Structural, electronic, and optical properties of ZrO2 from ab initio calculations

TL;DR

This study uses ab initio calculations to comprehensively analyze the structural, electronic, and optical properties of ZrO2 in various crystalline phases, providing results that align well with experimental data and highlighting the importance of relativistic effects.

Contribution

It presents detailed ab initio calculations of ZrO2's properties across multiple phases, emphasizing the role of relativistic effects and phonons in dielectric behavior.

Findings

Effective masses are highly anisotropic.

Calculated dielectric constants match experimental values.

Relativistic effects significantly influence electronic properties.

Abstract

Structural, electronic, and optical properties for the cubic, tetragonal, and monoclinic crystalline phases of ZrO2, as derived from it ab initio full-relativistic calculations, are presented. The electronic structure calculations were carried out by means of the all-electron full potential linear augmented plane wave method, within the framework of the density functional theory and the local density approximation. The calculated carrier effective masses are shown to be highly anisotropic. The results obtained for the real and imaginary parts of the dielectric function, the reflectivity, and the refraction index, show good agreement with the available experimental results. In order to obtain the static dielectric constant of ZrO2, we added to the electronic part, the optical phonons contribution, which leads to values of e1(0)~29.5, 26.2, 21.9, respectively along the xx, yy, and zz directions, for the monoclinic phase, in excellent accordance with experiment. Relativistic effects, including the spin-orbit interaction, are demonstrated to be important for a better evaluation of the effective mass values, and in the detailed structure of the frequency dependent complex dielectric function.