Rapid estimation of synthesizability windows of inorganic materials from first principles

Abstract: Fast prediction of the synthesizability conditions of materials remains challenging, even assuming synthesis under thermodynamic equilibrium. Approaches solely based on convex stability hulls neglect finite-temperature effects, while phonon-based phase diagram calculations are computationally demanding. Here, we demonstrate high-throughput generation of phase predominance diagrams as a function of temperature and partial pressures of gaseous reactants, helping bridge the gap between computational predictions and experimental synthesis. We employ fitting of elemental phase reference energies to zero-temperature total energies for improved calculation of formation enthalpies, along with machine-learned interatomic potentials for rapid determination of vibrational entropy and heat capacity. The resulting predominance diagrams can be intuitively understood by experimentalists and can be used to translate energies above stability hulls into synthesis conditions. Predominance diagrams are generated for selected oxide, nitride, sulfide, and phosphide systems, as well as for 48 more complex ternary metal phosphosulfide systems. The calculated predominance diagrams generally show good agreement with the experimental synthesis literature, with a drastic reduction in computational cost compared to a conventional approach relying on DFT-based phonon calculations. We identify several compounds predicted to be stable under well-defined thermodynamic windows, even though they appear as metastable in a zero-temperature stability hull picture. The method can be applied to rapidly estimate synthesis conditions for any inorganic material.