Tiju Thomas

Synthesis and photoluminescence properties of a novel Sr2CeO4:Dy3+ nanophosphor with enhanced brightness by Li+ co-doping

A series of Dy3+ (0.5–9 mol%) and Li+ (0.5–3 mol%) co-doped strontium cerate (Sr2CeO4) nanopowders are synthesized by low temperature solution combustion synthesis. The effects of Li+ doping on the crystal structure, chemical composition, surface morphology and photoluminescence properties are investigated. The X-ray diffraction results confirm that all the samples calcined at 900 °C show the pure orthorhombic (Pbam) phase. Scanning electron microscopy analysis reveals that the particles adopt irregular morphology and the porous nature of the product. Room temperature photoluminescence results indicate that the phosphor can be effectively excited by near UV radiation (290 to 390 nm) which results in the blue (484 nm) and yellow (575 nm) emission. Furthermore, PL emission intensity and wavelength are highly dependent on the concentration of Li+ doping. The emission intensity is enhanced by ∼3 fold with Li+ doping. White light is achieved by merely varying dopant concentration. The colour purity of the phosphor is confirmed by CIE co-ordinates (x = 0.298, y = 0.360). The study demonstrates a simple and efficient method for the synthesis of novel nanophosphors with enhanced white emission.

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 (β), 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.

Size Control and Magnetic Property Trends in Cobalt Ferrite Nanoparticles Synthesized Using an Aqueous Chemical Route

Cobalt ferrite (CoFe2O4) is an engineering material which is used for applications such as magnetic cores, magnetic switches, hyperthermia based tumor treatment, and as contrast agents for magnetic resonance imaging. Utility of ferrites nanoparticles hinges on its size, dispersibility in solutions, and synthetic control over its coercivity. In this work, we establish correlations between room temperature co-precipitation conditions, and these crucial materials parameters. Furthermore, post-synthesis annealing conditions are correlated with morphology, changes in crystal structure and magnetic properties. We disclose the synthesis and process conditions helpful in obtaining easily sinterable CoFe2O4 nanoparticles with coercive magnetic flux density (Hc) in the range 5.5-31.9 kA/m and Ms in the range 47.9-84.9 A·m2Kg-1. At a grain size of ~ 54±2 nm (corresponding to 1073 K sintering temperature), multi-domain behavior sets in, which is indicated by a decrease in Hc. In addition, we observe an increase in lattice constant with respect to grain size, which is the inverse of what is expected of in ferrites. Our results suggest that oxygen deficiency plays a crucial role in explaining this inverse trend. We expect the method disclosed here to be a viable and scalable alternative to thermal decomposition based CoFe2O4 synthesis. The magnetic trends reported will aid in the optimization of functional CoFe2O4 nanoparticles.

Self-assembled, aligned ZnO nanorod buffer layers for high-current-density, inverted organic photovoltaics.

Two different soft-chemical, self-assembly-based solution approaches are employed to grow zinc oxide (ZnO) nanorods with controlled texture. The methods used involve seeding and growth on a substrate. Nanorods with various aspect ratios (1-5) and diameters (15-65 nm) are grown. Obtaining highly oriented rods is determined by the way the substrate is mounted within the chemical bath. Furthermore, a preheat and centrifugation step is essential for the optimization of the growth solution. In the best samples, we obtain ZnO nanorods that are almost entirely oriented in the (002) direction; this is desirable since electron mobility of ZnO is highest along this crystallographic axis. When used as the buffer layer of inverted organic photovoltaics (I-OPVs), these one-dimensional (1D) nanostructures offer: (a) direct paths for charge transport and (b) high interfacial area for electron collection. The morphological, structural, and optical properties of ZnO nanorods are studied using scanning electron microscopy, X-ray diffraction, and ultraviolet-visible light (UV-vis) absorption spectroscopy. Furthermore, the surface chemical features of ZnO films are studied using X-ray photoelectron spectroscopy and contact angle measurements. Using as-grown ZnO, inverted OPVs are fabricated and characterized. For improving device performance, the ZnO nanorods are subjected to UV-ozone irradiation. UV-ozone treated ZnO nanorods show: (i) improvement in optical transmission, (ii) increased wetting of active organic components, and (iii) increased concentration of Zn-O surface bonds. These observations correlate well with improved device performance. The devices fabricated using these optimized buffer layers have an efficiency of ∼3.2% and a fill factor of 0.50; this is comparable to the best I-OPVs reported that use a P3HT-PCBM active layer.

Electric field induced short range to long range structural ordering and its influence on the Eu+3 photoluminescence in the lead-free ferroelectric Na1/2Bi1/2TiO3

Eu+3 was incorporated into the lattice of a lead-free ferroelectric Na1/2Bi1/2TiO3 (NBT) as per the nominal formula Na0.5Bi0.5-xEuxTiO3. This system was investigated with regard to the Eu+3 photoluminescence (PL) and structural behaviour as a function of composition and electric field. Electric field was found to irreversibly change the features in the PL spectra and also in the x-ray diffraction patterns below the critical composition x = 0.025. Detailed analysis revealed that below the critical composition, electric field irreversibly suppresses the structural heterogeneity inherent of the host matrix NBT and brings about a long range ferroelectric state with rhombohedral (R3c) distortion. It is shown that the structural disorder on the nano-scale opens a new channel for radiative transition which manifests as a new emission line branching off from the main D-5(0)-> F-7(0) line along with a concomitant change in the relative intensity of the other crystal field induced Stark lines with different J values. The study suggests that Eu+3 luminescence can be used to probe the relative degree of field induced structural ordering in relaxor ferroelectrics and also in high performance piezoelectric alloys where electric field couples very strongly with the lattice and structural degrees of freedom

