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研究生: 陳宗彥
Tsung-Yen Chen
論文名稱: 圖案化聚甲基丙烯酸乙酯高分子刷在矽晶片表面上的製備與應用
Fabrication and Application of the Patterned Poly(2-Hydroxyethyl methacrylate) Brushes on the Silicon Wafer
指導教授: 陳建光
Jem-Kun Chen
口試委員: 許應舉
none
邱顯堂
Hsien-Tang Chiu
林漢清
none
學位類別: 碩士
Master
系所名稱: 工程學院 - 材料科學與工程系
Department of Materials Science and Engineering
論文出版年: 2008
畢業學年度: 96
語文別: 中文
論文頁數: 85
中文關鍵詞: 原子轉移自由基聚合法高分子刷自組裝馬鐵蛋白
外文關鍵詞: Atom Transfer Radical Polymerization, Polymer brush, Self-assembled, Ferritin
相關次數: 點閱:323下載:3
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  • 本研究利用原子轉移自由基聚合法(atom transfer radical polymerization,ATRP),在矽晶片上接枝聚合聚甲基丙烯酸乙酯poly(2-Hydroxyethyl methacrylate,PHEMA)高分子刷;首先利用電子束微影(electron-beam lithography),於矽晶圓表面製造出光阻圖案,接著進行氧電漿處理,使無光阻區之矽表面產生氫氧基,然後利用此氫氧基,於表面進行起始劑自組裝反應,使矽晶片表面自組裝11-(2-Bromo-2-methyl)propionyloxyundecenyltrichlorosilane單層膜,此為原子轉移自由基聚合反應的起始劑,接著加入氯化亞銅、溴化銅、2,2’-Bypyridine以及甲基丙烯酸乙酯,分別做為金屬觸媒、螯合劑、接枝單體,進行原子轉移自由基聚合。
    使用化學分析電子光譜儀(electron spectroscopy for chemical analysis,ESCA),分析起始劑自組裝單分子層與PHEMA高分子刷之表面元素;使用橢圓測厚儀(Ellipisometer)量測PHEMA高分子刷之厚度,反應24小時之PHEMA高分子刷的厚度約為424 nm;使用原子力顯微鏡(atomic force microscopy,AFM)與掃描式電子顯微鏡(scanning electron microscope,SEM),分析圖案化PHEMA高分子刷與鐵蛋白分布。結果顯示,本研究建立了能於矽表面製備PHEMA高分子刷之製程並且成功的定位鐵蛋白於分子刷上。


    The patterned poly (2-Hydroxyethyl methacrylate) (PHEMA) polymer brushes were grafted on the silicon surface by using atom transfer radical polymerization (ATRP) method. The silicon wafer surface patterned by electron beam lithography was treated oxygen plasma to increase the hydroxyl groups, then the samples were immersed into the 11-(2-Bromo-2-methyl)propionyloxyundecenyltrichlorosilane as the initiator of self-assembled monolayer to modify the surface through the hydroxyl group on the silicon wafer. The PHEMA brushes on the silicon wafer surface were grafted by using 2,2’-Bypyridine、 CuCl、CuBr2 and 2-Hydroxyethyl methacrylate (HEMA) as the ligand, catalytic and monomer for ATRP, respectively. The Electron Spectroscopy for Chemical Analysis (ESCA) was utilized to analyze the surface element of SAMs of initiator and PHEMA polymer brushes. The thickness of PHEMA brushes polymerized after 24 hours was about 424 nm measured by ellipisometer. The morphology of patterned SAMs and PHEMA brushes were investigated by atomic force microscopy (AFM) and scanning electron microscopy (SEM). Therefore, the fabricated process of patterned PHEMA brushes on the silicon surface was established and the ferritin was successfully adhered to the pattered polymer brushes in this work.

    中文摘要I 英文摘要III 誌謝 V 目錄VI 圖表索引VIII 第一章緒論1 1-1研究背景1 1-2研究目的2 第二章文獻回顧3 2-1高分子刷簡介3 2-2自組裝單分子層6 2-2-1烷基硫醇自組裝單分子層 9 2-2-2烷基矽烷自組裝單分子層10 2-3原子轉移自由基聚合法11 2-4鐵蛋白19 2-5微影製程技術21 第三章實驗設備與方法24 3-1實驗材料24 3-2實驗儀器25 3-3實驗方法27 3-3-1平面高分子刷製備27 3-3-2圖案化高分子刷製備29 3-4鐵蛋白被覆38 3-5儀器原理39 3-5-1接觸角量測39 3-5-2原子力顯微鏡41 3-5-3掃描式電子顯微鏡46 3-5-4ESCA化學分析電子光譜儀50 第四章結果與討論53 4-1表面高分子刷改質結果分析53 4-1-1XPS分析53 4-1-2接觸角分析57 4-1-3 高分子刷厚度分析59 4-1-4AFM表面型態分析61 4-2PHEMA高分子刷圖案化之結果分析68 4-2-1AFM光阻表面形態分析68 4-2-2SEM光阻表面形態分析69 4-2-3AFM圖形化PHEMA分子刷分析70 4-2-4SEM圖形化PHEMA分子刷分析73 4-3馬鐵蛋白(Ferritin)於高分子刷表面吸附之結果分析75 4-3-1XPS表面分析75 4-3-2馬鐵蛋白於圖形化高分子刷上之SEM表面形態77 4-3-3鐵粒子之SEM與AFM表面形態78 第五章結論(Conclusion)80 第六章參考文獻(Reference)81 作者簡介85

    1.Milner, S. T. (1991) Polymer brushes. Science. 251: 905-914.
