研究生: |
鄭智文 Jheng, Jhih-Wun |
---|---|
論文名稱: |
苯硫酚與苯酚在Ge(100)表面的吸附與熱分解反應 Adsorption and Thermal Decomposition of Thiophenol and Phenol on Ge(100) |
指導教授: |
洪偉修
Hung, Wei-Hsiu |
學位類別: |
碩士 Master |
系所名稱: |
化學系 Department of Chemistry |
論文出版年: | 2014 |
畢業學年度: | 102 |
語文別: | 中文 |
論文頁數: | 84 |
中文關鍵詞: | Ge(100) 、苯硫酚 、苯酚 |
英文關鍵詞: | Ge(100), thiophenol, phenol |
論文種類: | 學術論文 |
相關次數: | 點閱:94 下載:1 |
分享至: |
查詢本校圖書館目錄 查詢臺灣博碩士論文知識加值系統 勘誤回報 |
利用程溫脫附質譜(TPD)量測脫附碎片,並以X光光電子能譜(XPS)作為輔助,研究巰基(SH)與羥基(OH)不同取代基於苯環上,並比較苯硫酚與苯酚其吸附及熱分解之反應機構。
苯硫酚於低溫105 K曝露於Ge(100)上,會以斷硫氫鍵鍵結於表面上,在低曝露量下, C6H5S上的苯環以平躺的方式吸附於表面上,於高曝露量時,C6H5S上的苯環以站立的方式吸附於表面,達高曝露量時,出現未分解的化學吸附態與多層覆蓋的物理吸附。
苯硫酚於升溫脫附過程中,C6H5SH、H2、GeS、H2S、C6H6為主要分解產物,575 K時有苯硫酚重組合脫附峰出現,苯環的生成為C6H5S斷碳硫鍵鍵結於表面上,而苯環有兩種不同吸附態,於程溫脫附質譜中看到,表面的氫原子會與自己重組合脫附,或與硫生成H2S脫附。而高溫時產生的硫化鍺以斷Ge-Ge的方式生成。
苯酚吸附與苯硫酚大致相同,但熱分解形式不同,因碳氧鍵穩定不易斷鍵,故熱分解路徑不同,根據文獻所示,氧化鍺與硫化鍺所產生機制相同,應於同一溫度出現,但氧化鍺出現的溫度比文獻所提還高,是因氧化鍺的生成需待碳氧鍵的斷裂。另外,在程溫脫附儀訊號上可看到三次苯酚重組合訊號,我們利用理論計算出的位能配合所做實驗數據共同解釋。
The adsorption and thermal reactions of thiophenol (C6H5SH) and phenol (C6H5OH) on Ge(100) surface were studied with temperature programmed desorption (TPD) and X-ray photoelectron spectroscopy (XPS) using synchrotron radiation. The desorbed products of thermal reactions could be measured by TPD, and the XPS was utilized to identify the surface species.
Most of the thiophenol adsorbed on Ge(100) at 105 K dissociated into surface C6H5S(a) and H(a). The thiophenoxy group lay flat in the low-exposure regime and stood upright upon higher exposures. The chemsorbed and physorbed thiophenol appeared on the Ge(100) at larger exposures.
The desorption products of C6H5SH were C6H5SH(g), H2(g), GeS(g), H2S(g), and C6H6(g). At 575K, the desorption of thiophenol resulted from the recombination of C6H5S(ad) and H(ad). The surface C6H5S(a) cleaved the carbon-sulfur bond to release the C6H5 bond and reacted with H to desorb benzene. According to the TPD spectra, we propose that benzene has two adsorption states. The desorption of hydrogen with recombination of H(ad) + H(ad) and some hydrogen reacted with surface S to become H2S(g).At 690K, GeS(g) desorbed from the surface due to the cleavage of the Ge-Ge bond.
The adsorption features of phenol and thiophenol are almost the same, but the thermal decomposition reactions are different because the carbon-oxygen bond is stable. Phenoxy group cleaves the carbon-oxide bond to produce GeO(g) at higher temperature in the TPD spectra. Three desorption peaks in TPD spectra are observed due to recombination reactions. According to the experimental data and computational result, we propose the reactions mechanisms of C6H5SH and C6H5OH thermal reaction on Ge(100).
第六章、參考文獻
1. Kamata, Y., High-k/Ge MOSFETs for future nanoelectronics. Materials Today 2008, 11 (1-2), 30-38.
2. Minjoo L. Lee, C. W. L., Z. Cheng, A. J. Pitera, T. Langdo, M. T. Currie, G. Taraschi, E. A. Fitzgerald and Dimitri A. Antoniadis Strained Ge channel p-type metal-oxide-semiconductor field-effect transistors grown on Si1-xGexSi virtual substrates. Applied Physics Letters 2001, 79, 3344-3346.
