Abstract
The impurity composition of 28SiH4, 29SiH4, and 30SiH4 silanes and 72GeH4, 73GeH4, 74GeH4, and 76GeH4 germanes isotopically enriched to above 99.9 at % has been studied by gas chromatography/mass spectrometry using capillary adsorption columns. Impurities have been identified by comparing their mass spectra with NIST data and information available in the literature, and by inferring their structure from fragment ions and retention times. We have identified 53 impurity substances in silanes and 42 in germanes: permanent gases; saturated, unsaturated, halogen-containing, and aromatic C1–C9 hydrocarbons; their homologues; alkyl derivatives of silane and germane; chlorogermane; siloxanes; fluorosiloxanes; sulfur compounds; and dioxane. The silicon- and germanium-containing impurities have been shown to be isotopically enriched, as the major component. The detection limits of the impurities are 5 × 10–8 to 3 × 10–5 vol %, comparing well with the best results in the literature.
Similar content being viewed by others
References
Bulanov, A.D., Devyatych, G.G., Gusev, A.V., et al., The highly isotopic enriched (99.9%), high-pure 28Si single crystal, Cryst. Res. Technol., 2000, vol. 9, pp. 1023–1026.
Becker, P., Schiel, D., Pohl, H.-J., et al., Large-scale production of highly enriched 28Si for the precise determination of the Avogadro constant, Meas. Sci. Technol., 2006, vol. 17, pp. 1854–1860.
Gusev, A.V., Gavva, V.A., Kozyrev, E.A., et al., Preparation of single-crystal 29Si, Inorg. Mater., 2011, vol. 47, no. 7, pp. 691–693.
Cardona, M.W. and Thewalt, M.L., Isotope effects on the optical spectra of semiconductors, Rev. Mod. Phys., 2005, vol. 77, no. 4, pp. 1173–1224.
Plotnichenko, V.G., Nazar’yants, V.O., Kryukova, E.B., et al., Near-to mid-IR refractive index of 28Si, 29Si, and 30Si monoisotopic single crystals, Kvantovaya Elektron., 2010, vol. 40, no. 9, pp. 753–755.
Kremer, R.K., Graf, K., Cardona, M., et al., Thermal conductivity of isotopically enriched 28Si: revisited, Solid State Commun., 2004, vol. 131, pp. 499–503.
Itoh, K., Hansen, W.L., Haller, E.E., et al., High purity isotopically enriched 70Ge and 74Ge single crystals: isotope separation, growth, and properties, J. Mater. Res., 1993, vol. 8, no. 6, pp. 1341–1347.
Detochenko, A.P., Denisov, S.A., Drozdov, M.N., et al., Epitaxially grown monoisotopic Si, Ge, and Si1–x Ge x alloy layers: production and some properties, Semiconductors, 2016, vol. 50, no. 3, pp. 345–348.
Churbanov, M.F., Gusev, A.V., Bulanov, A.D., et al., Monoisotopic silicon and germanium with high chemical and isotopic purity, Izv. Akad. Nauk, Ser. Khim., 2013, no. 2, pp. 275–280.
Gusev, A.V., Bulanov, A.D., Filimonov, S.V., et al., Preparation of high-purity isotopically enriched 76Ge germanium, Perspekt. Mater., 2011, no. 10, pp. 17–20.
Becker, P.P., Bettin, H., Danzebrink, H.-U., et al., Determination of the Avogadro constant via the silicon route, Metrologia, 2003, vol. 40, pp. 271–287.
Baranov, P.G., Ber, B.Ya., Godisov, O.N., et al., Specific features of transmutation doping of 30Si-enriched silicon crystals with phosphorus: studies by electron spin resonance, Semiconductors, 2006, vol. 40, no. 8, pp. 901–910.
Becker, P., Bettin, H., De Bievre, P., et al., The silicon-28 path to the Avogadro constant—first experiments and outlook, IEEE Trans. Instrum. Meas., 1995, vol. 45, pp. 522–525.
Shubin, A.N., Gilev, A.N., Kononov, D.B., et al., New requirements for enriched isotopes for experimental studies of neutrinoless beta beta decays (GERDA experiment), At. Energ., 2006, vol. 101, no. 2, pp. 588–592.
Churbanov, M.F., Gusev, A.V., Bulanov, A.D., et al., Monoisotopic silicon and germanium with high chemical and isotopic purity, Izv. Akad. Nauk, Ser. Khim., 2013, no. 2, pp. 275–280.
Scott Specialty Gases. http://www.scottsemicon.com. Cited April 20, 2016.
Matheson TriGas. http://www.mathesongas.com. Cited April 20, 2016.
Praxair. http://www.praxair.com. Cited April 20, 2016.
Devyatykh, G.G., Karpov, Yu.A., and Osipova, L.I., Vystavka-kollektsiya veshchestv osoboi chistoty (Exhibition–Collection of Extrapure Substances), Moscow: Nauka, 2003.
