![]() ![]() At a critical thickness of ~4 nm, A17 antimony undergoes a diffusionless shuffle transition from AB to AA stacked alpha-antimonene followed by a gradual relaxation to the A7 bulk-like phase. This metastability of the A17 phase is revealed by real-time studies unraveling its thickness-driven transition to the A7 phase and the concomitant evolution of its electronic properties. Herein, we demonstrate that these two phases not only co-exist during the vdW growth of antimony on weakly interacting surfaces, but also undertake a spontaneous transformation from the A17 phase to the thermodynamically stable A7 phase. On the other hand, bulk heavier elements are only stable in the A7 phase. Light group VA elements are found in the layered orthorhombic A17 phase such as black phosphorus, and can transition to the layered rhombohedral A7 phase at high pressure. ![]() Pnictogens have multiple allotropic forms resulting from their ns2 np3 valence electronic configuration, making them the only elemental materials to crystallize in layered van der Waals (vdW) and quasi-vdW structures throughout the group. Light group VA elements are found in the layered orthorhombic. Pnictogens Allotropy and Phase Transformation during van der Waals Growth
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