氟化物目前是應用於紫外光區或深紫外光區光學鍍膜上的材料。已經有很多技術被利用來改善氟化物薄膜的品質，包括熱蒸鍍法、離子束濺鍍法、電子槍蒸鍍法、磁控濺鍍法以及離子輔助蒸鍍法等。儘管如此，在光學性質與微結構上，氟化物薄膜仍舊需要改善。在本研究中，我們在室溫下使用熱蒸鍍法搭配離子輔助熱蒸鍍技術進行氟化物薄膜如：氟化鎂、氟化釓及氟化鋁的製鍍。在離子輔助熱蒸鍍的過程中，藉由使用六氟化硫當做工作氣體，會因為六氟化硫氣體所分解出來的氟離子，而達到改善氟化物薄膜化學匹配比的功用。除此之外，使用其他不同的工作氣體，如氬氣、氧氣與六氟化硫的混合氣體，以及不使用工作氣體，或者是使用六氟化硫當做環境氣體等條件下進行離子輔助熱蒸鍍氟化物薄膜，藉此研究不同的工作氣體製程下薄膜的光學性質與微結構。
在所有研究過程中，首要工作便是先找到離子輔助熱蒸鍍的最佳參數。接著利用穿透光譜儀、橢圓偏光儀和傅利葉紅外光光譜儀分析薄膜的光學性質，再利用原子力顯微鏡、場發射電子顯微鏡以及X光繞射儀檢驗薄膜的微結構性質。此外，我們還利用X光光電子能譜分析氟化物薄膜的組成、原子百分濃度與化學匹配比。藉著使用譜峰擬合軟體將所有光電子能譜分解成數個次峰後，Mg 2p, Gd 4d, Al 2p, O 1s 和 F 1s光電子能譜的束縛能移動情形已完成分析討論。而殘存於氟化物薄膜的汙染物，包括氬原子與硫原子，也同時利用X光光電子能譜進行鑑定。另外氟化物薄膜本身的組成、光學性質與物理性質其相關聯性，也一併於本研究中進行討論。
最後，從本研究可以發現在熱蒸鍍過程中，使用離子輔助熱蒸鍍技術並搭配六氟化硫當做工作氣體所製鍍出來的氟化鎂、氟化釓及氟化鋁薄膜，其光學性質、堆積密度以及化學組成結構上皆展現較佳的品質。

Fluorides are present used to accomplish optical coatings for UV and deep UV range applications. Many techniques such as thermal evaporation, ion beam sputtering, electron-beam evaporation, magnetron sputtering, and ion-assisted deposition (IAD) are applied to improve the quality of fluoride films. Nevertheless, improvements of their optical and microstructural qualities are still needed. In this study, fluoride films as magnesium fluoride (MgF2), gadolinium fluoride (GdF3) and aluminum fluoride (AlF3) were fabricated at room temperature by using a thermal evaporation method with an ion-assisted deposition technique. Using sulfur hexafluoride (SF6) as a working gas in the IAD process so that more F- ions can be created from the dissociation of SF6 gas to improve the stoichiometry of fluoride films. Furthermore, optical and microstructural properties of the films deposited by using different working gases such as argon (Ar), oxygen mixed sulfur hexafluoride (O2+SF6) and without using gas in the IAD process or using SF6 as an ambient gas to where investigated.
In this study, the optimal ion-assisted voltage and current in the IAD process were determined first. The optical properties of the films were analyzed by UV/Visible/NIR spectrophotometer, micro-spot spectroscopic ellipsometer and Fourier transform infrared spectrometer (FTIR). The microstructural properties of the films were examined by atomic force microscope (AFM), field emission scanning electron microscope (FE-SEM) and X-ray diffractometer (XRD). Moreover, X-ray photoelectron spectroscopy (XPS) was used to investigate the composition, atomic concentrations and stoichiometry of fluoride films. The binding energy (BE) shifts of Mg 2p, Gd 4d, Al 2p, O 1s and F 1s were analyzed after spectra were decomposed by some sub-peaks using a peak fitting software. The contaminants in the fluoride films such as Ar and S atoms were also identified by XPS. The correlations among the film composition, optical properties and physical properties were also discussed.
In conclusion, it was found that SF6 used as a working gas in the thermal evaporation process with an IAD technique, three fluoride films, MgF2, GdF3 and AlF3, all showed better optical qualities, packing densities and stoichiometric structures.

