LAUSR

Structural evolution of Li‐intercalated and pristine black phosphorous (BP) under high‐pressure (up to ≈8 GPa) is studied using in situ Raman spectroscopy. Even though both materials show a monotonic blueshift of the out‐of‐plane vibrational mode (A1g) with pressure, Li‐intercalated BP do not show a blueshift until a threshold pressure (2.4 GPa) is reached to compensate the structural expansion caused by intercalation. However, the in‐plane modes (B2g and A2g) in each sample respond differently. In the mid‐pressure region, they both show redshifts which in Li‐intercalated BP is also followed by abrupt blueshifts. Such behavior indicates pressure‐induced structural reorganizations inside the material. Computational modeling reveals the existence of a process of P─P bond breaking and reforming in the system due to the redistribution of intercalated Li atoms under pressure. This work shows the significance of combined effect of pressure and intercalation on structural changes in the search for new phases of BP and other two‐dimensional (2D) materials.