Chemically Tuning Stability and Superconductivity of P–H Compounds

Abstract

Experimental evidence has revealed superconductivity with a critical temperature, <i>T</i>_c, around 100 K in compressed solid phosphine, but theoretical studies have hitherto found no stable structure in any binary P-H system, leaving the characterization of the new superconductor unsettled. Here we present the findings of an advanced structure search and first-principles calculations unveiling the effect of Li as an electron donor that stabilizes the crystal structure and produces robust phonon-mediated superconductivity in the resulting Li-P-H compounds in wide ranges of stoichiometry and pressure. We showcase a trigonal LiP₂H₁₄ phase that reaches <i>T</i>_c of 169 K at 230 GPa and then decreases with rising pressure, which can be remedied by substituting Li with Be or Na, which considerably enhances <i>T</i>_c. These findings highlight the intricate and effective chemical tuning of stabilizing the crystal structure and enhancing the superconductivity in a distinct class of ternary hydrides, opening new avenues for designing and optimizing new high-<i>T</i>_c hydride superconductors.