Abstract
Heterostructured (β/γ)-AgI exhibits a spontaneous lattice polarization not accounted for in standard space-charge models. This polarization field dominates the positional variation of energies of isolated defects, and Ag(+) vacancies and interstitials are stabilized at alternate [β/γ] interfaces. This suggests enhanced Frenkel pair separation, analogous to electronic charge separation in polar semiconductor heterostructures. Stoichiometric systems are, however, characterized by associated Frenkel pairs due to strong V(Ag)-Ag(i) interactions and show no enhancement of defect numbers. In nonstoichiometric systems, lattice polarization does direct the distribution of the excess defect species, and defect-defect interactions enhance local Frenkel pair concentrations at interfaces, suggesting that nonstoichiometry is critical to the extreme room-temperature ionic conductivities observed in heterostructured AgI nanoplates.
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