Raman and optical spectroscopy characteristics of Se-doped Bi12SiO20 crystals

Crystals of BSO doped with Se in two different concentrations (BSO:Se(I) and BSO:Se(II)) were grown by the Czochralski method. It is established that doping with Se is accompanied with preferential absorption of Fe from the melt. According to the in-depth chemical analysis, it is assumed that the doping Se ions enter the tetrahedral positions by means of the substitution of 3Si4+ by (Se6+ + 2Fe3+) ions. The measured absorption spectrum of the low-concentration Se-doped crystal (BSO:Se(I)) confirms such a conclusion as the absorption coefficient is increased in a broad spectral interval (1.4–3.1 eV) – an effect typical for all Fe-doped Bi12SiO20 crystals. The polarized Raman spectra of BSO:SeI show that the doping-induced lattice distortions are small. The IR spectrum of the BSO:SeI crystal yields indications for local lowering of the symmetry of the Fe-occupied tetrahedral positions. Doping with Se at high concentration (BSO:Se(II)) leads to occasional second phase inclusions and to a downshift of practically all modes in the Raman spectrum by 2–5.5 cm−1. It is concluded that the doping with Se at high concentrations follows the same mechanism as that at low concentrations but the introduced lattice distortions are more significant, and lead to an enlargement of the unit cell while preserving the overall cubic symmetry.

► Growth of Bi12SiO20 crystals doped with Se.
► Doping Se ions enter tetrahedral positions replacing 3Si4+ by (Se6++ 2Fe3+) ions.
► Changes in the lattice parameter and shifts of Raman modes occur upon doping.
► We assume symmetry lowering in some tetrahedral positions upon doping with Fe and Se.
► Symmetry lowering allows forbidden modes in the IR spectrum.