Study of the Composition of Impurities in High-Purity Monosilane Obtained from Magnesium Silicide Using the Method of Chromatography–Mass Spectrometry

• Published in: Inorganic materials 2019-12, Vol.55 (14), p.1371-1376
• Main Authors: Sozin, A. Yu, Kotkov, A. P., Grishnova, N. D., Anoshin, O. S., Skosyrev, A. I., Arhiptsev, D. F., Chernova, O. Yu, Sorochkina, T. G.
• Format: Article
• Language: English
• Subjects: Ammonia; Ammonium chloride; Carbon dioxide; Chemistry; Chemistry and Materials Science; Chromatography; Composition; Homology; Hydrides; Hydrocarbons; Impurities; Industrial Chemistry/Chemical Engineering; Inorganic Chemistry; Intermetallic compounds; Ionization cross sections; Ions; Liquid ammonia; Low temperature; Magnesium; Mass spectra; Mass spectrometry; Mass spectroscopy; Materials Science; Mathematical analysis; Scientific imaging; Signal to noise ratio; Silanes; Silica gel; Silicides; Silicon dioxide; Siloxanes; Sorbents; Substances Analysis
• ISSN: 0020-1685; 1608-3172
• DOI: 10.1134/S0020168519140139

The method of chromatography–mass spectrometry is used to study the impurity composition in monosilane obtained in the reaction of magnesium silicide with ammonium chloride in liquid ammonia. To improve the reliability of the impurity identification, along with the study of pure monosilane samples, we analyzed monosilane fractions isolated upon purification by low temperature rectification. To separate the impurities of permanent gases, hydrocarbons C 1 –C 3 , volatile inorganic hydrides, disilane, and alkylsilanes, we used an adsorption capillary column GS-GasPro 60 m × 0.32 mm with a modified silica gel. To separate the homologs of monosilane, siloxanes, and alkylsilanes, we used a column 25 m × 0.26 mm, d f = 0.25 μm with a polytrimethylsilylpropyne (PTMSP) sorbent. The impurities were identified by comparison of their experimental mass spectra with the NIST database. In the absence of the mass spectra of analytes in the NIST electronic database or in the case of their low coincidence with the database spectra, the identification was performed using mass spectra and retention times published in the literature. The impurities of permanent gases, carbon dioxide, hydrocarbons C 1 –C 3 , volatile inorganic hydrides, monosilane homologies, siloxanes, and alkyl silanes were identified in monosilane. Quantitative determination of the impurities was carried out in the mode of selective ion detection using the mass numbers for which the signal-to-noise ratio was maximal. Their concentrations were calculated using a method of absolute calibration by the peak areas; in the case where reference samples were absent, the concentrations were determined using the dependence of the sensitivity coefficients of their detection on the magnitude of the total ionization cross sections. The detection limits of the impurities range within 1 × 10 –5 –2 × 10 –7 mol %. The accuracy of the analysis was verified by the method of sample size variation. The results of determination of the impurities in monosilane after synthesis, as well as in monosilane purified by low temperature rectification and in the isolated fractions with concentrated higher and lower boiling impurities, are reported.