Hostname: page-component-cd9895bd7-jn8rn Total loading time: 0 Render date: 2024-12-13T02:45:56.003Z Has data issue: false hasContentIssue false

Pulsed Plasma Enhanced Chemical Vapor Deposition from CH2F2, C2H2F4, and CHCIF2

Published online by Cambridge University Press:  10 February 2011

Catherine B. Labelle
Affiliation:
Department of Chemical Engineering, MIT Cambridge, MA 02139
Kenneth K. S. Lau
Affiliation:
Department of Chemical Engineering, MIT Cambridge, MA 02139
Karen K. Gleason
Affiliation:
Department of Chemical Engineering, MIT Cambridge, MA 02139
Get access

Abstract

Pulsed plasma enhanced chemical vapor deposition films have been grown from C2H2F4, CH2F2, and CHCLF2. C-Is x-ray photoelectron spectroscopy (XPS) indicates a prevalence of C-CF species in the films from C2H2F4 and CH2F2, whereas CF2 species dominate the films from CHC1F2. The CFx species distributions for the films are largely controlled by the competition between CF2-producing and HF elimination reactions in the pulsed plasmas. Dominance by HF elimination produces films with high C-CF and CF concentrations (e.g., CH2F2), whereas dominance by CF2-producing reactions leads to films with higher CF2 concentrations (e.g., CHCIF2). The % CF3 in the film is lowest for the precursor having the lowest F:H ratio, CH2F2. Little or no hydrogen was detected in the deposited films. Thermal degradation of films from C2H2F4 and CH2F2, as probed by solid-state nuclear magnetic resonance (NMR) spectroscopy, shows a loss through CF3 detachment and HF elimination. Pulsed plasma films from all three precursors gave dielectric constants of 2.4, with loss tangents on the order of 10−2. Dielectric measurements of pulsed plasma films from hexafluoropropylene oxide (HFPO) gave a dielectric constant of 2.0 ± 0.1 with a loss tangent of 0.009.

Type
Research Article
Copyright
Copyright © Materials Research Society 1998

Access options

Get access to the full version of this content by using one of the access options below. (Log in options will check for institutional or personal access. Content may require purchase if you do not have access.)

