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Abstract Transition metal nitrides, particularly those of 5 d 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 W ₂ N ₃ and W ₃ N ₅ , are successfully synthesized at 35 and 56 GPa, respectively, through a direct reaction between N ₂ and W in laser‐heated diamond anvil cells. Their crystal structure is determined using synchrotron single‐crystal X‐ray diffraction. While the W ₂ N ₃ solid's sole constituting nitrogenmore » species are N ^3‐ units, W ₃ N ₅ features both discrete N ^3‐ as well as N ₂ ^4‐ pernitride anions. The bulk modulus of W ₂ N ₃ and W ₃ N ₅ is experimentally determined to be 380(3) and 406(7) GPa, and their ultra‐incompressible behavior is rationalized by their constituting WN ₇ polyhedra and their linkages. Importantly, both W ₂ N ₃ and W ₃ N ₅ are recoverable to ambient conditions and stable in air. Density functional theory calculations reveal W ₂ N ₃ and W ₃ N ₅ 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 W ₂ N ₃ corroborate with the calculations.« less

We report this joint experimental and theoretical study of the structural and vibrational properties of β-In₂S₃ upon compression shows that this tetragonal defect spinel undergoes two reversible pressure-induced order–disorder transitions up to 20 GPa. We propose that the first high-pressure phase above 5.0 GPa has the cubic defect spinel structure of α-In₂S₃ and the second high-pressure phase ($$\phi$$-In₂S₃) above 10.5 GPa has a defect α-NaFeO₂-type (R$$\bar{3}$$) structure. This phase, related to the NaCl structure, has not been previously observed in spinels under compression and is related to both the tetradymite structure of topological insulators and to the defect LiTiO₂ phasemore » observed at high pressure in other thiospinels. Structural characterization of the three phases shows that α-In₂S₃ is softer than β-In₂S₃ while $$\phi$$-In₂S₃ is harder than β-In₂S₃. Vibrational characterization of the three phases is also provided, and their Raman-active modes are tentatively assigned. Our work shows that the metastable α phase of In₂S₃ can be accessed not only by high temperature or varying composition, but also by high pressure. On top of that, the pressure-induced β–α–$$\phi$$ sequence of phase transitions evidences that β-In₂S₃, a B^III₂X^V₃ compound with an intriguing structure typical of A^IIB^III₂X^VI₄ compounds (intermediate between thiospinels and ordered-vacancy compounds) undergoes: (i) a first phase transition at ambient pressure to a disordered spinel-type structure (α-In₂S₃), isostructural with those found at high pressure and high temperature in other B^III₂X^V₃ compounds; and (ii) a second phase transition to the defect α-NaFeO₂-type structure ($$\phi$$-In₂S₃), a distorted NaCl-type structure that is related to the defect NaCl phase found at high pressure in A^IIB^III₂X^VI₄ ordered-vacancy compounds and to the defect LiTiO₂-type phase found at high pressure in A^IIB^III₂X^VI₄ thiospinels. This result shows that In₂S₃ (with its intrinsic vacancies) has a similar pressure behaviour to thiospinels and ordered-vacancy compounds of the A^IIB^III₂X^VI₄ family, making β-In₂S₃ the union link between such families of compounds and showing that group-13 thiospinels have more in common with ordered-vacancy compounds than with oxospinels and thiospinels with transition metals.« less