Pressure-induced crystallization of amorphous red phosphorus

Structural transitions in amorphous red phosphorus were studied at ambient temperature and pressures up to 12 GPa. Amorphous (red) phosphorus was observed to transform into crystalline black phosphorus at 7.5 ± 0.5 GPa using diamond anvil cell Raman spectroscopy, x-ray diffraction and a direct equation of state (EoS) measurement. The transition was found to be irreversible and the material recovered upon pressure cycling to 10 to 12 GPa was crystalline orthorhombic black phosphorus. A third order Birch–Murnaghan EoS was fit to the data and a bulk modulus (B0) of 11.2 GPa was measured for amorphous red phosphorus.

► Amorphous (red) phosphorus transforms to crystalline black phosphorus at 7.5 GPa.
► Pressure induced crystallization (PIC) of amorphous red phosphorus is irreversible.
► A bulk modulus (B0B0) of 11.2 GPa was determined from the measured equation of state.