P. G. Sennikov

Ultrapurification of 76Ge-enriched GeH4 by distillation

Abstract76Ge-enriched germane has been ultrapurified by low-temperature distillation. The nature and concentration of molecular impurities in the germane samples were determined by gas chromatography/mass spectrometry, high-resolution Fourier transform IR spectroscopy, and gas chromatography. The distillate contains no more than 10−5 mol % hydrocarbons, 10−4 mol % carbon dioxide, 10−3 to 10−1 mol % digermane and trigermane, and <3 × 10−5 mol % other impurities. A distinctive feature of the impurity composition of the isotopically enriched germane samples is the presence of silicon tetrafluoride and sulfur hexafluoride impurities.

Molecular analysis of isotopically enriched 28SiF4 and 28SiH4 prepared from it

We have developed analytical techniques for the determination of impurities in isotopically enriched 28SiH4 and 28SiF4. The impurities in SiF4 were first determined by IR spectroscopy, and those in SiH4, by gas chromatography/mass spectrometry. High-sensitivity determination of organic impurities in SiH4 and SiF4 was performed by gas chromatography. SiF4 was found to contain C1–C4 hydrocarbons, hexafluorodisiloxane (Si2F6O), hydrogen fluoride, trifluorosilanol (SiF3OH), fluorosilanes, water, and carbon oxides. The impurities identified in SiH4 include C1–C4 hydrocarbons, disilane (Si2H6), inorganic hydrides, Si2H6O, alkylsilanes, and fluorinated and chlorinated organics. The detection limits of IR spectroscopy were 3 × 10−3 to 5 × 10−5 mol %, those of gas chromatography/mass spectrometry were 8 × 10−6 to 10−8 mol %, and those of gas chromatography were 6 × 10-6 to 2 × 10−7 mol %.

Impurities in monosilanes synthesized by different processes

Using high-resolution IR spectroscopy, we have compared the impurity compositions of monosilane (SiH4) fractions enriched in impurities in the process of cryofiltration and low-temperature distillation of monosilanes derived from silicon tetrafluoride (SiF4) and trichlorosilane (SiCl3H). The results demonstrate that the more volatile impurities present in both monosilanes are methane (CH4) and carbon dioxide (CO2), whereas the impurities specific to the fluoride-derived monosilane are SiF4, SiF3H, and SiF2H2. The less volatile impurities common to both monosilanes are ethane (C2H6), disiloxane (Si2H6O), and disilane (Si2H6); the impurities specific to the fluoride-derived monosilane are tetrafluoroethylene (C2F4) and monofluorosilane (SiFH3); and those specific to the chloride-derived monosilane are hydrogen chloride (HCl) and the chlorosilanes SiClH3, SiCl2H2, and SiCl3H.

Hydrocarbon impurities in SiF4 and SiH4 prepared from it

Using gas chromatography and high-resolution Fourier-transform IR spectroscopy, we have determined the concentrations of C1–C4 hydrocarbon impurities in isotopically unmodified silicon tetrafluoride before and after fine purification and in 28Si-enriched SiF4. The concentrations of C1–C4 hydrocarbon impurities in silicon tetrafluoride for SiH4 synthesis have been shown to correlate with those in the synthesized silane.

Thermochemical purification of sulfur from hydrocarbons

The behavior of carboniferous impurities during thermochemical purification of sulfur was studied. The integral absorption coefficient for the IR absorption band at 2920 cm-1, related to aliphatic hydrocarbons, was determined. The detection limit for aliphatic hydrocarbons in sulfur was evaluated to be 2 x 10-5 wt % (3σ criterion).

Formation of impurity Si2OH6 in silane synthesized from silicon tetrafluoride

The possibility of the reduction of hexafluorodisiloxane by calcium hydride in the synthesis of silane from silicon tetrafluoride has been studied. This reaction is shown to be not decisive for oxygen contamination of silane. The most likely reason for the appearance of impurity Si2OH6 in “fluoride” silane is the Ca(OH)2-catalyzed reaction of silane with trace water. The concentration of impurity Si2OH6 in silane at the stage of synthesis may be efficiently decreased by the preliminary purging of calcium hydride with a hydrogen (grade A) flow.

Determination of impurities in germanium tetrafluoride by IR spectroscopy and gas chromatography

Using high-resolution Fourier-transform IR spectroscopy and gas chromatography, we have identified more than 20 impurity species, in concentrations from 10−1 to 10−5 vol %, in GeF4 samples of different isotopic compositions. The germanium tetrafluoride samples are shown to contain C1–C4 hydrocarbons; hydrogen, carbon, silicon, and sulfur fluorides; fluorogermanes; fluorosilanes; and carbon and nitrogen oxides.