High-Pressure High-Temperature Synthesis of Mixed Nitridosilicatephosphates and Luminescence of AESiP3N7:Eu2+ (AE = Sr, Ba).

Tetrahedra-based nitrides with network structures have emerged as versatile materials with a broad spectrum of properties and applications. Both nitridosilicates and nitridophosphates are well-known examples of such nitrides that upon doping with Eu2+ exhibit intriguing luminescence properties, which makes them attractive for applications. Nitridosilicates and nitridophosphates show manifold structural variability; however, no mixed nitridosilicatephosphates except SiPN3 and SiP2N4NH have been described so far. The compounds AESiP3 N7 (AE=Sr, Ba) were synthesized by a high-pressure high-temperature approach using the multianvil technique (8 GPa, 1400-1700 °C) starting from the respective alkaline earth azides and the binary nitrides P3 N5 and Si3 N4 . The latter were activated by NH4 F, probably acting as a mineralizing agent. SrSiP3 N7 and BaSiP3 N7 were obtained as single crystals. They crystallized in the barylite-1O (M=Sr) and barylite-2O structure types (M=Ba), respectively, with P and Si being occupationally disordered. Cation disorder was further supported by solid-state NMR spectroscopy and energy-dispersive X-ray spectroscopy (EDX) mapping of BaSiP3 N7 with atomic resolution. Upon doping with Eu2+ , both compounds showed blue emission under UV excitation.