Band gap engineered zinc oxide nanostructures via a sol–gel synthesis of solvent driven shape-controlled crystal growth

Abstract

A reliable sol–gel approach, which combines the formation of ZnO nanocrystals and a solvent driven, shape-controlled, crystal-growth process to form well-organized ZnO nanostructures at low temperature is presented. The sol of ZnO nanocrystals showed shape-controlled crystal growth with respect to the solvent type, resulting in either nanorods, nanoparticles, or nanoslates. The solvothermal process, along with the solvent polarity facilitate the shape-controlled crystal growth process, augmenting the concept of a selective adhesion of solvents onto crystal facets and controlling the final shape of the nanostructures. The XRD traces and XPS spectra support the concept of selective adhesion of solvents onto crystal facets that leads to yield different ZnO morphologies. The shift in optical absorption maxima from 332 nm in initial precursor solution, to 347 nm for ZnO nanocrystals sol, and finally to 375 nm for ZnO nanorods, evidenced the gradual growth and ripening of nanocrystals to dimensional nanostructures. The engineered optical band gaps of ZnO nanostructures are found to be ranged from 3.10 eV to 3.37 eV with respect to the ZnO nanostructures formed in different solvent systems. The theoretical band gaps computed from the experimental XRD spectral traces lie within the range of the optical band gaps obtained from UV-visible spectra of ZnO nanostructures. The spin-casted thin film of ZnO nanorods prepared in DMF exhibits the electrical conductivity of 1.14 × 10⁻³ S cm⁻¹, which is nearly one order of magnitude higher than the electrical conductivity of ZnO nanoparticles formed in hydroquinone and ZnO sols. The possibility of engineering the band gap and electrical properties of ZnO at nanoscale utilizing an aqueous-based wet chemical synthesis process presented here is simple, versatile, and environmentally friendly, and thus may applicable for making other types of band-gap engineered metal oxide nanostructures with shape-controlled morphologies and optoelectrical properties.