3. Meuris, M., High κ strides reopen door to germanium. EE Times 2003.
4. Zandvliet, H. J. W., Physics Reports-Review Section of Physics Letters. Physics Letters 2003, 388, 1-4.
5. Rohit Gupta, W. J. Y., Yingqian Wang, Zerlinda Tan, Ganesh Samudra, Sungjoo Lee, Daniel S. H. Chan, Kian Ping Loh, L. K. Bera, N. Balasubramanian and Dim-Lee Kwong, Formation of SiGe nanocrystals in HfO using in situ chemical vapor deposition for memory applications. Applied Physics Letters 2004, 84 (21), 4331.
6. Chui, C. O. R., S.; Triplett, B. B.; McIntyre, P. C.; Saraswat, K. C., Germanium MOS Capacitors Incorporating Ultrathin High-k Gate Dielectric. IEEE ELECTRON DEVICE LETTERS 2002, 23, 473-475.
7. Zandvliet, H. J. W., The Ge(001) surface. Physics Reports 2003, 388 (1), 1-40.
8. Lu, Z. H., Air‐stable Cl‐terminated Ge(111). Applied Physics Letters 1996, 68 (4), 520-522.
9. Duke, C. B., Semiconductor Surface Reconstruction The Structural Chemistry of Two-Dimensional Surface Compounds. Chemical Reviews 1996, 96, 1237.
10. Kevan, S., Surface states and reconstruction on Ge(001). Physical Review B 1985, 32 (4), 2344-2350.
11. Culbertson, R. J. K., Y.; Feldman, L. C., Subsurface strain in the Ge(001) and Ge(111) surfaces and comparison to silicon. Surface Science 1986, 167, 127-140.
12. Lambert, W.; Trevor, P.; Cardillo, M.; Sakai, A.; Hamann, D., Surface structure of Ge(100) studied by He diffraction. Physical Review B 1987, 35 (15), 8055-8064.
13. Loscutoff, P. W.; Bent, S. F., Reactivity of the germanium surface: Chemical passivation and functionalization. Annual review of physical chemistry 2006, 57, 467-95.
14. Prabhakaran, K.; Maeda, F.; Watanabe, Y.; Ogino, T., Distinctly different thermal decomposition pathways of ultrathin oxide layer on Ge and Si surfaces. Applied Physics Letters 2000, 76 (16), 2244.
15. J. Christopher Love , L. A. E., Jennah K. Kriebel , Ralph G. Nuzzo , and George M. Whitesides Self-Assembled Monolayers of Thiolates on Metals as a Form of Nanotechnology. Chemical Reviews 2005, 105, 1103-1170.
16. Weser, T. B., A.; Konrad, B.; Schnell, R. D.; Schug, C. A.; Moritz, W.; Steinmann, W., Chemisorption of sulfur on Ge(100). Surface Science 1988, 201, 245-256.
17. Weser, T.; Bogen, A.; Konrad, B.; Schnell, R.; Schug, C.; Steinmann, a., Photoemission surface core-level study of sulfur adsorption on Ge(100). Physical Review B 1987, 35 (15), 8184-8188.
18. Boonstra, A. H. V. R., J., The adsorption of various gases on clean and oxidized Ge surfaces. Surface Science 1966, 4, 141-149.
19. Van Bommel, A. J. M., F., LEED measurement of H2S and H2Se adsorption on germanium (111). Surface Science 1967, 6, 391-394.
20. Nelen, L. M. F., K.; Greenlief, C. M., Adsorption and decomposition of H2S on the Ge(100) surface. surface Science 1999, 150, 65-72.
21. Anderson, G. W.; Hanf, M. C.; Norton, P. R.; Lu, Z. H.; Graham, M. J., The S-passivation of Ge(100)-(1×1). Applied Physics Letters 1995, 66 (9), 1123.
22. Bodlaki, D.; Yamamoto, H.; Waldeck, D. H.; Borguet, E., Ambient stability of chemically passivated germanium interfaces. Surface Science 2003, 543 (1-3), 63-74.
23. Hanrath, T. K., B. A., Chemical Surface Passivation of Ge Nanowires. Journal of the American Chemical Society 2004, 126, 15466-15472.
24. Lyman, P. F. S., O.; Marasco, D.L.; Lee, T.L.; Breneman, K.D.; Keane, D.T.; Bedzyk, M.J., Structure of a passivated Ge surface prepared from aqueous solution. Surface Science 2000, 462, L594-L598.
