臺灣博碩士論文加值系統

有機金屬框架 (Metal-Organic-Framework, MOF) 基於其高比表面積、結構中可調控的孔洞大小與官能基團，使其成為功能性極強的孔洞材料、被廣泛應用。而倘若能對客體分子於MOF結構間的擴散、空間分佈等相互關係有更進一步地認識，將有助於其於各領域中的應用與發展。不過，如今能夠直接分析客體—MOF複合結構內成份分佈的分析方法卻極為缺少。
二次離子質譜儀 (Secondary Ion Mass Spectroscopy, SIMS) 具有足夠的空間解析度與極高的偵測靈敏度(至少達ppm等級)，是全面性地提供樣品成份與分佈之相關資訊的絕佳工具。然而，以其進行縱深分析時，高劑量離子入射將導致分析物結構損傷進而使分子訊號強度下降，且對於有機—無機成份混雜的MOFs來說，入射離子造成的影響將更為複雜。因此，本研究旨在透過不同離子束、加速電壓、電流等參數的調整，設計出一系列實驗參數對MOF縱深分析結果進行探討，企圖找出能完整保留MOF結構中有機與無機成份訊號的實驗參數，以為MOFs建立一個直接、完整且有效的縱深分析方式，作為往後這類材料的分析方針。
本研究以化性穩定且發展成熟之UiO-66作為建構MOF薄膜縱深分析的平台，利用飛行時間式二次離子質譜儀 (ToF- SIMS) 以脈衝C60+ 作為分析離子源、不同能量密度 (energy per atom, E/n = 2~20) 的氬簇離子團 (Ar-GCIB) 搭配相異加速電壓或電流密度之Ar+ 做為共濺射離子源進行縱深分析的探討。研究結果顯示，單純使用 Ar-GCIB時，隨著E/n降低，入射離子對樣品造成的損傷累積較少，UiO-66結構中有機成份的保留程度較為理想，不過因Ar-GCIB對無機成份的濺射率遠低於移除有機成份的速率，故出現明顯差異侵蝕的現象，最終樣品表面剩下大量無法移除的無機成份，導致縱深分析無法向下建構。而當配合Ar+ 進行共濺射時，能量較強的單原子離子確實有助於提高金屬節點的濺射率；其中，以使用高電壓高電流 (500 V, 5 ×10-6 A/cm2) 的 Ar +共濺射之結果最為理想，不但大幅提升整體材料移除速率，亦有效清除表面破壞之化學結構，維持MOF成份的均勻，最小化偽影現象。
總的來說，良好的MOF縱深分析需利用共濺射的方式，以低能量Ar-GCIB (E/n=4) 保留有機成份訊號，並由高電壓—高電流的 Ar + 提高無機成份的濺射率，兩者各司其職，以於有限時間內替MOF樣品建構出真實而完整的成份分佈。

Metal-Organic framework (MOFs) is widely used as a highly functional porous material based on its high specific surface area, adjustable pore size and functional groups in the structure. Understanding the relationship to diffusion and spatial distribution between guest molecules and MOFs may help further advancing the development of MOFs and gaining more insights in its application in various fields. However, analytical techniques that can directly applied to obtain the component distribution in guest-MOF composite materials are extremely scarce.
With its sufficient spatial resolution (<100 nm lateral and ~nm depth) and extremely high detection sensitivity (~ppm), secondary ion mass spectroscopy (SIMS) is an excellent tool to provide comprehensive information about the composition and distribution of samples. However, the high-energy ion bombardment used during depth profiling analysis will break chemical bonds easily, cause a lot of damage on the surface, and thus reduce secondary ion signals, especially for organic components. Besides, for organic-inorganic hybrid materials like MOFs, the impact of incident ions will be more complicated because each component may have different response. Therefore, this research focus on tuning the cluster size of Ar-GCIB, acceleration voltage, current density of incident beams and different combinations of the co-sputtering method in an attempt to find optimal parameters of sputter beams to ensure the depth profile can completely retain the organic and inorganic component signals in MOFs and reflect the true distribution of the components. The optimized parameters we found will subsequently become a guideline for future analysis of this type of material.
In this study, the chemically stable UiO-66 was used as a model material to construct the depth profile of MOF films, and time-of-flight secondary ion mass spectrometer (ToF-SIMS) was utilized. For analysis, a pulsed C60+ was used as the acquisition ion beam. In sputter phase, sets of Ar-GCIB with different energy densities (energy per atom, E/n = 2~20) and Ar+ with different accelerating voltage or current density were used to cosputter the specimens. The results show that when using Ar-GCIB alone, the incident ions cause less damage to the sample as the E/n decreases, and thus, the retention of organic components in UiO-66 structure will be relatively ideal. However, preferential sputtering occurs due to the much lower removal rate of the inorganic components comparing to the organics in MOFs. In the end, a huge amount of inorganic components that cannot be removed are left on the surface of the sample, which makes it impossible to construct the depth profile downward. On the other hand, when cosputtering with Ar+, the more powerful atomic ions help to increase the sputtering rate of the metallic node. Among all of the Ar-GCIB+—Ar+ cosputtering parameters tested, the one with higher voltage and higher current density (500 V, 5 × 10-6 A/cm2) of Ar+ can obtain the most ideal result. The overall sputtering rate is not only greatly increased, but also effectively cleans up the damage accumulation on the surface. Therefore, the MOF composition are maintained uniformly, which minimizes the artifacts.
In conclusion, in order to obtain optimistic depth profile of MOFs, the use of Ar-GCIB+—Ar+ co-sputtering is required. Low energy (E/n=4) Ar-GCIB are used to retain the organic component signal, while high-voltage and high-current Ar+ contributes to improve the sputtering rate of inorganic components. By combining these two ion sources with the optimal parameters, the distribution of elemental and molecular component in the depth profile is righteously and thoroughly identified.

