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研究生： 簡儀禎
Chien, Yi-Chen
論文名稱： 超薄蝕刻阻劑在金的圖形製作表面之抗蝕刻機制研究
Anti-etching mechanism of the patterned ultra-thin SAMs-based resist on Au(111)-dominant surface
指導教授： 廖峻德
Liao, Jiunn-Der
學位類別： 碩士
Master
系所名稱： 工學院 - 材料科學及工程學系
Department of Materials Science and Engineering
論文出版年： 2006
畢業學年度： 94
語文別： 中文
論文頁數： 60
中文關鍵詞： 微觸壓印 、自組裝單分子層 、掃描式光電子顯微術 、金化學液相蝕刻
外文關鍵詞： Microcontact printing, Self-assembled monolayers, Au etchant, Scanning photoelectron microscopy
相關次數： 點閱：125  下載：5 
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    • 自組裝單分子層（Self-Assembled Monolayers, SAMs）排列整齊、結構穩定且可藉由選擇不同尾端官能基的硫醇分子促使SAMs形成具特定功能性的表面。其中，長鏈烷基硫醇分子於Au表面形成SAMs時以硫端與Au產生化學鍵結而形成一具有CH3 官能基之表面。且因CH3 官能基表面具化學惰性，針對特定化學蝕刻液擁有抵抗化學腐蝕之能力，以此特性將可應用於製作微奈米等級圖案的超薄蝕刻阻劑。本研究的重點在於研究探討以SAMs作為製作Au圖案的蝕刻阻劑時，SAMs對於特定蝕刻液抗侵蝕的機制。在本研究中，首先以橢圓偏光術及原子力顯微術針對於經化學蝕刻後試片表面之Au薄膜厚度及其表面相貌而訂定Au蝕刻終點。接著以微觸壓印（Microcontact Printing, μCP）的方法，使用PDMS將含有SAMs成分之圖形轉印於Au表面，而後使用特定配方之Au蝕刻液將轉印於Au表面之圖樣進行顯影。進一步，並將此具圖案的表面以掃描式光電子顯微儀（Scanning Photoelectron Microscope, SPEM）進行表面化學元素分布分析，並使用電子顯微鏡及原子力顯微鏡作圖形表面形貌分析。進一步並針對SAMs被破壞的情形與Au圖案之間的關係進行探討。研究結果顯示，從XPS能譜結果可得知在壓印圖像中SAMs化學結構，唯有接近圖形邊界處，S 2p與C 1s才有被破壞的跡象出現。對照AFM表面相貌圖結果推測，SAMs於特定化學液相蝕刻環境下可以有效正面阻擋蝕刻液侵蝕Au，但是對於蝕刻液之側向侵蝕阻擋力較弱，故SAMs以及Au在圖像邊界皆發現被蝕刻液破壞的現象。另外，使用μCP製作SAMs圖案時，未接觸到Au表面的軟模所吸附的硫醇分子會因擴散效應而產生非壓印圖案處有蝕刻未完全之現象，因此以未壓印SAMS的Au測得的蝕刻終點與μCP有落差，因此需以延長蝕刻時間或縮短壓印時間方可減輕因硫醇分子擴散而造成之蝕刻不完全現象。

    Self-assembled monolayers (SAMs) are capable to form a functionalized surface on a metal surface with good uniformity and stability. In this study, alkanethiolate molecules with -CH3 terminated tail group chemically adsorb upon Au substrate and form Au-S bonds, which potentially act as ultra-thin resist films with excellent uniformity in molecular order and high resistivity to chemicals. Anti-etching mechanism of the patterned self-assembled Octadecanethiol (ODT) on Au (111)-dominant surface has been mainly discussed. In the experiment, the end point of Au etching process was determined by ellipsometry and AFM. The patterned SAMs were fabricated using microcontact printing (μCP) technique and subsequent to be developed by Au etching solution. The images of element distribution on the patterned Au were investigated by SPEM. Subsequently surface morphology of the patterned Au was then characterized by AFM and SEM. At the same time, the damaged SAMs in association with the morphology of Au were discussed. Experimental results demonstrated that the damaged pattern at the boundary between the μCP SAMs and the etched part was clearly identified. The SAMs protected part was resistive to a specific etching solution, whereas SAMs at the patterned boundary exhibited weak in resisting the analogous solution. Potentially alkanethiols adsorbed on PDMS stamp tend to diffuse away from the region of contact; thereafter the residual Au in the non-contact region is unable to be removed completely during the etching process. It is suggested to reduce the effect of incomplete etching process by shortening the printing time or extending the etching time.