25. Schnell, R.; Himpsel, F.; Bogen, A.; Rieger, D.; Steinmann, W., Surface core-level shifts for clean and halogen-covered Ge(100) and Ge(111). Physical Review B 1985, 32 (12), 8052-8056.
26. Ikeda, K. I., S.; Matsumura, M., Atomic layer etching of germanium. Surface Science 1997, 112, 87-91.
27. Cullen, G. W. A., J. A.; Gerlich, D., The stabilization of germanium surfaces by ethylation. J. Electrochem. Soc. 1962, 102, 124-127.
28. Appelbaum, J. A. B., G. A.; Hamann, D. R.; Hagstrum, H. D.; Sakurai, T., hydrogen chemisorption on the 100(2x1) surfaces of Si and Ge. Surface Science 1978, 70, 654-673.
29. Chabal, Y. J., high-resolution infrared spectroscopy of adsorbates on semiconductor surface - hydrogen on Si(100) and Ge(100). Surface Science 1986, 168, 594-608.
30. Maeng, J. Y.; Lee, J. Y.; Cho, Y. E.; Kim, S.; Jo, S. K., Surface dihydrides on Ge(100): A scanning tunneling microscopy study. Applied Physics Letters 2002, 81 (19), 3555.
31. Papagno, L.; Shen, X.; Anderson, J.; Schirripa Spagnolo, G.; Lapeyre, G., Hydrogen adsorption on Ge(100) studied by high-resolution energy-loss spectroscopy. Physical Review B 1986, 34 (10), 7188-7191.
32. Choi, K. B., J. M., Hydrogermylation of Alkenes and Alkynes on Hydride-Terminated Ge(100) Surfaces. Langmuir 2000, 16, 7737-7741.
33. Buriak, J. M., Organometallic Chemistry on Silicon and Germanium Surfaces REVIW. Chemical Reviews 2002, 102, 1271-1308.
34. Teplyakov, A. V. L., P.; Noah, Y. A.; Bent, S. F., Evidence for a Retro-Diels−Alder Reaction on a Single Crystalline Surface Butadienes on Ge(100). Journal of the American Chemical Society 1998, 120, 7377-7378.
35. Teplyakov, A. V. K., M. J.; Bent, S. F., Vibrational Spectroscopic Studies of Diels−Alder Reactions with the Si(100)-2×1 Surface as a Dienophile. Journal of the American Chemical Society 1997, 119, 11100-11101.
36. Kachian, J. S. W., K. T.; Bent, S. F., Periodic Trends in Organic Functionalization of Group IV Semiconductor Surface. ACCOUNTS OF CHEMICAL RESEARCH 2010, 43, 346-355.
37. Ciampi, S.; Harper, J. B.; Gooding, J. J., Wet chemical routes to the assembly of organic monolayers on silicon surfaces via the formation of Si-C bonds: surface preparation, passivation and functionalization. Chemical Society reviews 2010, 39 (6), 2158-83.
38. Yan, L.; Zheng, Y. B.; Zhao, F.; Li, S.; Gao, X.; Xu, B.; Weiss, P. S.; Zhao, Y., Chemistry and physics of a single atomic layer: strategies and challenges for functionalization of graphene and graphene-based materials. Chemical Society reviews 2012, 41 (1), 97-114.
39. Hamers, R. J. C., S. K.; Ellison, M. D.; Hovis, J. S.; Padowitz, D. F.; Schwartz, M. P.; Greenlief, C. M.; Russell, J. N., cycloaddition chemistry of organic molecules with semiconductor surface. Accounts of Chemical Research 2000, 33.
40. Mui, C.; Han, J. H.; Wang, G. T.; Musgrave, C. B.; Bent, S. F., Proton Transfer Reactions on Semiconductor Surfaces. Journal of the American Chemical Society 2002, 124 (15), 4027-4038.
41. Tao, F.; Bernasek, S. L.; Xu, G.-Q., Electronic and Structural Factors in Modification and Functionalization of Clean and Passivated Semiconductor Surfaces with Aromatic Systems. Chemical Reviews 2009, 109 (9), 3991-4024.
42. Smeu, M.; Wolkow, R. A.; Guo, H., Conduction Pathway of π-Stacked Ethylbenzene Molecular Wires on Si(100). Journal of the American Chemical Society 2009, 131 (31), 11019-11026.
43. Calzolari, A.; Ruini, A.; Catellani, A., Anchor Group versus Conjugation: Toward the Gap-State Engineering of Functionalized ZnO(101̅0) Surface for Optoelectronic Applications. Journal of the American Chemical Society 2011, 133 (15), 5893-5899.
