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تسجيل مستخدم جديدThe role of disorder in the synthesis of metastable ternary nitrides
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In materials science, it is often assumed that ground state crystal structures predicted by density functional theory are the easiest polymorphs to synthesize. Ternary nitride materials, with many possible metastable polymorphs, provide a rich materials space to study what influences thermodynamic stability and polymorph synthesizability. For example, ZnZrN2 is theoretically predicted at zero Kelvin to have an unusual layered wurtsalt crystal structure with compelling optoelectronic properties, but it is unknown whether this structure can be realized experimentally under practical synthesis conditions. Here, we use combinatorial sputtering to synthesize hundreds of ZnxZr1-xNy thin film samples, and find metastable rocksalt-derived or boron-nitride-derived structures rather than the predicted wurtsalt structure. Using a statistical polymorph sampler approach, it is demonstrated that although rocksalt is the least stable polymorph at zero Kelvin, it becomes the most stable polymorph at effective temperatures > ~1150 K, corroborating experimental results since sputtering yields high effective temperatures. Additional calculations show that this temperature-induced change in phase stability is due to both entropic and enthalpic stabilization effects. Rocksalt- and boron-nitride-derived structures become the most stable polymorphs in the presence of disorder because of higher tolerances to cation cross-substitution and off-stoichiometry than the wurtsalt structure. This understanding of the role of disorder tolerance in the synthesis of competing polymorphs can enable more accurate predictions of synthesizable crystal structures and their achievable material properties.
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