Polar Step-Driven Metal Nucleation and Growth: The Ag/ZnO(10(1)over-bar0) Case

The morphology, epitaxy, band alignment, and optical response of silver nanoparticles on ZnO(10 (1) over bar0) have been analyzed by microscopy, electron diffraction, photoemission and differential reflectivity. At 700 K, clusters tend to nucleate and grow exclusively along [010]-oriented polar steps and corners and not on flat terraces or nonpolar [001] steps. This preference leads to a specific epitaxy Ag[1 (1) over bar0](111) II ZnO[010] (10 (1) over bar0) with a large lattice mismatch along the dense row of the metal. The experiments have been rationalized through ab initio simulations. A much lower adsorption energy is obtained for the O-terminated steps with a charge transfer from silver to oxygen that corroborates the variation of ionization energy observed in photoemission and the presence of cationic silver. This anisotropy of growth reverberates in the plasmonic response of the metallic particles. The growth and epitaxy of metals on polar (0001) and nonpolar (10 (1) over bar0) orientations of ZnO are discussed in terms of surface/step polarity compensation in the light of the present findings.