First-principles study of Ce~(3+)-doped lanthanum silicate nitride phosphors: Neutral excitation, Stokes shift, and luminescent center identification

摘要

We study from first principles two lanthanum silicate nitride compounds, LaSi_3N_5 and La_3Si_6N_(11), pristine as well as doped with Ce~(3+) ion, in view of explaining their different emission color, and characterizing the luminescent center. The electronic structures of the two undoped hosts are similar, and do not give a hint to quantitatively describe such difference. The 4f → 5d neutral excitation of the Ce~(3+) ions is simulated through a constrained density functional theory method coupled with a ΔSCF analysis of total energies, yielding absorption energies. Afterwards, atomic positions in the excited state are relaxed, yielding the emission energies and Stokes shifts. Based on these results, the luminescent centers in LaSi_3N_5:Ce and La_3Si_6N_(11):Ce are identified. The agreement with the experimental data for the computed quantities is quite reasonable and explains the different color of the emitted light. Also, the Stokes shifts are obtained within 20% difference relative to experimental data.