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Bimetallic nanoparticles (BNPs) exhibit diverse morphologies such ascore-shell, Janus, onion-like, quasi-Janus, and homogeneous structures.Although extensive effort has been directed towards understanding theequilibrium configurations of BNPs, kinetic mechanisms involved in theirdevelopment have not been explored systematically. Since these systems oftencontain a miscibility gap, experimental studies have alluded to spinodaldecomposition (SD) as a likely mechanism for the formation of such structures.We present a novel phase-field model for confined (embedded)systems to studySD-induced morphological evolution within a BNP. It initiates with theformation of compositionally modulated rings as a result of surface-directed SDand eventually develops into core-shell or Janus structures due tocoarsening/breakdown of the rings. The final configuration depends crucially oncontact angle and particle size -Janus is favored at smaller sizes and highercontact angles. Our simulations also illustrate the formation of metastable,kinetically trapped structures as a result of competition between capillarityand diffusion.

Competition of Core-Shell and Janus Morphology in Alloy Nanoparticles: Insights From a Phase-Field Model