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.

The red-emitting Sr ₂ Si ₅ N ₈ :Eu ²⁺ phosphor with a superior quantum efficiency and suitable emission spectrum has been widely used as a promising down-conversion material in white light-emitting diodes. However, its thermal degradation under high temperature handicaps its large scale application, and therefore must be reduced. Here, we proposed to increase the thermal stability of Sr ₂ Si ₅ N ₈ :Eu ²⁺ by coating a nanometer-order Al ₂ O ₃ film on each phosphor particle using an atomic layer deposition approach in a fluidized bed reactor. The deposited Al ₂ O ₃ layer was quite uniform and conformal when using O ₃ as the oxidizer, and its thickness could be controlled by the dosage type, deposition temperature and cycle numbers, which largely affects the photoluminescence properties and thermal degradation of the title phosphor. Thermal gravimetric analysis results showed that the oxidation temperature of the coated phosphor increased from 700 to 850 °C, suggesting that the coating layer has the function of anti-oxidation. Meanwhile, the coated phosphor particle surface became hydrophobic. Consequently, the thermal degradation of phosphor powders in air at 200 °C was greatly reduced and the stability of the fabricated LEDs with coated powders was also improved. Prospectively, the proposed approach provides a new strategy to improve the thermal stability of other phosphors.

A new sialon Eu_3.60LiSi_13.78Al_6.03O_6.82N_22.59 has been discovered via the single-particle diagnosis approach. Its crystal structure (space group P3m1) was solved and refined from single-crystal X-ray diffraction data. It has the interesting feature of two types of disorder at the Eu2 site: positional disorder (Eu2a/Eu2b) and substitutional disorder with (Si/Al)₂(O/N). The structure is generalized to the formula A_4-mB_nC_19+2mX_29+m (A = Sr, La, Eu, Ce; B = Li; C = Si, Al; X = O, N; 0 ≤ m ≤ 1; 0 ≤ n ≤ 1), of which Sr_3.61LiSi_14.27Al_5.61O_6.19N_23.25 (Sr-sialon, m = 0.41, n = 1) and La_2.85Sr_0.76LiSi_14.86Al_4.93O_2.89N_26.51 (LaSr-sialon, m = 0.40, n = 1) are two examples that have been obtained as a single-phase powder. Sr-sialon:Eu and LaSr-sialon:Eu both show blue to yellow emission, depending on the Eu concentration, whereas Sr-sialon:1% Ce shows a deep-blue emission band centered at 422 nm with a full width at half-maximum of 80 nm and an internal quantum efficiency of 80% (λ_ex = 355 nm). The latter phosphor has very good thermal stability of both emission intensity and color. A white light-emitting diode (LED) containing the newly discovered Sr-sialon:5% Ce as the blue phosphor component shows excellent color-rendering indices (R_a = 96 and R₁₂ = 97) with a correlated color temperature of 4255 K. This indicates that Sr-sialon:Ce is a highly promising deep-blue phosphor for illumination grade white LEDs.

Optical data of the Eu²⁺ doped nitridosilicates (M_xSi_yN_z) have been collected from the literature and have been analysed with regard to their dependence on structure and composition. Nitridosilicates with a higher degree of condensation, i.e. a higher Si/N ratio, generally have a higher Eu²⁺ 4f-5d absorption energy, a higher 5d-4f emission energy and a larger Stokes shift. The higher absorption and emission energies are due to the increase of the N by Si coordination number with increasing Si/N ratio. This results in more electrons on N that participate in the bonding with Si, and thus less electrons are available for Eu-N bonding, reducing the covalency of the Eu-N bonds. The lower covalency gives a weaker nephelauxetic effect, reducing the centroid shift of the 5d level. The lowest 4f-5d absorption energy further increases due to the reduction of the crystal field splitting of the 5d levels, as the Eu-N bonds become longer with increasing Si/N ratio. The Stokes shift increases with increasing degree of condensation despite an increase of lattice rigidity, ascribed to a decrease of local rigidity around the Eu²⁺ ion caused by the larger Eu-N bond lengths. Some nitridosilicates show deviations from the general trends attributed to peculiarities in their crystal structure and the way Eu²⁺ is substituted in the lattice. The relationships established in the present work will be helpful for the design and exploration of new Eu²⁺ doped nitride-based luminescent materials for practical applications.