Temperature dependence of the electronic structure of oxides: MgO, MgAl₂O₄ and Al₂O₃

We have studied the room temperature optical reflectivity of MgO, MgAl₂O₄, and α-Al₂O₃ from 5 to 40eV using a novel spectrophotometer with a laser plasma light source. Structure in the imaginary component of the dielectric response is analysed using critical point line shapes, and the origins of the major transitions in MgO and MgAl₂O₄ are determined using an ab initio pseudofunction band structure calculation of MgO. The exciton reflectivity has been studied in the three materials at temperatures between 300 and 1500 K, and exciton-phonon coupling appears to increase from MgO to α-Al₂O₃. The temperature dependence of the higher lying interband transitions in MgO has been determined to 1100 K, and we find that while the temperature dependence of the onset transitions at Γ and X are nearly identical (− 1.22meV/K at Γ), higher lying transitions have very different temperature dependences. Furthermore with increasing temperature the X point valence band separation increases at a rate of 0.38meV/K, while the conduction band separation at X decreases at −0.41meV/K.