Quantum cutting abilities of sol-gel derived LiGdF4:Eu powders

Optical properties of europium doped LiGdF₄ (LGF) powders synthesized by the sol-gel process were investigated in the VUV range. Emission of two visible photons (due to ⁵D₀→⁷F_J transitions on two Eu³⁺ ions) per absorbed VUV photon was demonstrated indicating that a quantum cutting phenomenon takes place. This mechanism is explained by a two-step energy transfer when exciting Gd³⁺ ions in their ⁶G_J high energy level. Best luminescence efficiency was recorded at room temperature for samples with a doping rate of 5 mol% in europium ions. Effect of rare-earth concentration on internal quantum cutting efficiency was studied. Temperature dependence was also investigated and showed that the down-conversion process upon excitation at 202 nm becomes inefficient at low temperature since energy transfer from Gd³⁺ ions to Eu³⁺ ions is not effective any more. Such a result was connected with the thermal population at room temperature of Eu³⁺⁷F₁ state which is involves in the first step of the energy transfer.     

Effects of cooling rate and post-heat treatment on properties of ZnO thin films deposited by sol-gel method

Sol-gel spin-coated ZnO thin films are cooled with different rates after the pre-heat treatment. Atomic force microscopy (AFM), X-ray diffraction (XRD), Raman, and photoluminescence (PL) were carried out to investigate the effects of the cooling rate during pre-heat treatment on structural and optical properties of the ZnO thin films. The ZnO thin films cooled slowly exhibit mountain chain structure while the ones cooled rapidly have smooth surface. The ZnO thin films cooled rapidly have higher c-axis orientation compared to the ones cooled slowly. The narrower and the higher near-band-edge emission (NBE) peaks are observed in the ZnO thin films cooled rapidly.     

Photoluminescence studies in sol-gel derived Zno films

The photoluminescence (PL) properties of high quality ZnO thin films grown on Si (1 0 0) substrates using spin coating technique are investigated as a function of temperature in the range 10-300 K. The PL spectra shows dominant donor bound excitonic emission along with free exciton related emission in the UV region. The corresponding activation energy of thermal quenching is found to be . The parameters that describe the temperature dependent red shift of the band-edge transition energy are evaluated using different models. The broadening of the PL peak due to increase in temperature is mainly attributed to the exciton-LO phonon coupling.     

Effects of non-stoichiometry on crystallinity, photoluminescence and afterglow properties of Sr2MgSi2O7:Eu, Dy phosphors

Eu²⁺, Dy³⁺ co-doped Sr₂MgSi₂O₇ phosphors with deficient, stoichiometric or excess amounts of silicon are prepared by solid-state reaction. XRD and SEM results indicate that all the samples studied are found to be free from impurities and samples with SiO₂ excess possess better crystallinity and larger grain size. Photoluminescence reveals that the position of Eu²⁺ emission is not changed with various compositions. However, both photoluminescence intensity and afterglow properties are increased by an incorporation of excess SiO₂ and are decreased by SiO₂ deficiency. The thermoluminescence results show that the corresponding increase or decrease in afterglow is associated with trap density, but no change in trap depth. The underlying reason of photoluminescence and afterglow enhancement is discussed.     

Optical properties of Eu(fod)3-doped polymers using supercritical carbon dioxide

X-ray diffraction pattern of solvated Eu(fod)₃(H₂O)_1,5(i-PrOH)_0,5 form of Eu(fod)₃ complex (fod=6,6,7,7,8,8,8-heptafluoro-2,2-dimethyl-3,5-octanedionate) is presented. The photoluminescence (PL) spectra of Eu³⁺ ions in polycrystalline powder Eu(fod)₃ and also in Eu(fod)₃-doped polymethylmethacrylate (PMMA), polypropylene (PP) and polydimethylsiloxane (PDMS) were investigated. It is revealed that the matrix influences the temperature quenching of PL intensity in the range 20-100 °C. A polycrystalline powder Eu(fod)₃ and Eu(fod)₃-doped PP are the most effective materials for PL quenching. It is shown that water molecules in the first coordinating sphere of Eu³⁺ ions increase PL intensity temperature quenching.     

Influence of pH value on the quality of sol-gel derived ZnO films

In sol-gel derived ZnO films the pH value of the sol plays an important role in controlling their properties. In this study, the influence of adding monoethanolamine to zinc acetate solution in methanol on structural, surface morphology and optical properties has been investigated. Addition of monoethanolamine to zinc acetate solution transforms the nature of the sol from acidic to alkaline by changing the pH value from 6.4 to 10.6. The investigations indicate that high quality ZnO films are obtained by using sol having monoethanolamine to zinc acetate ratio of 1:1 and pH value of 10.6.     

