Estudo teórico das propriedades estruturais, eletrônicas e ópticas dos compostos Bi4Ge3O12 e Bi4Si3O12

Abstract

This dissertation presents a theoretical study, based on density functional theory (DFT), upon structural, electronic and optical properties of Bi4Ge3O12 (Bismuth germanate, BGO) and Bi4Si3O12 (Bismuth silicate, BSO) compounds. As a computational tool it was utilized Full Potential Linear Augmented Plane Wave Method (FPLAPW), implemented into WIEN2k computer code and considered as one of the most precise tools for electronic structure calculations of solid materials. Exchange and correlation e ects were simulated by LDA, GGA-PBEsol, BJ, mBJ-original, mBJ P-present and mBJ P-semiconductor functionals. Lattice parameters and all atomic positions within the BGO and BSO unit cells were computationally optimized in order to reach minimum energy con guration. The resulting structural parameters showed good agreement with experimental data. The results of electronic structure calculations (band structure and density of electron states DOS) were best tted to experiment while using the mBJ P-semiconductor functional. They revealed a nature and size of the compound's fundamental band gaps, as well as predominant orbital character of bands around it. According to the results, the BGO and BSO have indirect fundamental gaps of 5.05 and 5.36 eV in excellent concordance with the experimental value 5.0 eV (BGO) and 5.4 eV (BSO). For both compounds the valence band top is dominated by the O 2p-states, with non-negligible amount of the Bi 6s-states, while the conduction band bottom is consisted mostly of the Bi 6p-states. This work was also calculated dielectric function "(!) of the BGO and BSO, and its refractive index n(!) and re ectivity R(!). The best agreement with experimental data was again achieved by using mBJ P-semiconductor functional. The analysis "(!) enabled interpretation of optical absorption spectrum of BGO and BSO in terms of electronic transitions between bands. The results showed that the greater ow of energy transfer occurs 2p states to the states of Bi 6p, which consists of the steps of the scintillation process in BGO and BSO. Was concluded that experimental optical spectra of BGO and BSO exhibit strong temperature dependency, and that theoretical results presented in this dissertation describe con dently electronic and optical properties when measured at low temperatures.