Pushing the Boundaries of Multicomponent Alloy Nanostructures: Hybrid Approach of Liquid Phase Separation and Selective Leaching Processes

[Image: see text] Alloying, or mixing of multiple metallic elements, is the classical way of novel materials development since the Bronze age. Increased numbers of principal elements expand the compositional space for alloy design vastly, leading to nearly endless possibilities of unexpected and unique materials properties. In contrast to bulk alloying processes represented by casting of molten metal mixtures, the fabrication of multicomponent alloy (MCA) nanostructures such as nanoparticles and nanofoams with more than three elements is often challenging, and a few methodologies for directly synthesizing alloy nanostructures up to denary systems have been suggested recently. However, forming alloy nanoparticles inside another metal matrix, instead of inside aqueous media in wet-chemical synthesis, is a fairly well understood strategy in terms of physical metallurgy. Extracting those alloy nanophases from the matrix could provide an alternative way to fabricate novel MCA nanostructures. In this Account, we describe a hybrid approach of metallurgical bottom-up and chemical top-down processes for fabricating MCA nanostructures including nanoparticles and nanofoams. The former utilizes a liquid-state phase separation process that resembles “oil and water” but occurs at the nanoscale due to thermodynamic mixing relations among alloying elements and a rapid quenching process. Thermodynamic prediction of the immiscible boundary in a temperature–composition space (miscibility gap) plays a key role in designing precursor alloys for MCA nanostructures. Selective leaching, the chemical top-down process for extracting the alloy nanostructures from the precursors, uses the chemical reactivity difference between the embedded nanostructures and the matrix phase against a certain chemical solution. We discuss here that the precise control of alloy composition and cooling rate based on thermodynamic assessments enables researchers to prepare phase-separating precursor alloys for fabricating both nanoparticles and nanofoams with a broad size range from a few nanometers to a few hundred nanometers. Depending on the alloy systems, the atomic structure of alloy nanostructures could be controlled from fully amorphous to nanocrystalline and even to quasicrystalline structure. We demonstrate how the different sizes of alloy nanostructures fabricated by a single hybrid procedure can be effectively exploited for investigating size-dependent physical properties. The future and potential research directions for this hybrid approach are also briefly discussed. This unique approach for fabricating nanosized alloys provides an extended methodology to discover novel metallic nanomaterials with promising properties in diverse compositional spaces of MCA systems.