Adhara Baldassarre

Black phosphorus was studied by state-of-the-art synchrotron X-ray diffraction in a Diamond Anvil Cell during room temperature compression in the presence of He, H₂, N₂ and Daphne Oil 7474. The data demonstrate that the existence of the pseudo simple-cubic (p-sc) structure above 10.5 GPa is an intrinsic feature of P independent from the pressure transmitting medium. In the case of He, the pressure evolution of the lattice parameters and unit cell volume of P across the A17, A7 and p-sc structures was obtained and the corresponding EOS derived, providing a deeper insight on the recently reported p-sc structure. The results presented in this letter highlight the key role of the s–p orbital mixing in the formation and stabilization of the p-sc structure up to ∼30 GPa, solving apparent contradictions emerging from previous literature and finally bringing order to the sequence of the high pressure A7 layered structure in group 15 elements.

Black phosphorus was compressed at room temperature across the A17, A7 and simple‐cubic phases up to 30 GPa, using a diamond anvil cell and He as pressure transmitting medium. Synchrotron X‐ray diffraction showed the persistence of two previously unreported peaks related to the A7 structure in the pressure range of the simple‐cubic phase. The Rietveld refinement of the data demonstrates the occurrence of a two‐step mechanism for the A7 to simple‐cubic phase transition, indicating the existence of an intermediate pseudo simple‐cubic structure. From a chemical point of view this study represents a deep insight on the mechanism of interlayer bond formation during the transformation from the layered A7 to the non‐layered simple‐cubic phase of phosphorus, opening new perspectives for the design, synthesis and stabilization of phosphorene‐based systems. As superconductivity is concerned, a new experimental evidence to explain the anomalous pressure behavior of T_c in phosphorus below 30 GPa is provided.

Black phosphorus was compressed at room temperature across the A17, A7 and simple‐cubic phases up to 30 GPa, using a diamond anvil cell and He as pressure transmitting medium. Synchrotron X‐ray diffraction showed the persistence of two previously unreported peaks related to the A7 structure in the pressure range of the simple‐cubic phase. The Rietveld refinement of the data demonstrates the occurrence of a two‐step mechanism for the A7 to simple‐cubic phase transition, indicating the existence of an intermediate pseudo simple‐cubic structure. From a chemical point of view this study represents a deep insight on the mechanism of interlayer bond formation during the transformation from the layered A7 to the non‐layered simple‐cubic phase of phosphorus, opening new perspectives for the design, synthesis and stabilization of phosphorene‐based systems. As superconductivity is concerned, a new experimental evidence to explain the anomalous pressure behavior of T_c in phosphorus below 30 GPa is provided.