Defects and oxygen vacancies tailored structural, optical and electronic structure properties of Co-doped ZnO nanoparticle samples probed using soft X-ray absorption spectroscopy

Abstract

The structural, optical and electronic structure properties of all the Zn1-xCoxO nanoparticles [x = 0.01, 0.03, and 0.05], synthesized using co-precipitation method have been studied using X-ray diffraction (XRD), Surface Enhanced Raman Spectroscopy (SERS), UV–Vis–NIR spectroscopy and X-ray Absorption Spectroscopy measurements. The XRD and SERS analysis have confirmed the formation of hexagonal wurtzite structure (space group C46v). UV–Vis–NIR spectra indicate the blue shifting of the absorbance edge and the band gap is found to decrease with doping. The electronic structure of undoped and Co-doped ZnO nanoparticles have been investigated using site selective and element sensitive X-ray absorption spectroscopy. From the XAS spectra at Zn L3,2, Co L3,2 and O K-edges we have found that Zn ions are in +2 valence state in undoped and Co-doped ZnO nanoparticles. From the XAS analysis it can be seen that proper incorporation of Co-ion in the host lattice take place in t2geg state Co+2 (d7) under tetrahedral symmetry and maintain the crystal symmetry with lattice distortion. The Co-ion doping in the ZnO nano-matrix leads to creation of various defects & oxygen vacancies, which results in the blue shift in band-gap energy makes them useful for various applications e.g. photocatalytic water splitting, hydrogen generation, spintronics and optoelectronics.