Microenvironment of the Eu Interstitial in β-SiAlON:Eu ²⁺ Green Phosphor

The precise atomic-scale structure around Eu 2+ activators in the β-Si 6– z Al z O z N 8– z:Eu 2+ commercial green phosphor remains elusive. We use the first-principles ΔSCF excited-state method, embedding of the interatomic force constants for supercells up to 3501 atoms, and Huang–Rhys theory to clarify this issue. Monte Carlo exploration is used to identify representative low-energy structural models spanning different levels of Al/O concentration z . For the lowest-energy structure at low z, our computed photoluminescence spectrum reproduces the experimental vibronic peaks at 6 K with excellent agreement in peak positions and intensities, validating the Eu–N 9 coordination model with Al, O, and Eu confined to the same crystallographic plane. Analysis of the low-energy structures reveals that the electron–phonon coupling is weak ( S ≈ 2.15) with a robust characteristic phonon signature across different Al/O arrangements, explaining the surprising persistence of resolved phonon replicas with increasing z . We explain the experimentally observed red-shift of emission with increasing z through systematic trends in zero-phonon line energies, modest increases in Huang–Rhys factors, and larger configurational diversity at higher compositions.