Mechanical Characterization and Electrochemical Sensor Applications of Zinc Oxide Nanostructures

Abstract: Nanotechnology is emerging to be one of the most important scientific disciplines that physics, chemistry and biology truly overlap with each other. Over the last two decades science and technology have witnessed tremendous improvement in the hope of unveiling the true secrets of the nature in molecular or atomic level. Today, the regime of nanometer is truly reached.ZnO is a promising material due to the wide direct band gap (3.37 eV) and the room temperature large exciton binding energy (60 meV). Recent studies have shown considerable attraction towards ZnO nanostructures, particularly on one-dimensional ZnO nanorods, nanowires, and nanotubes due to the fact that, for a large number of applications, shape and size of the ZnO nanostructures play a vital role for the performance of the devices. The noncentrosymmetric property of ZnO makes it an ideal piezoelectric material for nanomechanical devices. Thus, mechanical characterization of one dimensional ZnO nanostructures including strength, toughness, stiffness, hardness, and adhesion to the substrate is very important for the reliability and efficient operation of piezoelectric ZnO nanodevices. Moreover, owing to the large effective surface area with high surface-to-volume ratio, the surface of one dimensional ZnO nanowires, nanorods, and nanotubes is very sensitive to the changes in surface chemistry and hence can be utilized to fabricate highly sensitive ZnO electrochemical sensors.This thesis studies mechanical properties and electrochemical sensor applications of ZnO nanostructures.The first part of the thesis deals with mechanical characterization of vertically grown ZnO nanorods and nanotubes including buckling, mechanical instability, and bending flexibility. In paper I, we have investigated mechanical instability and buckling characterization of vertically aligned single-crystal ZnO nanorods grown on Si, SiC, and sapphire substrates by vapor-liquid-solid (VLS) method. The critical loads for the ZnO nanorods grown on Si, SiC, and sapphire were measured and the corresponding buckling and adhesion energies were calculated. It was found that the nanorods grown on SiC substrate have less residual stresses and are more stable than the nanorods grown on Si and sapphire substrates.Paper II investigates nanomechanical tests of bending flexibility, kinking, and buckling failure characterization of vertically aligned single crystal ZnO nanorods/nanowires grown by VLS and aqueous chemical growth (ACG) methods. We observed that the loading and unloading behaviors during the bending test of the as-grown samples were highly symmetrical and the highest point on the bending curves and the first inflection and critical point were very close. The results also show that the elasticity of the ZnO single crystal is approximately linear up to the first inflection point and is independent of the growth method.In Paper III, we quantitatively investigated the buckling and the elastic stability of vertically well aligned ZnO nanorods and ZnO nanotubes grown on Si substrate by nanoindentation technique. We found that the critical load for the nanorods was five times larger than the critical load for nanotubes. On the contrary, the flexibility for nanotubes was five times larger than nanorods. The discovery of high flexibility for nanotubes and high elasticity for nanorods can be utilized for designing efficient piezoelectric nanodevices.The second part of this thesis investigates electrochemical sensor applications of ZnO nanorods, nanotubes , and nanoporous material.In paper IV, we utilized functionalized ZnO nanorods on the tip of a borosilicate glass capillary coated with ionophore-membrane to construct intracellular Ca2+ selective sensor. The sensor exhibited a Ca2+-dependent electrochemical potential difference and the response was linear over a large dynamic concentration range, which enabled this sensor to measure Ca2+ concentrations in human adipocytes or in frog oocytes. The results were consistent with the values of Ca2+ concentrations reported in the literature.In paper V, ZnO nanotubes and nanorods were used to create pH sensor devices. The developed ZnO pH sensors display good reproducibility, repeatability, and long-term stability. The ZnO pH sensors exhibited a pH-dependent electrochemical potential difference over a large dynamic pH range. We found that the ZnO nanotubes provide sensitivity as high as twice that of the ZnO nanorods. The possible reasons of enhanced sensitivity were explained.Paper VI investigates an improved potentiometric intracellular glucose biosensor based on the immobilization of glucose oxidase on the ZnO nanoporous material. We demonstrated that using ZnO nanoporous material as a matrix material for enzyme immobilization improves the sensitivity of the biosensor as compared to using ZnO nanorods. In addition, the fabrication method of the intracellular biosensor was simple and excellent performance in sensitivity, stability, selectivity, reproducibility, and anti-interference was achieved.