Density functional theory analysis of novel ZrO2 polymorphs: Unveiling structural stability, electronic structure, vibrational and optical properties

The importance of advanced materials like zirconium dioxide (ZrO2) in diverse medical, industrial, and technological contexts is underscored by contemporary technology. ZrO2 ' s unique combination of properties renders it indispensable for a broad spectrum of applications, suggesting its enduring importance. This study presents the very first investigation into the physical properties, structural stability, and ground-state characteristics of sixteen distinct ZrO2 polymorphs through the application of density functional theory (DFT). Motivated by the potential of ZrO2 polymorphs to substitute for SiO2, we conducted calculations to ascertain their dielectric properties. A comprehensive analysis was conducted on all structural features, and their stability was assessed. ZrO2 polymorphs exhibit a wide bandgap with the type of bandgap also examined. Calculated zone-center phonon frequencies demonstrate the dynamical stability of ZrO2, with existing polymorphs showing strong agreement with experimental frequencies, particularly within the monoclinic polymorph. Raman and infrared (IR) spectra of ZrO2 polymorphs were simulated using density functional perturbation theory. ZrO2 demonstrates notable mechanical stability, as evidenced by calculated hardness (moduli), ductility, improved ductility, and higher elasticity. Calculated optical properties, including the dielectric constant and refractive index of ZrO2 polymorphs, play a pivotal role in optimizing their performance in various applications such as optoelectronic devices and antireflective materials.