Crucial Role of Donor Density in the Performance of Oxynitride Perovskite LaTiO2N for Photocatalytic Water Oxidation

LaTiO2 N photocatalysts were prepared by thermal ammonolysis of flux-synthesized La2 Ti2 O7 and La2 TiO5 , and were investigated for water oxidation. Though LaTiO2 N derived from La2 TiO5 appears defect-free by UV/Vis/near-IR and electron paramagnetic resonance (EPR) spectroscopy, its performance is much lower than that of conventional La2 Ti2 O7 -derived LaTiO2 N with defects. It is shown by Mott-Schottky analysis that La2 TiO5 -derived LaTiO2 N has significantly lower donor density; this can result in insufficient built-in electric field for the separation of photogenerated electrons and holes. The lower donor density is also consistent with the smaller difference between the Fermi level and the valence-band maximum, which accounts for a lower oxidative power of the holes. In light of this discovery, the donor density was increased substantially by introducing anion vacancies through annealing in Ar. This resulted in improved performance. The CoOx -assisted La2 TiO5 -derived LaTiO2 N annealed at 713 °C has a higher quantum efficiency (25 %) at 450 nm than high-performance conventional CoOx /LaTiO2 N (21 %).

Nanorod to quantum dot conversion in ZnO dispersions with co-surfactants

A chemically-induced nanorod to quantum dot transition is reported in ZnO. This transition is achieved using co-surfactants in a marginally polar solvent in chimie douce (soft chemical) conditions. This is different from the physical instability driven transitions reported so far in metal nanowires and polymers. We propose a suitable mechanism for the observed phenomenon.

High pressure luminescence studies of europium doped GaN

We reported on the high pressure luminescence spectra of polycrystalline Eu-doped GaN material synthesized in the reaction between alloys of gallium, bismuth and europium in ammonia atmosphere. The integrated luminescence intensity of the dominant Eu3+ ion transition (5D0→7F2) at 622 nm increased approximately one order of magnitude whereas its spectral position and line width did not change significantly between ambient and 6.8 GPa pressure, respectively. Moreover, material was characterized with photo- and cathodo-luminescence, and photoluminescence excitation spectra at different temperatures. It was found that the Eu3+ ions occupying substitutional Ga site created different centers which could be effectively excited with above band gap excitation and from excitons resonantly photoexcited at the I2 bound exciton energy. Furthermore, the less efficient Eu3+ ions excitation path existed through intrinsic impurities and defects generating shallow energy levels in the forbidden gap. It was proposed that reduction of the thermal quenching and consequent enhancement of Eu3+ ion emission intensity resulted from stronger localization of bound exciton on RESI trap induced by applied pressure.

Yellow-emitting carbon-dots-impregnated carboxy methyl cellulose/poly-vinyl-alcohol and chitosan: stable, freestanding, enhanced-quenching Cu2+-ions sensor

Carbon dots (CDs) have a combination of desirable fluorescence and chemical properties, which makes them relevant for sensing in aqueous environments. However, CDs suffer from aggregation-induced instabilities in their sensing performance. In this study, we attempted to address this problem by focusing on Cu2+-ions detection compliant with US Environment Protection Agencys (EPA) standards (i.e. requiring detection as low as 1.3 ppm). The as-prepared yellow-emitting carbon dots (y-CDs) prepared via a one-step hydrothermal process had high water dispersivity and prominent fluorescence properties. However there were two contrary mechanisms (aggregation-caused quenching vs. the chelation-enhanced fluorescence effect) for y-CDs with the addition of Cu2+ ions. The y-CDs/polymer composite sensor reported here comes in two forms: y-CDs impregnated with: (a) carboxy methyl cellulose/poly-vinyl-alcohol or (b) chitosan. Although selectivity existed in both (a) and (b), the sensor response of (b) films was remarkably more sensitive than that of (a) films, due to the chelation mechanism of chitosan with Cu2+ ions. Through an optimized sample of system (b), a 10 nM/1.3 ppm detection limit for Cu2+ ions was achieved, which shows it was EPA compliant.

Coordination Polymer-Derived Multishelled Mixed Ni–Co Oxide Microspheres for Robust and Selective Detection of Xylene

Multishell, stable, porous metal-oxide microspheres (Ni-Co oxides, Co3O4 and NiO) have been synthesized through the amorphous coordination polymer-based self-templated method. Both oxides of Ni and Co show poor selectivity to xylene, but the composite phase has substantial selectivity (e.g., Sxylene/ Sethanol = 2.69) and remarkable sensitivity (11.5-5 ppm xylene at 255 °C). The short response and recovery times (6 and 9 s), excellent humidity-resistance performance (with coefficient of variation = 11.4%), good cyclability, and long-term stability (sensitivity attenuation of ∼9.5% after 30 days and stable sensitivity thereafter) all show that this composite is a competitive solution to the problem of xylene sensing. The sensing performances are evidently due to the high specific surface area and the nano-heterostructure in the composite phase.