P_1-xTa_8+xN₁₃ (x=0.1-0.15): A Phosphorus Tantalum Nitride Featuring Mixed-Valent Tantalum and P/Ta Disorder Visualized...

We report on the synthesis, crystal, and electronic structure, as well as the magnetic, and electric properties of the phosphorus-containing tantalum nitride P_1-xTa_8+xN₁₃ (x=0.1-0.15). A high-pressure high-temperature reaction (8 GPa, 1400 °C) of Ta₃N₅ and P₃N₅ with NH₄F as a mineralizing agent yields the compound in the form of black, rod-shaped crystals. Single-crystal X-ray structure elucidation (space group C2/m (no. 12), a=16.202(3), b=2.9155(4), c=11.089(2) Å, β=126.698(7)°, Z=2) shows a network of face- and edge-sharing Ta-centered polyhedra that contains small vacant channels and PN₆ octahedra strands. Atomic resolution transmission electron microscopy reveals an unusual P/Ta disorder. Mixed-valent tantalum atoms exhibit interatomic distances similar to those in metallic tantalum, however, the electrical resistivity is quite high in the order of 10¹ Ω cm. The density of states and the electron localization function indicate localized electrons in both covalent and ionic bonds between P/Ta and N atoms, combined with less localized electrons that do not contribute to interatomic bonds.