Thermodynamics-inspired high-entropy oxide synthesis

Abstract High-entropy oxide (HEO) thermodynamics transcend temperature-centric approaches, spanning a multidimensional landscape where oxygen chemical potential plays a decisive role. Here, we experimentally demonstrate how controlling the oxygen chemical potential coerces multivalent cations into divalent states in rock salt HEOs. We construct a preferred valence phase diagram based on thermodynamic stability and equilibrium analysis, alongside a high throughput enthalpic stability map derived from atomistic calculations leveraging machine learning interatomic potentials. We identify and synthesize seven equimolar, single-phase rock salt compositions incorporating Mn, Fe, or both, as confirmed by X-ray diffraction and fluorescence. Energy-dispersive X-ray spectroscopy confirms homogeneous cation distribution, whereas X-ray absorption fine structure analysis reveals predominantly divalent Mn and Fe states, despite their inherent multivalent tendencies. Ultimately, we introduce oxygen chemical potential overlap as a key complementary descriptor for predicting HEO stability and synthesizability. Although we focus on rock salt HEOs, our methods are chemically and structurally agnostic, providing a broadly adaptable framework for navigating HEOs thermodynamics and enabling a broader compositional range with contemporary property interest.