Raman scattering,luminescence, and absorption edge under hydrostatic pressures of layered BiI3 and SbI3

Raman scattering from BiI₃ and SbI₃ crystals has been studied at hydrostatic pressures up to 2 GPa. The wavenumbers monotonically increased with pressure for all modes in BiI₃. Although both crystals belong to the same space group, the pressure coefficients of SbI₃ were significantly different from those of BiI₃. At pressure P₀ = 0.92 ± 0.01 GPa, the pressure coefficients of all modes changed. Above P₀, all modes in SbI₃ had positive pressure coefficients as they have in BiI₃. By comparing this unusual behavior of the Raman lines in SbI₃ around P₀ with the results in BiI₃ and comparing the two lattice structures, we suggest that the type of bonding of SbI₃ changes to become more ionic and hence more similar to the bonding of BiI₃. This change in structure is supported by changes in the bandwidth of the self‐trapped exciton (STE) luminescence and the slope of the absorption edge photon energy versus pressure. Copyright © 2007 John Wiley & Sons, Ltd.