Photophysical analysis of the organic complex [Eu(C12H8N2)2](NO3)3

We have determined the photophysical properties of [Eu(C₁₂H₈N₂)₂](NO₃)₃, (EuPhen), a complex which is very promising for photonic and optoelectronic applications, because of its easy synthetic procedure and high thermal stability (up to 300 °C) combined with large sensitization efficiency and good emission quantum yield. Available experimental absorption and emission data have been analyzed by using Judd-Ofelt analysis. Moreover, semi-empirical calculations have been used to determine the structure of the complex and to interpret the convoluted shape of the absorption spectrum.     

Layer‐by‐layer fabrication of hierarchical structures in sol–gel templated thin titania films

The fabrication of titania nanostructures with hierarchical order of different structural levels is investigated. The nanostructures are prepared with a diblock‐copolymer assisted sol–gel process. By iterative spin‐coating of the solution onto silicon substrates a thin polymer‐nanocomposite film is deposited and transformed to purely anatase titania nanostructures via calcination. In total, this procedure is repeated three times on top of the substrate. The approach is monitored with grazing incidence small angle X‐ray scattering after each fabrication step. With scanning electron microscopy the final hierarchical structure is imaged. From the characterization different structural levels are clearly identified.

     

Epitaxially grown ZnO thin films on 6H-SiC(0 0 0 1) substrates prepared by spin coating-pyrolysis

Epitaxially grown ZnO thin film on 6H-SiC(0 0 0 1) substrate was prepared by using a spin coating-pyrolysis with a zinc naphthenate precursor. As-deposited film was pyrolyzed at 500 °C for 10 min in air and finally annealed at 800 °C for 30 min in air. In-plane alignment of the film was investigated by X-ray pole-figure analysis. Field emission-scanning electron microscope, scanning probe microscope, and He-Cd laser (325 nm) was used to analyze the surface morphology, the surface roughness and photoluminescence of the films. In the photoluminescence spectra, near-band-edge emission with a broad deep-level emission was observed. The position of the near-band-edge peak was around 3.27 eV.     

The influence of the dielectric on the properties of dielectromagnetic soft magnetic composites. Investigations with silica and silica hybrid sol–gel derived model dielectric

Dielectromagnetics made from organic–inorganic hybrid silica-coated iron powders were characterised by determination of their physical, mechanical and magnetic properties. The influence of three main factors, dielectric composition, addition level and heat treatment conditions were investigated. Results showed that these factors have significant effects on the performance of the dielectromagnetics. Increase in the organic phase content in these dielectric coatings tends to increase both the electrical resistivity and magnetic permeability of dielectromagnetics, although the strength and density are slightly impaired. Increasing the coating thickness leads to improvements in resistivity and thus reduced eddy current losses, but these are offset by reductions in density, strength and particularly magnetic permeability. A hybrid organic–inorganic coating formulation based on 40 mol% MTMS and 60 mol% TEOS precursors was found to be the optimum composition investigated. Addition levels between 0.1% and 0.3% were found to offer a good compromise between maximum permeability (μ_max>400) and minimum loss (typically <8 W/kg) for operation at 50 Hz/1 T, and the system can be optimised within this range for the desired performance.     

The role of defect states in the creation of photoluminescence in SrTiO<Subscript>3</Subscript>

We discuss the nature of visible photoluminescence at room temperature in amorphous strontium titanate in the light of the results of a recent experimental and quantum mechanical theoretical study. Our calculation of the electronic structure involves the use of first-principles molecular calculations to simulate the variation of the electronic structure in the strontium titanate crystalline phase, which is known to have a direct band gap, and we also make an in-depth examination of amorphous strontium titanate. The results of our simulations of amorphous strontium titanate indicate that the formation of five-fold coordination in the amorphous system may introduce delocalized electronic levels in the highest occupied molecular orbital and the lowest unoccupied molecular orbital. These delocalized electronic levels are ascribed to the formation of a tail in the absorbance-spectrum curve. Optical absorption measurements experimentally showed the presence of a tail. The results are interpreted by the nature of these exponential optical edges and tails associated with defects promoted by the disordered structure of the amorphous material. We associate them with localized states in the band gap. Received: 15 January 2002 / Accepted: 7 August 2002 / Published online: 4 December 2002 RID="*" ID="*"Corresponding author. Fax: +55-16/2615-215, E-mail: derl@power.ufscar.br     