    第一章　序論..................................................................01 1-1　前言....................................................................01 1-2　文獻回顧................................................................02 1-2.1　自組裝單分子層........................................................02 1-2.2　微觸印刷術............................................................04 1-3　研究動機與目的..........................................................06 第二章　理論基礎..............................................................07 2-1　自我排列單分子層........................................................07 2-1.1　自組裝原理............................................................07 2-1.2　自組裝單分子層的結構及種類............................................08 2-1.3　硫醇類自組裝單分子層..................................................09 2-2　微觸壓印................................................................11 2-2.1　母模..................................................................12 2-2.2　印章..................................................................13 2-2.3　墨水..................................................................14 2-3　濕式化學蝕刻............................................................14 2-3.1　濕式化學蝕刻原理......................................................15 2-3.2　金的蝕刻..............................................................16 2-4　同步輻射光..............................................................17 2-5　XPS與SPEM...............................................................18 2-5.1　XPS 原理..............................................................18 2-5.2　掃描式光電子顯微儀....................................................19 2-6　原子力顯微鏡............................................................21 2-7　橢圓偏光術以及光學模型的建立............................................22 2-7.1　橢圓偏光術............................................................22 2-7.2　模型的建立............................................................23 第三章　材料與方法............................................................25 3-1　Au薄膜製備..............................................................25 3-2　Au蝕刻終止點............................................................26 3-3　微觸壓印的SAMs分析以及Au圖案的製作與分析................................27 第四章　結果與討論............................................................32 4-1　Au表面性質評估..........................................................32 4-1.1　晶格排列..............................................................32 4-1.2　表面粗糙度............................................................34 4-1.3　膜厚均勻性............................................................34 4-2　Au蝕刻速率以及蝕刻終止點................................................35 4-2.1　橢圓偏光儀量測Au殘留厚度..............................................36 4-2.2　AFM觀察蝕刻過程中的Au表面形貌.........................................39 4-3　微觸壓印之自組裝單分子層分析............................................40 4-3.1　自組裝單分子層的表面潤濕性質..........................................41 4-3.2　自組裝單分子層的光學模型建立以及膜厚量測..............................42 4-3.3　自組裝單分子層的XPS分析...............................................44 4-4 　Au圖像解析.............................................................46 4-4.1　SPEM..................................................................46 4-4.2　AFM...................................................................51 4-4.3　微觸壓印的Au蝕刻終點..................................................54 結論..........................................................................59 參考文獻

    參考文獻
    【1】W. M. Moreau, “Semiconductor Lithography: Principles and Materials”, Plenum, 1988.
    【2】Y. Xia, X. M. Zhao and G. M. Whitesides, “Pattern Transfer：Self-Assembled Monolayers as Ultrathin Resists”, Microelectronic Engineering, Vol. 32, pp. 255-268, 1996.
    【3】A. Kumar and G. M. Whitesides, “Features of Gold Having Micrometer to Centimeter Dimensions Can Be Formed Through a Combination of Stamping with an Elastomeric Stamp and an Alkanthiol “Iink” Followed by Chemical Etching”, Apply Physics Letters, Vol. 63, pp. 2002-2004, 1993.
    【4】M. J. Lercel, H. G. Craighead, A. N. Parikh, K. Seshadri and D. L. Allara, “Sub-10 nm Lithography with Self-assembled Monolayers”, Applied Physics Letters, Vol. 68, pp. 1504-1506, 2000.
    【5】C. David, H. U. Muller, B. Volkel and M. Grunze, “Low Energy Electron Proximity Printing Using a Self-Assembled Monolayer Resist”, Microelectronic Engineering, Vol. 30, pp.57-60, 1999.
    【6】H. S. Sugimura, T. Hanji, O. Takai, T. Masuda and H. Misawa, “Photolithography Based on Organosilane Self-Assembled Monolayer Resist”, Electrochimica Acta, Vol. 47, pp.103-107, 2001.
    【7】R. Klauser, M. L. Huang, S. C. Wang, C. H. Chen, T. J. Chuang, A. Terfort and M. Zharnikov, “Lithography with a Focused Soft X-ray Beam and a Monomolecular Resist”, Langmuir, Vol. 20, pp. 2050-2053, 2004.
    【8】J. Xin, K. Mitsunori, S. Taku and Y. Yasushi, “ Positive and Negative Patterning of Ethanethiol, Decanethiol, and Hexadecanethiol Self-Assembled Monolayers by Using a Metastable Helium Beam”, Thin Solid Films, Vol. 464-465, pp. 420-424, 2004.
    【9】G. Y. Liu, S. Xu and Y. Qian, “Nanofabrication of Self-Assembled Monolayers Using Scanning Probe Lithography”, Accounts of Chemical Research, Vol. 33, pp. 457-466, 2000.
