Beschreibung:
Sillenite-type ceramics are non-centrosymmetric phases of ongoing research interest because of their structural defects and optoelectronic properties. We report a series of sillenite compounds with a general composition Bi12(Bi3+4/5−3xIn3+5x□1/5−2x)O19.2+3x□0.8−3x for x = 0.03–0.27 to understand how the crystal–physicochemical properties change with a successive filling of empty Bi3+ positions in the tetrahedral site by In3+ cation. Conventional solid-state synthesis method is used to prepare the microcrystalline samples. Each sample is characterized by X-ray diffraction, Raman, UV/Vis diffuse reflectance spectroscopy, and thermogravimetry (TG/DSC). X-ray powder data Rietveld refinement reveals that phase-pure samples can be obtained for x = 0.03–0.08 in the space group I23. Appearance of starting In2O3 as minor phases with the final products for 0.10 < x < 0.27 suggests for xmax = 0.08. The successive decrease of the lattice parameter indicates the incorporation of smaller In3+ cations in the structure. The effect of the lone electron pairs of Bi3+ and the structural cation vacancies lead to the modification of the interatomic bond lengths. At least one Raman active phonon mode shows hardening for decreasing cation vacancy concentration in the system. The bandgap energy increases with increasing indium content. An additional absorption band at lower energy for x = 0.03–0.08 complements the theoretical study, which completely disappears for x > 0.08. The stronger In–O bonds play pivotal roles in the thermal stability of the phases studied by TGA/DSC analysis.