High‐Pressure Synthesis of Tantalum Nitride Having Orthorhombic U₂S₃ Structure

Abstract Among binary compounds, there is a high potential for discovery of novel members (polymorphic phases or compounds) of the nitrides of transition metals group due to a pronounced dependence of the oxidation state of the metals (M) on pressure. The power of high pressure–high temperature (HP‐HT) route for synthesis of binary nitrides has already been demonstrated by the discovery of cubic nitrides of the group 4 and 14 elements, of crystalline polymorphs of P₃N₅, and by reports on formation of four noble metal nitrides. It is anticipated that such HP products exhibit, in addition to enhanced elastic and mechanical behavior, other functional properties making them interesting for industrial applications. Here, HP–HT synthesis research is extended to nitrides of group 5 elements, resulting in the discovery of a novel hard tantalum nitride, exhibiting U₂S₃ structure: η‐Ta₂N₃ (Pbnm, a = 8.1911(17) Å, b = 8.1830(17) Å, c = 2.9823(3) Å). The stoichiometry is supported by two independent means, verifying that η‐Ta₂N₃ is the first thermodynamically stable transition metal nitride with a N:M ratio exceeding 4:3. Due to its high hardness and peculiar texture (needle‐like and granular crystallites), η‐Ta₂N₃ may find practical applications as a hard fracture resistant material.