Origin of Spinel Nanocheckerboards via First Principles

Abstract

Self-organizing nanocheckerboards have been experimentally fabricated in Mn-based spinels, but have not yet been explained with first principles. Using density-functional-theory, we explain the phase diagram of the $\mathrm{ZnM}{\mathrm{n}}_{\mathrm{x}}\mathrm{G}{\mathrm{a}}_{2-\mathrm{x}}{\mathrm{O}}_4$ system and the origin of nanocheckerboards. We predict total phase separation at zero temperature, then show the combination of kinetics, thermodynamics, and Jahn-Teller physics that generates the system's observed behavior. We find the {011} surfaces are strongly-preferred energetically, which mandates checkerboard ordering by purely geometrical considerations.