 6-2 實驗方法和過程 79 6-2-1電子槍離子助鍍法(E-gun with Ion-beam-assisted Deposition) 79 6-2-2 射頻離子濺鍍法( Radio-Frequency Ion-beam Sputter) 80 6-2-3 直流電漿磁控濺鍍法(DC Magnetron Sputter) 82 6-3 實驗結果和討論 84 6-3-1 殘留應力量測 84 6-3-2 光學特性量測 85 6-3-3 表面粗糙度量測 86 6-4 結論 87 第七章 熱回火對TiO2光學薄膜穩定度的影響 88 7-1 前言 88 7-2 實驗方法 89 7-3 實驗結果與分析 90 7-4 結論 92 第八章 結論 94 參考文獻 96

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