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Abstract Interest in high‐entropy inorganic compounds originates from their ability to stabilize cations and anions in local environments that rarely occur at standard temperature and pressure. This leads to new crystalline phases in many‐cation formulations with structures and properties that depart from conventional trends. The highest‐entropy homogeneous and random solid solution is a parent structure from which a continuum of lower‐entropy offspring can originate by adopting chemical and/or structural order. This report demonstrates how synthesis conditions, thermal history, and elastic and chemical boundary conditions conspire to regulate this process in Mg_0.2Co_0.2Ni_0.2Cu_0.2Zn_0.2O, during which coherent CuO nanotweeds and spinel nanocuboids evolve. We do so by combining structured synthesis routes, atomic‐resolution microscopy and spectroscopy, density functional theory, and a phase field modeling framework that accurately predicts the emergent structure and local chemistry. This establishes a framework to appreciate, understand, and predict the macrostate spectrum available to a high‐entropy system that is critical to rationalizing property engineering opportunities. 

The prototype high-entropy oxide (HEO) Y0.2La0.2Ce0.2Pr0.2Sm0.2O2−δ represents a particularly complex class of HEOs with significant anion sublattice entropy. The system takes either a fluorite or bixbyite-type crystal structure, depending on synthesis kinetics and thermal history. Here, we synthesize bulk ceramics and epitaxial thin films of Y0.2La0.2Ce0.2Pr0.2Sm0.2O2−δ and use diffraction to explore crystal symmetry and phase. Thin films exhibit the high symmetry fluorite phase, while bulk ceramics adopt the lower symmetry bixbyite phase. The difference in chemical ordering and observed symmetry between vapor-deposited and reactively sintered specimens suggests that synthesis kinetics can influence accessible local atomic configurations, i.e., the high kinetic energy adatoms quench in a higher-effective temperature, and thus higher symmetry structure with more configurational entropy. More generally, this demonstration shows that recovered HEO specimens can exhibit appreciably different local configurations depending on synthesis kinetics, with potential ramifications on macroscopic physical properties. 

Abstract High‐entropy materials defy historical materials design paradigms by leveraging chemical disorder to kinetically stabilize novel crystalline solid solutions comprised of many end‐members. Formulational diversity results in local crystal structures that are seldom found in conventional materials and can strongly influence macroscopic physical properties. Thermodynamically prescribed chemical flexibility provides a means to tune such properties. Additionally, kinetic metastability results in many possible atomic arrangements, including both solid‐solution configurations and heterogeneous phase assemblies, depending on synthesis conditions. Local disorder induced by metastability, and extensive cation solubilities allowed by thermodynamics combine to give many high‐entropy oxide systems utility as electrochemical, magnetic, thermal, dielectric, and optical materials. Though high‐entropy materials research is maturing rapidly, much remains to be understood and many compositions still await discovery, exploration, and implementation.