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Reactions of silicon tetrachloride and germanium tetrachloride with oxygen and oxides of nitrogen

Published online by Cambridge University Press:  31 January 2011

R. M. Atkins
Affiliation:
AT & T Bell Laboratories, Murray Hill, New Jersey 07974
V. A. Hohan*
Affiliation:
AT & T Bell Laboratories, Murray Hill, New Jersey 07974
*
a)Bell Laboratories Summer Research Program Participant, 1986.
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Abstract

The reactions of SiCl4 and GeCl4 with oxygen and oxides of nitrogen have been studied in a continuous flow system. SiCl4 is found to react with nitrous oxide at a considerably lower temperature (700 °C vs 1050 °C) than with oxygen. In both cases the formation of silicon oxychlorides (hexachlorodisiloxane and octachlorocyclo-tetrasiloxane) was observed for the first 300 °C after reaction initiates. Activation energies of 115 kcal/mole and 40 kcal/mole were determined for the reactions with oxygen and nitrous oxide, respectively (under conditions of 100-fold excess oxidizer). GeCl4 is also found to react with nitrous oxide at a lower temperature than with oxygen; however, in this case no oxychloride species were observed. Activation energies of 53 kcal/mole and 48.6 kcal/mole were determined for the reactions with oxygen and nitrous oxide, respectively (under conditions of 70-fold excess oxidizer). Reactions of GeCl4 with nitric oxide and nitrogen dioxide are also reported. The use of N2O as an oxidant in optical fiber fabrication processes is discussed.

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Copyright
Copyright © Materials Research Society 1989

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