    【10】陳守仁,巫震華,何侑倫,王維漢,陳來勝,”奈米轉印技術發展現況”, 機械工業, Vol. 267, pp. 36-46, 2005.
    【11】R. G. Nuzzo and D. L. Allara, “Adsorption of Bifunctional Organic Disulfides on Gold Surface”, Journal of the American Chemical Society, Vol. 105, pp. 4481-4483, 1983.
    【12】R. G. Nuzzo, B. R. Zegarski and L. H. Dubois, “Fundamental Study of the Chemisorption of Organosulfur Compounds on Au(111). Implications for Molecular Self-Assembly on Gold Surface”, Journal of the American Chemical Society, Vol.109, pp. 733-740, 1987.
    【13】N. Camillone III, C. E. D. Chidsey, G. Y. Liu and G. Scoles, “Superlattice Structure at the Surface of a Monolayer of Octadecanethiol Self-Assembled on Au(111)”, The Journal of chemical physics, Vol. 98, No. 4, pp. 3503-3511, 1993.
    【14】C. D. Bain and G. M. Whitesides, “Formation of Monolayers by the Coadsorption of Thiols on Gold：Variation in Length of Alkyl Chain”, Journal of the American Chemical Society, Vol. 111, pp. 7164-7175, 1989.
    【15】 J. P. Folkers, P. E. Laibinis and G. M. Whitesides, “Self-Assembled Monolayers of Alkanethiols on Gold：Comparisons of Monolayers Containing Mixture of Shortand Long-Chain Constituents with CH3 and CH2OH Terminal Groups”, Langmuir, Vol. 8, pp. 1330-1341, 1992.
    【16】P. E. Laibinis, G. M. Whiteside, D. L. Allara, Y. T. Tao, A. N. Parikh and R. G. Nuzzo, “Comparison of the Structures an Wetting Properties of Self Assembled Monolayers of n-Alkanethiols on the Coinage Metal Surfaces, Cu, Ag, Au”, Journal of the American Chemical Society, Vol. 113, pp. 7152-7167, 1991.
    【17】A. Ulman, “An Introduction to Ultrathin Organic Films From Langmuir-Blodgett to Self-Assembly”, Rochester, 1991.
    【18】T. Ishida, M. Hara, I. Kojima, S. Tsuneda, N. Nishida, H. Sasabe and W. Knoll, “High Resolution X-ray Spectroscopy Measurements of Octadecanethiol Self-Assembled Monolayers on Au(111)”, Langmuir, Vol. 14, pp. 2092-2096, 1998.
    【19】T. Ishida, N. Choi, W. Mizutani, H. Tokumoto and I. Kojima, “High Resolution X-ray Photoelectron Spectra of Organosulfur Monolayers on Au(111)：S(2p) Spectral Dependence on Molecular Species”, Langmuir, Vol. 15, pp. 6799-6806, 1999.
    【20】R. Yamada, H. Wano and K. Uosaki, “Effect of Temperature on Structure of the Self-Assembled Monolayer of Decanethiol on Au(111) Surface”, Langmuir, Vol. 16, pp. 5523-5525, 2000.
    【21】Y. Xia, X.-M. Zhao, E. Kim and G. M. Whitesides, “A Selective Etching Solution for Use with Patterned Self-Assembled Monolayers of Alkanethiolates on Gold”, Chemestry of Materials, Vol. 7, pp. 2332-2337, 1995.
    【22】N. B. Larsen, H. Biebuyck, E. Delamarche and B. Michel, “Order in Microcontact Printed Self-Assembled Monolayers”, Journal of the American Chemical Society, Vol. 119, pp. 3017-3026, 1997.
    【23】E. Delamarche, H. Schmid, A. Bietsch, N. B. Larsen, H. Rothuizen, B. Michel and H. Biebuyck, “Transport Mechanisms of Alkanethiols during Microcontact Printing on Gold”, Journal of Physical Chemistry B, Vol. 102, pp. 3324-3334, 1998.
    【24】Y. Xia and G. M. Whitesides, “Soft Lithography”, Angewandte Chemie-International Edition, Vol. 37, pp. 550-575, 1998 .
    【25】E. Delamarche, M. Geissler, H. Wolf and B. Michel, “Positive Microcontact Printing”, Journal of the American Chemical Society, Vol. 124, pp. 3834-3835, 2002.
    【26】M. Geissler, H. Wolf, R. Stutz, E. Delamarche, U. W. Grummt, B. Michel and A. Bietsch, “Fabrication of Metal Nanowires Using Microcontact Printing”, Langmuir, Vol. 19, pp. 6301-6311, 2003.
