臺灣博碩士論文加值系統

掃描穿隧顯微術具有原子或分子等級的解析度，可以觀察分子吸附在石墨表面上的二維的分子排列。本論文以掃描穿隧顯微術研究石墨上C36H30O3Si3和H8Si8O12分子薄膜的結構。
C36H30O3Si3分子薄膜的穿隧圖像顯示有規則的排列。比對掃描穿隧圖像與分子結構，發現在掃描穿隧圖像中一個亮點代表一個C36H30O3Si3分子。依穿隧圖像中規則排列的亮點，可畫出此C36H30O3Si3分子在石墨上有兩種單位格子，一種單位格子為10.8 ± 0.2 × 25.3 ± 0.2 Å2， 夾角為93o ± 2 o，另一種為15.3 ± 0.2 × 21.8 ± 0.2 Å2其夾角為105o ± 2 o。將此穿隧圖像的單位格子與C36H30O3Si3的晶體結構比對後，發現有兩個晶系的晶面非常符合，分別是C36H30O3Si3斜方晶系(110)晶面與三斜晶系(101)晶面。
H8Si8O12分子薄膜的穿隧圖像亦有規則的排列，比對掃描穿隧圖像與分子結構，其穿隧圖像中一個亮點代表一個H8Si8O12分子，依穿隧圖像中規則排列的亮點可畫出此H8Si8O12分子在石墨上有兩種單位格子，一種單位格子為8.3 ± 0.2 × 9.2 ± 0.2 Å2， 夾角為114o ± 2o，另一種是6.8 ± 0.2 × 7.1 ± 0.2 Å2，其夾角為110o ± 2 o。H8Si8O12晶體的晶面並無類似於這二種薄膜表面結構。

It has established that adsorbed molecules of regular two-dimensional arrangements on HOPG can be imaged with near atomic or molecular resolution by scanning tunneling microscopy (STM). The layer structures of C36H30O3Si3 and H8Si8O12 on HOPG have been investigated by this technique.
The STM image of the C36H30O3Si3 shows an ordered array of bright lobes. From the comparisons between the STM image and the molecular structure, it strongly suggests that the each bright lobe in the STM image is due to one C36H30O3Si3 molecule. It is established that the order layer structure of C36H30O3Si3 on HOPG shown in the STM images has two kinds of unit cell, one is 10.8 ± 0.2 × 25.3 ± 0.2 Å2 with an included angle of 93o ± 2 o and the other is 15.3 ± 0.2 × 21.8 ± 0.2 Å2 with an included angle of 105o ± 2 o. The periodicities are corresponding to orthorhombic (110) plane and triclinic (101) plane determined by X-ray crystallography.
The STM image of the C36H30O3Si3 also shows an ordered array of bright lobes. From the comparisons between the STM image and the molecular structure, it strongly suggests that each bright lobe in the STM image is due to one H8Si8O12 molecule. It is established that the ordered-layer of H8Si8O12 on HOPG shown in the STM images also has two kinds of unit cell. One is 8.3 ± 0.2 × 9.2 ± 0.2 Å2 with an included angle of 114 ± 2 o and the other is 6.8 ± 0.2 × 7.1 ± 0.2 Å2 with an included angle of 110 ± 2 o. No comparable crystallographic planes of H8Si8O12 are found for the order-layer structure of the H8Si8O12 on HOPG.

