  Two-dimensional (2D) antimony (Sb, antimonene) recently attracted interest
due to its peculiar electronic properties and its suitability as anode material
in next generation batteries. Sb however exhibits a large
polymorphic/allotropic structural diversity, which is also influenced by the
Sb's support. Thus understanding Sb heterostructure formation is key in 2D Sb
integration. Particularly 2D Sb/graphene interfaces are of prime importance as
contacts in electronics and electrodes in batteries. We thus study here
few-layered 2D Sb/graphene heterostructures by atomic-resolution (scanning)
transmission electron microscopy. We find the co-existence of two Sb
morphologies: First is a 2D growth morphology of layered beta-Sb with
beta-Sb(001)||graphene(001) texture. Second are one-dimensional (1D) Sb
nanowires which can be matched to beta-Sb with beta-Sb[2-21] perpendicular to
graphene(001) texture and are structurally also closely related to
thermodynamically non-preferred cubic Sb(001)||graphene(001). Importantly, both
Sb morphologies show rotational van-der-Waals epitaxy with the graphene
support. Both Sb morphologies are well resilient against environmental bulk
oxidation, although superficial Sb-oxide layer formation merits consideration,
including formation of novel epitaxial Sb2O3(111)/beta-Sb(001)
heterostructures. Exact Sb growth behavior is sensitive on employed processing
and substrate properties including, notably, the nature of the support
underneath the direct graphene support. This introduces the substrate
underneath a direct 2D support as a key parameter in 2D Sb heterostructure
formation. Our work provides insights into the rich phase and epitaxy landscape
in 2D Sb and 2D Sb/graphene heterostructures.
