Localized levels play a major role in the electro‐optic properties of Bi12SiO20 (BSO) crystals. The activation energy of trapping levels was studied by different laboratories using various methods (e.g., thermally stimulated currents and photoinduced current transient spectroscopy). A more sensitive investigation of traps in undoped BSO single crystals has been performed by optical charging spectroscopy. The presence of traps in the energy range 0.2–1.1 eV was found, and the results are in good agreement with previous studies. On the other hand, this method led us to suggest that the trapping levels observed can be both electron traps and hole traps. For deep trapping levels at higher temperatures, a strong temperature dependence of the cross section was observed.

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