  Two-dimensional (2D) crystals' edge structures not only influence their
overall properties but also dictate their formation due to edge-mediated
synthesis and etching processes. Edges must be carefully examined because they
often display complex, unexpected features at the atomic scale, such as
reconstruction, functionalization, and uncontrolled contamination. Here, we
examine atomic-scale edge structures and uncover reconstruction behavior in
bilayer phosphorene. We use in situ transmission electron microscopy (TEM) of
phosphorene/graphene specimens at elevated temperatures to minimize surface
contamination and reduce e-beam damage, allowing us to observe intrinsic edge
configurations. Bilayer zigzag (ZZ) edge was found the most stable edge
configuration under e-beam irradiation. Through first-principles calculations
and TEM image analysis under various tilting and defocus conditions, we find
that bilayer ZZ edges undergo edge reconstruction and so acquire closed,
self-passivated edge configurations. The extremely low formation energy of the
closed bilayer ZZ edge and its high stability against e-beam irradiation are
confirmed by first-principles calculations. Moreover, we fabricate bilayer
phosphorene nanoribbons with atomically-sharp closed ZZ edges. The identified
bilayer ZZ edges will aid in the fundamental understanding of the synthesis,
degradation, reconstruction, and applications of phosphorene and related
structures.