References

1 Laxman, R. K., Semiconductor Intl. 18, 7174 (1995).Google Scholar
2 Singer, p., Semiconductor Intl. 19, 8896 (1996).Google Scholar
3 Savage, C. R., Timmons, R. B., and Lin, J. W., Chem. Mater. 3, 575577 (1991).Google Scholar
4 Savage, C. R., Timmons, R. B., and Lin, J. W., in Advances in Chemistry Series; Vol.236 (American Chemical Society, 1993), p. 745768.Google Scholar
5 Endo, K., MRS Bulletin 22, 5558 (1997).Google Scholar
6 Endo, K. and Tatsumi, T., J. Appl. Phys. 78, 13701372 (1995).Google Scholar
7 Lee, W. W. and Ho, P. S., MRS Bulletin 22, 1923 (1997).Google Scholar
8 Labelle, C. B., Limb, S. J., Gleason, K. K., and Bums, J. A., in Characterization of Pulsed-Plasma Enhanced Chemical Vapor Deposited Fluorocarbon Thin Films, Santa Clara, CA, 1997 (DUMIC), p. 98105.Google Scholar
9 Cobum, J. W. and Winters, H. F., Journal of Vacuum Science and Technology 16, 391 (1979).Google Scholar
10 d'Agostino, R., Capezzuto, P., Bruno, G., and Cramarossa, F., Pure and Applied Chemistry 57, 1287 (1985).Google Scholar
11 Yasuda, H., Plasma Polymerization (Academic Press, Inc., New York, 1985).Google Scholar
12 Yasuda, H., Macromol, J.. Sci.–Chem. A10, 383420 (1976).Google Scholar
13 Morosoff, N., Crist, B., Bumgarner, M., Hsu, T., and Yasuda, H., Macromol, J.. Sci.–Chemr. A10, 451471 (1976).Google Scholar
14 Labelle, C. B., Limb, S. J., and Gleason, K. K., J. Appl. Phys. 82, 17841787 (1997).Google Scholar
15 Limb, S. J., Edell, D. J., Gleason, E. F., and Gleason, K. K., Journal of Applied Polymer Science 67, 14891502 (1998).Google Scholar
16 Limb, J., Gleason, K. K., Edell, D. J., and Gleason, E. F., J. Vac. Sci. Technol. A 15, 18141818 (1997).Google Scholar
17 Knickelbein, M. B., Webb, D. A., and Grant, E. R., in New Devices for the Production of Intense Pulsed Jets of CF2: Laser Spectroscopic Characterization, Boston, MA, 1984 (Materials Research Society), p. 2333.Google Scholar
18 Limb, S. J., Labelle, C. B., Gleason, K. K., Edell, D. J., and Gleason, E. F., Appl. Phys. Lett. 68, 28102812 (1996).Google Scholar
19 C. Labelle, B., Karecki, S., Reif, R. R., and Gleason, K. K.. (manuscript in progress).Google Scholar
20 Lau, K. K. S. and Gleason, K. K., Journal of Physical Chemistry B 101, 6839 (1997).Google Scholar
21 K. Lau, K. S. and Gleason, K. K.. (submitted to J. Phys. Chem. B).Google Scholar
22 Martinez, R., Castano, F., Rayo, M. N. S., and Pereira, R., Chemical Physics 172, 349361 (1993).Google Scholar
23 Millward, G. E., Hartig, R., and Tschuikow-Roux, E., J. Phys. Chem. 75, 31953201 (1971).Google Scholar
24 Su, M.-C., Kumaran, S. S., Lim, K. P., Michael, J. V., and Wagner, A. F., J. Phys. Chem. 100, 1582715833 (1996).Google Scholar
25 Edwards, J. W. and Small, P. A., Nature 202, 1329 (1964).Google Scholar
26 Barnes, G. R., Cox, R. A., and Simmons, R. F., Journal of the Chemical Society (B) 6, 11761180 (1971).Google Scholar
27 Atkins, p. W., Physical Chemistry, 4th ed. (W. H. Freeman and Company, NY, NY, 1990).Google Scholar
28 Limb, S. J., Edell, D. J., Gleason, E. F., and Gleason, K. K.. (submitted to Chemistry of Materials).Google Scholar
29 d'Agostino, R., Cramarossa, F., Fracassi, F., and Illuzzi, F., in Plasma Deposition, Treatment, and Etching of Polymers, edited by R., d'Agostino (Academic Press, San Diego, CA, 1990), p. 95162.Google Scholar
30 Politanskii, S. F. and Shevchuk, V. U., Kinetika i Kataliz 9,496503 (1968).Google Scholar
31 Millward, G. E., Hartig, R., and Tschuikow-Roux, E., Journal of the Chemical Society, Chemical Communications, 465466 (1971).Google Scholar
32 Tserepi, A. D., Derouard, J., Booth, J. P., and Sadeghi, N., J. Appl. Phys. 81, 21242130 (1997).Google Scholar
33 McMurry, j., Organic Chemistry, 3rd ed. (Brooks/Cole Publishing Company, Pacific Grove, CA, 199).Google Scholar
34 Danilich, M. J., Burton, D. J., and Marchant, R. E., Vibrational Spectroscopy 9, 229234 (1995).Google Scholar
35 Silverstein, R. M., Bassler, G. C., and Morrill, T. C., Spectroscopic Identification of Organic Compounds, 5th ed. (Wiley & Sons, Inc., NY, NY, 1991).Google Scholar
36 Solymar, L. and Walsh, D., Lectures on the electrical properties of materials (Oxford University Press, New York, NY, 1984).Google Scholar
37 DiBenedetto, A. T., The Structure and Properties of Materials (McGraw-Hill Book Company, New York, NY, 1967).Google Scholar
38 Theil, J. A., Kooi, G., Mertz, F., Ray, G., and Seaward, K., in The Effect of Thermal Cycling on a-C:F,H Low Dielectric Constant Films Deposited by ECR Plasma Enhanced Chemical Vapor Deposition, San Francisco, CA, 1998.Google Scholar
39 Theil, J. A., Mertz, F., Yairi, M., Seaward, K., Ray, G., and Kooi, G., in Thermal Stabiility of a-C:F,H Films Deposited by Electron Cyclotron Resonance Plasma Enhanced Chemical Vapor Deposition, San Francisco, CA, 1997 (Materials Research Society).Google Scholar