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The formation of β‐SiC during rapid thermal chemical vapor deposition of an epitaxial Si layer on a (100) Si substrate has been demonstrated using high‐resolution cross‐sectional transmission electron microscopy and secondary ion mass spectrometry (SIMS) depth profiling. Ellipsoidal β‐SiC precipitates (3×10 nm2 average size) were found with a density of (6±1)×109 cm-2 along the epilayer/substrate interface. SIMS revealed about 0.2 monolayer of carbon concentrated at the interface. The precipitates were shown to form during the hydrogen prebake as a result of improper surface cleaning. The crystalline quality of the epitaxial layer, however, was unaffected by the presence of the β‐SiC.