目錄

摘要 i
Abstract iii
致謝 v
目錄 vii
表目錄 xii
圖目錄 xiv
第一章 緒論 1
1.1 研究背景與動機 1
1.2 常見研究方法 4
1.3 本研究目的與研究方法 6
1.4 本研究所使用之工作氣體 7
1.5 本研究所使用之氟化物材料特性 8
第二章 實驗理論與材料特性 10
2.1 薄膜生長理論 10
2.1.1表面吸附 10
2.1.2成核過程 11
2.1.3生長過程 12
2.2 物理氣相沉積法－熱阻舟蒸鍍法 14
2.3 無柵極end-Hall型離子源 15
2.3.1 離子助鍍法 17
2.3.2 電漿態SF6氣體分子主要反應機制 17
2.4 介電質材料的透明區 19
2.5 造成薄膜能量損耗的原因 20
2.5.1 正離子缺位與負離子缺位 21
2.5.2 雜質 21
2.5.3 次要鍵結 21
2.5.4 散射 23
2.6 X光光電子能譜儀 23
2.6.1 光電效應 24
2.6.2 化學位移 24
2.6.3 能譜譜線數據處理 24
2.6.3.1 Smoothing 25
2.6.3.2 Deconvolution 25
2.6.3.3 Background removal 26
2.6.3.4 Curve fitting 27
第三章 實驗裝置與分析儀器 28
3.1 樣品製備 28
3.1.1 真空系統裝置 28
3.1.2 熱電阻加熱裝置與離子源輔助系統 30
3.2 樣品量測 31
3.2.1 穿透光譜儀 32
3.2.2 橢圓偏光儀 32
3.2.3 原子力顯微鏡 35
3.2.4 X光繞射儀 36
3.2.5 場發射掃描式電子顯微鏡 37
3.2.6傅立葉紅外線光譜儀 39
3.2.7 X光光電子能譜儀 41
第四章 實驗結果與討論 45
4.1基材特性與實驗參數 45
4.1.1基材特性 45
4.1.2實驗參數 46
4.2 氟化鎂之研究分析 47
4.2.1氟化鎂薄膜之光學性質 49
4.2.2不同製程下氟化鎂薄膜性質之比較 52
4.2.2.1光學性質之比較 52
4.2.2.2堆積密度之比較 56
4.2.2.3表面粗糙度與膜層結構之比較 57
4.2.3不同製程下氟化鎂薄膜之組成與化學匹配比 62
4.2.3.1 XPS全光譜掃描 62
4.2.3.2 碳(C 1s)元素的微區分析 64
4.2.3.3 氧(O 1s)元素的微區分析 68
4.2.3.4 氟(F 1s)元素的微區分析 71
4.2.3.5 鎂(Mg 2p)元素的微區分析 74
4.2.3.6 氬(Ar 2p)與硫(S 2p)元素的微區分析 77
4.2.3.7 薄膜組成與化學匹配比綜合分析 78
4.3 氟化釓之研究分析 84
4.3.1氟化釓薄膜之光學性質 84
4.3.2不同製程下氟化釓薄膜性質之比較 86
4.3.2.1光學性質與堆積密度之比較 86
4.3.2.2表面粗糙度與膜層結構之比較 89
4.3.3不同製程下氟化釓薄膜之組成與化學匹配比 93
4.3.3.1 XPS全光譜掃描 93
4.3.3.2 碳(C 1s)元素的微區分析 94
4.3.3.3 氧(O 1s)元素的微區分析 98
4.3.3.4 氟(F 1s)元素的微區分析 102
4.3.3.5 釓(Gd 4d)元素的微區分析 106
4.3.3.6 硫(S 2p)元素的微區分析 109
4.3.3.7 薄膜組成與化學匹配比綜合分析 110
4.4 氟化鋁之研究分析 116
4.4.1氟化鋁薄膜之光學性質 116
4.4.2不同製程下氟化鋁薄膜性質之比較 118
4.4.2.1光學性質之比較 118
4.4.2.2表面粗糙度與膜層結構之比較 121
4.4.3不同製程下氟化鋁薄膜之組成與化學匹配比 126
4.4.3.1 XPS全光譜掃描 126
4.4.3.2 碳(C 1s)元素的微區分析 127
4.4.3.3 氧(O 1s)元素的微區分析 130
4.4.3.4 氟(F 1s)元素的微區分析 133
4.4.3.5 鋁(Al 2p)元素的微區分析 136
4.4.3.6 硫(S 2p)元素的微區分析 138
4.4.3.7 薄膜組成與化學匹配比綜合分析 139
第五章 結論 146
參考文獻 151

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