P1-xTa8+xN13 (x = 0.1-0.15): A Phosphorus Tantalum Nitride Featuring Mixed-Valent Tantalum and P/Ta Disorder Visualized by Scanning Transmission Electron Microscopy.
Angew Chem Int Ed Engl
; : e202411441, 2024 Jul 23.
Article
em En
| MEDLINE
| ID: mdl-39041462
ABSTRACT
We report on the synthesis, crystal, and electronic structure, as well as the magnetic, and electric properties of the phosphorus-containing tantalum nitride P1-xTa8+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, ß = 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.
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Coleções:
01-internacional
Base de dados:
MEDLINE
Idioma:
En
Revista:
Angew Chem Int Ed Engl
Ano de publicação:
2024
Tipo de documento:
Article
País de afiliação:
Alemanha