Identification and Characterization of Monomeric, Volatile SiCl3NH2 as Product of the Reaction between SiCl4 and NH3: An Important Intermediate on the Way to Silicon Nitride?

• Published in: Chemistry : a European journal Vol. 9; no. 6; pp. 1387 - 1393
• Main Authors: Himmel, Hans-Jörg, Schiefenhövel, Nils, Binnewies, Michael
• Format: Journal Article
• Language: English
• Published: Weinheim WILEY-VCH Verlag 17.03.2003; WILEY‐VCH Verlag
• Subjects: ammonolysis; density functional calculations; IR spectroscopy; mass spectrometry; silanes
• ISSN: 0947-6539; 1521-3765
• DOI: 10.1002/chem.200390158

We studied the reaction of SiCl4 with NH3 by mass spectrometry and IR spectroscopy. By means of mass spectrometry, SiCl3NH2 was for the first time identified as an intermediate generated in significant amounts in the course of the reaction. In additional experiments, SiCl3NH2 was formed as a stable gaseous product of the ammonolysis of SiCl4, and the product was identified and characterized in detail by IR spectroscopic methods (gas phase and matrix isolation) in combination with quantum‐chemical calculations. The calculations also gave access to important thermodynamical data. Ammonolysis of SiCl4 has been studied by means of mass spectrometry and IR spectroscopy in the gas phase and under matrix‐isolation conditions, as well as by quantum chemical calculations. Aminotrichlorosilane (see picture for the calculated structure) was identified as the primary molecular reaction product and characterized in detail.