Charge compensation assisted enhancement of photoluminescence in combustion derived Li+ co-doped cubic ZrO2:Eu3+ nanophosphors.

Red light emitting cubic Zr0.99Eu0.01O2:Li+ (0-9 mol%) nanoparticles are synthesized by a low temperature, self-propagating solution combustion method using oxalyl di-hydrazide (ODH) as fuel. In this study, we report systematic investigation of the effect of lithium ion (Li+) concentration on the structural properties and the photoluminescence of zirconia. With increasing lithium concentration, the crystallinity of the samples increases and the lattice strain decreases. The higher crystallinity is likely due to charge compensation achieved by replacing one Zr4+ ion by a Eu3+ and a Li+ ion. Scanning electron micrographs (SEM) reveal a mesoporous structure characteristic of combustion derived nanomaterials. Photoluminescence (PL) spectra show that the intensity of the red emission (606 nm) is highly dependent on Li+ ion concentration. Furthermore there is a promising enhancement in the associated lifetime. Upon Li+ doping, the PL intensity of the samples is found to increase by two fold compared to the undoped sample. Variation of PL intensity with Li+ concentration is attributed to the differences in probability of non-radiative recombination (relaxing). Intensity parameters (Ω2, Ω) and radiative properties such as transition rates (A), branching ratios (ß), stimulated emission cross-section (σe), gain bandwidth (σe × Δλeff) and optical gain (σe × τ) are calculated using the Judd-Ofelt theory. The calculated values suggest that in optimally co-doped samples, in addition to improved crystallinity and charge compensation, the lowering of Eu3+ site symmetry and the increase in the covalency of Eu-O bonding due to interstitial Li are responsible for the observed enhancement in PL intensity.

Low temperature synthesis of pure cubic ZrO2 nanopowder: structural and luminescence studies.

Pure cubic zirconia (ZrO2) nanopowder is prepared for the first time by simple low temperature solution combustion method without calcination. The product is characterized by Powder X-ray Diffraction (PXRD), Scanning Electron Microscopy (SEM), Transmission Electron Microscopy (TEM), Fourier Transform Infra Red spectroscopy (FTIR) and Ultraviolet-Visible spectroscopy (UV-Vis). The PXRD showed the formation of pure stable cubic ZrO2 nanopowders with average crystallite size ranging from 6 to 12 nm. The lattice parameters were calculated from Rietveld refinement method. SEM micrograph shows fluffy, mesoporous, agglomerated particles with large number of voids. TEM micrograph shows honey comb like arrangement of particles with particle size ∼10 nm. The PL emission spectrum excited at 210 nm and 240 nm consists of intense bands centered at ∼365 and ∼390 nm. Both the samples show shoulder peak at ∼420 nm, along with four weak emission bands at ∼484, ∼528, ∼614 and ∼726 nm. TL studies were carried out pre-irradiating samples with γ-rays ranging from 1 to 5 KGy at room temperature. A well resolved glow peak at 377 °C is recorded which can be ascribed to deep traps. With increase in γ radiation there is linear increase in TL intensity which shows the possible use of ZrO2 as dosimetric material.