Effect of Passivation on Stability and Electronic Structure of Bulk-like ZnO Clusters

Electronic structure of nearly stoichiometric and nonstoichiometric clusters of ZnO having bulk-like wurtzite geometry passivated with fictitious hydrogen atoms are comparatively analyzed for structural evolution using density functional theory-based electronic structure calculations. A parameter, average binding energy per atomic number (ABE-number), is introduced for better insight of structural evolution. The stability of a cluster is determined by binding energy per atom and ABE-number, whereas structural evolution on the basis of spin-polarized energy spectrum is studied via site projected partial density of states (l-DOS). The overall structural evolution is mapped for bare and passivated ZnO clusters to l-DOS. The study has established a correlation between the stability of clusters and their l-DOS. O-excess and O-surfaced clusters are found to be more stable. The HOMO-LUMO gap varies from 0 to 6.3 eV by tuning the size, composition, and surface termination of the clusters. Present results reported for clusters of sizes up to ∼1 nm can pave a path for formulating strategies for experimental synthesis of ZnO nanoparticles for tuning the HOMO-LUMO gap.