Devyatykh, G.G. and Zorin, A.D., Letuchie neorganicheskie gidridy osoboi chistoty (Extrapure Volatile Inorganic Hydrides), Moscow: Nauka, 1974.
Belov, E.P., Lebedev, E.N., Grigorash, Yu.P., et al., Monosilan v tekhnologii poluprovodnikovykh materialov (Monosilane in Semiconductor Materials Technology), Moscow: NII Tekhniko-Ekonomicheskikh Issledovanii, 1989.
Krylov, V.A., Chernova, O.Yu., and Sozin, A.Yu., Identification of impurities in silane of natural isotopic composition and enriched with 28Si by gas chromatography/mass spectrometry, Anal. Kontrol, 2011, vol. 5, no. 4, pp. 421–428.
Krylov, V.A., Sozin, A.Yu., Zorin, V.A., et al., Gas chromatography/mass spectrometry determination of impurities in high-purity isotopically enriched silane, Mass-Spektrom., 2008, vol. 4, pp. 225–233.
Krylov, V.A., Chernova, O.Yu., and Sozin, A.Yu., Gas chromatography/mass spectrometry identification of impurities in isotopically enriched silane, Mass-Spektrom., 2007, no. 4, pp. 125–130.
Sozin, A.Yu., Analysis of high-purity isotopically enriched silane by gas chromatography/mass spectrometry, Perspekt. Mater., 2008, no. 5, pp. 226–231.
Aref'ev, D.G., Vasin, S.A., Dolgov, S.V., et al., Application of monogermane in germanium isotope separation in gas centrifuges, Perspekt. Mater., 2010, no. 8, pp. 19–24.
Krylov, V.A., Sennikov, P.G., Chernova, O.Yu., et al., Molecular analysis of isotopically enriched 28SiF4 and 28SiH4 prepared from it, Inorg. Mater., 2008, vol. 44, no. 7, pp. 766–772.
Churbanov, M.F., Krylov, V.A., Chernova, O.Yu., et al., Impurity composition of isotopically enriched monogermane, Perspekt. Mater., 2010, no. 8, pp. 105–115.
Sennikov, P.G., Kosheleva, I.A., Bulanov, A.D., et al., Impurity composition of isotopically enriched germane studied by high-resolution Fourier transform IR spectroscopy, Perspekt. Mater., 2011, no. 10, pp. 93–98.
Krylov, V.A., Analysis of high-purity volatile compounds, J. Anal. Chem., 2002, vol. 57, no. 8, pp. 660–671.
Chuprov, L.A., Sennikov, P.G., Tokhadze, K.G., et al., High-resolution Fourier-transform IRspectroscopic determination of impurities in silicon tetrafluoride and silane prepared from it, Inorg. Mater., 2006, vol. 42, no. 8, pp. 924–931.
Ezheleva, A.E., Baturina, N.M., Krylov, V.A., et al., Gas chromatographic determination of methane, hydrogen, carbon monoxide, and carbon dioxide impurities in high-purity monogermane using selective electron capture sensitization, Vysokochist. Veshchestva, 1989, no. 4, pp. 231–235.
Devyatykh, G.G., Zasavitskii, I.I., Il’in, V.M., et al., Tunable-laser-diode IR spectrometer for molecular analysis of high-purity volatiles, Vysokochist. Veshchestva, 1990, no. 6, pp. 106–114.
Krivtsun, V.M., Kuritsyn, Yu.A., Snegirev, E.P., et al., Measurement of low PH3 concentrations in GeH4 with a tunable-laser-diode spectrometer, Zh. Prikl. Spektrosk., 1985, vol. 63, pp. 571–576.
Ezheleva, A.E., Snopatin, G.E., and Malygina, L.S., Application of a flame-photometric detector in chromatographic analysis of high-purity volatile inorganic hydrides, Zh. Anal. Khim., 1979, vol. 34, no. 12, pp. 2308–2311.
Krylov, V.A., Krasotskii, S.G., Malyshev, V.M., and Salganskii, Yu.M., Cryogenic preconcentration of hydrogen, argon, oxygen, and nitrogen in the gas chromatographic determination of their impurities in volatile inorganic hydrides, J. Anal. Chem., 2001, vol. 56, no. 11, pp. 996–1001.
Zorin, A.D., Frolov, I.A., Karabanov, N.T., et al., Chromatographic analysis of silane and germane for organic impurities, Zh. Anal. Khim., 1970, vol. 25, no. 10, pp. 389–391.
Vorotyntsev, V.M., Mochalov, G.M., Suvorov, S.S., and Shishkin, A.O., Gas-chromatographic determination of the impurity composition of permanent gases, methane, carbon monoxide, and carbon dioxide in extrapure monogermane, J. Anal. Chem., 2010, vol. 65, no. 6, pp. 634–639.
