Lanthanide doped TiO2: Coexistence of discrete and continuous dopant distribution in anatase phase

Abstract Despite extensive studies on lanthanide (Ln) doped TiO2 nanoparticles, there is still considerable uncertainty as to whether Ln reside in the bulk (either as substitutional or interstitial dopant) or on the surface. Herein, new Ln (Eu, Sm, Nd and Er) discrete substitutional centers are identified in the anatase phase using low temperature, site selective time-gated luminescence spectroscopy. The excitation wavelength spanned UV (TiO2 host absorption) to visible excitation range into Ln f-f absorption transitions. The Ln multisite distribution is described in terms of fingerprint emission/excitation spectra and emission decays. The emission of Ln centers cover the visible (Eu, Sm) to near-infrared range (Nd, Er) and display narrow emission with full width at half maximum (FWHM) as small as 0.2 nm. The role of TiO2 host in sensitization of Ln emission is emphasized for each center. We have also found that besides discrete distribution, Ln distribute continuously on closely related anatase lattice sites. In this case, the Ln emission is significantly broader, with FWHM around 20 nm and change continuously in spectral shape and intensity with the excitation wavelength. The challenges encountered while identifying the Ln centers in TiO2 and comparison with case of CeO2 and SnO2 are also discussed.