Crystal Chemistry, Optical Properties and Electronic Structure of R3Fe0.1Ga1.6S7 (R – La, Ce, Pr, Nd, Tb) Sulfides
DOI:
https://doi.org/10.15407/ujpe71.9.717Keywords:
rare-earth elements (REE), energy-dispersive X-ray spectroscopy, X-ray powder diffraction, Tauc plot method, density functional theoryAbstract
X-ray powder diffraction data were used to determine the crystal chemical parameters of R3Fe0.1Ga1.6S7 (R – La, Ce, Pr, Nd, Tb) sulfides, which crystallize in the La3CuSiS7 structural type (space group (SG) P63). The crystal structure of these compounds is formed by an interconnected three-dimensional framework of various coordination polyhedral types, including seven-coordinated [R S7] polyhedra, mixed-occupancy [M (Fe, Ga) S6] octahedra, and [Ga S4] tetrahedra. The qualitative and quantitative elemental composition of the synthesized sulfides was confirmed by energy-dispersive X-ray spectroscopy combined with scanning electron microscopy (EDX/SEM). Dynamic light scattering was used to characterize the particle size distribution and degree of homogeneity in colloidal systems (dispersion in isopropyl alcohol) to determine the polydispersity indices. The optical parameters of the sulfides were determined using the Tauc plot method, revealing band gaps from 1.95 to 2.50 eV for direct interband transitions and from 1.21 to 2.70 eV for indirect ones, demonstrating composition-dependent variability of the electronic structure. For the sulfides containing La and Ce, quantum-chemical modeling was performed within the framework of density functional theory (DFT; ab initio approach) to calculate the band structure.
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