    2.Prucker, O., and Ruhe, J. (1998) Polymer Layers through Self-Assembled Monolayers of Initiators. Langmuir. 14(24): 6893-6898.
    3.Prucker, O., and Ruhe, J. (1998) Synthesis of Poly (styrene) Monolayers Attached to High Surface Area Silica Gels through Self-Assembled Monolayers of Azo Initiators. Macromolecules. 31(3): 592-601.
    4.Minko, S., Patil, S., Datsyuk, V., Simon, F., Eichhorn, KJ., Motornov, M., Usov, D., Tokarev, I and Stamm, M. (2002) Synthesis of Adaptive Polymer Brushes via ‘Grafting to’ Approach from Melt. Langmuir. 18, 289-296
    5.Luzinov, I., Julthongpiput, D., Malz, H., Pionteck, J., and Tsukruk, V., (2000) Polystyrene Layers Grafted to Epoxy-Modified Silicon Surface. Macromolecules. 33, 1043-1048
    6.Bigelow, W. C., Pickettl, D. L., and Zisman, W. A.(1946)Oleophobic monolayers-films adsorbed from solution in non-polar liquids. Journal of Colloid and Interface Science. 1: 513-583.
    7.Sagiv, J. (1980) Organized monolayers by adsorption. 1. Formation and structure of oleophobic mixed monolayers on solid surfaces. Journal of the American Chemical Society. 102(1): 92-98.
    8.Nuzzo, R. G., and Allara, D. L. (1983) Adsorption of bifunctional organic disulfides on gold surfaces. Journal of the American Chemical Society. 105(13): 4481-4483.
    9.Jordan, R., and Ulman, A. (1998) Surface Initiated Living Cationic Polymerization of 2-Oxazolines. Journal of the American Chemical Society. 120(2): 243-247.
    10.Jordan, R., Ulman, A., Kang, J. F., Raffailovich, M. H., and Sokolov, J. (1999) Surface-Initiated Anionic Polymerization of Styrene by Means of Self-Assembled Monolayers. Journal of the American Chemical Society. 121(5): 1016-1022.
    11.Delamarche, E., Michel, B., Kang, H., and Gerber, C. (1994) Thermal Stability of Self-Assembled Monolayers. Langmuir. 10 : 4103-4108.
    12.Tao, Y. T., Lee, M. T., and Chang, S. C. (1993) Effect of biphenyl and naphthyl groups on the structure of self-assembled monolayers: packing, orientation, and wetting properties. Journal of the American Chemical Society. 115(21): 9547-9555.
    13.Brzoska, J. B., Azouz, I. B., and Rondelez, F. (1994) Silanization of solid sub-strates: A step toward reproducibility. Langmuir. 10(11): 4367-4373.
    14.Kato, M., Kamigaito, M., and Sawamoto, M. (1995) Polymerization of Methyl Methacrylate with the Carbon Tetrachloride / Dichlorotris- (triphenylphosphine) ruthenium(II) / Methylaluminum Bis (2,6-di-tert-butylphenoxide) Initiating System: Possibility of Living Radical Polymerization. Macromolecules. 28(5): 1721-1723.
    15.Wang, J. S., and Matyjaszewski, K. (1995) Controlled / "living" radical polymerization. atom transfer radical polymerization in the presence of transition-metal complexes. Journal of the American Chemical Society. 117(20): 5614-5615.
    16.Grimaud, T., and Matyjaszewski, K. (1997) Controlled/"Living" Radical Polymerization of Methyl Methacrylate by Atom Transfer Radical Polymerization. Macromolecules. 30(7): 2216-2218.
    17.Patten, T. E., and Matyjaszewski, K. (1998) Atom Transfer Radical Polymerization and the Synthesis of Polymeric Materials. Advanced Materials. 10(12): 901-915.
