Stoichiometric evolutions of PH(3) 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 H(2)S. 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, PH(3) 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. PH(3) 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, P(2)H(4) and P(4)H(6), were verified experimentally and can be recovered to ambient pressure. Under further compression above 35 GPa, the P(4)H(6) directly decomposed into elemental phosphorus. Low temperature can greatly hinder polymerization/decomposition under high pressure and retains P(4)H(6) up to at least 205 GPa. The superconductivity transition temperature of P(4)H(6) 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 P(2)H(4) and P(4)H(6) are the only stable P–H compounds between PH(3) and elemental phosphorus, which is helpful for shedding light on the superconducting mechanism.