Effects of transition metal doping on the growth and properties of Rutile TiO_2 nanoparticles

Abstract

Rutile TiO_2 nanoparticles doped with V, Cr, or Mn ions have been synthesized via a modified Pechini method using polymeric precursors. The final particle sizes range between 20 and 500 nm depending on the selected dopant. The TiO_2 rutile phase has been stabilized in the doped nanoparticles at 650 degrees C. Microstructural analysis shows a good crystallinity and cationic homogeneity of the doped nanoparticles. The cathodoluminescence study of the doped and undoped nanoparticles shows a luminescence signal related to the structural defects of the samples and the presence of dopants. In particular, an intense 1.52 eV emission associated with Ti^3+ interstitials dominates the luminescence of undoped nanoparticles, which also exhibit less intense emissions extending from 2 to 3.4 eV. The presence of V, Cr, or Mn in the rutile TiO_2 nanoparticles induces variations in the associated cathodoluminescence signal which would be useful in order to achieve a deeper understanding of the doping process and spread future optical applications. X-ray photoelectron spectroscopy (XPS) confirmed the presence of Ti^3+ in the near-surface region of the nanoparticles, the concentration of which decreases when doping. The presence of Ti^3+ interstitials related states in the band gap is discussed.