目錄
第一章緒論…………………………………………………………………………1
1.1 簡介……………………………………………………………………………1
1.2 掃描穿隧原理…………………………………………………………………3
1.3 取像方式………………………………………………………………………5
1.3.1 定電流取像法………………………………………………………………6
1.3.2 定高度取像法………………………………………………………………7
1.3.1 電流密度取像法……………………………………………………………7
1.4 石墨的結構……………………………………………………………………9
1.5 矽氧環狀分子晶體結構………………………………………………………10
1.5.1 Hexaphenylcyclotrisiloxane(HPhTS)晶體結構 …………………10
1.5.2 Octahydridosilasesquioxane(H8Si8O12)晶體結構………………11
1.6 相關的研究……………………………………………………………………12
1.6.1 Copper(Ⅱ)2,3,9,10,16,17,23,24-octakis(octyloxy)-29H,31H- phthalocyanine(CuPcOC8) 分子在HOPG表面……………………………………12
1.6.2 DNA薄膜在矽(111)表面上結構 ……………………………………13
1.7 研究動機………………………………………………………………………15
第一章實驗系統及實驗方法 …………………………………………………16
2.1 儀器……………………………………………………………………………16
2.2 掃瞄穿隧顯微儀架構和各主要組成元件的功能……………………………16
2.2.1 掃瞄頭 ………………………………………………………………17
2.2.2電腦……………………………………………………………………18
2.2.3 避震系統及隔音箱……………………………………………………18
2.3 掃瞄探針顯微儀的探針製作…………………………………………………18
2.4 藥品……………………………………………………………………………20
2.5 實驗方法………………………………………………………………………21
2.5.1 樣品的製備…………………………………………………………………21
2.5.2 石墨表面上形成分子薄膜…………………………………………………22
2.5.3 掃瞄穿隧圖像………………………………………………………………22
2.6 H8Si8O12晶體的製備和鑑定 ………………………………………………23
2.6.1 H8Si8O12晶體合成 ………………………………………………………23
2.6.2 H8Si8O12晶體鑑定 ………………………………………………………24
第三章 結果與討論 ………………………………………………………………26
3.1石墨表面掃瞄穿隧圖像與穿隧能譜 …………………………………………26
3.1.1石墨表面掃瞄穿隧圖像 ……………………………………………………26
3.1.2穿隧能譜 ……………………………………………………………………31
3.2 石墨上H3PW12O40分子薄膜結構研究的回顧 ………………………………34
3.3 Hexaphenylcyclotrisiloxane(HPhTS)分子薄膜在石墨上的結構研究 ………………………………………………………………………………………37
3.4 Octahydridosilasesquioxane (H8Si8O12)分子吸附在Si(111)
7 × 7、Au(111)和Si(100)-2 × 1掃描穿隧研究的回顧 ………………………46
3.4.1 (H8Si8O12)分子吸附在Si(111)- 7 × 7掃描穿隧研究…………………46
3.4.2 (H8Si8O12)分子吸附在Au (111)紅外線光譜及X光光電子譜研究 ……47
3.4.3 (H8Si8O12)分子吸附在Si(100)-2 × 1掃描穿隧研究 …………………48
3.5 Octahydridosilasesquioxane (H8Si8O12)分子薄膜在石墨的掃描穿隧研究……………………………………………………………………………………51
第四章 結論……………………………………………………………………59
參考文獻……………………………………………………………………………60

[ 1 ] C. J. Chen, " Introduction to Scanning Tunneling Microscopy " , Oxford University Press, Oxford, 1993.
[ 2 ] R. Wiesendanger, " Scanning Probe microscopy and Spectroscopy " , Cambridge University Press, Cambridge, 1994.
[ 3 ] G. Binning, and H. Rohrer, Helv. Phys. Acta. 55, 726, 1982.
[ 4 ] H. Neddermeyer, " Scanning Tunneling Microscopy " , Kluwer Academic Publisher, Boston, 1993.
[ 5 ] D. A. Skoog, F. J. Holler, and T. A. Nieman, " Principle of Instrument Analysis ", saunders college publishing. 1998.
[ 6 ] H. J. Guntherodt, and R. Wiesendabger," Scanning Tunneling MicroscopyⅠ". 1992.
[ 7 ] 儀器總覽、表面分析儀器，行政院國家科學委員會精密儀器發展中心，87年。
[ 8 ] G. Binning, and H. Rohrer Nobel lecture, " Scanning Tunneling Microscopy-From Birth to Adolesce " , December 8, 1986.
[ 9 ] L. smart, and E. Moore, " Solid State Chemistry An introduction " , P43, 1992.
[10] 國立編譯館主編，余樹楨著，晶體之結構與性質，第249-252頁。
[11] P. E. Tomlines, J. E. Lydon, D. Akrigg, and B. Sheldrick, Acta. Cryst. C41, 249-294, 1985.
[12] B. Ziemer, M. Backer, and N. Auner, Acta. Cryst. C54, 1111-1113, 1998.
[13] J. F. Hyde, L. K. Frevel, H. S. Nutting, and P. S. Petrie, J. Am. Chem. Soc. 69, 488-492, 1947.
[14] N. G. Bokii, G. N. Zakharova, and Y. T. Struchkov, Zh. Strukt. Khim. 13, 291-297, 1972.
[15] K. W. Tornroos, Acta. Cryst. C50, 1646-1648, 1994.
