Role of disorder in the synthesis of metastable zinc zirconium nitrides

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 ground-state 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 high effective temperatures similar to those achieved using this sputter deposition method, and thus corroborates experimental results. Additional calculations show that this destabilization of the wurtsalt polymorph is due to configurational entropic and enthalpic effects, and that vibrational contributions are negligible. Specifically, 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.

Automated summary

In this study, combinatorial sputtering was used to synthesize ZnxZr1-xNy thin-film samples, and it was found that rocksalt-derived or boron-nitride-derived structures were formed instead of the predicted wurtsalt structure. At high temperatures, the rocksalt structure became the most stable polymorph, validating the experimental results. The destabilization of the wurtsalt polymorph was attributed to configurational entropic and enthalpic effects, with vibrational contributions being negligible. The rocksalt and boron-nitride-derived structures exhibited higher disorder tolerance, making them more stable in the synthesis of competing polymorphs.