Domain formation and phase transitions in the wurtzite-based heterovalent ternaries: a Landau theory analysis

Characterizing the crystalline disorder properties of heterovalent ternary semiconductors continues to challenge solid-state theory. Here, a Landau theory is developed for the wurtzite-based ternary semiconductor ZnSnN₂. It is shown that the symmetry properties of two nearly co-stable phases, with space groups Pmc2₁ and Pbn2₁, imply that a reconstructive phase transition is the source of crystal structure disorder via a mixture of phase domains. The site exchange defect, which consists of two adjacent antisite defects, is identified as the nucleation mechanism of the transition. A Landau potential based on the space-group symmetries of the Pmc2₁ and Pbn2₁ phases is constructed from the online databases in the ISOTROPY software suite and this potential is consistent with a system that undergoes a paraelectric to antiferroelectric phase transition. It is hypothesized that the low-temperature Pbn2₁ phase is antiferroelectric within the c-axis basal plane. The dipole arrangements within the Pbn2₁ basal plane yield a nonpolar spontaneous polarization and the electrical susceptibility derived from the Landau potential exhibits a singularity at the Néel temperature characteristic of antiferroelectric behavior. These results inform the study of disorder in the broad class of heterovalent ternary semiconductors, including those based on the zincblende structure, and open the door to the application of the ternaries in new technology spaces.