Nikolaeva, L.G. and Agafonov, I.L., Determination of impurities in extrapure volatile inorganic substances by mass spectrometry and gas chromatography, in Poluchenie i analiz veshchestv osoboi chistoty (Preparation and Analysis of Extrapure Substances), Moscow: Nauka, 1978, pp. 168–174.
Sennikov, P.G., Kotkov, A.P., Adamchik, S.A., et al., Impurities in monosilanes synthesized by different processes, Inorg. Mater., 2010, vol. 46, no. 4, pp. 358–363.
Krylov, V.A., Berezkin, V.G., Chernova, O.Yu., et al., Use of capillary gas chromatography for determining hydrocarbons in high-purity silane, J. Anal. Chem., 2005, vol. 60, no. 9, pp. 851–854.
De Saint Etienne, C. and Mettes, J., Gas phase impurities in silane determined by gas chromatography–mass spectrometry, Analyst, 1989, vol. 114, pp. 1649–1653.
Morisaco, I., Kato, T., Ino, Y., et al., Trace gas detection in high purity gases for semiconductor fabrication with a new GC/MS system, Int. J. Mass Spectrom. Ion Phys., 1983, vol. 48, pp. 19–22.
Krylov, V.A., Chernova, O.Yu., Kireev, S.M., et al., Determination of impurities in high-purity germane by gas chromatography/mass spectrometry, Perspekt. Mater., 2008, no. 6, pp. 227–229.
Krylov, V.A., Chernova, O.Yu., and Sozin, A.Yu., Identification of impurities in high-purity monogermane by gas chromatography/mass spectrometry, Zavod. Lab., Diagn. Mater., 2012, vol. 78, no. 2, pp. 11–15.
Krylov, V.A., Chernova, O.Yu., Sozin, A.Yu., et al., Gas chromatography/mass spectrometry analysis of high-purity germane, Anal. Kontrol, 2015, vol. 19, no. 1, pp. 45–51.
Krylov, V.A., Chernova, O.Yu., and Sozin, A.Yu., Composition of molecular impurities in high-pure germane, Inorg. Mater., 2015, vol. 51, no. 10, pp. 965–971.
Krylov, V.A., Chernova, O.Yu., and Sozin, A.Yu., Highly sensitive gas chromatography/mass spectrometry determination of impurities in high-purity monogermane with the use of a carbon sorbent-packed capillary adsorption column, Zavod. Lab., Diagn. Mater., 2016, vol. 82, no. 2, pp. 23–27.
Devyatykh, G.G., Dianov, E.M., Bulanov, A.D., et al., Preparation of high-purity monoisotopic silane: 28SiH4, 29SiH4, and 30SiH4, Dokl. Chem., 2003, vol. 391, nos. 4–6, pp. 204–205.
Bulanov, A.D., Troshin, O.Yu., Kotkov, A.P., et al., Preparation of high-purity monoisotopic 29SiH4 and 30SiH4, Perspekt. Mater., 2010, no. 8, pp. 341–344.
Zhigach, A.F. and Stasinevich, D.S., Khimiya gidridov (The Chemistry of hydrides), Leningrad: Khimiya, 1969.
Potapov, A.M., Kurganova, A.E., Bulanov, A.D., et al., Isotope analysis of 72GeH4, 73GeH4, 74GeH4, and 76GeH4 monogermanes by inductively-coupled plasma high-resolution mass spectrometry (ICP–MS), J. Anal. Chem., 2016, vol. 71, no. 7, pp. 667–675.
Berezkin, V.G., Korolev, A.A., and Khotimskii, V.S., Polytrimethylsilylpropyne as a chromatographic adsorbent in capillary gas chromatography, Dokl. Phys. Chem., 2000, vol. 370, nos. 1–3, pp. 1–4.
Van Der Kelen, G.P., The mass spectra of mono-and digermane, Bull. Soc. Chim. Belg., 1960, vol. 69, pp. 504–516.
Agafonov, I.L. and Devyatykh, G.G., Mass-spektrometricheskii analiz gazov i parov osoboi chistoty (Mass Spectrometric Analysis of Extrapure Gases and Vapors), Moscow: Nauka, 1980.
Author information
Authors and Affiliations
Corresponding author
Additional information
Original Russian Text © A.Yu. Sozin, A.D. Bulanov, M.F. Churbanov, O.Yu. Chernova, T.G. Sorochkina, L.B. Nushtaeva, 2017, published in Neorganicheskie Materialy, 2017, Vol. 53, No. 1, pp. 3–10.
Rights and permissions
About this article
Cite this article
Sozin, A.Y., Bulanov, A.D., Churbanov, M.F. et al. Impurity composition of high-purity isotopically enriched monosilane and monogermane. Inorg Mater 53, 27–34 (2017). https://doi.org/10.1134/S0020168517010162
Received:
Published:
Issue Date:
DOI: https://doi.org/10.1134/S0020168517010162