Temperature-triggered self-assembly of ZnO: from nanocrystals to nanorods to tablets.

ZnO nanocrystals, nanorods, and tablets were prepared at 110, 140, and 180 °C in a water−ethanol system. Nanorods (∼2 × 40 nm) arranged in serpentine morphologies formed by the oriented coalescence of anhedral ZnO nanocrystals (∼3.5 nm diameter), while tabular ZnO grew by [1210] textural attachment of the nanorods. The development of these crystal habits is believed to proceed via a dissolution and growth mechanism mediated by a transient amorphous phase. Materials synthesized at intermediate temperatures (125 and 160 °C) possessed microstructures containing mixed crystal forms in the expected orientation relationship. Photoluminescent spectra of the nanocrystals and nanorods showed blue shifts of 0.16 and 0.13 eV with respect to the bulk ZnO band gap (3.26 eV) due to quantum confinement, with the narrow emission peaks typical of particles possessing uniform size and shape. The larger tablets displayed a less energetic emission (3.10 eV) ascribed to exciton−exciton collisions.