In this thesis, one dimensional (1D) ZnO nanostructures with controlled morphologies, defects and alignment have been fabricated by a simple vapor transfer method. The crystal structures, interfaces, growth mechanisms and optical properties of ZnO nanostructures have been investigated by scanning electron microscopy (SEM), transmission electron microscopy (TEM) and photoluminescence (PL) spectroscopy. Great efforts have been devoted to the patterned growth and assembly of ZnO nanostructures as well as the stability of ZnO nanowires (NWs)....[ Read more ]

In this thesis, one dimensional (1D) ZnO nanostructures with controlled morphologies, defects and alignment have been fabricated by a simple vapor transfer method. The crystal structures, interfaces, growth mechanisms and optical properties of ZnO nanostructures have been investigated by scanning electron microscopy (SEM), transmission electron microscopy (TEM) and photoluminescence (PL) spectroscopy. Great efforts have been devoted to the patterned growth and assembly of ZnO nanostructures as well as the stability of ZnO nanowires (NWs).

Using carbonized photoresists, a simple and very effective method has been developed for fabricating and patterning high-quality ZnO NW arrays. ZnO NWs from this method show excellent alignment, crystal quality, and optical properties that are independent of the substrates. The carbonized photoresists provide perfect nucleation sites for the growth of aligned ZnO NWs and also perfectly connect to the NWs to form ideal electrodes. This approach is further extended to realize large area growth of different forms of ZnO NW arrays (e.g., the horizontal growth and multilayered ZnO NW arrays) on other kinds of carbon-based materials. In addition, the as-synthesized vertically aligned ZnO NW arrays show a low weighted reflectance (R_w) and can be used as antireflection coatings. Moreover, non c-axis growth of 1D ZnO nanostructures (e.g., nanochains, nanobrushes and nanobelts) and defect related 1D ZnO nanostructures (e.g., Y-shaped twinned nanobelts and hierarchical nanostructures decorated by flowers induced by screw dislocations) is also present.

Using direct oxidization of pure Zn at high temperatures in air, uniformed ZnO NWs and tetrapods have been fabricated. The spatially-resolved PL study on these two kinds of nanostructures suggests that the defects leading to the green luminescence (GL) should originate from the structural changes along the legs of the tetrapods. Surface defects in these ZnO nanostructures play an unimportant role for the GL emission. On the other hand, those ZnO tapered structures fabricated by a modified carbon thermal method with the assistance of Au catalysts display strong UV emission, indicating a good crystallization quality.

The stability, structural degradation and related PL property of ZnO NWs under different environments of surface treatments have been investigated by high-resolution transmission electron microscopy (HRTEM) and near field optical microscopy (NSOM). For high-quality ZnO NWs, the UV emission shows no change and no DL emission was generated during the structural degradation. For those ZnO NWs showing GL emission, the commonly used treatment methods e.g., post-annealing can not effectively eliminate the GL emission. The chemical stability and biocompatibility of ZnO nanostructures in simulated physiological solution (SPS) are studied by electron diffraction and HRTEM. ZnO nanostructures fabricated by the thermal evaporation method were found to survive much longer in SPS than those fabricated using a hydrothermal solution method. Calcium hydrogen phosphate amorphous layers structures have been observed to have excellent interfacial contacts with ZnO NWs. The shapes of the voids formed in the ZnO NWs are due to the interesting anisotropic etching behaviors in SPS which can be used to identify the polar directions of ZnO nanocrystals.

Using hydrothermal reaction, TiO₂/ZnO (TZO) nanohybrid structures have been found to form through the site-specific deposition of TiO2 on ZnO nanorods (NRs). TEM studies have revealed each ZnO NR to be assembled with one TiO₂ cap at the Zn terminated (0001) surface. The polarity of the ZnO (0001) surface plays an important role in the formation of the TZO nanohybrid structures. The TZO nanohybrids contain uniform and atomically flat interfaces between ZnO and TiO₂ with tunable crystal phases, which can be amorphous, anatase and rutile through annealing treatments. These nanohybrid structures demonstrate an enhanced photocatalytic activity due to the improved interface structures for a better interfacial charge-transfer/spatially separation process of photogenerated charge carriers. The site-specific deposition method has also been applied to assemble TiO₂ on the (0001) surfaces of other ZnO nanostructures such as tetrapods, nanofilms, nanoflowers and NW arrays produced by different synthesis techniques. Through high temperature annealing, the TZO nanohybrid structures can be further converted into Zn₂TiO₄/ZnO nanostructures with certain orientation relationships. These nanohybrid structures may synergize the properties of both components and lead to many promising applications.