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Edge‐defined film‐fed‐growth (EFG) Si is investigated using deep‐level transient spectroscopy and surface photovoltage. An impurity energy level of CrB was found at 0.27 eV above the valence band in EFG Si contaminated with Cr. The Cr diffusion coefficient in EFG Si was obtained as 2×10-17 cm2/s at room temperature using association and dissociation of CrB pairs after a 210 °C dissociation anneal. Most of the deep‐level transient spectroscopy (DLTS) spectra are not analyzable with conventional methods due to abnormally broad peaks. DLTS spectra of as‐grown EFG Si are modeled using a Gaussian distribution of impurity energy states. The simulated DLTS peaks agree well with measured data explaining the origin of the deep‐level impurities of EFG Si. © 1995 American Institute of Physics.