Title

利用聚焦軟X光進行自組裝單分子層尾部官能基改質及其選擇性吸附之研究

Translated Titles

Modification and Selective Adsorption of Functional Tail-Group on Self-Assembled Monolayers by Focused Soft X-ray Beam

DOI

10.6845/NCHU.2007.00785

Authors

廖婉伶

Key Words

自組裝單分子層 ; 同步輻射 ; X光光電子能譜 ; 掃描式光電子顯微儀 ; self-assembled monolayers(SAMs) ; synchrotron radiation ; X-ray photoelectron spectroscopy(XPS) ; Scanning photoelectron microscope(SPEM)

PublicationName

中興大學材料科學與工程學系所學位論文

Volume or Term/Year and Month of Publication

2007年

Academic Degree Category

碩士

Advisor

許薰丰

Content Language

繁體中文

Chinese Abstract

本研究利用軟X光照射芳香族(aromatic)自組裝單分子層(self-assembled monolayers ,SAMs)進行表面化學微影術(lithography)。使用的SAMs為成長在Au(111)上的4-硝基-1,1二苯環-4-硫醇(4'-nitro-1',1'-biphenyl-4- thiol, NBPT)自組裝單分子層。實驗入射光源及分析儀器在國家同步輻射研究中心(NSRRC)的掃描式光電子顯微儀(Scanning photoelectron microscope, SPEM)實驗站進行。當軟X光(480 eV)照射在NBPT SAMs時,其尾部官能基會由硝基(nitro, NO2)轉變成胺基(amino, NH2),並以照光處理前、後的區域與三氯乙酸酐進行選擇性醯化反應來驗證此光轉換效應。接續,以SPEM將軟X光聚焦至奈米尺度,對SAMs進行次微米微影圖案的化學選擇性吸附作用;由micro X光光電子能譜(XPS)以及光電子影像的實驗結果得知,利用SPEM可成功地對NBPT SAMs進行微區化學選擇性吸附的改質作用;也可藉由控制入射X光劑量(dosage)改變NBPT SAMs尾部官能基的反應量。

English Abstract

In this study,surface chemical lithorgaphy on aromatic self-assembled monolayers (SAMs) has been achieved by exposing the monomolecular resist to focused soft X-ray beam. The SAMs used in this study was nitrobiphenylthiolate (NO2(C6H4)2SH;NBPT) grown on gold. The scanning photoelectron microscope (SPEM) at National Synchrotron Radiation Research Center (NSRRC) was utilized to pattern and obtain the chemical information from the monomolecular resist. Upon the soft X-ray(480 eV) irradiation, the functional tail group of the NBPT film was transferred from nitro group(NO2) into amino group(NH2), which can be confirmed by photoelectron spectroscopy and ex-situ anhydride adsorption. With the micro X-ray photoelectron spectroscopy(XPS) and photoelectron image, we demonstrated that chemical selective adsorption can be achieved in submicron area of NBPT/Au SAMs by focused soft X-ray beam. Also, the transformation of functional tail-group can be controlled by incidenced soft X-ray dosage.

