Anodic copper oxide nanowire and nanopore arrays with mixed phase content: synthesis, characterization and optical limiting response

Abstract

Thin films consisting of copper oxide nanowires (NWs) containing a mixture of copper oxide phases were formed by electrochemical anodization in de-ionized water (DI) and methanol based electrolytes. Well-defined arrays of vertical nanopores were obtained via anodization in ethylene glycol (EG)-based electrolytes. Optical absorption spectra revealed the electronic bandgap of the NWs formed in DI and methanol to be 2.50 eV, and that of nanopores formed in EG electrolytes to be 1.94 eV. The nanostructures were found to exhibit p-type conduction through Mott–Schottky analysis. The as-formed nanostructures exhibited two photon photoluminescence with lifetimes ranging between 200 and 1100 ps. They also displayed strong optical limiting in the form of a 25% decrease in optical transmission at 800 nm at a relatively low fluence of 0.1 J cm−2 and an absolute transmittance <50% over the entire range of laser fluence values used in this study. The optical transmittance decreased from 40% at an incident Ti-sapphire laser fluence of 20 mJ cm−2 to ∼9% when the fluence was increased to 700 mJ cm−2. Furthermore, the damage threshold of 0.7 J cm−2 compares favorably with advanced optical limiting materials such as gold-graphene composites and single-walled carbon nanotube composites even without further optimization of nanoscale morphology to maximize scattering. Therefore the nanostructures of mixed copper oxide films studied in this report are particularly promising as optical limiters for protecting low damage threshold (<1 J cm−2) photonic devices and are an important addition to the narrow selection of optical limiting materials that are currently available.