One-Pot Synthesis of Single-Source Precursors for Nanocrystalline LED Phosphors M₂Si₅N₈:Eu²⁺ (M = Sr, Ba)

Highly efficient red-emitting nitridosilicate phosphors Sr2Si5N8:Eu and Ba1.5Sr0.5Si5N8:Eu (doping level 1 %) applicable to phosphor converted pc-LEDs were synthesized in nanocrystalline form at low temperatures employing a novel single-source precursor approach. Synthesis starts from nanocrystalline silicon and uses mixed metal amides M(NH2)2 with M ) Sr, Ba, Eu as reactive intermediates. In a second approach, a single-source precursor mixture obtained from a one-pot reaction of the corresponding elements (Sr/Ba, Eu, Si) was obtained in supercritical ammonia. Thermoanalytical in situ investigations gain a deeper insight into the degradation mechanism of the mixed metal amide precursors and revealed the onset for the formation of the 2-5-8 phosphor materials at temperatures slightly above 900 °C. Formation of the products is complete below 1400 °C. Under these conditions, the nitridosilicate phosphors form spherically shaped particles with crystallites of 200 nm in size. Spherical particles are desirable for phosphor application because light extraction may be improved by decreased light trapping and re-absorption losses. As a major advantage of the one-pot precursor approach, the exact Sr/Ba content in the solid solution series Sr2-xBaxSi2N8:Eu and the doping concentration of Eu2+ can easily be controlled in a wide range by the relative amount of the elemental starting materials (Sr, Ba, Eu, Si). Simultaneously, thorough mixing of these elements down to an atomic level (Sr, Ba, Eu) or at least at nanoscopic dimensions (silicon) is achieved by the solution approach. As a consequence, no milling and pre-reaction steps are necessary which might give rise to contamination. Advantageously, this approach can easily be extended to large-scale processes by simultaneously preserving complete mixing. Furthermore, the influence of the starting materials (single-source precursor, nanocrystalline silicon) and the reaction conditions on the crystal shape and finally on the luminescence properties of the products was investigated. The obtained nanophosphors exhibit luminescence properties comparable to coarsely crystalline nitridosilicate phosphor powders prepared by conventional high-temperature processing.