  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 A17
phase such as black phosphorus, and can transition to the layered rhombohedral
A7 phase at high pressure. On the other hand, bulk heavier elements are only
stable in the A7 phase. 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. 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. 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. Furthermore, the electronic structure of
this intermediate phase is found to be determined by surface self-passivation
and the associated competition between A7- and A17-like bonding in the bulk.
These results highlight the critical role of the atomic structure and
interfacial interactions in shaping the stability and electronic
characteristics of vdW layered materials, thus enabling a new degree of freedom
to engineer their properties using scalable processes.
