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The results of a study of the structure and phase composition of epitaxial layers of silicon carbide (SiC) formed on silicon substrate with orientation (100) under rapid vacuum thermal processing are presented. Planar-view transmission electron microscopy investigation revealed the formation of epitaxial layers of cubic polytype SiC (3C-SiC) on silicon in the process of carbidisation at 1100 °C during 30 s, using a gas mixture of propane (10 %) and argon (90 %) as a carbon source. The formation of a monocrystalline 3C-SiC with polycrystalline inclusions and twins on all possible planes {111} was found. A rather narrow band of 793 cm–1 transverse optical phonon mode SiC on Raman spectra confirms the formation of a cubic polytype SiC. It is noted that the presence of a 180 cm–1 spectral line and a 793 cm–1 half-width band on Raman spectra indicate the presence of deformation defects in SiC.