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Low Temperature CVD of TiN from Ti(NR2)4 and NH3: FTIR Studies of the Gas-Phase Chemical Reactions

Published online by Cambridge University Press:  15 February 2011

Bruce H. Weiller
Bruce H. Weiller*
Affiliation:
The Aerospace Corporation, Mechanics and Materials Technology Center, PO Box 92957/M5-753, Los Angeles, CA 90009-2957
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Abstract

The gas-phase chemical reaction between Ti(NMe2)4 and NH3 is a critical step in the Metallorganic Chemical Vapor Deposition (MOCVD) of TiN at low temperatures. We have examined this reaction using a flow-tube reactor coupled to an FTIR spectrometer. A sliding injector provides control over the reaction time and the kinetics of reactive species can be measured as a function of the partial pressure of an added reagent. The disappearance of Ti(NMe2)4 was measured as a function of reaction time and NH3 pressure at 26°C. The resulting bimolecular rate constant is (1.1±0. 1) x 10-16 cm3molecules−1s−1 Dimethylamine is observed as a direct product from this reaction consistent with other studies. We have also measured the rate constant using ND3 and find a substantial isotope effect, kh/kd ≈2.4± 0.4. This indicates that H-atom transfer is involved in the rate limiting step. We show that these results can be explained by a mechanism comprised of transamination reactions with NH3.

Type
Research Article
Information
MRS Online Proceedings Library (OPL) , Volume 335: Symposium Y – Metal-Organic Chemical Vapor Deposition of Electronic Ceramics , 1993 , 159
Copyright
Copyright © Materials Research Society 1994

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References

1. a) Fix, R. M., Gordon, R. G., and Hoffman, D. M., Mat. Res. Soc. Symp. Proc. 168, 357–362 (1990).CrossRefGoogle Scholar
b) Fix, R. M., Gordon, R. G., and Hoffman, D. M., J. Am. Chem. Soc. 112, 7833–7835 (1990),Google Scholar
c) Ishihara, K., Yamazaki, K., Hamada, H., Kamisako, K, and Tarui, Y., Jpn. J. Appl. Phys. 29, 2103–2105 (1990).CrossRefGoogle Scholar
d) Fix, R. M., Gordon, R. G., and Hoffman, D. M., Chem. Mater. 3, 1138–1148 (1991).Google Scholar
2. Dubois, L. H., Zegarski, B. R., and Girolami, G. S. J. Electrochem. Soc. 139, 3603 (1992).Google Scholar
3. Weiller, B. H., MRS Symp. Proc. 282, 605 (1993).Google Scholar
4. Weiller, B. H., MRS Symp. Proc., in pressGoogle Scholar
5. Herzberg, G., Infrared and Raman Spectra of Polyatomic Molecules, 1st ed. (Van Nostrand Reinhold Company, New York, 1945), p. 295.Google Scholar
6. The vapor pressure at 25°C is 0.11 torr, Roberts, D., The Schumacher Corporation, personal communication.Google Scholar
7. Prybyla, J. A., Chiang, C.-M., and Dubois, L. H. J. Electrochem. Soc. 140, 2695 (1993).CrossRefGoogle Scholar
8. Braun, W., Herron, J. T., Kahaner, D. K., Int. J. Chem. Kinet. 20, 51 (1988).Google Scholar