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研究生: 黃彥翔
論文名稱: 十八硫醇與十八烯分子藉由一步化製成自組裝於矽(111)表面的製備與鑑定
Fabrication and Characterization of Octadecylthiolate and Octadecyl SAMs on Si(111) via UV-enhanced Method in One-cell Process
指導教授: 洪偉修
學位類別: 碩士
Master
系所名稱: 化學系
Department of Chemistry
論文出版年: 2011
畢業學年度: 99
語文別: 英文
論文頁數: 81
中文關鍵詞: 自組裝分子膜十八硫醇十八烯矽(111)
英文關鍵詞: self-assembled monolayer, octadecylthiol, octadecene, Si(111)
論文種類: 學術論文
相關次數: 點閱:180下載:3
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  • 在之前的文獻中,單層自組裝分子膜在矽化氫表面的成長製程總是先進行氧化矽的蝕刻,使成為氫化矽表面,然後再將氫化矽置入充滿惰性氣體的反應瓶中進行分子自組裝反應,在這過程中,不可避免地,氫化矽表面會與空氣接觸,使的氫化矽在轉移的過程中會被氧化或吸附空氣中的氧氣,影響分子膜的成長。
    本篇論文探討藉由兩層溶液的系統來改良分子自組裝製程,兩層溶液系統的組成是由上層的有機層與下層的水相層所組成,藉由此系統,在下層蝕刻完成的矽化氫將不必經過空氣而進入有機相溶液,進而進行自組裝分子膜反應。反應完成的自組裝分子膜藉由水滴接觸角來判斷成膜品質,而原子力顯微鏡則用來觀察分子膜表面狀態,橢圓儀測量厚度和IR來鑑定分子官能基,另外,X光光電子能譜儀可用來鑑定矽表面的氧化狀態。
    我們利用octadecylthiol和octadecene來進行自組裝反應,實驗結果顯示octadecylthiol及octadecene分子膜的水滴接觸角分別達到101度及102度,表現出疏水的性質。另外透過AFM的表面鑑定,兩者在表面構形上皆呈現階梯狀的形貌,與蝕刻過的氫化矽表面有同樣的構形,不過粗度卻下降些許,顯示分子膜的存在;膜厚的部分大約在2奈米左右,而IR的官能基鑑定也證實CH3及CH2的存在,另外X光光電子能譜儀顯示C 1s的訊號,以上的資訊都顯示分子膜確實存在於氫化矽上。
    另外,為了測試分子膜對氫化矽的保護效果,我們將分子膜修飾後的矽化氫置於空氣中一天到七天,然後藉由XPS觀察矽的氧化程度,結果顯示我們所修飾的分子膜有抗氧化能力。透過以上的量測和鑑定,我們可以確認利用兩層溶液的方法,可以成功的製備單層分子膜於氫化矽表面,並且達到抗氧化效果

    In previous studies of SAMs on oxide-free Si(111), the SAM procedures always begin at the etching of the silicon surface; afterward, the etched silicon wafers are enclosed in reaction vase which provides inner surrounding to avoid SiOx forming while SAMs molecules react with silicon.
    In this work, we utilized a two-layer system which consists of organic phase and aqueous phase to proceed the SAM process without attachment to air. And the characterization of composition of SAM was carried out with X-ray photoelectron spectroscopy (XPS), atomic force microscopy (AFM), water contact angle (CA), and attenuated total reflectance infrared spectroscopy (ATR-IR).
    The result of contact angle shows that our SAMs possess hydrophobic property that the angle is 102゚ for octadecene (ODC) SAMs and 101゚for octadecythiol (ODT) SAMs. The AFM images show the step by step morphologies of both ODC and ODT SAMs. The XPS data show nearly no remaining silicon oxide in the Si 2p region (95-104 eV) from 1day to 7 days oxidation test.
    According to these data, we successfully fabricated a monolayer on oxide-free Si(111) surface, and our strategy of one-step method can be applied on the fabrication of ODT and ODC SAMs on oxide-free Si(111) surface. The one-step method providing an oxygen free surroundings can be applied on many surface-modification manufactures of semiconductors in the future.

    Abstract 2 摘要 3 Chapter 1 Introduction 6 Chapter 2 principle 11 2.1 The Hydrogen terminated silicon surface 11 2.1.1 Si(111) etched by NH4F solution 11 2.2 The methods of SAM on oxide-free Si(111) surface 15 2.2.1 thermal hydrosilylation27 of unsaturated molecules initiated by radicals 15 2.2.2 Alkylation of halide-terminated silicon surface 17 2.2.3 Direct attachment of alkylation through Grignard reagent 18 2.2.4 Photochemical reaction for alkylation onto Si(111) furface 19 2.3 Chemical constitution identification of SAM 20 2.4 surface roughness identification of SAM 24 2.5 Monolayer thickness determination 25 2.6 Measurement of wettability 27 Chapter 3 Experimental 29 3.1 experimental procedure 29 3.1.1 Cleaning(remove particles) 29 3.1.2 Etching(remove native oxides) 29 3.1.3 SAMs procedure via 2-step method 30 3.1.4 SAMs procedure via 1-step method 30 3.1.5 Clean post irradiation 31 3.2 XPS (X-ray photoelectron spectroscopy) 32 3.3 ATR-IR (Attenuated Total Reflectance Infrared) 32 3.4 Contact angle measurement 32 3.5 AFM (atomic force microscopy) 33 3.6 Ellipsometry 33 3.7 The teflon cell of one-step process 34 Chapter 4 Results and discussion 36 4.1 the preparation of Si before SAM grafting 36 4.1.1 Si(111) wafer clean 36 4.1.2 Si(111) Surface Hydrogenation 37 4.2 Grafting of organic molecules via two-step method 38 4.2.1 water contact angle measurement of thin films 38 4.2.2 AFM measurement of thin films 40 4.2.3 XPS spectra of alkanthiol SAM on Si(111) via 2-step method 45 4.2.4 XPS spectra of octadecene SAM on Si(111) via 2-step method 48 4.3 Grafting of Organic molecular via one-step method 51 4.3.1 Contact angle measurement of SAMs on Si(111) via method. 51 4.3.2 Surface morphology of thin film by AFM 54 4.3.3 XPS spectra of octadecylthiol SAM 58 4.3.4 XPS spectra of octadecene SAMs 62 ATR-IR 65 4.5 long-term oxidation test of SAMs 67 4.5.1 The 7 days oxidation of alkylthiol SAMs via 2-step method. 67 4.5.2 The 7 days oxidation of alkanethiol SAMs via 1-step method. 69 4.5.3 The 7 days oxidation of octadecene SAMs via 1-step method 70 Chapter 5 Conclusion 72 Appendix A Solvent effect 74 Appendix B Chemicals 76 Appendix C references 77

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