Optical absorption study of iron-substituted zirconia and yttria-stabilized zirconia using experimental measurements and many-body perturbation theory

Yttria-stabilized zirconia (YSZ) coatings have been developed for high temperature energy applications including gas turbines. The objective of this work is to understand how aliovalent Fe substitution affects the optical absorption spectrum of the host YSZ and ${\mathrm{ZrO}}_2$ systems in the ultraviolet–visible–near infrared wavelength range (from 245 to 2500 nm) using both experimental and computational techniques. In the Fe-substituted ${\mathrm{ZrO}}_2$ system, phase-pure ($>99$% purity) samples were synthesized in the monoclinic crystal structure, whereas Fe substitution in YSZ resulted in a two-phase mixture of coexisting tetragonal and monoclinic phases. Optical property characterization performed at room temperature revealed two broad absorption bands in both systems: one centered around 1000 nm and the other centered around 500 nm. Tauc plot analysis of the optical absorption data showed that as the Fe concentration increases, the optical band gaps of both materials systems decrease. Many-body perturbation theory methods, based on $G_0{W}_0$ and the Bethe-Salpeter equation, were used to computationally model the optical absorption spectrum as a function of Fe substitution in the tetragonal and monoclinic crystal structures of YSZ and ${\mathrm{ZrO}}_2$. Supercells were constructed and several Fe- and/or Y-atom configurations were explored in Zr sites. Charge compensating O vacancies were introduced to maintain electrical neutrality. The computations reveal that the observed optical excitations centered around 1000 nm likely have an excitonic character due to defect states, whose origin is traced to the electronic transitions between $\mathrm{Fe}\text{−}3d$ and $\mathrm{Fe}\text{−}3d$ orbitals. Intriguingly, both the tetragonal and monoclinic crystal structures appear to support local polyhedral distortions that promote excitations in the 1000 nm wavelength region. The excitation centered around 500 nm is attributed to the optical band gap of these materials. The outcomes of this work shed light on the radiative properties of Fe-substituted YSZ with implications in thermal barrier coating composition design.