Pnictogens Allotropy and Phase Transformation during van der Waals Growth

TL;DR

This study investigates the phase transformation and electronic property evolution of antimony during van der Waals growth, revealing a spontaneous transition from A17 to A7 phases influenced by thickness and surface effects.

Contribution

It demonstrates the real-time, thickness-dependent phase transition of antimony from A17 to A7 during vdW growth, highlighting the role of atomic structure and interfaces in stability and electronic properties.

Findings

A17 antimony transitions to A7 at ~4 nm thickness.

Intermediate alpha-antimonene phase observed during transformation.

Electronic properties are influenced by surface passivation and bonding competition.

Abstract

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.