[16] P. E. Thomas, H. B. Burgi, H. Burgy, and K. W. Tornroos, Chimia. 45, 38-40, 1991.
[17] K. S. Schneider, K. T. Nicholson, D. R. Fosnacht, B. G. Orr, and M. M. Banaszak Holl, Langmuir 8116-8122, 2002.
[18] K. S. Schneider, Z. Zhang, M. M. Banaszak Holl, B. G. Orr, and U. C. Pernisz, Phy. Rev. Lett. 85, 602-605, 2000.
[19] C. Marcolli, and G. Calzaferrit, Appl. Organometal. Chem. 13, 213-226, 1999.
[20] X.D. Wang, T. Hashizume, and T. Sakurai, Modern phys. Lett. B8, 1597, 1994.
[21] K. Miyake, K. Akutsu, T. Yamada, K. Hata, R. Morita, M. Yamashita, and H. Shigekawa, Ultramicroscopy. 73, 185-189, 1998.
[22] J. K. Gimzewski, S. Modesti, C. Gerber, and R. R.Schlitter, Chem. Phys. Lett. 213, 401, 1993.
[23] B. Susla, R. Czajka, W. S. Gordon, S. Szuba, and J. Rauluszkiewicz, Mater. Sci. Eng. A217, 419-423, 1996.
[24] S. A. Contera, and H. Iwasaki, Ultramicroscopy. 91, 231-243, 2002.
[25] J. S. Foster, and J. E. Formmer, Nature 333, 542-544, 1988.
[26] D. P. E. Smith. H. Horber, C. Gerber, and G. Binng, Science 245, R43-45, 1989.
[27] C. L. Claypool, F. Faglioni, W. A. Goddard, and N. S. Lewis, J. Phys. Chem. B, 103,7077-7080, 1999.
[28] X. Qiu, C. W. Shuxia, Q. Zeng, B. Xu, and C. Bai, J. Phys. Chem. B, 104, 3570-3574, 2000.
[29] S. N. Patole, A. R. Pike, B. A.Connolly, B. R. Horrocks, and A. Houlton, Langmuir. 19, 5457-5463, 2003.
[30] G. S.Hanan, D. Volkmer, U. S. Schubert, J. M. Lehn, G. Baum, and D. Fenske, Angew. Chem. Ed. 36, 1842, 1997.
[31] O. Waldmann, J. Hassmann, P. Muller, G. S. Hanan, D. Volkmer, U. S. Schubert, and J. M. Lehn, Phys. Rev. Lett. 78, 3390, 1997.
[32] R. V. Slone, D. I. Yoon, R. M. Calhoun, and J. T. Hupp, J. Am. Chem. Soc. 117, 11813, 1995.
[33] R. V. Slone, K. D. Benkstein, S. B’elanger, J. T. Guzei, and A. L. Rheingold, Coord. Chem. Rev. 171, 221, 1998.
[34] P. L. Feist, J. Chem. Edu. 78, 3, 351-352, 2001.
[35] P. A. Agaskar, Inorg. Chem. 30, 2708-2713, 1991.
[36] P. A. Agaskar, and W. G. Klemperer, Inorganica Chimica Acta. 229, 355-364, 1995.
[37] J. Osing, and I. V. Shvets, Surf. Sci. 417, 145-150, 1998.
[38] J. C. Victor, L. P. David, and P. Beebe, Surf. Sci. 329, 141-148, 1995.
[39] D. Tomanek, and S. Louie, Phys. Rev. B. 37. 8327. 1988.
[40] D. A. Bonnell, " Scanning Tunneling Microscopy and Spectroscopy Theory, Techniques, and Applications " , 1993.
[41] M. S. Kaba, I. K. Song, and M. A. Barteau, J. Phys. Chem. B, 106, 2337-2342, 2002.
[42] M. S. Kaba, I. K. Song, D. C. Duncan, C. L. Hill, and M. A. Barteau, Inorg. Chem. 37, 398-406, 1998.
[43] K. S. Schneider, T. M. Owens, K. T. Nicholson, B. J. Ludwig, J. N. Greeley, B.G. Orr, and M. M. Banaszak Holl, Langmuir, 18, 6233-6241, 2002.
[44] K. T. Nicholson, K. Z. Zhang, and M. M. Banaszak Holl, J. Am. Chem. Soc. 121, 3232-3233, 1999.