Ordered Electronic Reconstruction of the (112¯0$11\bar{2}0$) ZnO Single Crystal

Three-dimensional (3D) charge-written periodic peak and valley nanoarray surfaces are fabricated on a ((Formula presented.)) ZnO single crystal grown via chemical vapor transport. Because the grown ZnO crystals exhibit uniform n-type conduction, 3D periodic nanoarray patterns are formed via oxygen annealing. These periodically decorated structures show that the peak arrays are conducting at the nanoampere level, whereas the valley arrays are less conductive. Energy dispersive spectroscopy indicates that the valley arrays are deficient in zinc by ≈4–6 at%, and that the peak arrays are deficient in oxygen, respectively. Kelvin probe force microscopy reveals the presence of periodic wiggles featuring variations of ≈70–140-meV between the peak and valley arrays. A significant decrease in the Fermi level of the valley region is observed (≈190 meV), which corresponds to a high zinc vacancy doping density of 2 × 10¹⁸ cm⁻³. This result indicates the periodic generation of an extremely large electric field (≈11 000 V cm⁻¹) in the vicinity of the peak–valley arrays. Computational analysis corroborates the experimentally observed generation of V_Zn and the preferential formation of surface protrusions on ZnO ((Formula presented.)) rather than on (0001), based on surface effects, along with the generation of peak and valley features.