P-Type Nitrogen-Doped ZnO Nanostructures with Controlled Shape and Doping Level by Facile Microwave Synthesis

We report herein the development of a facile microwave irradiation (MWI) method for the synthesis of high-quality N-doped ZnO nanostructures with controlled morphology and doping level. We present two different approaches for the MWI-assisted synthesis of N-doped ZnO nanostructures. In the first approach, N-doping of Zn-poor ZnO prepared using zinc peroxide (ZnO2) as a precursor is carried out under MWI in the presence of urea as a nitrogen source and oleylamine (OAm) as a capping agent for the shape control of the resulting N-doped ZnO nanostructures. Our approach utilizes the MWI process for the decomposition of ZnO2, where the rapid transfer of energy directly to ZnO2 can cause an instantaneous internal temperature rise and, thus, the activation energy for the ZnO2 decomposition is essentially decreased as compared to the decomposition under conductive heating. In the second synthesis method, a one-step synthesis of N-doped ZnO nanostructures is achieved by the rapid decomposition of zinc acetate in a mixture of urea and OAm under MWI. We demonstrate, for the first time, that MWI decomposition of zinc acetate in a mixture of oAm and urea results in the formation of N-doped nanostructures with controlled shape and N-doping level. We report a direct correlation between, the intensity of the Raman scattering bands in N-doped ZnO and the concentration of urea used in the synthesis. Electrochemical measurements demonstrate the successful synthesis of stable p-type N-doped ZnO nanostructures using the one-step MWI synthesis and, therefore, allow us to investigate, for the first time, the relationship between the doping level and morphology of the ZnO nanostructures. The results provide strong evidence for the control of the electrical behavior and the nanostructured shapes of ZnO nanoparticles using the facile MWI synthesis method developed in this work.