Yellow-Orange-Emitting CaAlSiN3:Ce3+ Phosphor: Structure, Photoluminescence, and Application in White LEDs

The crystal structure and photoluminescence properties of undoped and Ce3+-doped CaAlSiN3 as well as the application of white-light LEDs are reported. CaAlSiN3 and CaAlSiN3:Ce3+ have been synthesized, starting from Ca3N2, AlN, Si3N4, and CeN or CeO2 with and without Li3N, by a solid state reaction at 1700 °C for 4 h under high purity nitrogen atmosphere. Instead of an ideal CaAlSiN3, a more appropriate formula is proposed to be CaAl1−4δ/3Si1+δN3 (δ ≈ 0.3−0.4) with an Al/Si ratio of about 1:2 on the basis of the bond valence sum calculations, in which Al/Si is disorderly occupied on the 8b site within Cmc21 space group. Ce3+ can be incorporated into the host lattice of CaAlSiN3, and the estimated maximum solubility of Ce3+ is about x = 0.02 (e.g., 2.0 mol % with respect to Ca) of Ca1−2xCexLixAlSiN3. CaAlSiN3:Ce3+ can be efficiently excited by blue light (450−480 nm) and yields yellow-orange emission with a broadband peaking in the range of 570−603 nm, originating from the 5d1 → 4f1 transition of Ce3+. With an increase of Ce concentration, the emission band of Ce3+ shifts to longer wavelengths due to the increased Stokes shift corresponding to structural relaxation and energy transfer of Ce3+. Upon excitation in blue light range (450−480 nm), the absorption and external quantum efficiency are about 70% and 56%, respectively, for both Ca1−2xCexLixAlSiN3 and Ca1−xCexAlSiN3−2x/3O3x/2 at x = 0.01. In addition, Ca1−2xCexLixAlSiN3 and Ca1−xCexAlSiN3−2x/3O3x/2 show high thermal stability in air with the quenching temperature above 300 °C for x = 0.01. Using single CaAlSiN3:Ce3+ as the wavelength conversion phosphor combined with a blue InGaN LED-chip (450 nm), warm white-light LEDs can be generated, yielding the luminous efficacy of about 50 lm/W at color temperature 3722 K and the color rendering index (Ra) of 70, which demonstrates that CaAlSiN3:Ce3+ is a highly promising yellow-orange phosphor for use in white-light LEDs.