none

Two most useful families of copper CVD precursors that have been utilized widely are the Cu(I) and Cu(II) β-diketone complexes. The Cu(II)precursors require the use of an external reducing agent such as hydrogen to
deposit copper films, i.e. CuII(β-diketonate)2 + H2 → Cu0+2 β-diketonate.
The Cu(I) precursors deposit pure copper films without the use of an external
agent via a disproportionation reaction that produces a Cu(II)β-diketonate in
conjunction with other organic byproducts, i.e. 2CuI(β-diketonate)L →
Cu0+ CuII(β-diketonate)2+2L where L is a typical Lewis base neutral ligand.
However, Do those ligands resulting from the dissociation of the precursors
simply desorb intact from the substrate or the growing films, or react further on the surface? To understand the surface chemistry of these ligands may provide better knowledge for designing more superior precursors and improvement of fabrication processes.
Cu(hfac)(VTMS) and Cu(hfac)(MHY) are the most promising Cu(I) precursors, as shown in Scheme 1.1. Here we report studies on the chemistry
of VTMS, MHY and hfacH on a Cu(111) surface. It should be noted that the hfacH is the simplest molecule containing the hfac, so we use it as a reference for β-diketonate ligand. The Cu(111) single crystal was used to mimic the reactivity of these ligands on a growing Cu film during copper CVD. In situ analysis of ligand surface chemistry is carried out by TPD/R
(temperature-programmed desorption/reaction) and RAIRS (reflection adsorption infrared spectroscopy) to elucidate plausible reaction mechanisms by which ligands decompose and eventually lead to impurity incorporation
into the growing films, and to suggest means of minimizing such reactions.

Chapter 1 Introduction………………………………………….1
Chapter 2 Experimental Section…………………………….4
Chapter 3 Results
3.1 VTMS
3.1.1 TPD/R Study of VTMS on Cu(111)………………………..6
3.1.2 RAIRS Study of VTMS on Cu(111)………………………14
3.2 MHY
3.2.1 TPD/R Study of MHY on Cu(111)………………………..20
3.2.2 RAIRS Study of MHY on Cu(111)……………………….25
3.3 hfacH
3.3.1 TPD/R Study of hacH on Cu(111)………………………...31
3.3.2 RAIRS Study of hacH on Cu(111)………………………..39
Chapter 4 Discussion
4.1 Formation of Acetylene from VTMS via C-Si Bond
Scission and β-hydride Elimination…………………...46
4.2 Strong MHY-surface Interactions Facilitate CVD …..49
4.3 Mimicking hfac Ligand by Adsorption of hfacH on
Cu(111)……………………………………………………51
Chapter 5 Conclusions…..…………………………………….54

1. Doppelt, P., Combellas, C.; Kanoufi, F.; Chen, T. Y.; Richardson, S.;
Thiebault, A. Electrochem. Eng. 2000, 50, 383-390.
2. 楊正杰, 張鼎張, 鄭晃忠工業材料167 期11 月89 年.
3. Lide, D. R. CRC Handbook of Chemistry and Physics, 71st ed.; 1990.
p12-23.
4. Kodas, T. T.; Hampden-Smith, M. J. The Chemistry of Metal CVD, VCH:
Weinheim, 1994.
5. Redhead P. A. Vacuum 1962, 12, 203-211.
6. Dubois, L. H.; Zegarski, B. P. J. Electrochem. Soc. 1992, 139, 3295.
7. NIST Standard Reference Database, http://webbook.nist.gov/chemistry/
8. Girolami, G. S.; Jeffries, P. M.; Dubois, L. H. J. Am. Chem. Soc. 1993, 115,
1015-1024.
9. Lin-Vien, D.; Colthup, N. B.; Fateley, W. G.; Grasselli, J. G. The Handbook
of Infrared and Raman Characteristic Frequencies of Organic Molecules,
Academic Press, Inc., Boston, c1991.
10. Pouchert, C. J. The Aldrich Library of Infrared Spectra; Milwaukee:
Alerich Chemical Co., c1975.
11. Roeges, N. P. G. A Guide to the Complete Interpretation of Infrared
Spectra of Organic Structures, John Wiley & Sons 1994.
12. Vickerman, J. C. Surface Analysis-The Principal Techniques, John Wiley
& Sons 1997.
13. Liu, Z.-M.; Zhou, X.-L.; Buchanan, D. A.; Kiss, J.; White, J. M. J. Am.
Chem. Soc. 1992, 114, 2031-2039.
14. Zeara, F.; Bernstein, N. J. Am. Chem. Soc. 1994, 116, 4881-4887.
15. Zaera, F.; Hall, R. B. Surface Science, 1987, 180, 1-18.
16. Doppelt, P.; Baum, T. H. J. Organomet. Chem. 1996, 517, 53-62.
17. Baum, T. H.; Larson, C. E. Chem. Mater. 1992, 4, 365-369.
18. Chen, T. –Y.; Vaissermann, J.; Ruiz, E.; Senateur, J. P.; Doppelt, P. Chem.
Mate. 2001, 13(11), 3993-4004.
19. Chen, T. –Y.; Vaissermann, J.; Doppelt, P. Inorg. Chem. 2001, 40(24),
6167-6171.
20. Davies, B. W. ; N. C. J. Organmet. Chem. 1975, 99, 315.
21. Steger, R.; Masel, R. Thin Solid Films 1999, 342, 221-229.
22. Parmeter, J. E. J. Phys. Chem. 1993, 97, 44.
23. Hou, Y. C.; Chiang, C. M. J. J. Am. Chem. Soc. 1999, 121, 8816-8817.
24. Lin, W.; Wiegand, B. C.; Nuzzo, R. G.; Girolami; G. S. J. Am. Chem. Soc.
1996,118,5977-5987.
25. Crane, E. L.; You, Y.; Nuzzo, R. G.; Girolami; G. S. J. Am. Chem. Soc.
2000,122,3422-3435.
26. Myli, K. B.; Grassion, V. H. J. Phys. Chem. 1995,99,1498-1504.
27. Seel, F.; Flaccos, R. D. J. Fluorine Chem. 1978, 12,81.
28. Clark, G. R.; Hoskins, S. V.; Jones, T. C.; Roper, W. R. J. Chem. Soc.
Chem. Commun. 1983, 719.
29. Andersohn, L.; Kochanski, G. P.; Norman, J. A. T.; Hinch, B. J. J. Vac. Sci.
Technol.. B 14(2), 1996.
30. Chiu, W. Y.; Chiang, C. M. Paper submitted.