Stoichiometric evolutions of PH₃ under high pressure: implication for high-T _c superconducting hydrides

The superconductivity of hydrides under high pressure has attracted a great deal of attention since the recent observation of the superconducting transition at 203 K in strongly compressed H₂S. It has been realized that the stoichiometry of hydrides might change under high pressure, which is crucial in understanding the superconducting mechanism. In this study, PH₃ was studied to understand its superconducting transition and stoichiometry under high pressure using Raman, IR and X-ray diffraction measurements, as well as theoretical calculations. PH₃ is stable below 11.7 GPa and then it starts to dehydrogenate through two dimerization processes at room temperature and pressures up to 25 GPa. Two resulting phosphorus hydrides, P₂H₄ and P₄H₆, were verified experimentally and can be recovered to ambient pressure. Under further compression above 35 GPa, the P₄H₆ directly decomposed into elemental phosphorus. Low temperature can greatly hinder polymerization/decomposition under high pressure and retains P₄H₆ up to at least 205 GPa. The superconductivity transition temperature of P₄H₆ is predicted to be 67 K at 200 GPa, which agrees with the reported result, suggesting that it might be responsible for superconductivity at higher pressures. Our results clearly show that P₂H₄ and P₄H₆ are the only stable P-H compounds between PH₃ and elemental phosphorus, which is helpful for shedding light on the superconducting mechanism.