Probing site-selective doping and charge compensating defects in KMgF₃: insights from a hybrid DFT study

Design of optoelectronic materials with tunable properties using activators and defect clusters has become one of the prime interests of current research. In this study, detailed Density Functional Theory based calculations have been presented to investigate the geometries and electronic structures of various possible defect clusters using Eu-KMgF₃ as a probe which has numerous technological and industrial applications. Using a more reliable hybrid density functional, we have calculated defect formation energies and thermodynamic transition levels to get knowledge about the site selectivity of Eu. It has been observed that the electronic structure of Eu-KMgF₃ is not only dependent on the site of doping but also on the oxidation state of Eu (2+/3+). The present study also investigates the relative stability of different kinds of defects and defect clusters under various synthetic growth conditions. The ultimate aim is to find out the microscopic origin of the fundamental optical properties of Eu-KMgF₃ and provide an unambiguous explanation of available experimental results. Thus, it has been revealed that doping with Eu results in the spontaneous formation of intrinsic defects, which contribute to the observed optical behaviour. We have also extended our study to investigate the role of codoping with Li in determining the geometry and electronic structure of Eu-KMgF₃ aiming to explain its impact on the optical properties. Thus, a complete presentation of the influence of the activator in the absence and presence of lattice defects on the optical properties of KMgF₃ has been accomplished in the current study. We strongly believe that the present study will be helpful in designing tunable phosphor materials by a defect-controlled synthesis strategy.