本研究以反應式磁控濺鍍系統 (Reactive magnetron sputtering) 於不同氧流量下，改變沉積時間，經不同溫度熱退火處理，製備相同晶相不同結晶程度之二氧化鈦 (TiO2) 薄膜，以了解其與室溫鐵磁性 (Room temperature ferromagnetism, RTFM) 之間的關係。使用 X 光繞射儀 (XRD) 分析薄膜表面結構、場發射掃描式電子顯微鏡 (FE-SEM) 觀察其表面形貌、超導量子干涉磁量儀 (SQUID) 量測其磁學性質。
　　本研究中發現，矽基板以包括 HF 之流程進行清潔後，保存於大氣環境中約 72 小時，其磁性表現會單一的由逆磁性轉變為同時存在逆磁性與鐵磁性。因此本研究於實驗過程中，矽基板於清潔後皆即刻置入真空腔體中，以降低與空氣接觸的機會從而減少汙染物的沾粘或氧化矽的生成。
　　藉由改變二氧化鈦薄膜製程時間，於 6 sccm 之氧氣條件下製備大約 470 nm 與 60 nm 後，再以不同溫度於大氣下退火。可發現 400°C 退火的 470 nm 樣品，相對於初鍍薄膜或 350°C 退火的樣品，其 anatase 與 rutile 相之結晶性較佳，且與非晶相二氧化鈦同時存在於薄膜內，使得結晶/非晶或不同相之間的接觸界面 (interfaces) 較多，故具有較高的飽和磁化量，達 0.16 emu/cc；由於晶粒成長時易受到薄膜厚度的限制，故於樣品 400°C 退火的 60 nm 樣品中，僅可於其表面觀察到許多小團簇生成，單位體積薄膜中不同結構相之界面數量變多，因此其飽和磁化量可達到最高 0.44 emu/cc。將氧流量改為 7 sccm，而薄膜厚度仍為約 60 nm 之條件下所製備之 TiO2 薄膜，可在經過 280°C 大氣退火後，恰好觀察到類結晶粒 (pseudo - grain) 的生成，使其不同結構間相互接觸的界面增加，而使其飽和磁化量達到 39 emu/cc。然而，當薄膜已經形成數結晶性相對良好之 Anatase 時，樣品中之界面數量明顯少於其他結晶性較差的樣品，因而無法表現出室溫鐵磁性。
　　本研究中亦發現當二氧化鈦薄膜的厚度在 ~56 nm至 ~67 nm 時，對於退火溫度的變化較 470 nm 之薄膜為敏感，僅數奈米差異之膜厚，即可使二氧化鈦薄膜恰好由非晶相轉變為結晶相或類結晶粒時之臨界溫度 (critical temperature)，由 280°C 降至 250°C 以下。此外，具有最大飽和磁化量 39 emu/cc 之樣品，O7-60A280 經靜置一個月後卻驟降至 1.3 emu/cc，可見樣品之穩定性不如預期。因而使得二氧化鈦薄膜於室溫鐵磁性相關研究中的再現性難度大大提高。
　　綜合以上結果推測：氧化物薄膜中容易累積於晶粒表面的許多缺陷，如氧空缺、間隙鈦、間隙氧等，可能為其室溫鐵磁性之來源，因此在薄膜結構過於單一 (太過混亂或過於整齊排列) 的樣品中，並無法觀測到鐵磁性現象。

　　The purpose of this study is to investigate the effect of heat treatment and crystallinity on the RTFM (room temperature ferromagnetism) properties of TiO2 films prepared by magnetron sputtering system.
　　TiO2 thin films were deposited under different oxygen flow rate and the film thickness controlled by varying deposition time. After deposition, the samples were annealed under different temperatures by RTA (rapid thermal anneal) to vary their phase and crystallinity. From the results, the possible source for RTFM might be the point defects of oxide thin film accumulating on the interfaces, such as oxygen vacancies, interstitial Ti and O. Therefore, the hysteresis feature was no longer valid when the thin film structure was a homogeneous phase, either completely crystalline or amorphous.
　　Reactive sputtering method was used to prepare titanium dioxide thin films on Si(100) p-type substrates. Magnetic properties changed from pure diamagnetic to both diamagnetic and ferromagnetic due to the formation of silicon oxides on surface. Accordingly, the silicon substrates were placed in a vacuum chamber immediately after cleaning, to reduce contact with air and formation of silicon oxide.
　　Titanium dioxide films were prepared under oxygen flow rate at 6 sccm with two different thickness 470 nm and 60 nm. Annealing films in the same conditions, grain size and grain growth was usually limited by film thickness. This phenomenon could be favorable to increase the number of interfaces between different phases within the films. Hence, the maximum saturation magnetization reached up to 0.44 emu/cc.
　　The critical topography of the 60 nm films had changed from amorphous to pseudo-grain under the oxygen flow rate at 7 sccm and annealed in air via different temperatures between 250°C and 300°C. The sample annealed under 280°C in air processed mixed phases of anatase and amorphous TiO2 and exhibited the highest MS (saturated magnetization) up to 39 emu/cc. This could be due to the increase in the number of interfaces between crystalline anatase crystallites and amorphous phase. However, the MS of the same film dropped to 1.3 emu/cc after residing for one month, indicating that the sample deteriorated with time.
　　All in all, the critical annealing temperature range to initiate the 60 nm thick TiO2 film to transform from amorphous to crystalline or pseudo-grain was sensitive to subtle temperature change and thickness within few nanometers. The stringent conditions make it troublesome to repeat the experimental results.

致謝 i
摘要 iii
Abstract vii
目錄 xi
第一章 序論 1
1.1 前言 1
1.2 研究動機 3
第二章 簡介與文獻回顧 7
2.1 磁學簡介 7
2.2 磁性種類 8
2.3 室溫鐵磁性半導體研究 18
2.3.1 Ⅲ-Ⅴ 族半導體 18
2.3.2 氧化物半導體摻雜過度金屬元素 19
2.3.3 未摻雜之氧化物半導體 23
2.4 TiO2 簡介 31
2.5 物理氣相沉積 (PVD) 38
2.6 電漿放電與濺鍍 39
2.7 薄膜成長機制 44
第三章 實驗設備及製程 49
3.1 樣品製備之儀器與方法 49
3.1.1 反應式磁控濺鍍系統 52
3.1.2 基材準備 55
3.1.3 實驗製程 56
3.2 薄膜分析與量測方法 57
3.2.1 三維表面輪廓儀 (3D-surface profiler) 57
3.2.2 X 光繞射儀 (X-Ray Diffraction, XRD) 59
3.2.3 場發射掃描電子顯微鏡 (FE-SEM) 63
3.2.4 超導量子干涉磁量儀 (MPMS-SQUID) 64
第四章 結果與討論 69
4.1 氧流量 6 sccm 膜厚 470 nm 之 TiO2 薄膜之性質 71
4.1.1 試片準備 71
4.1.2 結構分析 73
4.1.3 表面形貌分析 75
4.1.4 M-H 量測結果 76
4.2 氧流量 6 sccm 膜厚 60 nm 之 TiO2 薄膜之性質 78
4.2.1 試片準備 78
4.2.2 結構分析 80
4.2.3 表面形貌分析 82
4.2.4 M-H 量測結果 84
4.3 氧流量 7 sccm 膜厚 60 nm 之 TiO2 薄膜性質與穩定性 86
4.3.1 試片準備 86
4.3.2 結構分析 88
4.3.3 表面形貌分析 92
4.3.4 M-H 量測結果 95
4.4 樣品之穩定性與綜合討論 98
第五章 結論 105
參考文獻 107

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