44. Loscutoff, P. W.; Wong, K. T.; Bent, S. F., Reaction of Phenyl Isocyanate and Phenyl Isothiocyanate with the Ge(100)-2 × 1 Surface. The Journal of Physical Chemistry C 2010, 114 (33), 14193-14201.
45. Wolkow, R. A., controlled molecular adsorption on silicon-laying a foundation for molecular devices. Annual review of physical chemistry 1999, 50, 413-441.
46. Bent, S. F., Organic functionalization of group IV semiconductor surface-principles, examples, applications, and prospects. Surface Science 2002, 500, 879-903.
47. Young Hwan Min, S. J. J., Young -Sang Youn, Do Hwan Kim, and Sehun Kim,, STM Tip Catalyzed Adsorption of Thiol Molecules at the Nanometer Scale. Journal of the American Chemical Society 2010, 132, 9014-9019.
48. http://www.nsrrc.org.tw/chinese/img/pdf/info.pdf.
49. ROSEI, M. C. a. R., Photoemission and adsorption spectroscopy of solid and interfaces with synchrotron radiation. 1990.
50. Yeh., j.-j., Atomic Calculation of photoionzation Cross-section and Asymmetry Parameter. Gordon and Breach Science 1989.
51. Gasser, R. P. H., An Introduction to chemisorption and catalysis by metal. Oxford University Press 1985.
52. An Introduction to Surface Chemistry. http://www.chem.qmw.ac.uk/surfaces/scc/.
53. Fink, A.; Menzel, D.; Widdra, W., Symmetry and Electronic Structure of Benzene Adsorbed on Single-Domain Ge(100)-(2×1) and Ge/Si(100)-(2×1)†. The Journal of Physical Chemistry B 2001, 105 (18), 3828-3837.
54. Hwang, Y. J.; Kim, A.; Hwang, E.; Kim, S., Chiral Attachment of Styrene Mediated by Surface Dimers on Ge(100). Journal of the American Chemical Society 2005, 127 (14), 5016-5017.
55. Sarah K. Coulter, M. P. S., and Robert J. Hamers, Sulfur Atoms as Tethers for Selective Attachment of Aromatic Molecules to Silicon(001) surface. The Journal of Physical Chemistry B 2001, 105, 3079-3087.
56. Jeon, S. M.; Jung; Lim, D. K.; Kim, H.-D.; Lee, H.; Kim, S., Self-Induced 1-D Molecular Chain Growth of Thiophene on Ge(100). Journal of the American Chemical Society 2006, 128 (19), 6296-6297.
57. Jung; Lee, J. Y.; Hong, S.; Kim, S., Study of Adsorption and Decomposition of H2O on Ge(100). The Journal of Physical Chemistry B 2005, 109 (51), 24445-24449.
58. Miller, T. R., E.; Chiang, T. C., Surface core-level shifts for Ge(100)(2 × 1). Solid State Communications 1983, 47, 935-938.
59. J. Roche, P. R., G.J. Hughes, Core level photoemission studies of the sulphur terminated Ge(100) surface. Applied Surface Science 2001, 174, 271-274.
60. Tsung-Fan Teng, W.-L. L., , Yi-Fu Chang, Jyh-Chiang Jiang, Jeng-Han Wang, and Wei-Hsiu Hung,, Adsorption and Thermal Reactions of H2O and H2S on Ge(100). The Journal of Physical Chemistry C 2010, 114, 1019-1027.
61. Naumkin, F. Y.; Polanyi, J. C.; Rogers, D., Reaction of chlorinated benzenes with Si(100)2×1: a theoretical study. Surface Science 2003, 547 (3), 335-348.
62. Bae, S.-S. K., D. H.; Kim, A.; Jung, S. J.; Hong, S.; Kim, S., Dissociative Chemisorption of Methanol on Ge(100). The Journal of Physical Chemistry C 2007, 111, 15013-15019.
63. Shong, B.; Bent, S. F., Transition in the Molecular Orientation of Phenol Adsorbates on the Ge(100)-2 × 1 Surface. The Journal of Physical Chemistry C 2012, 116 (14), 7925-7930.
64. Bae, S.-S.; Kim, D. H.; Kim, A.; Jung; Hong, S.; Kim, S., Dissociative Chemisorption of Methanol on Ge(100). The Journal of Physical Chemistry C 2007, 111 (41), 15013-15019.
65. Casaletto, M. P.; Carbone, M.; Piancastelli, M. N.; Horn, K.; Weiss, K.; Zanoni, R., A high resolution photoemission study of phenol adsorption on Si(100)2×1. Surface Science 2005, 582 (1-3), 42-48.