Nitrogen plasma treatment of ZnO and TiO2 nanowire arrays for polymer photovoltaic applications

Abstract

This work reports on a simple, yet unique approach to improving the opto-electronic properties of vertically-aligned arrays of rutile TiO2 and Wurzite ZnO nanowires by means of controlled nitrogen doping during exposure to highly kinetic radio-frequency generated N2 plasma radicals. Morphologically, the plasma treatment causes a distortion of the vertical alignment of the nanowires due to a dissociation of the weak Van der Waals force clustering the nanowires. Optical spectroscopy show that plasma treatment increases the light transmission of TiO2 arrays from 48% to 90%, with the ZnO arrays exhibiting an increase from 70% to 90% in the visible to UV range. The as-synthesized TiO2 array has an indirect band gap of 3.13 eV, which reduces to 3.03 eV after N2 treatment, with the ZnO equivalent decreasing from 3.20 to 3.17 eV post plasma exposure. A study of the 3d transition metal near edge fine structure of both Ti and Zn show that the N2 plasma treatment of the nanowires results in nitrogen doping of both TiO2 and ZnO lattices; this is confirmed by scanning transmission electron microscopy coupled with energy dispersive spectroscopy x-ray maps collected of single nanowires, which show a clear distribution of nitrogen throughout the metal-oxide. Application of these structures in P3HT:PCBM polymer blends shows progressive improvement in the photoluminescence quenching of the photoactive layer when incorporating both undoped and nitrogen-doped nanowires.