Compressed few-layer black phosphorus nanosheets from semiconducting to metallic transition with the highest symmetry

The high-pressure response of few-layer black phosphorus (BP) nanosheets remains elusive, despite the special interest in it particularly after the achievement of an exotic few-layer BP based field effect transistor. Here, we identified a pressure-induced reversible phase transition on few-layer BP nanosheets by performing in situ ADXRD and Raman spectroscopy with the assistance of DAC apparatus. The few-layer BP nanosheets transformed from orthorhombic semiconductors to simple cubic metal with increasing pressure, which is well interpreted using the pressure-induced inverse Peierls distortion. The obtained simple cubic BP nanosheets exhibited an enhanced isothermal bulk modulus of 147.0(2) GPa, and negative Grüneisen parameters that were attributed to the pressure-driven softening of phonon energies. Note that the simple cubic BP nanosheets adopted the highest symmetry which is in stark contrast to the general phase transformation under high pressure. First-principles calculations indicated that the metallic BP was significantly related to the band overlapped metallization, resulting from the traversing of density of states across the Fermi level at high pressure. Such findings paved a potential pathway to design targeted BP nanostructures with functional properties at extremes, and opened up possibilities for conceptually new devices.