Influence of composition and structure on the thermal quenching of the 5d–4f emission of Eu2+ doped M–Si–N (M = alkali, alkaline earth, rare earth) nitridosilicates

Abstract

Experimental data from literature on the thermal quenching of the Eu²⁺ 5d–4f emission in the M_xSi_yN_z (M = alkali, alkaline earth or rare earth) nitridosilicates have been collected and evaluated. No clear correlation was observed between the activation energy for thermal quenching and the Stokes shift, suggesting that non-radiative relaxation via a thermally excited cross-over from the 5d excited state to the 4f ground state is not the main reason for thermal quenching in the nitridosilicates. Based on literature data on rare-earth charge transfer transitions, host-lattice bandgap and Eu²⁺ 5d–4f emission energy, the energy difference between the Eu²⁺ 5d level and the bottom of the host-lattice conduction band has been determined. This energy difference correlates fairly well with the quenching temperature, suggesting that thermal ionization of the 5d electron to the conduction band is responsible for the thermal quenching of the Eu²⁺ 5d–4f emission in the nitridosilicates. The energy difference between the lowest 5d level and the bottom of the conduction band, and consequently the quenching temperature, increases with increasing Si/N ratio of the nitridosilicates. From this, it is concluded that the combined effect of the larger Stokes shift and the raise in energy of the bottom of the host lattice conduction band with increasing Si/N ratio is stronger than the decrease of the centroid shift and crystal field splitting of the Eu²⁺ 5d level.