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Epitaxial layers of silicon grown on a Si(100) substrate by molecular‐beam epitaxy (MBE) and solid‐phase epitaxy (SPE) have been investigated by slow positron beam analysis methods. Results of Doppler broadening measurements revealed that the S parameter of the SPE material is considerably higher than the value measured for the MBE layer, indicative of a higher concentration of open‐volume defects in the former material. This was confirmed by measurements of the positronium fraction at elevated temperatures.