Determination of optical properties in nanostructured thin films using the Swanepoel method

We present the methodological framework of the Swanepoel method for the spectrophotometric determination of optical properties in thin films using transmittance data. As an illustrative case study, we determined the refractive index, thickness, absorption index, and extinction coefficient of a nanostructured 3 mol% Y₂O₃-doped ZrO₂ (yttria stabilized zirconia, 3YSZ) thin film prepared by the sol-gel method and deposited by dipping onto a soda-lime glass substrate. In addition, using the absorption index obtained with the Swanepoel method, we calculated the optical band gap of the film. The refractive index was found to increase, then decrease, and finally stabilize with increasing wavelength of the radiation, while the absorption index and extinction coefficient decreased monotonically to zero. These trends are explained in terms of the location of the absorption bands. We also deduced that this 3YSZ thin film has a direct optical band gap of 4.6 eV. All these results compared well with those given in the literature for similar thin films. This suggests that the Swanepoel method has an important role to play in the optical characterization of ceramic thin films.     

Effects of sic buffer layer on the optical properties of ZnO films grown on Si (1 1 1) substrates

ZnO films have been grown by a sol-gel process on Si (1 1 1) substrates with and without SiC buffer layers. The influence of SiC buffer layer on the optical properties of ZnO films grown on Si (1 1 1) substrates was investigated. The intensity of the E₂ (high) phonon peak in the micro-Raman spectrum of ZnO film with the SiC buffer layer is stronger than that of the sample without the SiC buffer layer, and the breadth of E₂ (high) phonon peak of ZnO film with the SiC buffer layer is narrower than that of the sample without the SiC buffer layer. These results indicated that the crystalline quality of the sample with the SiC buffer layer is better than that of the sample without the SiC buffer layer. In photoluminescence spectra, the intensity of free exciton emission from ZnO films with the SiC buffer was much stronger than that from ZnO film without the SiC buffer layer, while the intensity of deep level emission from sample with the SiC buffer layer was about half of that of sample without the SiC buffer layer. The results indicate the SiC buffer layer improves optical qualities of ZnO films on Si (1 1 1) substrates.     

Structure, dielectric and ferroelectric properties of highly (1 0 0)-oriented BaTiO3 grown under low-temperature conditions

The highly (1 0 0)-oriented BaTiO₃ thin films were fabricated on LaNiO₃(1 0 0)/Pt/Ti/SiO₂/Si substrates under low-temperature conditions. Substrate temperatures throughout the fabrication process remained at or below 400 °C, which allows this process to be compatible with many materials commonly used in integrated circuit manufacturing. X-ray diffraction data provided the evidence for single BaTiO₃ phase. Field-emission scanning electron microscopy was used to study the columnar structure of the films. The dielectric properties as a function of frequency in the range of 1 kHz to 1 MHz was obtained. The room temperature remanent polarization (2P_r) and coercive field were found to be ∼5 μC/cm² and 50 kV/cm, respectively. The BTO film maintains an excellent fatigue-free character even after 10⁹ switching cycles.     

Effect of ion nitriding on the crystal structure of 3 mol% Y2O3-doped ZrO2 thin-films prepared by the sol-gel method

We investigated the effect of ion nitriding on the crystal structure of 3 mol% Y₂O₃-doped ZrO₂ (3YSZ) thin-films prepared by the sol-gel method. For this purpose, we used X-ray diffractometry to determine the crystalline phases, the lattice parameters, the crystal sizes, and the lattice microstrains, and glow discharge-optical emission spectroscopy to obtain the depth profiles of the elemental chemical composition. We found that nitrogen atoms substitute oxygen atoms in the 3YSZ crystal, thus leading to the formation of unsaturated-substitutional solid solutions with reduced lattice parameters and Zr_0.94Y_0.06O_1.72N_0.17 stoichiometric formula. We also found that ion nitriding does not affect the grain size, but does generate lattice microstrains due to the increase in point defects in the crystalline lattice.     

Enhanced luminescence of GdTaO4:Eu thin-film phosphors by K doping

The effect of K⁺ ions on GdTaO₄:Eu³⁺ thin-film phosphors was investigated in order to improve their luminescent properties. The GdTaO₄:Eu_0.1, K_x thin films were synthesized by sol-gel process, and characterized through measuring their microstructure and luminescence. The results indicated that photoluminescence (PL) intensity of GdTaO₄:Eu³⁺ film was improved remarkably by K doping. There were two maxima in the curve of PL intensity against K⁺ dopant concentration, where one was improved up to 2.1 times at x = 0.001 and the other was enhanced up to 2.7 times at x = 0.05. The first maximum was regarded as the alteration of the local environment surrounding the Eu³⁺ activator by incorporation of K⁺ ions, and the second maximum was due to the flux effect. Additionally, the luminescence increased with the increase of firing temperature from 800 °C to 1200 °C.     

