High‐Pressure Synthesis of Ultra‐Incompressible, Hard and Superconducting Tungsten Nitrides.

Transition metal nitrides, particularly those of 5<italic>d</italic> metals, are known for their outstanding properties, often relevant for industrial applications. Among these metal elements, tungsten is especially attractive given its low cost. In this high‐pressure investigation of the W–N system, two novel ultra‐incompressible tungsten nitride superconductors, namely W2N3 and W3N5, are successfully synthesized at 35 and 56 GPa, respectively, through a direct reaction between N2 and W in laser‐heated diamond anvil cells. Their crystal structure is determined using synchrotron single‐crystal X‐ray diffraction. While the W2N3 solid's sole constituting nitrogen species are N3‐ units, W3N5 features both discrete N3‐ as well as N24‐ pernitride anions. The bulk modulus of W2N3 and W3N5 is experimentally determined to be 380(3) and 406(7) GPa, and their ultra‐incompressible behavior is rationalized by their constituting WN7 polyhedra and their linkages. Importantly, both W2N3 and W3N5 are recoverable to ambient conditions and stable in air. Density functional theory calculations reveal W2N3 and W3N5 to have a Vickers hardness of 30 and 34 GPa, and superconducting transition temperatures at ambient pressure (50 GPa) of 11.6 K (9.8 K) and 9.4 K (7.2 K), respectively. Additionally, transport measurements performed at 50 GPa on W2N3 corroborate with the calculations. [ABSTRACT FROM AUTHOR]