Phase Structure and Luminescence Properties of Eu3+-Doped TiO2 Nanocrystals Synthesized by Ar/O2 Radio Frequency Thermal Plasma Oxidation of Liquid Precursor Mists

Abstract

Eu3+-doped TiO2 luminescent nanocrystals have been synthesized in this work via Ar/O2 thermal plasma oxidizing mists of liquid precursors containing titanium tetra-n-butoxide and europium(III) nitrate, with varied O2 input in the plasma sheath (10-90 L/min) and Eu3+ addition in the precursor solution (Eu/(Ti + Eu) = 0-5 atom%). The resultant nanopowders are mixtures of the anatase (30-36 nm) and rutile (64-83 nm) polymorphs in the studied range, but the rutile fraction increases steadily at a higher Eu3+ addition, as revealed by X-ray diffraction (XRD) and Raman spectroscopy, because of the creation of oxygen vacancies in the TiO2 gas clusters by substitutional Eu3+ doping. The amount of Eu3+ that can be doped into a TiO2 lattice was limited up to 0.5 atom%, above which Eu2Ti2O7 pyrochlore was formed in the final products. High resolution transmission electron microscopy (HRTEM) observation indicates that the particles are dense and have sizes ranging from several nanometers up to 180 nm. Efficient nonradiative energy transfer from the TiO2 host to Eu3+ ions, which was seldom reported in the wet-chemically derived nanoparticles or thin films of the current system, was confirmed by combined studies of excitation, UV-vis (ultraviolet-visible), and PL (photoluminescence) spectroscopy. As a consequence of this, bright red emissions were observed from the plasma-generated nanopowders either by exciting the TiO2 host with UV light shorter than 405 nm or by directly exciting Eu3+ at a wavelength beyond the absorption edge (405 nm) of TiO2.