Nonclassical growth of immiscible high-entropy materials

The thermodynamic instability of phase separation in multi-metal crystal growth has been a long-standing challenge. Therefore, overcoming miscibility obstacle due to high lattice symmetry without extremely high temperatures has been elusive. Here, we developed a general nonclassical growth route to address metal miscibility under mild conditions, which was ascribed to in-plane atomic attachment due to the supersaturated confinement effect of the thermosensitive superstructure (TSS) substrate, a metastable intermediate. The structure exhibits an oscillatory growth pattern and evolves from short-range order to medium-range order, allowing significant reduction in the binding energy of surface heteroatoms. This prevents individual atoms from collapsing into a disordered state under the heat generated upon binding. We confirmed adsorbate-substrate interactions via an inverted volcano trend scaling relationship from 28 metals based on thousands of scale active learning calculations. As a proof of principle, we synthesized both high-entropy single atoms with anti-sintering temperatures exceeding 1200 K and highly-conductive high-entropy metallenes sheathing extremely immiscible elements. These revelations forge a new frontier for high-entropy materials, holding profound implications for interdisciplinary scientific progresses.