Phonon Scattering and Electron Doping by 2D Structural Defects in In/ZnO

In/ZnO bulk compounds have been synthesized using a simple solid-state process. In this study, both the structural features and thermoelectric properties of the Zn1–x In x O series with ultralow indium content (0 ≤ x ≤ 0.02) have been studied. High-angle annular dark-field scanning transmission electron microscopy analyses highlight that indium has the ability to create multiple basal plane and pyramidal defects that produce ZnO domains with inverted polarity starting from dopant concentrations as low as 0.25 atom %. Interestingly, the formation of parallel inversion boundaries consisting of InO6 octahedra in the ZnO4 tetrahedra matrix is responsible for phonon scattering while increasing electrical conductivity, thereby enhancing the thermoelectric properties. This effect of multiple extended two-dimensional defects on the thermoelectric properties of ZnO is reported for the first time with such low indium doping. On the chemistry side, the present results point toward a lack of In solubility in the ZnO structure. Moreover, this study is a step forward to the synthesis of other thermoelectric compounds where dopant-induced planar defects in bulk transition metal compounds have the potential to enhance both phonon scattering and electronic conductivity.