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Phase selection in deeply undercooled liquids and devitrified glasses duringheating involves complex interplay between the barriers to nucleation and theability for these nuclei to grow. During the devitrification of glassy alloys,complicated metastable structures often precipitate instead of simpler, morestable compounds. Here, we access this unconventional type of phase selectionsby investigating an Al-10%Sm system, where a complicated cubic structure firstprecipitates with a large lattice parameter of 1.4 nm. We not only solve thestructure of this "big cubic" phase containing ~140 atoms but establish anexplicit interconnection between the structural orderings of the amorphousalloy and the cubic phase, which provides a low-barrier nucleation pathway atlow temperatures. The surprising rapid growth of the crystal is attributed toits high tolerance to point defects, which minimize the short-scale atomicrearrangements to form the crystal. Our study suggests a new scenario ofdevitrification, where phase transformation proceeds initially withoutpartitioning through a complex intermediate crystal phase.

Unconventional phase selection in high-driven systems: A complex metastable structure prevails over simple stable phases