誌謝 i
中文摘要 ii
ABSTRACT iv
目錄 vi
圖目錄 ix
表目錄 xiii
第一章 緒論 1
第二章 文獻回顧 4
2.1 有機金屬框架 (Metal-Organic Framework) 4
2.1.1 有機金屬框架簡介 4
2.1.2 現階段有機金屬框架與其客體之相關研究 9
2.2 二次離子質譜儀之原理與技術介紹 11
2.2.1 質譜法之簡介 11
2.2.2 二次離子質譜法 (Secondary Ion Mass Spectrometry, SIMS) 12
2.2.3 動態和靜態二次離子質譜儀 14
2.2.4 二次離子質譜儀之基本應用 15
2.2.5 縱深分布分析 (Depth Profile) 17
2.2.5.1 基本運作原理 17
2.2.5.2 損傷截面積 (Damage Cross Section) 19
2.2.5.3 濺射率 (Sputter Yield) 21
2.2.5.4 縱深分析常見之問題 23
2.2.6 單原子以及團簇離子源 25
2.2.6.1 單原子與簇原子離子源於二次離子質譜中之應用與演進 25
2.2.6.2 簇離子源之濺射機制 28
2.2.7 氣體簇離子源介紹 (Gas Cluster Ion Beam, GCIB) 31
2.2.7.1 氣體簇離子之產生 31
2.2.7.2 氣體簇離子源的特性與優勢 32
2.2.7.3 氣體簇離子源之能量密度 (Energy per Atom, E/n) 36
2.3 二次離子質譜儀應用於有機—無機複合材料 39
2.3.1.1 離子分析應用於有機—無機複合材料 39
2.3.1.2 UiO-66 簡介 44
第三章 實驗及儀器介紹 45
3.1 藥品與基材 45
3.2 實驗儀器與原理 45
3.2.1 X光繞射分析儀 (X-ray Diffractometer, XRD) 45
3.2.2 掃描式電子顯微鏡 (Scanning Electron Microscope, SEM) 46
3.2.3 原子力顯微鏡 (Atomic Force Microscope, AFM) 46
3.2.4 飛行式二次離子質譜儀 (Time of Flight Secondary Ion Mass Spectrometry, ToF-SIMS) 48
3.3 實驗流程 60
3.3.1 UiO-66之合成 60
3.3.2 試片製備 61
3.3.2.1 金基板的清洗 61
3.3.2.2 薄膜的製備 61
3.3.2.3 藥物的摻入 62
3.3.3 XRD分析 62
3.3.4 SEM觀測 62
3.3.5 AFM量測 63
3.3.6 ToF-SIMS分析 63
第四章 實驗結果與討論 65
4.1 UiO-66之XRD鑑定 65
4.2 UiO-66薄膜覆蓋率與截面觀測 66
4.3 UiO-66薄膜的表面起伏 68
4.4 ToF-SIMS量測 69
4.4.1 正負離子模式的選定與特徵破片的選擇 69
4.4.2 Ar1000,2500+ 能量密度對縱深分析之影響 73
4.4.3 以C60+ 單獨濺射之縱深分析 77
4.4.4 簇離子源 (C60+ 和 Ar1000,2500+) 與Ar+共濺射之結果 79
4.4.4.1 C60+—Ar+共濺射之縱深分析 80
4.4.4.2 Ar1000,2500+ 能量密度與Ar+共濺射對縱深分析之影響 83
4.4.5 Ar1000,2500+ 能量密度與Ar+共濺射對縱深分析影響之綜合比較 91
4.4.6 摻入藥物之 UiO-66 96
4.4.6.1 咖啡因特徵破片的選用 96
4.4.6.2 摻入咖啡因之UiO-66的縱深分析 99
第五章 結論 101
第六章 未來展望 102
第七章 參考資料 103

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