Topic Category 工學院 > 材料科學與工程學系所
工程學 > 工程學總論
Reference
  1. [1] K. W. Kolasinski, Surface Science: Foundations of Catalysis and Nanoscience, John Wiley & Sons: New York, 2002.
    連結:
  2. [2] L.H. Dubois and R.G. Nuzzo, “Synthesis, structure, and Properties of Model Organic Surface”, Annu. Rev. Phys. Chem. 43 (1992) 437.
    連結:
  3. [3] A. Ulman, “Thin film: self-assembled monolayers of thiols”, Academic,SanDiego, CA, (1998).
    連結:
  4. [4] T. Ishida, M. Hara, I. Kojima, S. Tsuneda, N. Nishida, H. Sasabe, and W. Knoll, “High Resolution X-ray Photoelectron Spectroscopy Measurements of Octadecanethiol Self-Assembled Monolayers on Au(111)”, Langmuir 14 (1998) 2092.
    連結:
  5. [5] T. Ishida, N. Choi, W. Mizutani, H. Tokumoto, I. Kojima, H. Azehara, H. Hokari, U. Akiba, and M. Fujihira, “High-Resolution X-ray Photoelectron Spectra of Organosulfur Monolayers on Au(111): S(2p) Spectral Dependence on Molecular Species”, Langmuir 15 (1999) 6799.
    連結:
  6. [6] R. K. Smith, P. A. Lewis, and P. S. Weiss, “Review Patterning self-assembled monolayers”, Prog. Surf. Sci. 75 (2004) 1.
    連結:
  7. [7] W. Geyer, V. Stadler, W. Eck, M. Zharnikov, A. Gölzhäuser, and M.Grunze, “Electron-induced crosslinking of aromatic self-assembled monolayers: Negative resists for nanolithography”, Appl. Phys. Lett. 75(1999) 2401.
    連結:
  8. [8] W. Eck, V. Stadler, W. Geyer, M. Zharnikov, A. Gölzhäuser, and M. Grunze, “Generation of Surface Amino Groups on Aromatic Self-Assembled Monolayers by Low Energy Electron BeamsÐA First Step Towards Chemical Lithography”, Adv. Mater. 12 (2000) 805.
    連結:
  9. [10] N. Inagaki, S. Tasaka, T. Horiuchi, and R. Suyama, “Surface modification of poly(aryl ether ether ketone) film by remote oxygen plasma”, J. Appl. Poly. Sci. 68 (1998) 271.
    連結:
  10. [11] M. C. Wang, J. D. Liao, C. C. Weng, R. Klauser, S. Frey, M. Zharnikov, and M. Grunze, “The Effect of the Substrate on Response of Thioaromatic Self-Assembled Monolayers to Free Radical-Dominant Plasma”, J. Phys. Chem. B 106 (2002) 6220.
    連結:
  11. [12] C. C. Weng, J. D. Liao, Y. T. Wu, M. C. Wang, R. Klauser, and M.Zharnikov, “Modification of Monomolecular Self-Assembled Films by Nitrogen-Oxygen Plasma”, J. Phys. Chem. B 110 (2006) 12523.
    連結:
  12. [13] H. Sugimura, K. Ushiyama, A. Hozumi, and O. Takai, “Micropatterning of Alkyl- and Fluoroalkylsilane Self-Assembled Monolayers Using Vacuum Ultraviolet Light”, Langmuir 16(2000) 885.
    連結:
  13. [14] M. S. Chen, C. S. Dulcey, L. A. Chrisey, and W. J. Dressick, “Deep-UV Photochemistry and Patterning of (Aminoethylaminomethyl) phenethylsilox- ane Self-Assembled Monolayers”, Adv. Funct. Mater. 16 (2006) 774.
    連結:
  14. [15] N. Ballav, T. Weidner, K. Röβler, H. Lang, and M. Zharnikov, “ A New Approach for the Fabrication of Strongly Heterogeneous Mixed Self-Assembled Monolayers”, Chem. Phys. Chem. 8 (2007) 819.
    連結:
  15. [18] T. C. Albert, V. Douglas, “X-ray Data Booklet”, Lawrence Berkeley National Laboratory University of California, 2001.
    連結:
  16. [19] 柯正浩, “同步輻射軟X光掃描式光電子能譜顯微儀”, 物理雙月刊, 20 (1998) 510.
    連結:
  17. [21] S. Günther, B. Kaulich, and L. Gregoratti, “Photoelectron microscopy and applications in surface and materials science”, Prog. Surf. Sci. 70 (2002) 187.
    連結:
