Importance of long-range channel Sr displacements for the narrow emission in Sr[Li$_2$Al$_2$O$_2$N$_2$]:Eu$^{2+}$ phosphor

Abstract

The recently discovered Sr[Li$_2$Al$_2$O$_2$N$_2$]:Eu$^{2+}$ red phosphor, candidate for the next generation of eco-efficient white light-emitting diodes, exhibits excellent emission spectral position and exceptionally small linewidth. It belongs to the UCr$_4$C$_4$-structure family of phosphors, containing many potential candidates commercial phosphors, whose small linewidth, tentatively ascribed to the high-symmetry cuboid environment of the doping site, has drawn the attention of researchers in the last five years. We use density functional theory, $\Delta$SCF method and configuration coordinate models (CCM) to provide a complete characterization of this material. Using a multi-dimensional CCM, an accurate description of the coupling of the vibronic structure with the electronic 5d$\rightarrow$4f transition is obtained, including the partial Huang-Rhys factors and frequency of the dominant modes. We show that, in addition to the first-coordination shell cuboid deformation mode, low-frequency phonon modes involving chains of strontium atoms along the tetragonal axis shape the emission linewidth in Sr[Li$_2$Al$_2$O$_2$N$_2$]:Eu$^{2+}$. This finding sheds new light on the emission properties of UCr$_4$C$_4$-structure phosphors, possessing similar Ca/Sr/Ba channel. Our approach provides a robust theoretical framework to systematically study the emission spectra of such Eu-doped phosphors, and predict candidates with expected similar or even sharper linewidth.