A direct route for the investigation of crystalline field effects on the spectral properties of Eu³⁺ ions in designed nanostructures

The spectral properties of lanthanide ions doped in a solid-state matrix, especially the Stark splitting and emission shifts, are strongly influenced by the local crystalline field. Here, we use a direct approach to quantitatively investigate the crystalline field effect on these spectral properties of Eu³⁺ ions in our designed β-PbF₂:Eu³⁺ and BaF₂:Eu³⁺ nanostructures. The extremely similar structures in which the central Eu³⁺ ions have the same site symmetry allow the local crystalline field to be simplified as the same point charge electrostatic field model. In this model, the direction and intensity of the electrostatic field are related to the distortion and expansion degree of the charge cloud of the luminescent center, respectively, and further determine the Stark splitting and emission shift. The theoretical analysis and charge-cloud stimulations were in good agreement with the experimental results. The direction and intensity of the crystalline field were calculated, and showed that the emission spectra shift to red with the increase in intensity. This work provides a comprehensive understanding of the spectral changes induced by a crystalline field, which is of great significance for the design of materials with the desired spectral properties