Growth of highly-oriented CaCu3Ti4O12 thin films on SrTiO3 (1 0 0) substrates by a chemical solution route

Highly-oriented CaCu₃Ti₄O₁₂ (CCTO) thin films deposited directly on SrTiO₃ (1 0 0) substrates have been developed successfully using a chemical solution coating method. X-ray diffraction (XRD), scanning electron microscopy (SEM), and atomic force microscopy (AFM) were employed to characterize the structure and the morphology. It was observed that the CCTO thin films had the 1 μm × 1 μm domain-like microstructure that consists of compact grains of about 0.1 μm in size. The cross sectional SEM image shows that the CCTO grains grow regularly close to the clear interface between the CCTO film and the SrTiO₃ substrate. The result was discussed in terms of lattice mismatch between CCTO and SrTiO₃.     

Study on crystalline properties of Er-Si-O compounds in relation to Er-related 1.54 μm photoluminescence and electrical properties

Er-Si-O crystalline compounds, which exhibit superlattice structures and sharp and strong Er-related 1.54 μm photoluminescence (PL) spectra at room temperature have been formed by self-assembling growth mechanism. Oxidation of the starting materials which have Si and Er at an atomic ratio of 2:1 are prepared and then oxidation and succeeding high-temperature annealing in Ar above 1250 °C cause a self-assembled superlattice-structured Er-Si-O crystalline compounds. The control of the ratio of Si and Er, as well as the following oxidation and annealing processes, is found to be sensitive to the crystalline properties, PL spectra and electrical properties. In this study, Er-Si-O crystalline thin films are formed on Si substrates by sol-gel and MOMBE methods, and their crystalline properties such as crystalline orientation and concentration ratio of Er, Si and O are investigated. Crystalline Er-Si-O films of high orientation are successfully grown on Si(1 0 0) and its inclined surface. The PL and excitation spectra, fluorescence decay and the electrical properties are found to be strongly related to the crystalline properties. Excess O causes a broader 1.54 μm PL spectra, slower fluorescence decay, lower carrier-mediated excitation and higher resistivity. A precise control of O is found to be necessary to grow superlattice-structured Er-Si-O compounds, which are semiconducting and are excitable via carrier-mediated excitation mechanism.     

Raman spectroscopy of sol–gel derived titanium oxide thin films

Raman spectra of TiO₂ films prepared via the sol–gel process were studied by UV and visible Raman spectroscopy. The evolution of the phases of TiO₂ films during annealing was investigated, and the relative intensities of the Raman bands excited with 325 nm were found to be distinct from those of the bands excited with 514 nm. The transmittance and FTIR spectra of the films annealed at different temperatures were characterized. The crystallization process of the powders and thin films treated by different annealing methods were also studied with Raman spectroscopy. The results show that the change in the relative intensities is caused by the resonance Raman effect. The anatase to rutile transition of the powder occurs at 700 °C, while that of the thin film occurs at 800 °C. The analysis of Raman band shape (peak position and full width at half‐maximum) after conventional furnace annealing and rapid thermal annealing indicates the influence of the non‐stoichiometry and phonon confinement effect. Copyright © 2011 John Wiley & Sons, Ltd.     

Highly enhanced photoluminescence and X-ray excited luminescence of Li doped Gd2O3:Eu thin films

Transparent Li-doped Gd₂O₃:Eu³⁺ thin-film phosphors were prepared by a modified sol-gel method. The effect of the Li⁺ ions on luminescent properties of the thin film was investigated. The results indicated that incorporation of Li⁺ ions into Gd₂O₃ lattice could result in a remarkable increase on photoluminescence or X-ray excited luminescence, and the strongest emission was observed from Gd_1.84Li_0.08Eu_0.08O_3−δ film, in which the intensity was increased by a factor of 1.9 or 2.3 in comparison with that of Gd_1.92Eu_0.08O₃ film. And it could be achieved the highest intensity for sintering the Gd_1.84Li_0.08Eu_0.08O_3−δ film at 700 °C. Such a temperature is much lower than the typical solid-state reaction temperature for its powder phosphors. This kind of transparent thin-film phosphors may promise for application to micro X-ray imaging system.