  18. [23] 陳家浩, “從光電效應到光電子顯微鏡”, 物理雙月刊 27 (2005) 666.
    連結:
  19. [25] D. H. Wei, Y. J. Hsu, R. Klauser, I. H. Hong, G. C. Yin, and T. J. Chuang, “Photoelectron Microscopy Projects at SRRC”,Surf. Rev. Lett. 10(4) (2003) 617.
    連結:
  20. [31] S. Frey, V. Stadler, K. Heister, W. Eck, M. Zharnikov, M. Grunze, B. Zeysing, and A. Terfort, “Structure of Thioaromatic Self-Assembled Monolayers on Gold and Silver”, Langmuir 17 (2001) 2408.
    連結:
  21. [32] M. Zharnikov and M. Grunze, “Spectroscopic characterization of thiolderived self-assembling monolayers”, J. Phys.: Condens. Matter 13
    連結:
  22. (2001) 11333.
    連結:
  23. [33] R. Klauser, I. H Hong, S. C. Wang, M. Zharnikov, A. Paul, A. Gölzhäuser, A. Terfort, and T. J. Chuang, “Imaging and Patterning of Monomolecular Resists by Zone-Plate-Focused X-ray Microprobe”, J. Phys. Chem. B 107 (2003) 13133.
    連結:
  24. [35] T. Ishida, M. Hara, I. Kojima, S. Tsuneda, N. Nishida, H. Sasabe, and W. Knoll, “High Resolution X-ray Photoelectron Spectroscopy Measurements of Octadecanethiol Self-Assembled Monolayers on Au(111)”, Langmuir 14 (1998) 2092.
    連結:
  25. [36] T. Ishida, N. Choi, W. Mizutani, H. Tokumoto, I. Kojima, H. Azehara, H. Hokari, U. Akiba, and M. Fujihira, “High-Resolution X-ray Photoelectron Spectra of Organosulfur Monolayers on Au(111): S(2p) Spectral Dependence on Molecular Species”, Langmuir 15 (1999) 6799.
    連結:
  26. [38] G. Beamson and D. Briggs, “High Resolution of XPS of Organic Polymers, The Scienta ESCA 300 Database”, John Wiley & Sons: New York, 1992.
    連結:
  27. [39] J.Yue and A. J. Epstein, “XPS study of Self-Doped Conducting Polyaniline and Parent Systems”, Macromolecules 24 (1991) 4441.
    連結:
  28. [40] M. Wirde, U. Gelius, T. Dunbar, and D. L. Allara, “Modification of self-assembled monolayers of alkanethiols gold by ionizing radiation”, Nucl. Instr. and Meth. in Phys. Res. B 131 (1997) 245.
    連結:
  29. [9] A. Gölzhäuser, W. Eck, W. Geyer, V. Stadler, T. Weimann, P. Hinze, and M. Grunze, “Chemical Nanolithography with Electron Beams”, Adv. Mater. 13 (2001) 806.
  30. [16] 丁南宏 等,“真空技術與應用”, 行政院國家科學委員會精密儀器發展中心 (民90).
  31. [17] 國家同步輻射研究中心,同步加速器光源簡介.
  32. [20] 潘扶民, “化學分析電子儀分析”, 汪建民(主編),“材料分析”, 中國材料科學學會, 台北, (2005) pp. 353-368.
  33. [22] 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29 (2000) 21.
  34. [24] C. H. Chen, R. Klauser, S. Heun, Y. Watanabe, and M. Zharnikov,unpublished results.
  35. [26] J. C. Vickerman; Surface Analysis – The Principle Technique; John Wiley & Sons: New York, 1983.
  36. [27] D. Briggs and M. P. Seah, Practical Surface Analysis 2nd edition, Wiley & Sons: New York, 1994.
  37. [28] NSRRC Beamline Handbook,國家同步輻射研究中心,新竹, 2003.
  38. [29] D. Briggs, M. P. Seah, Practical Surface Analysis; Eds.; John Wiley & Sons: New York, 1983.
  39. [30] H. Ronald, Unifit for Windows Spectrum Processing, Analysis and Presentation Software for Core Level Photoelectron Spectra, University of Leipzig Wilhelm-Ostwald-Institute for Physical and Theoretical Chemistry, 1999
  40. [34] D. Briggs, M. P. Seah, “In Practical Surface Analysis”, John Wiley & Sons: New York, 1983.
  41. [37] C.D. Wanger, J.F. Moulder, L.E. Davis, and W.M. Riggs, “Handbook of X-ray photoelectron spectroscopy”, Perking-Elmer Corporation, Physical Electronics Division (end of book).