Tuning phase and photoluminescent properties of ZrO2:Eu3+ coatings formed by plasma electrolytic oxidation and Judd-Ofelt analysis of composite materials

Abstract

Eu3+ doped Zirconia coatings were synthesized by the electrochemical plasma electrolytic oxidation method in only 8 min from the pure zirconium substrate. The phase constitution from pure monoclinic to pure tetragonal and exactly in between was achieved by using different concentrations of Na3PO4 and NaAlO2 electrolytes. The complex emission spectra composed of Eu2+, Eu3+, and ZrO2 defect emission greatly depend on the excitation wavelength and phase constitution. Eu3+ photoluminescence properties depend on the phase, which is reflected by the different Stark splitting and different intensities of transitions. Thus, both phase and photoluminescent properties of ZrO2 coatings are fine-tuneable. Judd-Ofelt analysis was performed from the emission and excitation spectra, showing that all 3 intensity parameters depend linearly on the phase constitution, being largest in the pure monoclinic phase. The mixed phase has Judd-Ofelt parameters between those in pure phases. Eu3+ has 2.45 times more preference to get incorporated into the tetragonal than in the monoclinic phase in the mixed phase samples. The general equation for Judd-Ofelt parameters in a compound with mixed constituents and probability of incorporation is introduced, allowing also for a prediction of the spectrum shape based on the Judd-Ofelt parameters of pure-phase compounds. Python software code for estimating the percent of incorporation by multiple linear regression model is also provided.