Sodium-Induced Reordering of Atomic Stacks in Black Phosphorus

While theoretical simulations predict contradictory results about how the intercalation of foreign metal atoms affects the order of atomic layers in black phosphorus (BP), no direct experimental visualization work has yet clarified this ambiguity. By in situ electrochemical sodiation of BP inside a high-resolution transmission electron microscope and first-principles calculations, we found that sodium intercalation induces a relative glide of¹/₂ ⟨010⟩ {001}, resulting in reordering of atomic stacks from AB to AC in BP. The observed local amorphization in our experiments is triggered by lattice constraints. We predict that intercalation of sodium or other metal atoms introduces n-type carriers in BP. This potentially opens a new field for two-dimensional electronics based on BP.