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High‐Pressure Synthesis and Phase Stability of Nickel Pernitride

MetadataDetails
Publication Date2019-08-16
JournalEuropean Journal of Inorganic Chemistry
AuthorsKen Niwa, Riku Fukui, Toshiki Terabe, Takuya Kawada, Daiki Kato
InstitutionsNagoya University
Citations30

The high‐pressure nitridation of nickel was investigated using a laser‐heated diamond‐anvil cell. Marcasite‐type nickel pernitride (NiN 2 ) was synthesized at approximately 40 GPa, and it transformed into the tetragonal phase at approximately 3 GPa along with the decompression. The structural refinement of marcasite‐type NiN 2 at 36 GPa gives an N‐N distance of 1.24 Å. The first‐principles calculation reveals that the marcasite‐type NiN 2 is a narrow‐gap semiconductor, and high‐pressure in‐situ X‐ray diffraction measurements revealed a zero‐pressure bulk modulus of 172(6) GPa. The axial ratios (c/a and b/a) of marcasite‐type NiN 2 are close to the upper‐limit values of marcasite‐type structures, which suggests that the stability of marcasite‐type transition metal pernitrides strongly depends on the d ‐electrons.