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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*
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
Copyright
Copyright © Materials Research Society 1994

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