    18.Percec, V., and Barboiu, B. (1995) "Living" Radical Polymerization of Styrene Initiated by Arenesulfonyl Chlorides and CuI (bpy) nCl. Macromolecules. 28(23): 7970-7972.
    19.Davis, K. A., Paik, H., and Matyjaszewski, K. (1999) Kinetic Investigation of the Atom Transfer Radical Polymerization of Methyl Acrylate. Macromolecules. 32(6): 1767-1776.
    20.Gromada, J., and Matyjaszewski, K. (2001) Simultaneous Reverse and Normal Initiation in Atom Transfer Radical Polymerization. Macromolecules. 34(22): 7664-7671.
    21.Matsumoto, M., (1994) Spread Monolayers of a Water-Soluble Protein (Ferritin) and Its Two and Three Dimensional Arrays. Langmuir. 10, 3922-3925.
    22.Matsui, T., Matsukawa, N., Iwahori, K., Sano, K. I., Shiba, K., and Yamashita, I., (2007) Realizing a Two-Dimensional Ordered Array of Ferritin Molecules Directly on a Solid Surface Utilizing Carbonaceous Material Affinity Peptides. Langmuir. 23, 1615-1618.
    23.Yamashita, I., (2001) Fabrication of a Two-Dimensional Array of Nano-Particles Using Ferritin Molecule. Thin Solid Films. 393, 12-18
    24.Hikono, T., Uraoka, Y., Fuyuki, T., and Yamashita, I., (2003) Novel Method for Making Nanodot Arrays Using a Cage-like Protein. Jpn. J. Appl. Phys. 42, 398-399
    25.Mackle, P., Charnock, J. M., and Garner, C. D., (1993) Characterization of the Manganese Core of Reconstituted Ferritin by X-ray Absorption Spectroscopy. J. Am. Chem. Soc. 115, 8471-8472
    26.Douglas, T., Dickson, D., Betteridge, S., Charnock, J., Garner, C.D., and Mann, S., (1995) Synthesis and Structure of an Iron(III) Sulfide-Ferritin Bioinorganic Nanocomposite. Science. 269, 5220, 54-57
    27.Kubota, T., Baba T., and Samukawa, S., (2004) A 7-nm Nanocolumn Structure Fabricated by Using a Ferritn Iron-core Mask and Low-energy Cl Neutral Beams. Applied Physics Letters. 84, 9, 1555-1557
    28.Kim, W., Choi, H, C., Shim, M., Li, Y., Wang, D., and Dai, H., (2002) Synthesis of Ultralong and High Percentage of Semiconducting Single-walled Carbon Nanotubes. Nano Letters. 2, 7, 703-708
    29.King, C, G., Choi, H, S., Chu, S. H., Kim, J. W., Park, Y., Lillehei, P., Watt, G. D., Davis, R., and Harb, J. N., (2004) Development of a Bio-nanobattery for Distributed Power Storage System. Proc SPIE. 5389, 461
    30.Ahn, S. J., Kaholek, M., Lee, W. K., LaMattina, B., LaBeam, T. H., and Zauscher, S., (2004) Surface-Initiated Polymerization on Nanopatterns Fabricated by Electron-Beam Lithography. Advanced Material. 16, 23-24, 2141-2145
    31.Zhou, F., Zheng, Z., Yu, B., Liu, W., and Huck, W. S., (2006) Multicomponent Polymer Brushes. J. Am. Chem. Soc. 128, 16253-16258.
    32.Matyjaszewski, K., Miller, P. J., Shukla, N., Immaraporn, B., Gelman, A., Luokala, B., Siclovan, T., Kickelbick, G., Vallant, T., Hoffmann, H., and Pakula, Tadeusz., (1999) Polymers at Interfaces: Using Atom Transfer Radical Polymerization in the Control Growth of Homopolymers and Block Copolymers from Silicon Surface in the Absence of Untethered Sacrificial Initiator. Macromolecules. 32, 8716-8724.
    33.Xu, F. J., Cai, Q. J., Kang, E. T., and Neoh, K.G., (2005) Surface-Initiated Atom Transfer Radical Polymerization from Halogen-Terminated Si(111) (Si-X, X=Cl, Br) Surfaces for the Preparation of Well-Defined Polymer-Si Hybrids. Langmuir. 21, 3221-3225.
    34.Huang, W., Kim, J. B., Bruening, M., and Baker, G., (2002) Functionalization of Surface by Water-Accelerated Atom Transfer Radical Polymerization of Hydroxyethyl Methacrylate and Subsequent Derivatization. Macromolecules. 35, 1175-1179.
    35.Zhao, B., and Brittain, W., (2000) Synthesis, Characterization, and Properties of Tethered Polystyrene-b-polyacrylate Brushes on Flat Silicate Substrates. Macromolecules. 33, 8813-8820.

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