Electronic and optical properties of the SiB2O4 (B=Mg, Zn, and Cd) spinel oxides: An ab initio study with the Tran–Blaha-modified Becke–Johnson density functional

We report ab initio density functional theory calculations of the structural, electronic and optical properties of the spinel oxides SiMg2O4, SiZng2O4, and SiCd2O4 using the full-potential linearized augmented plane-wave method. The structural parameters calculated using both the local density and generalized gradient approximations to the exchange-correlation potential are consistent with the literature data. To calculate the electronic properties, the exchange-correlation potential is treated with various functionals, and we find that the newly developed Tran–Blaha-modified Becke–Johnson functional significantly improves the band gap. We predict a direct band gap in all of the considered SiB2O4 compounds, and the band gaps continuously decrease as the atomic size of the B element increases. The decrease in the fundamental direct band gap (Γ–Γ) from SiMg2O4 to SiZn2O4 to SiCd2O4 can be attributed to p–d mixing in the upper valence bands of SiZn2O4 and SiCd2O4. The lowest conduction band is well dispersive, similar to that found for transparent conducting oxides such as ZnO. This band is mainly defined by the s and p electrons of the Si and B (B=Mg, Zn, Cd) atoms. The topmost valence band is considerably less dispersive and is defined by O-2p and B–d electrons. The charge-carrier effective masses are evaluated at the topmost valence band and at the bottommost conduction band that were calculated. The frequency-dependent complex dielectric function, absorption coefficient, refractive index, extinction coefficient, reflectivity and electron energy loss function were estimated. We find that the value of the zero-frequency limit of the dielectric function ε(0)ε(0) increases as the band gap decreases. The origins of the peaks and structures in the optical spectra are determined in terms of the calculated energy band structures.