    【27】張立德、牟季美，”奈米結構自組織和分子自組織合成和性能”，滄海書局，pp. 349，2002
    【28】A. Ulman, “Formation and Structure of Self-Assembled Monolayers”, Chemistry Review, Vol. 96, pp. 1533-1554, 1996.
    【29】H. Sellers, A. Ulman, Y. Shnidman and J. E. Eilers, “Structure and Bonding of Alkanethiolates on Gold and Silver surfaces: Implications for Self-Assembled Monolayers”, Journal of the American Chemical Society, Vol. 115, pp. 9389-9401, 1993.
    【30】T. Pompe, A. Fery and S. Herminghaus, “Submicron Contact Printing on Silicon Using Stamp Pads”, Langmuir, Vol. 15, pp. 2398-2401, 1999.
    【31】M. Wang, K. M. Liechti, Q. Wang and J. M. White, “Self-Assembled Silane Monolayers：Fabrication with Nanoscale Uniformity”, Langmuir, Vol. 21, pp. 1848-1857, 2005.
    【32】N. Shirahata, Y. Masuda, T. Yonezawa and K. Koumoto, “Atomic Scale Flattening of Organosilane Self-assembled Monolayer and Patterned Tin Hydroxide Thin Films”, Journal of the European Ceramic Society, Vol. 24, pp. 427-434, 2004.
    【33】S. Asakura, A. Hozumi, T. Yamaguchi and A. Fuwa, “Fabrication of High-density Copper Microstructures Using Vacuum Ultraviolet Light Lithography and Hydrofluoric Acid Etching Treatment”, Thin Solid Films, Vol. 467, pp. 127-132, 2004.
    【34】M. Saalmink, C. van der Marel, H. R. Stapert and D. Burdinski, “Positive Microcontact Printing with Mercaptoalkyloligo(ethyleneglycol)s”, Langmuir, Vol. 22, pp. 1016-1026, 2006.
    【35】J. F. Kunzler, “Silicone Hydrogels for Contact Lens Application”, Trends in Polymer Science, Vol. 4, pp. 52-59, 1996.
    【36】T. E. Balmer, H. Schmid, R. Stutz, E. Delamarche, B. Michel, N. D. Spencer and H. Wolf, “Diffusion of Alkanethiols in PDMS and Its Implications on Microcontact Printing (μCP)”, Langmuir, Vol. 21, pp. 622-632, 2005.
    【37】D.G. Hill, K.L. Lear and J. S. Harris, “Two Selective Etching Solutions for GaAs on InGaAs and GaAs/AlGaAs on InGaAs”, Journal of the Electrochemical Society, Vol. 137, pp. 2912-2914, 1990.
    【38】S.M. Sze and G.Y. Chang, “ULSI Technology”, McGraw-Hill, 1996.
    【39】施敏、張俊彥,”半導體元件與物理與製作技術”, 高立圖書公司, 1996.
    【40】F. P. Zamborini and R. M. Crooks, “Corrosion Passivation of Gold by n-Alkanethiol Self-Assembled Monolayers: Effect of Chain Length and End Group”, Langmuir, Vol. 14, pp. 3279-3286, 1998.
    【41】郭正次, “激發光光譜分析”, 材料分析, Ch. 10, 中國材料學會.
    【42】潘扶民, “化學分析電子儀分析”, 材料分析, Ch. 13, 中國材料學會.
    【43】P. A. Tipler and R. A. Llewellyn, “Modern Physics”, Llewellyn, 2002.
    【44】C. M. Chan, “Polymer Surface Modification and Characterization”, Hanser, 1994.
    【45】洪一弘, 李德輝, 殷廣鈐, 魏德新, 但唐諤, 柯陸詩, 陳建德, 曾金榮, 莊東榮, “掃描式光電子能譜顯微儀簡介”, 科學發展月刊, Vol. 29, pp. 21-28, 2000.
    【46】D. Bonnell, “Scanning Probe Microscopy and Spectroscopy Theory, Techniques and Applications”, Wiley, 2001.
    【47】H. G. Tompkins and W. A. McGahan, “Spectroscopic Ellipsometry and Reflectometry：A User’s Guide”, Wiley, 1999.
    【48】S. Kobayashi, T. Nishikawa, T. Takenobu, S. Mori, T. Shimoda, T. Mitani, H. Shimotani, N. Yoshimoto, S. Ogawa and Y. Iwasa, “Control of Carrier Density by Self-assembled Monolayers in Organic Field-effect Transistors”, Nature Materials, Vol. 3, pp. 317-322, 2004.

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